Hybrid supported metallocene catalyst and method for preparing polyethylene using same

Abstract

The present invention provides: a hybrid supported metallocene catalyst useful for the production of polyethylene that exhibits high impact strength as well as excellent processability; and a method for preparing polyethylene using the catalyst.

Description

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

[0001] The present invention relates to a hybrid supported metallocene catalyst useful for the production of polyethylene exhibiting high impact strength characteristics along with excellent processability, and a method for producing polyethylene using the same.

[0002] Cross-citation with related applications

[0003] The present application claims the benefit of priority based on Korean Patent Application No. 10-2024-0160187 filed November 12, 2024 and Korean Patent Application No. 10-2025-0090265 filed July 4, 2025, and all contents disclosed in the documents of said Korean patent applications are incorporated herein as part of the specification.

[0004]

[0005] Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Since its invention in the 1950s, the Ziegler-Natta catalyst has been widely applied in existing commercial processes. However, because it is a multi-site catalyst with multiple active sites, it is characterized by a wide molecular weight distribution of the polymer and has a problem in that there are limitations in securing desired properties due to the non-uniform compositional distribution of the comonomer.

[0006]

[0007] On the other hand, metallocene catalysts consist of a combination of a main catalyst, which is primarily composed of a transition metal compound, and a co-catalyst, which is an organometallic compound primarily composed of aluminum. Such catalysts are homogeneous complex catalysts and single-site catalysts; due to their single-site characteristics, they produce polymers with a narrow molecular weight distribution and a uniform compositional distribution of comonomers. Furthermore, they possess the ability to alter the stereoregularity, copolymerization characteristics, molecular weight, and degree of crystallinity of the polymer by modifying the catalyst's ligand structure and changing the polymerization conditions.

[0008]

[0009] Meanwhile, linear low-density polyethylene (LLDPE) is produced by copolymerizing ethylene and alpha-olefins at low pressure using a polymerization catalyst. It is a resin with a narrow molecular weight distribution, short-chain branches of uniform length, and no long-chain branches. In addition to the characteristics of general polyethylene, linear low-density polyethylene films have high breaking strength and elongation, as well as excellent tear strength and drop impact strength. Consequently, their use is increasing in applications such as stretch films and overlap films where conventional low-density polyethylene or high-density polyethylene is difficult to apply.

[0010]

[0011] Recently, along with decarbonization, there has been an increasing demand for high-performance linear low-density polyethylene to improve recyclability. Along with this, there is also a growing demand for high-transparency linear low-density polyethylene that offers excellent drop impact strength and processability.

[0012]

[0013] Dart drop impact strength is a very important mechanical property for verifying the various impact resistances of resins.

[0014]

[0015] However, linear low-density polyethylene has the disadvantage of poor processability as a blown film and low transparency compared to its excellent mechanical properties. A blown film is a film manufactured by blowing air into molten plastic to inflate it, and it is also called an inflation film.

[0016]

[0017] Lower density is characterized by improved transparency and increased drop impact strength. However, using a large amount of alpha-olefin comonomers to manufacture low-density polyethylene leads to problems such as a higher frequency of fouling during the slurry polymerization process; therefore, in the slurry polymerization process, a density of 0.915 g / cm³ 3 We are producing a large number of the above products.

[0018]

[0019] This density 0.915 g / cm³ 3 When long-chain branches (LCB) are introduced into the above LLDPE, it is possible to achieve high transparency while maintaining excellent mechanical properties and increasing processability, and with these properties, high-value-added products such as shrink films can be expected.

[0020]

[0021] In addition, linear low-density polyethylene generally uses comonomers with six or more carbon atoms, such as 1-hexene and 1-octene, to achieve the aforementioned properties, but these comonomers with six or more carbon atoms are relatively expensive due to the complex production process.

[0022]

[0023] Accordingly, there is a need for a catalyst that can produce polyethylene with properties similar to LLDPE produced using comonomers with 6 or more carbon atoms, even when using relatively inexpensive comonomers with a low number of carbon atoms.

[0024]

[0025] To solve the problems of the prior art described above, the present invention aims to provide a hybrid supported metallocene catalyst useful for the production of polyethylene, which exhibits high impact strength characteristics along with excellent processability.

[0026]

[0027] In addition, the present invention aims to provide a method for manufacturing polyethylene exhibiting excellent drop impact strength characteristics using the above-described hybrid supported metallocene catalyst.

[0028]

[0029] 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 or Chemical Formula 2; a second transition metal compound represented by the following Chemical Formula 3; a co-catalyst; and a support:

[0030] [Chemical Formula 1]

[0031]

[0032] In the above chemical formula 1,

[0033] X 11 and X 12 C each independently 1-20 It is an alkyl, or halogen, and

[0034] R 11 to R 15 are independently hydrogen, C 1-20 Alkyl, C 2-20 Alkoxyalkyl, C 6-20 Aril, C 7-20 alkylaryl of, or C 7-20 It is an arylalkyl of, or R 11 to R 15 Among them, two adjacent substituents combine to form a substituted or unsubstituted C 6-20 It forms an aromatic ring,

[0035] R 16 to R 20 are independently hydrogen, C 1-20 alkyl, or C 2-20It is an alkoxyalkyl, and

[0036] [Chemical Formula 2]

[0037]

[0038] In the above chemical formula 2,

[0039] M2 is a group 4 transition metal, and

[0040] X 21 and X 22 are independently, C 1-20 It is an alkyl, or halogen, and

[0041] A2 is carbon, silicon, or germanium, and

[0042] Q 21 and Q 22 are independently, halogen, C 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, provided that Q 21 and Q 22 At least one of them is C 2-20 It is an alkoxyalkyl, and

[0043] R 21 and R 22 Each independently, hydrogen or C 1-20 It is alkyl, and

[0044] R 23 and R 24 Each independently, hydrogen, or C 1-20 C that is alkyl, or bonded to one another, substituted or unsubstituted 6-20 It forms an aromatic ring,

[0045] R 25 is C 1-20 It is alkyl, and

[0046] [Chemical Formula 3]

[0047]

[0048] In the above chemical formula 3,

[0049] M3 is a group 4 transition metal, and

[0050] X 31 and X 32are independently, C 1-20 It is an alkyl or halogen, and

[0051] R 31 to R 35 Each independently, hydrogen, or C 1-20 It is alkyl, provided that R 31 to R 35 At least four of them are C 1-20 It is alkyl, and

[0052] R 36 and R 37 Each is independently C substituted or unsubstituted with hydrogen, one or more halogens. 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, provided that R 36 and R 37 At least one of them is C substituted with one or more halogens. 1-20 alkyl, or C 2-20 It is an alkoxyalkyl.

[0053]

[0054] In addition, the present invention provides a method for producing polyethylene comprising the step of slurry polymerizing an ethylene monomer and an olefin monomer while introducing hydrogen in the presence of the aforementioned hybrid supported metallocene catalyst.

[0055]

[0056] In the present invention, terms such as first, second, etc. are used to describe various components, and these terms are used solely for the purpose of distinguishing one component from another.

[0057] Furthermore, the terms used herein are used merely to describe exemplary embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising,” “comprising,” or “having” are intended to specify the existence of the implemented features, numbers, steps, components, or combinations thereof, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0058] Additionally, "~" indicating a numerical range in this specification includes both the upper and lower limits of the numerical range. For example, in the case of A~B, it means A or greater and B or less.

[0059] 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.

[0060]

[0061] Hereinafter, the hybrid supported metallocene catalyst of the present invention and the method for manufacturing polyethylene using the same will be described in detail.

[0062]

[0063] The hybrid supported metallocene catalyst according to the present invention comprises: a first transition metal compound represented by the following Chemical Formula 1 or Chemical Formula 2; a second transition metal compound represented by the following Chemical Formula 3; a co-catalyst; and a support:

[0064] [Chemical Formula 1]

[0065]

[0066] In the above chemical formula 1,

[0067] X 11 and X 12 C each independently 1-20 It is an alkyl, or halogen, and

[0068] R 11 to R 15 are independently hydrogen, C 1-20 Alkyl, C 2-20 Alkoxyalkyl, C 6-20 Aril, C 7-20 alkylaryl of, or C 7-20 It is an arylalkyl of, or R 11 to R 15 Among them, two adjacent substituents combine to form a substituted or unsubstituted C 6-20 It forms an aromatic ring,

[0069] R 16 to R 20 are independently hydrogen, C 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, and

[0070] [Chemical Formula 2]

[0071]

[0072] In the above chemical formula 2,

[0073] M2 is a group 4 transition metal, and

[0074] X 21 and X 22 are independently, C 1-20 It is an alkyl, or halogen, and

[0075] A2 is carbon, silicon, or germanium, and

[0076] Q 21 and Q 22 are independently, halogen, C 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, provided that Q 21 and Q 22 At least one of them is C 2-20 It is an alkoxyalkyl, and

[0077] R 21and R 22 Each independently, hydrogen or C 1-20 It is alkyl, and

[0078] R 23 and R 24 Each independently, hydrogen, or C 1-20 C that is alkyl, or bonded to one another, substituted or unsubstituted 6-20 It forms an aromatic ring,

[0079] R 25 is C 1-20 It is alkyl, and

[0080] [Chemical Formula 3]

[0081]

[0082] In the above chemical formula 3,

[0083] M3 is a group 4 transition metal, and

[0084] X 31 and X 32 are independently, C 1-20 It is an alkyl or halogen, and

[0085] R 31 to R 35 Each independently, hydrogen, or C 1-20 It is alkyl, provided that R 31 to R 35 At least four of them are C 1-20 It is alkyl, and

[0086] R 36 and R 37 Each is independently C substituted or unsubstituted with hydrogen, one or more halogens. 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, provided that R 36 and R 37 At least one of them is C substituted with one or more halogens. 1-20 alkyl, or C 2-20 It is an alkoxyalkyl.

[0087]

[0088] In the present invention, the substituents of the above chemical formula are described in more detail as follows.

[0089]

[0090] Halogens can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0091]

[0092] The above 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 group 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, etc.

[0093]

[0094] 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.

[0095]

[0096] C 2-20The 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 alkoxyalkyl group having 2 to 20 carbon atoms 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.

[0097]

[0098] C 6-20 The aryl of may refer to monocyclic, bicyclic, or tricyclic aromatic hydrocarbons. Specifically, the aryl having 6 to 20 carbon atoms may be a phenyl group, a naphthyl group, or anthracenyl group, etc.

[0099]

[0100] 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, di-tert-butylphenyl, or cyclohexylphenyl, etc.

[0101]

[0102] C 7-20 The arylalkyl of may refer to a substituent in which one or more hydrogens of the alkyl group are substituted by an aryl group. Specifically, the above C 7-20 The arylalkyl group can be a benzyl group, phenylpropyl or phenylhexyl, etc.

[0103]

[0104] In addition, group 4 transition metals may include titanium, zirconium, hafnium, etc.

[0105]

[0106] The hybrid supported metallocene catalyst according to the present invention is a hybrid catalyst comprising a first transition metal compound of high molecular weight and high copolymerization and a second transition metal compound of low molecular weight and low copolymerization.

[0107]

[0108] Specifically, the first transition metal compound represented by Chemical Formula 1 or Chemical Formula 2 contributes to making a high molecular weight copolymer having a high SCB content, and the second transition metal compound represented by Chemical Formula 3 contributes to making a low molecular weight copolymer having a low SCB (short chain branch) content.

[0109]

[0110] Accordingly, the hybrid supported metallocene catalyst of the present invention can exhibit high copolymerization in polyethylene in the high molecular weight range due to the action of the first transition metal compound, while exhibiting low copolymerization 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 has a high content of the fraction that contributes significantly to drop impact strength, and the low-crystallinity and high-crystallinity content is appropriately balanced, thereby exhibiting excellent drop impact strength and processability, as well as outstanding transparency.

[0111] In particular, as confirmed in the examples and experimental examples described below, polyethylene produced using the hybrid supported metallocene catalyst according to the present invention can maintain drop impact strength, processability, and transparency equivalent to that of polyethylene produced using a comonomer with 6 or more carbon atoms, such as 1-hexene, even when using inexpensive 1-butene as a comonomer, thereby also securing price competitiveness.

[0112]

[0113] 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, low-crystallinity copolymer and exhibits a relatively high comonomer incorporation rate compared to the second transition metal compound.

[0114]

[0115] Specifically, in the above chemical formula 1, X 11 and X 12 are independently, C 1-20 It is an alkyl or halogen, preferably C 1-6 It may be an alkyl or halogen, and more preferably chloro(Cl) or methyl.

[0116] The first transition metal compound represented by the above chemical formula 1 contains Hf (hafnium) as the central metal, and compared to when other group 4 elements such as Zr are included, the effect of increasing molecular weight due to the incorporation of the comonomer is greater, and as a result, it is effective for producing high molecular weight copolymers that maintain a low crystalline state.

[0117]

[0118] R 11 to R 15 are independently hydrogen, C 1-20 Alkyl, C 2-20 Alkoxyalkyl, C 6-20 Aril, C 7-20 alkylaryl of, or C 7-20 It is an arylalkyl of, or R 11 to R 15 Among them, two adjacent substituents combine to form a substituted or unsubstituted C 6-20 Forming an aromatic ring, preferably hydrogen, C 1-6 Alkyl, or -(CH2) n -R a (Above R a is C 3-6 It is a branched alkoxy group, and is an alkoxyalkyl (where n is an integer from 2 to 10), or R 11 to R 15Among them, two adjacent substituents can bond with each other to form a benzene ring. More preferably, R 11 to R 15 are each independently hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, tert-butoxyethyl, tert-butoxypropyl, tert-butoxybutyl, tert-butoxypentyl, or tert-butoxyhexyl, or R 11 to R 15 Among them, two adjacent substituents can bond with each other to form a benzene ring. R 11 to R 15 In the case where two adjacent substituents combine to form a benzene ring, the benzene ring is unsubstituted, or C 1-6 It can be substituted with alkyl.

[0119]

[0120] R 16 to R 20 are independently hydrogen, C 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, preferably hydrogen, C 1-6 Alkyl, or -(CH2) n -R a (Above R a is C 3-6 It may be a branched alkoxy group, where n is an integer from 2 to 10, and may be an alkoxyalkyl. More preferably, R 16 to R 20 Each can independently be hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl.

[0121]

[0122] Specific examples of the first transition metal compound represented by the above chemical formula 1 include compounds having the following structure, but the present invention is not limited thereto.

[0123]

[0124]

[0125] The first transition metal compound represented by the above-described chemical formula 1 can be synthesized by applying known reactions, and a more detailed synthesis method can be referenced in the examples.

[0126]

[0127] Meanwhile, the first transition metal compound represented by Chemical Formula 2 has a structure in which a cyclic compound containing thiophene and an amine-based compound are cross-linked, allowing for easy control of the electronic and stereochemical environment around the transition metal. As a result, the amount of comonomer incorporated into the synthesized polyethylene can be controlled, allowing for easy adjustment of properties such as crystallinity and molecular weight to a desired level.

[0128] Specifically, within the structure of the transition metal compound represented by the above chemical formula 2, the cyclic compound containing thiophene can increase the basic molecular weight by exerting a heterovalence electron-donating effect, and the amine compound can influence the control of the comonomer incorporation amount together with the central metal.

[0129]

[0130] In the above chemical formula 2, M2 is a group 4 transition metal, preferably zirconium (Zr) or titanium (Ti), and more preferably titanium (Ti).

[0131] X 21 and X 22 are independently, C 1-20 It is an alkyl or halogen, preferably C 1-6 It may be alkyl, and more preferably, methyl.

[0132] When titanium (Ti) is included as the central metal of the first transition metal compound represented by the above chemical formula 2, the size of the active site can be appropriately maintained compared to when other group 4 elements such as Zr, Hf, etc. are included, and as a result, a superior comonomer incorporation effect can be achieved.

[0133]

[0134] In addition, the compound represented by the above chemical formula 2 is a cyclic compound containing thiophene and an amine bridge group A2(Q 21 )(Q 22 It includes a ) group. In the above chemical formula 2, A2 is carbon, silicon, or germanium, and preferably may be silicon.

[0135] And, Q, a substituent of A2 21 and Q 22 are independently, halogen, C 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, provided that Q 21 and Q 22 At least one of them is C 2-20 It is an alkoxyalkyl. Preferably, Q is a substituent of A2. 21 and Q 22 At least one of them is C 2-20 It may include an alkoxyalkyl tether group. In this way, having a tether group prevents leaching of the catalyst precursor during the polymerization reaction, and as a result, fouling caused by the reaction between the leached catalyst precursor and the co-catalyst can be prevented.

[0136] In addition, if the above bridge group includes a tether group, Q, which is a substituent of A2, 21 and Q 22 One of them is C 2-20 It is an alkoxyalkyl, and the other one is C 1-20 It can be an alkyl group. As a bridge group connecting two ligands in this way, Q 21 and Q22 One of them is C 2-20 When an alkoxyalkyl tether group is included, in addition to the effect of preventing leaching of the aforementioned catalyst precursor, superior catalytic activity can be exhibited as monomer access is facilitated during the polymerization reaction due to the larger atomic size and increased soluble angle compared to carbon bridges in conventional metallocene compounds. This effect is attributed to Q in the tether. 21 and Q 22 One of them is -(CH2)nR b (Above R b is C 1-6 Alkoxy group, more specifically C 1-6 Linear alkoxy groups or C 3-6 It can be a branched alkoxy group, and more specifically, C such as a tert-butoxy group 3-6 If it is a branched alkoxy, and n is an integer from 2 to 10 or from 3 to 9, furthermore, the remaining one is C 1-4 It may be further increased in the case of alkyl. Preferably, Q 21 and Q 22 One of them may be tert-butoxyhexyl and the other may be methyl.

[0137]

[0138] In addition, in the first transition metal compound represented by the above chemical formula 2, R 21 and R 22 Each independently, hydrogen or C 1-20 It is alkyl, and R 23 and R 24 Each independently, hydrogen, or C 1-20 C that is alkyl, or bonded to one another, substituted or unsubstituted 6-20 Forms an aromatic ring, and R 25 is C 1-20 It is an alkyl. Preferably, R 21 , R 22 and R 25 are independently, C 1-6 It can be alkyl, and R 23 and R 24Each independently, hydrogen, or C 1-6 They can be alkyl or bond with each other to form a benzene ring. More preferably, R 21 , R 22 and R 25 Each can independently be methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl, and R 23 and R 24 are each independently hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl, or R 23 and R 24 They can combine with each other to form a benzene ring. R 23 and R 24 When they combine to form a benzene ring, the benzene ring is unsubstituted, or C 1-6 It can be substituted with alkyl.

[0139]

[0140] Specific examples of the first transition metal compound represented by the above chemical formula 2 include compounds having the following structure, but the present invention is not limited thereto.

[0141]

[0142]

[0143] The first transition metal compound represented by the above-described chemical formula 2 can be synthesized by applying known reactions, and a more detailed synthesis method can be referenced in the examples.

[0144]

[0145] Meanwhile, the second transition metal compound represented by Chemical Formula 3 has a structure in which hydrogenated indene, specifically a 4,5,6,7-tetrahydro-1-indene derivative compound and a cyclopentadiene derivative compound are non-crosslinked, allowing for easy control of the electronic / steric environment around the transition metal. As a result, characteristics such as the molecular weight of the synthesized polyethylene and the copolymerization of the comonomer can be easily controlled.

[0146]

[0147] Specifically, in the above chemical formula 3, M3 is a group 4 transition metal, preferably zirconium (Zr) or titanium (Ti), and more preferably zirconium (Zr).

[0148] When Zr is included as the central metal of the second transition metal compound represented by Chemical Formula 3 above, the size of the active site can be effectively controlled compared to when other Group 4 elements such as Hf are included. This facilitates the inflow of hydrogen in the catalytic reaction, contributing to the production of polyethylene with a relatively low molecular weight, and limits the inflow of comonomers, thereby helping the polyethylene to exhibit low copolymerization. Furthermore, when the second transition metal compound having such characteristics is used together with the first transition metal compound represented by Chemical Formula 1 or Chemical Formula 2 above, an appropriate synergistic effect can be achieved.

[0149]

[0150] X 31 and X 32 are independently, C 1-20 It may be an alkyl or halogen, preferably a halogen, and more preferably chloro(Cl).

[0151]

[0152] In addition, in the second transition metal compound represented by the above chemical formula 3, the cyclopentadiene derivative compound is R 31 to R 35Superior catalytic activity can be exhibited through an inductive effect that can supply sufficient electrons by being substituted with a substituent, and impact strength and processability can be simultaneously improved by appropriately controlling the molecular weight and comonomer distribution of polyethylene prepared by using it together with a first transition metal compound represented by Chemical Formula 1 or Chemical Formula 2.

[0153] Substituent R of the above cyclopentadiene derivative compound 31 to R 35 Each independently, hydrogen, or C 1-20 It is alkyl, provided that R 31 to R 35 At least four of them are C 1-20 It is an alkyl. More specifically, R 31 to R 35 Each independently, hydrogen, or C 1-6 It is alkyl, provided that R 31 to R 35 At least four of them are C 1-6 It may be alkyl. More preferably, R 31 to R 35 are each independently hydrogen, or methyl, and R 31 to R 35 At least four of them may be methyl. Here, at least four are R 31 to R 35 It means four or five substituents out of five substituents.

[0154]

[0155] In addition, by including a hydrogenated inden group, namely a 4,5,6,7-tetrahydro-1-indene group, as a ligand, it exhibits superior hydrogen reactivity compared to cases where a conventional inden group is included, thereby reducing the amount of hydrogen input and wax generated during the polymerization reaction, and as a result, improving process stability.

[0156] In addition, the second transition metal compound represented by Chemical Formula 3 above may have the 1st and 3rd positions of the 4,5,6,7-tetrahydro-1-indene group unsubstituted or substituted. 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 36 and R 37 Each is independently C substituted or unsubstituted with hydrogen, one or more halogens. 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, provided that R 36 and R 37 At least one of them is C substituted with one or more halogens. 1-20 alkyl, or C 2-20 It is an alkoxyalkyl.

[0157] Specifically, R 36 and R 37 One of them is hydrogen, or C 1-6 C is alkyl, and the other is substituted or unsubstituted with one or more halogens. 1-6 Alkyl, or -(CH2) n -R c (Above R c is C 3-6 It may be a branched alkoxy group, where n is an integer from 2 to 10) and may be an alkoxyalkyl. In addition, the above -(CH2) n -R c In R c is C 3-6 C such as branched alkoxy groups, more specifically tert-butoxy groups 3-6 It is a branched alkoxy, and n can be an integer from 3 to 9. Preferably, R 36 and R 37 One of them is hydrogen, or C 1-6 C is an alkyl, and the other is substituted or unsubstituted with one or more fluorine (F) groups. 1-6 Alkyl, or -(CH2) n -R c (Above R c is C 3-6It may be a branched alkoxy group, where n is an integer from 2 to 10) and may be an alkoxyalkyl.

[0158]

[0159] Specific examples of the second transition metal compound represented by the above chemical formula 3 include compounds having the following structure, but the present invention is not limited thereto.

[0160]

[0161]

[0162]

[0163] The second transition metal compound represented by the above-described chemical formula 3 can be synthesized by applying known reactions, and a more detailed synthesis method can be referenced in the examples.

[0164]

[0165] Meanwhile, the hybrid supported metallocene catalyst according to the present invention can increase catalytic activity and further improve the physical properties of the polymer produced by controlling the molar ratio of the first and second transition metal compounds.

[0166]

[0167] For example, the hybrid supported metallocene catalyst may contain a first and a second transition metal compound in a molar ratio of 1:10 to 10:1. When the above mixing ratio conditions are satisfied, the activity of the catalyst is maintained excellently, and the high copolymerization and low copolymerization of polyethylene produced from the hybrid supported catalyst are optimized, thereby further improving not only drop impact strength but also transparency and processability. More specifically, considering the individual catalytic activity of each transition metal, the molar ratio of the first and second transition metal compounds may be 1:10 or more, or 1:5 or more, or 1:4 or more, or 1:3 or more, or 1:2 or more, or 1:1 or more, while being 10:1 or less, or 5:1 or less, or 4:1 or less, or 3:1 or less, or 2:1 or less.

[0168]

[0169] In addition, the hybrid supported metallocene catalyst according to the present invention includes a co-catalyst. When the hybrid supported metallocene catalyst includes a co-catalyst, it can improve process stability while exhibiting high catalytic activity.

[0170] Specifically, the above co-catalyst may include one or more of the compounds represented by the following chemical formula 4.

[0171] [Chemical Formula 4]

[0172] -[Al(R 41 )-O]a-

[0173] In the above chemical formula 4,

[0174] R 41 is a halogen; or C substituted or unsubstituted with a halogen 1-20 It is hydrocarbil;

[0175] a is an integer greater than or equal to 2.

[0176]

[0177] Meanwhile, in this specification, the hydrocarbyl group is a monovalent functional group in which a hydrogen atom has been removed from a hydrocarbon, and may include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, aralkenyl groups, aralkynyl groups, alkylaryl groups, alkenylaryl groups, and alkynylaryl groups, etc. Furthermore, 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.

[0178]

[0179] Examples of compounds represented by the above chemical formula 4 include alkylaluminoxan compounds such as methylaluminoxan, ethylaluminoxan, isobutylaluminoxan, or butylaluminoxan, and any one or more of these may be used.

[0180]

[0181] Among the compounds mentioned above, the co-catalyst may be, more specifically, an alkylaluminoxan-based co-catalyst such as methylaluminoxan.

[0182]

[0183] In addition, the amount of the above co-catalyst used can be appropriately adjusted according to the physical properties or effects of the desired catalyst and polyethylene. For example, when silica is used as a carrier as described below, the above co-catalyst may 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 1000 g of silica per weight of the carrier.

[0184]

[0185] Additionally, the hybrid supported metallocene catalyst according to the present invention may include a support. When the hybrid supported metallocene catalyst includes a support, the first and second transition metal compounds are used in the form of a supported catalyst supported on the support.

[0186]

[0187] As the above carrier, a carrier having highly reactive hydroxyl groups, silanol groups, or siloxane groups on its surface may be used, 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.

[0188]

[0189] 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.

[0190]

[0191] When used in the form of a supported catalyst, the particle shape and bulk density of the polymer produced are excellent, and it can be used in conventional slurry polymerization, bulk polymerization, or gas phase polymerization processes. In addition, among the various supports, since the functional groups of the transition metal compound are chemically bonded to the silica support, there is almost no catalyst released from the surface of the support during the ethylene polymerization process, and as a result, fouling caused by the entanglement of polymer particles on the reactor walls or between each other can be minimized when producing polyethylene by slurry or gas phase polymerization.

[0192]

[0193] The above-mentioned carrier may have an average particle size (D50) of 20 to 40 μm. When having the above-mentioned particle size, transition metal compounds can be supported with superior efficiency, and as a result, catalytic activity can be increased. More specifically, it may be 20 μm or more, or 25 μm or more, and 40 μm or less, or 30 μm or less.

[0194]

[0195] In addition, when supported on the above carrier, the first and second transition metal compounds may be supported in a content range of, for example, 1 mmol or more, 3 mmol or more, 5 mmol or more, 7 mmol or more, or 10 mmol or more, respectively, and 100 mmol or less, or 80 mmol or less, or 60 mmol or less, or 50 mmol or less, based on 1 g of silica carrier. When supported in the above content range, appropriate supported catalyst activity is exhibited, which may be advantageous in terms of maintaining catalyst activity and economic efficiency.

[0196]

[0197] A hybrid supported metallocene catalyst according to the present invention having the above-described configuration, and a catalyst composition having the above-described configuration, can be manufactured by a manufacturing method comprising the steps of: supporting a co-catalyst compound on a carrier; and supporting the first and second transition metal compounds on the carrier. In this case, the order of supporting the co-catalyst and the first and second transition metal compounds may be changed as needed, and the order of supporting the first and second transition metal compounds may also be changed as needed. The first and second transition metal compounds may be supported simultaneously. Considering the effect of the supported catalyst with a structure determined by the order of support, among these, sequentially supporting the first and second transition metal compounds after supporting the co-catalyst on the carrier allows the manufactured supported catalyst to achieve superior process stability along with high catalytic activity in the polyethylene manufacturing process.

[0198]

[0199] 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 a specific structure. Accordingly, the hybrid supported metallocene catalyst can be suitably used for the polymerization of ethylene monomers and olefin monomers.

[0200]

[0201] Accordingly, the present invention provides a method for producing polyethylene comprising the step of polymerizing an ethylene monomer and an alpha-olefin monomer while introducing hydrogen in the presence of the hybrid supported metallocene catalyst.

[0202]

[0203] 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-eicocene, norbornene, norvonadiene, 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. Preferably, the alpha-olefin monomer may be 1-butene, 1-hexene, or 1-octene, and more preferably, 1-butene.

[0204] The amount of the alpha-olefin monomer added above can be determined according to the physical properties of the polyethylene to be manufactured. For example, considering the effect of improving the physical properties, transparency, and processability of the polyethylene to be realized in the present invention, the alpha-olefin monomer may be added in an amount of 5 to 20 weight percent 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 5 weight percent or more, or 6 weight percent or more, or 7 weight percent or more, or 8 weight percent or more, and 25 weight percent or less, or 23 weight percent or less, or 21 weight percent or less, or 20 weight percent or less based on the total weight of the monomers including the ethylene monomer and the alpha-olefin monomer.

[0205]

[0206] The above polymerization reaction is carried out under conditions of hydrogen input.

[0207] Specifically, based on the total weight of the monomers including ethylene monomer and alpha-olefin monomer, hydrogen may be introduced in an amount of 5 to 500 ppm, more specifically 5 ppm or more, or 10 ppm or more, and 500 ppm or less, or 450 ppm or less, or 400 ppm or less, or 350 ppm or less, or 300 ppm or less, or 250 ppm or less. When introduced within the above range, it may be easier to achieve the physical properties of the polyethylene described above. When the polymerization reaction is performed under conditions without hydrogen introduction, the melt index (MI) of the polyethylene produced may be significantly lowered.

[0208]

[0209] The above polymerization reaction can be carried out as a slurry polymerization reaction.

[0210] Accordingly, it can be carried out using a single continuous slurry polymerization reactor or a loop slurry reactor.

[0211] In addition, the above-mentioned hybrid supported catalyst may be dissolved or diluted and injected in 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, 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.

[0212]

[0213] 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 at 110°C or lower, or 100°C or lower, or 90°C or lower. Furthermore, if the pressure conditions during the polymerization reaction are further controlled, the reaction may be carried out under a pressure of 5 bar or higher, or 10 bar or higher, or 20 bar or higher, and at 50 bar or lower, or 45 bar or lower, or 40 bar or lower. When polymerization is carried out under these temperatures and pressures, the desired physical properties of polyethylene can be more easily realized.

[0214]

[0215] Polyethylene produced by the above-described manufacturing method has excellent processability represented by processing pressure, impact strength measured by drop impact strength, and transparency measured by haze. In a preferred embodiment, the polyethylene may be an ethylene / 1-butene copolymer.

[0216]

[0217] Specifically, the polyethylene produced using the above hybrid supported metallocene catalyst satisfies the following conditions (i) to (ii):

[0218] (i) Density measured according to ASTM D1505 standard: 0.910 to 0.930 g / cm³ 3

[0219] (ii) Drop impact strength of 700 g or more as measured according to ASTM D1709 [Method A].

[0220]

[0221] More specifically, the polyethylene has a density of 0.910 g / cm³ as measured according to ASTM D1505. 3 Above, or 0.915 g / cm³ 3 That is all, 0.930 g / cm³ 3 Less than or equal to 0.926 g / cm³ 3 It is as follows.

[0222]

[0223] In addition, the above polyethylene is manufactured using a film making machine to produce a polyethylene film (with 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 700 g or more, more specifically 800 g or more, 850 g or more, or 900 g or more, or 950 g or more, or 1000 g or more, while being 2000 g or less, or 1500 g or less, or 1400 g or less.

[0224]

[0225] In addition, the above polyethylene may have a processing pressure (processing load, (bar)) measured using a Haake extruder at cylinder-1 / -2 / -3 / die = 180 / 185 / 185 / 190 and a speed of 40 rpm of 350 bar or less, more specifically 320 bar or less, or 300 bar or less, or 280 bar or less, or 260 bar or less. Since a lower limit value of the processing pressure is better when it is smaller, it is not specifically limited, but for example, it may be 100 bar or more, or 110 bar or more, or 120 bar or more, or 130 bar or more, or 140 bar or more, or 150 bar or more. The method of measuring the above processing pressure may be specified in the examples described later.

[0226]

[0227] In addition, the polyethylene may have a haze of 20% or less, or 18% or less, or 16% or less, or 15% or less, or 14% or less as measured according to ISO 13468. Since a lower limit value of haze is better the smaller it is, it is not specifically limited, but for example, it may be 1.0% or more, or 2.0% or more, or 3.0% or more, or 4.0% or more, or 5.0% or more. The method for measuring the haze may be specified in the examples described below.

[0228]

[0229] 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.

[0230]

[0231] Accordingly, polyethylene produced using the above-mentioned hybrid supported metallocene catalyst has excellent drop impact strength, processability, and transparency, and can be usefully used for applications such as films.

[0232]

[0233] Preferred embodiments are presented below to aid in understanding the invention. However, the following embodiments are merely illustrative of the invention and do not limit the invention to these embodiments.

[0234]

[0235] Preparation of Transition Metal Compounds

[0236] Synthesis Example 1-1

[0237] (Cat 1-1)

[0238]

[0239] I purchased and used the PC-1316 product from SPCI Co., Ltd.

[0240]

[0241] Synthesis Example 1-2

[0242]

[0243] (Cat 1-2)

[0244] 1-iodopropane (1 equiv.) was added to THF (tetrahydrofuran, 0.3 M) under Ar2. -25 oAfter cooling to C, NaCp (20 wt% in THF, 1 eq) was slowly added dropwise. After stirring overnight at room temperature, H2O was added, and the mixture was transferred to a separatory funnel to perform the work-up. The organic layer was dehydrated with MgSO4 and filtered. The resulting mixture was dried to synthesize n-propyl cyclopentadiene.

[0245] The above-mentioned n-propyl cyclopentadiene (1 equiv.) was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-butyl lithium (2.5 M in hexane, 1 eq) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, HfCl4 (Hafnium(IV) chloride, 0.5 eq) was dissolved in Toluene (1 M) and added as a slurry. After stirring overnight at room temperature, all solvent was dried. Dichloromethane (DCM) was added, and the filtrate was obtained by filtration. This filtrate was dried to obtain bis(n-propylcyclopentadiene)hafnium dichloride. HfCl4 (1 equiv.) and Toluene (0.5 M) were added to the obtained bis(n-propylcyclopentadiene)hafnium dichloride (1 equiv.). After stirring overnight with reflux and cooling to room temperature, the solution was filtered to obtain n-propylcyclopentadiene hafnium trichloride.

[0246] t-Butyl-O-(CH2)6-Cl was prepared using chlorohexanol (6-chlorohexanol) according to the method presented in the literature (Tetrahedron Lett. 2951 (1988)), and t-Butyl-O-(CH2)6-C5H5 was obtained by reacting NaCp with it. This t-butyl-O-(CH2)6-C5H5 (1 equiv.) was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5 M, 1 eq) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, the previously obtained n-propylcyclopentadiene hafnium trichloride (1 equiv.) was added. After stirring overnight at room temperature, all solvent was dried. DCM was added and the filtrate was obtained by filtering, and the filtrate was dried to obtain Cat 1-2 transition metal compounds.

[0247] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.16-1.19 (14H, m), 1.31-1.39 (4H, m), 1.51-1.57 (4H, m), 1.71-1.85 (2H, m), 2.62-2.65 (4H, m), 3.42(2H, t), 5.96(2H, s), 6.03 (2H, s), 6.22(2H, s), 6.30(2H, s)

[0248]

[0249] Synthesis Example 1-3

[0250] (Cat 1-3)

[0251]

[0252] Indene (1 equiv.) was added to THF (0.3M) under Ar2. -25 o After cooling to C, n-BuLi(2.5M, 1 eq) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 oAfter cooling to C, t-Butyl-O-(CH2)6-Cl (1 equiv.) synthesized in Synthesis Example 1-2 above and NaI (sodium iodide, 0.1 equiv.) were added. After stirring overnight at room temperature, H2O was added, and the mixture was transferred to a separatory funnel to perform the work-up. The organic layer was filtered after removing moisture with MgSO4. This was dried to obtain 3-(t-butyl-O-(CH2)6)-Indene.

[0253] The above-mentioned 3-(t-butyl-O-(CH2)6)-Indene (1 equiv.) was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi(2.5M, 1 eq) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, n-propylcyclopentadiene hafnium trichloride (1 equiv.) synthesized in Synthesis Example 1-2 above was added. After stirring overnight at room temperature, all solvent was dried. DCM was added and a filtrate was obtained by filtering, and this filtrate was dried to obtain the transition metal compound of Cat 1-3.

[0254] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.18-1.20 (14H, m), 1.33-1.38 (4H, m), 1.52-1.56 (4H, m), 1.72-1.86 (2H, m), 2.61-2.64 (4H, m), 3.43(2H, t), 6.22(2H, s), 6.25(1H, s), 6.30(2H, s), 7.25(1H, t), 7.35(1H, t), 7.42(1H, d), 7.51(1H, d).

[0255]

[0256] Synthesis Example 1-4

[0257] (Cat 1-4)

[0258]

[0259] The transition metal compound of Cat 1-4 was obtained in the same manner as in Synthesis Example 1-3, except that 1-iodobutane (1 equiv.) was used instead of t-Butyl-O-(CH2)6-Cl and NaI in Synthesis Example 1-3.

[0260] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 0.98(3H, t), 1.17(3H, t), 1.42-1.48(2H, m), 1.71-1.89(4H, m), 2.60-2.65(4H, m), 6.21(2H, s), 6.24(1H, s), 6.30(2H, s), 7.24(1H, t), 7.34(1H, t), 7.41(1H, d), 7.50(1H, d).

[0261]

[0262] Synthesis Example 1-5

[0263] (Cat 1-5)

[0264]

[0265] I purchased and used the PC-1314 product from SPCI Co., Ltd.

[0266]

[0267] Synthesis Example 1-6

[0268] (Cat 1-6)

[0269]

[0270] Indene (1 equiv.) was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5M, 1 equiv.) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 oAfter cooling to C, n-propylcyclopentadiene hafnium trichloride (1 equiv.) synthesized in Synthesis Example 1-2 above was added. After stirring overnight at room temperature, all solvent was dried. DCM was added and a filtrate was obtained by filtering, and this filtrate was dried to obtain the transition metal compounds of Cat 1-6.

[0271] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.18(3H, t), 1.79-1.82(2H, m), 2.62(2H, t), 6.17(2H, s), 6.20(2H, s), 6.30(2H, s), 6.32(1H, t), 7.28(2H, m), 7.59(2H, m).

[0272]

[0273] Synthesis Example 1-7

[0274] (Cat 1-7)

[0275]

[0276] The t-Butyl-O-(CH2)6-C5H5 (1 equiv.) synthesized in Synthesis Example 1-2 was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5M, 1 equiv.) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, TMCpHfCl3 (tetramethylcyclopentadienyl hafnium trichloride, 1 equiv.) was added. After stirring overnight at room temperature, all solvent was dried. DCM was added and the filtrate was obtained by filtering, and the filtrate was dried to obtain Cat 1-7 transition metal compounds.

[0277] 1H NMR (500 MHz, CDCl3, 7.26 ppm): 1.16-1.19(11H, m), 1.32-1.38(4H, m), 1.54-1.58(4H, m), 1.98(6H, s), 2.02(3H, s), 2.19(3H, s), 2.65(2H, t), 3.30(2H, t), 5.90(1H, s), 6.22 (2H, s), 6.29(2H, s).

[0278]

[0279] Synthesis Example 1-8

[0280] (Cat 1-8)

[0281]

[0282] The transition metal compounds of Cat 1-8 were obtained by the same method as in Synthesis Example 1-7, except that PMCpHfCl3 (pentamethylcyclopentadienyl hafnium trichloride) was used instead of TMCpHfCl3 (tetramethylcyclopentadienyl hafnium trichloride) in Synthesis Example 1-7.

[0283] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.14-1.18(11H, m), 1.33-1.38(4H, m), 1.54-1.59(4H, m), 2.04(15H, s), 2.67(2H, t), 3.32(2H, t), 6.22 (2H, s), 6.28(2H, s).

[0284]

[0285] Synthesis Example 1-9

[0286] (Cat 1-9)

[0287]

[0288] The transition metal compound of Cat 1-9 was obtained in the same manner as in Synthesis Example 1-7, except that 3-(t-butyl-O-(CH2)6)-Indene (1 equiv.) synthesized in Synthesis Example 1-3 was used instead of t-Butyl-O-(CH2)6-C5H5 (1 equiv.) in Synthesis Example 1-7.

[0289] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.17-1.18(11H, m), 1.32-1.36(4H, m), 1.55-1.58(4H, m), 1.99(6H, s), 2.03(3H, s), 2.20(3H, s), 2.66(2H, t), 3.31(2H, t), 5.50(1H, s), 5.91(1H, dd), 6.42(1H, dd), 7.20(1H, t), 7.29(1H, t), 7.48(1H, t), 7.63(1H, t)

[0290]

[0291] Synthesis Example 2-1

[0292] (Cat 2-1)

[0293]

[0294] A transition metal compound of the structural formula Cat 2-1 was prepared according to Preparation Example 1 of Korean Published Patent No. 10-2016-0067803.

[0295]

[0296] Synthesis Example 2-2

[0297] (Cat 2-2)

[0298]

[0299] A transition metal compound of the structural formula Cat 2-2 was prepared according to Preparation Example 3 of Korean Published Patent No. 10-2016-0067803.

[0300]

[0301] Synthesis Example 3-1

[0302] (Cat 3-1)

[0303]

[0304] 3-(t-butyl-O-(CH2)6)-Indene (1 equiv.) synthesized in Synthesis Examples 1-3 was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5M, 1 equiv.) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, TMCpZrCl3 (tetramethylcyclopentadienyl zirconium trichloride, 1 equiv.) was added. After stirring overnight at room temperature, all solvent was dried. DCM was added, and a filtrate was obtained by filtering. This filtrate was completely dried to obtain an intermediate.

[0305] The above dried intermediate was melted in DCM (0.3 M) in the glove box and introduced into a high-pressure bomb reactor along with Pd / C (10 wt% Pd, 10 mol%), after which it was moved out of the glove box. Subsequently, 10 barg of H2 gas was filled and 40 o It was stirred overnight at C. The residual H2 gas was vented, filtered, and the filtrate dried. Then, hexane was added and stirred at room temperature for 3 hours. After that, the solid was filtered and dried to obtain a Cat 3-1 transition metal compound.

[0306] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.17-1.18(11H, m), 1.32-1.36(4H, m), 1.55-1.61(6H, m), 1.82(2H, m) 1.99(6H, s), 2.03(3H, s), 2.21(3H, s), 2.55-2.60(4H, m), 2.71-2.75(2H, m) 3.31(2H, t), 5.12(1H, d), 5.50(1H, s) 5.61(1H, d).

[0307]

[0308] Synthesis Example 3-2

[0309] (Cat 3-2)

[0310]

[0311] t-Butyl-O-(CH2)4-Cl was prepared using chlorobutanol (4-chlorobutanol) according to the method presented in the literature (Tetrahedron Lett. 2951 (1988)). Indene (1 equiv.) was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5 M, 1 equiv.) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, t-Butyl-O-(CH2)4-Cl (1 equiv.) and NaI (sodium iodide, 0.1 equiv.) were added. After stirring overnight at room temperature, H2O was added, and the mixture was transferred to a separatory funnel to perform the work-up. The organic layer was filtered after removing moisture with MgSO4. This was dried to synthesize 3-(t-butyl-O-(CH2)4)-Indene.

[0312] The above-mentioned 3-(t-butyl-O-(CH2)4)-Indene (1 equiv.) was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5 M, 1 equiv.) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, TMCpZrCl3 (tetramethylcyclopentadienyl zirconium trichloride, 1 equiv.) was added. After stirring overnight at room temperature, all solvent was dried. DCM was added, and a filtrate was obtained by filtering. The filtrate was dried to obtain an intermediate.

[0313] The above dried intermediate was melted in DCM (0.3 M) in the glove box and introduced into a high-pressure bomb reactor along with Pd / C (10 wt% Pd, 10 mol%), after which it was moved out of the glove box. Subsequently, 10 barg of H2 gas was filled and 40 o It was stirred overnight at C. The residual H2 gas was vented, filtered, and the filtrate dried. Then, hexane was added and stirred at room temperature for 3 hours. After that, the solid was filtered and dried to obtain a Cat 3-2 transition metal compound.

[0314] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.17-1.19(11H, m), 1.33-1.38(4H, m), 1.55-1.58(2H, m), 1.82(2H, m) 2.00(6H, s), 2.05(3H, s), 2.28(3H, s), 2.60-2.63(4H, m), 2.71-2.75(2H, m) 3.35(2H, t), 5.15(1H, d), 5.51(1H, s) 5.62(1H, d).

[0315]

[0316] Synthesis Example 3-3

[0317] (Cat 3-3)

[0318]

[0319] The transition metal compound of Cat 3-3 was obtained in the same manner as in Synthesis Example 3-2, except that chloroethanol (2-chloroethanol) was used instead of chlorobutanol (4-chlorobutanol) in Synthesis Example 3-2.

[0320] 1H NMR (500 MHz, CDCl3, 7.26 ppm): 1.16-1.18(11H, m), 1.52(2H, m), 1.82(2H, m) 1.98(6H, s), 2.03(3H, s), 2.20(3H, s), 2.63(2H, t), 3.36(2H, t), 5.14(1H, d), 5.51(1H, s) 5.61(1H, d).

[0321]

[0322] Synthesis Example 3-4

[0323] (Cat 3-4)

[0324]

[0325] 3-(t-butyl-O-(CH2)6)-Indene (1 equiv.) synthesized in Synthesis Examples 1-3 was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5M, 1 equiv.) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, MeI(Iodomethane, 2 equiv.) was added. After stirring overnight at room temperature, H2O was added, and the mixture was transferred to a separatory funnel to perform the work-up. The organic layer was filtered after removing moisture with MgSO4. This was dried to synthesize 1-Me-3-(t-butyl-O-(CH2)6)-Indene.

[0326] The above-mentioned obtained 1-Me-3-(t-butyl-O-(CH2)6)-Indene (1 equiv.) was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5 M, 1 equiv.) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 oAfter cooling to C, TMCpZrCl3 (tetramethylcyclopentadienyl zirconium trichloride, 1 equiv.) was added. After stirring overnight at room temperature, all solvent was dried. DCM was added, and a filtrate was obtained by filtering. The filtrate was dried to obtain an intermediate.

[0327] The above dried intermediate was melted in DCM (0.3 M) in the glove box and introduced into a high-pressure bomb reactor along with Pd / C (10 wt% Pd, 10 mol%), after which it was moved out of the glove box. Subsequently, 10 barg of H2 gas was filled and 40 o It was stirred overnight at C. The residual H2 gas was vented, filtered, and the filtrate dried. Then, hexane was added and stirred at room temperature for 3 hours. After that, the solid was filtered and dried to obtain Cat 3-4 transition metal compounds.

[0328] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.15-1.16(11H, m), 1.31-1.37(4H, m), 1.54-1.60(6H, m),1.76(3H, s) 1.80(2H, m) 1.99(6H, s), 2.02(3H, s), 2.20(3H, s), 2.53-2.58(4H, m), 2.70-2.75(2H, m), 3.30(2H, t), 5.50(1H, s) 5.53(1H, s).

[0329]

[0330] Synthesis Example 3-5

[0331] (Cat 3-5)

[0332]

[0333] The transition metal compound of Cat 3-5 was obtained by the same method as in Synthesis Example 3-1, except that PMCpZrCl3 (pentamethylcyclopentadienyl zirconium trichloride, 1 equiv.) was used instead of TMCpZrCl3 (tetramethylcyclopentadienyl zirconium trichloride, 1 equiv.) in Synthesis Example 3-1.

[0334] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.14-1.18(11H, m), 1.33-1.37(4H, m), 1.54-1.61(6H, m), 1.82(2H, m) 2.08(15H, s), 2.51-2.54(4H, m), 2.70-2.74(2H, m), 3.30(2H, t), 5.10(1H, d), 5.60(1H, d).

[0335]

[0336] Synthesis Example 3-6

[0337] (Cat 3-6)

[0338]

[0339] The transition metal compound of Cat 3-6 was obtained by the same method as in Synthesis Example 3-4, except that PMCpZrCl3 (pentamethylcyclopentadienyl zirconium trichloride, 1 equiv.) was used instead of TMCpZrCl3 (tetramethylcyclopentadienyl zirconium trichloride, 1 equiv.) in Synthesis Example 3-4.

[0340] 1H NMR (500 MHz, CDCl3, 7.26 ppm): 1.15-1.18(11H, m), 1.31-1.38(4H, m), 1.52-1.58(6H, m),1.81(3H, s) 1.85(2H, m) 2.07(15H, s), 2.52-2.57(4H, m), 2.71-2.75(2H, m), 3.31(2H, t), 5.50(1H, s).

[0341]

[0342] Synthesis Example 3-7

[0343] (Cat 3-7)

[0344]

[0345] CF3CH2OH (2,2,2-trifluoro-1-ethanol, 1 equiv.) and Trifluoromethanesulfonic anhydride (1.2 equiv.) are refluxed (80) into a neat state o C) The mixture was stirred for 3 hours under these conditions. After cooling to room temperature, the reflux condensate was removed and the fractional distillation condensate was collected. The temperature was gradually increased, and CF3CH2Otf (2,2,2-trifluoroethyl triflate) was obtained by fractional distillation.

[0346] Indene (1 equiv.) was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5M, 1 equiv.) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, the previously obtained CF3CH2Otf (2,2,2-trifluoroethyl triflate, 1.1 equiv.) was added. After stirring overnight at room temperature, H2O was added, and the mixture was transferred to a separatory funnel to perform the work-up. The organic layer was filtered after removing moisture with MgSO4. This was dried to synthesize 3-CF3CH2-Indene.

[0347] The above-mentioned 3-CF3CH2-Indene (1 equiv.) was added to THF (0.3 M) under Ar2. -25 o After cooling to C, n-BuLi (2.5M, 1 equiv.) was slowly added dropwise. Stirred at room temperature for 3 hours, and -25 o After cooling to C, TMCpZrCl3 (tetramethylcyclopentadienyl zirconium trichloride, 1 equiv.) was added. After stirring overnight at room temperature, all solvent was dried. DCM was added, and a filtrate was obtained by filtering. This filtrate was dried to obtain an intermediate.

[0348] The above dried intermediate was melted in DCM (0.3 M) in the glove box and introduced into a high-pressure bomb reactor along with Pd / C (10 wt% Pd, 10 mol%), after which it was moved out of the glove box. Subsequently, 10 barg of H2 gas was filled and 40 o The mixture was stirred overnight at C. The residual H2 gas was vented, filtered, and the filtrate dried. Then, hexane was added and the mixture was stirred at room temperature for 3 hours. After that, the solid was filtered and dried to obtain Cat 3-7 transition metal compounds.

[0349] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.57-1.62(1H, m), 1.64-1.69(1H, m), 1.77-1.81(1H, m), 1.87-1.92(1H, m), 2.02(6H, s), 2.03(6H, s), 2.49-2.57(2H, m), 2.71-2.82(2H, m), 2.97-3.06(1H, m), 3.18-3.28(1H, m), 5.63(1H, d), 5.86(1H, s), 6.01(1H, d)

[0350]

[0351] Synthesis Example 3-8

[0352] (Cat 3-9)

[0353]

[0354] The transition metal compound of Cat 3-8 was obtained by the same method as in Synthesis Example 3-7, except that CF3CH2CH2OH ((3,3,3-trifluoro-1-propanol)) was used instead of CF3CH2OH in Synthesis Example 3-7.

[0355] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.25-1.33(2H, m), 1.53-1.67(2H, m), 1.83-1.99(2H, m), 2.03(6H, s), 2.04(6H, s), 2.33-2.39(1H, m), 2.42-2.48(2H, m), 2.71-2.81(3H, m), 5.28(1H, d), 5.66(1H, s), 5.59(1H, d)

[0356]

[0357] Synthesis Example 3-9

[0358] (Cat 3-9)

[0359]

[0360] The transition metal compound of Cat 3-9 was obtained by the same method as in Synthesis Example 3-7, except that C2F5CH2OH (2,2,3,3,3-Pentafluoro-1-propanol) was used instead of CF3CH2OH in Synthesis Example 3-7.

[0361] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.57-1.71(2H, m), 1.77-1.92(2H, m), 2.02(6H, s), 2.03(6H, s), 2.47-2.60(2H, m), 2.70-2.81(2H, m), 2.95-3.05(1H, m), 3.17-3.28(1H, m), 5.66(1H, d), 5.86(1H, s), 6.02(1H, d)

[0362]

[0363] Synthesis Example 3-10

[0364] (Cat 3-10)

[0365]

[0366] Transition metal compounds of Cat 3-10 were obtained by the same method as in Synthesis Example 3-7, except that C3F7CH2OH (2,2,3,3,4,4,4-Heptafluoro-1-butanol) was used instead of CF3CH2OH in Synthesis Example 3-7.

[0367] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.56-1.70(2H, m), 1.76-1.92(2H, m), 2.02(6H, s), 2.04(6H, s), 2.45-2.59(2H, m), 2.70-2.82(2H, m), 2.92-3.04(1H, m), 3.17-3.28(1H, m), 5.68(1H, d), 5.86(1H, s), 6.01(1H, d)

[0368]

[0369] Synthesis Example 3-11

[0370] (Cat 3-11)

[0371]

[0372] The transition metal compound of Cat 3-11 was obtained by the same method as in Synthesis Example 3-7, except that PMCpZrCl3 (pentamethylcyclopentadienyl zirconium trichloride, 1 equiv.) was used instead of TMCpZrCl3 (tetramethylcyclopentadienyl zirconium trichloride, 1 equiv.) in Synthesis Example 3-7.

[0373] 1H NMR (500 MHz, CDCl3, 7.26 ppm): 1.58-1.69(2H, m), 1.88-2.01(2H, m), 2.04(15H, s), 2.48-2.55(2H, m), 2.72-2.88(3H, m), 3.24-3.34(1H, m), 5.40(1H, d), 5.76(1H, d)

[0374]

[0375] Synthesis Example 3-12

[0376] (Cat 3-12)

[0377]

[0378] The transition metal compounds of Cat 3-12 were obtained by the same method as in Synthesis Example 3-9, except that PMCpZrCl3 (pentamethylcyclopentadienyl zirconium trichloride, 1 equiv.) was used instead of TMCpZrCl3 (tetramethylcyclopentadienyl zirconium trichloride, 1 equiv.) in Synthesis Example 3-9.

[0379] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.55-1.67(2H, m), 1.84-1.99(2H, m), 2.02(15H, s), 2.44-2.53(2H, m), 2.67-2.91(3H, m), 3.21-3.31(1H, m), 5.39(1H, d), 5.75(1H, d)

[0380]

[0381] Synthesis Example 4-1

[0382] (Cat 4-1)

[0383]

[0384] A transition metal compound of the structural formula Cat 4-1 was prepared in the same manner as in Preparation Example 4 of Korean Published Patent No. 10-2016-0084181.

[0385]

[0386] Synthesis Example 4-2

[0387] (Cat 4-2)

[0388]

[0389] A transition metal compound of the structural formula Cat 4-2 was prepared in the same manner as Preparation Example 5 of Korean Published Patent No. 10-2016-0084181.

[0390]

[0391] Synthesis Example 4-3

[0392] (Cat 4-3)

[0393]

[0394] A transition metal compound of the structural formula Cat 4-3 was prepared in the same manner as in Preparation Example 1 of Korean Published Patent No. 10-2019-0074963.

[0395]

[0396] Synthesis Example 4-4

[0397] (Cat 4-4)

[0398]

[0399] I purchased and used the 447862 product from Sigma Aldrich.

[0400]

[0401] Synthesis Example 4-5

[0402] (Cat 4-5)

[0403]

[0404] A transition metal compound of the structural formula Cat 4-5 was prepared in the same manner as in Preparation Example 3 of Korean Published Patent No. 10-2019-0074963.

[0405]

[0406] Synthesis Example 4-6

[0407] (Cat 4-6)

[0408]

[0409] A transition metal compound of structural formula Cat 4-6 was prepared by the same method as chemical formula 4 of Korean published patent No. 10-2015-0052803.

[0410]

[0411] Synthesis Example 4-7

[0412] (Cat 4-7)

[0413]

[0414] Transition metal compounds of structural formulas Cat 4-7 were prepared in the same manner as in Organometallics (2006), 25(5), 1217-1229.

[0415]

[0416] Preparation of Hybrid Supported Metallocene Catalysts

[0417] Preparation Example 1

[0418] 2.0 kg of toluene and 1000 g of silica (Grace Davison, SP2410) were added to a 20 L SUS high-pressure reactor, and stirring was performed while raising the reactor temperature to 40 ℃. 5.4 kg of methylaluminoxan (10 wt% in toluene, manufactured by Albemarle) was added to the reactor, the temperature was raised to 70 ℃, and stirring was performed at approximately 200 rpm for about 12 hours. Subsequently, the reactor temperature was lowered to 40 ℃, and stirring was stopped. The reaction product was then allowed to stand for about 10 minutes, followed by decantation. Again, 2.0 kg of toluene was added to the reaction product and stirred for about 10 minutes; stirring was then stopped, and the product was allowed to stand for about 30 minutes, followed by decantation.

[0419] 2.0 kg of toluene was added to the reactor, followed by the first transition metal compound of structural formula Cat 1-1 prepared in Synthesis Example 1-1, the second transition metal compound of structural formula Cat 3-1 prepared in Synthesis Example 3-1, and 1000 mL of toluene. The temperature of the reactor was raised to 85 ℃ and stirred for about 90 minutes.

[0420] Subsequently, the temperature of the reactor was lowered to room temperature, stirring was stopped, and the reaction product was allowed to stand for about 30 minutes, after which the reaction product was decanted. Next, 3 kg of hexane was added to the reactor, and the hexane slurry solution was transferred to a 20 L filter dryer to filter the solution, and then dried under reduced pressure at 50 ℃ for about 4 hours to obtain about 1.5 kg of hybrid supported metallocene catalyst.

[0421]

[0422] Preparation Examples 2 to 24 and Comparative Preparation Examples 1 to 11

[0423] As described in Table 1 below, a hybrid supported metallocene catalyst was prepared by performing the same method as in Preparation Example 1 above, except that the types and amounts of the first and second transition metal compounds were changed.

[0424]

[0425] First Transition Metal Compound Second Transition Metal Compound Type Usage Amount (mmol per g SiO2) Type Usage Amount (mmol per g SiO2) Preparation Example 1 Cat 1-140 Cat 3-120 Preparation Example 2 Cat 1-140 Cat 3-220 Preparation Example 3 Cat 1-140 Cat 3-320 Preparation Example 4 Cat 1-140 Cat 3-425 Preparation Example 5 Cat 1-140 Cat 3-520 Preparation Example 6 Cat 1-140 Cat 3-625 Preparation Example 7 Cat 1-140 Cat 3-730 Preparation Example 8 Cat 1-140 Cat 3-830 Preparation Example 9 Cat 1-140 Cat 3-940 Preparation Example 10 Cat 1-140 Cat 3-1040 Preparation Example 11 Cat 1-140 Cat 3-1130 Preparation Example 12 Cat 1-140 Cat 3-1230 Preparation Example 13 Cat 1-220 Cat 3-730 Preparation Example 14 Cat 1-320 Cat 3-730 Preparation Example 15 Cat 1-440 Cat 3-730 Preparation Example 16 Cat 1-540 Cat 3-730 Preparation Example 17 Cat 1-640 Cat 3-730 Preparation Example 18 Cat 1-720 Cat 3-730 Preparation Example 19 Cat 1-820 Cat 3-730 Preparation Example 20 Cat 1-920 Cat 3-730 Preparation Example 21 Cat 2-130 Cat 3-120 Manufacturing Example 22 Cat 2-230 Cat 3-730 Manufacturing Example 23 Cat 2-130 Cat 3-120 Manufacturing Example 24 Cat 2-230 Cat 3-730 Comparative Manufacturing Example 1 Cat 2-130 Cat 4-130 Comparative Manufacturing Example 2 Cat 2-130 Cat 4-230 Comparative Manufacturing Example 3 Cat 2-130 Cat 4-320 Comparative Manufacturing Example 4 Cat 2-130 Cat 4-430 Comparative Manufacturing Example 5 Cat 2-130 Cat 4-520 Comparative Manufacturing Example 6 Cat 2-230 Cat 4-130 Comparative Manufacturing Example 7 Cat 2-230 Cat 4-230 Comparative Manufacturing Example 8 Cat 2-230 Cat 4-320 Comparative Manufacturing Example 9 Cat 2-230 Cat 4-520 Comparative Manufacturing Example 10 Cat 4-640 Cat 3-120 Comparative Manufacturing Example 11 Cat 4-740 Cat 3-120

[0426] Manufacture of Polyethylene

[0427] Examples 1 to 24 and Comparative Examples 1 to 11

[0428] A 140L continuous polymerization reactor capable of an isobutene slurry loop process was prepared and operated at a reaction flow rate of approximately 7 m / s. Then, the reactants required for polyethylene polymerization were continuously fed into the reactor as described in Table 2. The catalyst used in each polymerization reaction was one prepared in the preparation example or comparative preparation example described in Table 1, and the catalyst was mixed into the isobutene slurry and fed. The polymerization reaction was carried out at a pressure of approximately 40 bar and a temperature of approximately 85°C.

[0429]

[0430] Reference Example 1

[0431] ExxonMobil's Exceed TM 1018 product (ethylene / 1-hexene copolymer) was purchased and used.

[0432]

[0433] The main conditions of the above polymerization reaction are shown in Table 2.

[0434] Catalyst ethylene input amount (kg / hr) 1-butene input amount 1 (wt%) Hydrogen input amount 2(ppm)Activity (kgPE / kgSiO2·hr) Example 1 Preparation Example 1 20.5 15.1 1503.1 Example 2 Preparation Example 2 258.1 282.8 Example 3 Preparation Example 3 24.5 14.5 342.8 Example 4 Preparation Example 4 24.8 12.5 914.1 Example 5 Preparation Example 5 27.5 12.8 1502.2 Example 6 Preparation Example 6 24.8 9.8 2403.5 Example 7 Preparation Example 7 21.8 13.5 102.8 Example 8 Preparation Example 8 2612.5 282.0 Example 9 Preparation Example 9 26.2 12.4 613.1 Example 10 Preparation Example 10 2413.3 182.5 Example 11 Manufacturing Example 112211.9392.9 Example 12 Manufacturing Example 1222.411.21403.8 Example 13 Manufacturing Example 13249.91802.7 Example 14 Manufacturing Example 1423.5122402.5 Example 15 Manufacturing Example 1520.913.1502.5 Example 16 Manufacturing Example 162512.51603.0 Example 17 Manufacturing Example 172411.12403.0 Example 18 Manufacturing Example 182521202.6 Example 19 Manufacturing Example 192412.21003.1 Example 20 Manufacturing Example 2023.514.31402.7 Example 21 Manufacturing Example 212515.11062.7 Example 22 Manufacturing Example 2227.114.1544.0 Example 23 Manufacturing Example 2326.915.8192.8 Example 24 Manufacturing Example 2424.218.1402.9 Comparative Example 1 Comparative Manufacturing Example 120.814.5603.0 Comparative Example 2 Comparative Manufacturing Example 22420.2611.9 Comparative Example 3 Comparative Manufacturing Example 325.39.5842.4 Comparative Example 4 Comparative Manufacturing Example 42415.41942.0 Comparative Example 5 Comparative Manufacturing Example 523.217.3102.6 Comparative Example 6 Comparative Manufacturing Example 622.815.91852.5 Comparative Example Comparative Manufacturing Example 7 25.115.8 262.4 Comparative Example 8 Comparative Manufacturing Example 8 25.117.6 953.1 Comparative Example 9 Comparative Manufacturing Example 9 24.8 20732.8 Comparative Example 10 Comparative Manufacturing Example 10 22.115.4 422.5 Comparative Example 11 Comparative Manufacturing Example 11 24.5 15.8 352.7

[0435] In Table 2 above, the activity (kgPE / kgSiO2·hr) was calculated as the ratio of the weight of the polymer produced (kg PE) to the weight of the supported catalyst used per unit time (hr).

[0436] In addition, the 1-butene input amount (wt%) is calculated as a percentage of the 1-butene input amount based on the total weight of the monomer containing ethylene and 1-butene, and the hydrogen input amount (ppm) is based on the total weight of the monomer containing ethylene and 1-butene.

[0437]

[0438] <Experimental Example>

[0439] The physical properties of the polyethylene prepared in the examples and comparative examples were measured as follows, and the results are shown in Table 3 below.

[0440]

[0441] (1) Density (g / cm²) 3 )

[0442] Measured according to ASTM D1505 standard.

[0443]

[0444] (2) Melt Index (MI 2.16 )

[0445] It was measured according to ISO 1133 (190 ℃, 2.16 kg load).

[0446]

[0447] (3) Drop impact strength (g)

[0448] Drop impact strength was measured for 50 μm thick films manufactured by the following method according to ASTM D1709 [Method A], and the average value was taken after measuring at least 20 times per film sample.

[0449]

[0450] Film Manufacturing

[0451] 1500 ppm of antioxidant (Songnox 1076 (Songwon):Songnox 1680 (Songwon) = 1:2 weight ratio) and 300 ppm of 3M Dynamar Polymer Processing Additive FX5929 were added and mixed based on the total weight of the polyethylene prepared in the above examples or comparative examples, and extruded at an extrusion temperature of 190 ℃ and an extrusion rate of 35 kg / hr using a twin screw extruder (TEK 30 MHS, manufactured by SMPLATECH CO., diameter 32 phi, L / D=40) to produce a pellet-shaped film-forming composition of about 18 kg.

[0452]

[0453] A film was manufactured by inflation molding the film-forming composition prepared above under the following film extrusion conditions.

[0454] <Film Forming Conditions>

[0455] Single Screw Extruder (Yujin Engineering Single Screw Extruder, Blown Film M / C, 50 pi, L / D=32)

[0456] Melting temperature (or extrusion temperature): 180 ℃

[0457] Die Gap: 2.0 mm

[0458] Die diameter: 120 mm

[0459] Blown-Up Ratio: 2.5

[0460] Maintain Frost Line Height 200~250 mm

[0461] Sample extrusion rate: 300~500 g / min

[0462] Cooling: Uses dual air rings

[0463] Film thickness: 50 µm

[0464]

[0465] (4) Machining pressure (machining load, bar)

[0466] Using a Haake extruder, the machining pressure (bar) was measured at cylinder-1 / -2 / -3 / die=180 / 185 / 185 / 190 and a speed of 40 rpm.

[0467]

[0468] (5) Haze (%)

[0469] Haze was measured for the film manufactured in the above drop impact strength measurement according to ISO 13468 standards.

[0470]

[0471] Density (g / cm³) 3 )MI 2.16(g / 10min) Drop Impact Strength (g) Processing Pressure (bar) Haze (%) Example 1 0.9 1900 0.9 10 10 20 24 4 14.0 Example 2 0.9 195 0.9 74 120 0 24 0 12.4 Example 3 0.9 160 0.9 96 115 0 24 5 11.5 Example 4 0.9 215 1.00 110 5 0 26 0 10.4 Example 5 0.9 25 10.8 94 ​​12 10 28 0 13.8 Example 6 0.9 179 1.1 00 130 0 310 10.5 Example 7 0.9 18 10.9 89 10 80 32 11 0.2 Example 8 0.9 19 11.00 112 9 0 28 0 13.5 Example 90.91670.939130029616.4 Example 100.91750.91212003209.8 Example 110.91890.880109029012.4 Example 120.91800.916130024213.1 Example 130.92481.115131028013.5 Example 140.91671.08512002808.9 Example 150.92080.890122025015.7 Example 160.92001.002109025112.4 Example 170.91980.928111031218.5 Example 180.91940.876131024018.5 Example 190.91780.912122024511.5 Example 200.91691.084101024012.4 Example 210.91911.152120029117.4 Example 220.91840.987113024414.0 Example 230.92411.108114026010.4 Example 240.91800.984104028014.1 Comparative Example 10.91741.11055036015.1 Comparative Example 20.91680.89945034813.5 Comparative Example 30.92101.06438041018.4 Comparative Example 40.91670.92064037017.5 Comparative Example 50.92411.21148034018.1 Comparative Example 60.92301.14564033016.1 Comparative Example 70.91840.89446037014.5 Comparative Example 80.91991.10446034016.4 Comparative Example 90.92100.91157032015.1 Comparative Example 100.91801.01025035020.8 Comparative Example 110.91820.99228034019.6 Reference Example 10.91801.006115027616.7.

[0472] As can be seen in Table 3 above, the polyethylene of the example prepared using a hybrid supported metallocene catalyst comprising a first transition metal compound represented by Formula 1 or Formula 2 and a second transition metal compound represented by Formula 3 according to the present invention exhibited a combination of high molecular weight high copolymerization characteristics expressed from the first transition metal compound and low molecular weight high copolymerization characteristics expressed from the second transition metal compound, while also showing excellent processability and transparency due to low processing pressure.

[0473]

[0474] In addition, the polyethylene of the example is an ethylene / 1-butene copolymer manufactured using a relatively inexpensive 1-butene comonomer, but it can achieve density, drop impact strength, processability, and transparency equivalent to the general-purpose ethylene / 1-hexene copolymer of Reference Example 1, thereby also securing price competitiveness.

[0475]

[0476] Meanwhile, it was confirmed that the polyethylene of the comparative example, prepared using a hybrid supported metallocene catalyst containing a transition metal compound of the comparative example, had a significantly lower drop impact strength compared to the polyethylene of the example.

Claims

A first transition metal compound represented by the following chemical formula 1 or chemical formula 2; A second transition metal compound represented by the following chemical formula 3; Co-catalyst; and including a carrier Hybrid supported metallocene catalyst: [Chemical Formula 1] In the above chemical formula 1, X 11 and X 12 C each independently 1-20 It is an alkyl, or halogen, and R 11 to R 15 are independently hydrogen, C 1-20 Alkyl, C 2-20 Alkoxyalkyl, C 6-20 Aril, C 7-20 alkylaryl of, or C 7-20 It is an arylalkyl of, or R 11 to R 15 Among them, two adjacent substituents combine to form a substituted or unsubstituted C 6-20 It forms an aromatic ring, R 16 to R 20 are independently hydrogen, C 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, and [Chemical Formula 2] In the above chemical formula 2, M2 is a group 4 transition metal, and X 21 and X 22 are independently, C 1-20 It is an alkyl, or halogen, and A2 is carbon, silicon, or germanium, and Q 21 and Q 22 are independently, halogen, C 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, provided that Q 21 and Q 22 At least one of them is C 2-20 It is an alkoxyalkyl, and R 21 and R 22 Each independently, hydrogen or C 1-20 It is alkyl, and R 23 and R 24 Each independently, hydrogen, or C 1-20 C that is alkyl, or bonded to one another, substituted or unsubstituted 6-20 It forms an aromatic ring, R 25 is C 1-20 It is alkyl, and [Chemical Formula 3] In the above chemical formula 3, M3 is a group 4 transition metal, and X 31 and X 32 are independently, C 1-20 It is an alkyl or halogen, and R 31 to R 35 Each independently, hydrogen, or C 1-20 It is alkyl, provided that R 31 to R 35 At least four of them are C 1-20 It is alkyl, and R 36 and R 37 Each is independently C substituted or unsubstituted with hydrogen, one or more halogens. 1-20 alkyl, or C 2-20 It is an alkoxyalkyl, provided that R 36 and R 37 At least one of them is C substituted with one or more halogens. 1-20 alkyl, or C 2-20 It is an alkoxyalkyl. In paragraph 1, R 11 to R 15 are independently hydrogen, C 1-6 Alkyl, or -(CH2) n -R a (Above R a is C 3-6 It is a branched alkoxy group, and is an alkoxyalkyl (where n is an integer from 2 to 10), or R 11 to R 15 Among them, two adjacent substituents bond together to form a benzene ring, Hybrid supported metallocene catalyst. In paragraph 1, R 16 to R 20 are independently hydrogen, C 1-6 Alkyl, or -(CH2) n -R a (Above R a is C 3-6 a branched alkoxy group, where n is an integer from 2 to 10) and is an alkoxyalkyl, Hybrid supported metallocene catalyst. In paragraph 1, The compound represented by the above chemical formula 1 is any one selected from the group consisting of the following compounds, Hybrid supported metallocene catalyst: . In paragraph 1, M2 is titanium (Ti), and X 21 and X 22 C each independently 1-6 alkyl, Hybrid supported metallocene catalyst. In paragraph 1, A2 is silicon, and Q 21 and Q 22 One or more of -(CH2) n -R b (Above R b is C 3-6 a branched alkoxy group, where n is an integer from 2 to 10) and is an alkoxyalkyl, Hybrid supported metallocene catalyst. In paragraph 1, R 21 , R 22 and R 25 are independently, C 1-6 It is alkyl, and R 23 and R 24 Each independently, hydrogen, or C 1-6 They are alkyl, or bond with each other to form a benzene ring, Hybrid supported metallocene catalyst. In paragraph 1, The compound represented by the above chemical formula 2 is any one selected from the group consisting of the following compounds, Hybrid supported metallocene catalyst: . In paragraph 1, M3 is zirconium (Zr), and X 31 and X 32 Each independently, the halogen, Hybrid supported metallocene catalyst. In paragraph 1, R 31 to R 35 At least four of them are methyl, Hybrid supported metallocene catalyst. In paragraph 1, R 36 and R 37 One of them is hydrogen, or C 1-6 It is alkyl, and The other one is C substituted or unsubstituted with one or more halogens. 1-6 Alkyl, or -(CH2) n -R c (Above R c is C 3-6 a branched alkoxy group, where n is an integer from 2 to 10) and is an alkoxyalkyl, Hybrid supported metallocene catalyst. In paragraph 1, The compound represented by the above chemical formula 3 is any one selected from the group consisting of the following compounds, Hybrid supported metallocene catalyst: . In paragraph 1, The first transition metal compound and the second transition metal compound are included in a molar ratio of 1:10 to 10:1, Hybrid supported metallocene catalyst. In paragraph 1, The above co-catalyst is one or more selected from the group consisting of compounds represented by the following chemical formula 4, Hybrid supported metallocene catalyst: [Chemical Formula 4] -[Al(R 41 )-O]a- In the above chemical formula 4, 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. In paragraph 1, The above carrier comprises silica, alumina, magnesia, or a mixture thereof, Hybrid supported metallocene catalyst. A method comprising the step of polymerizing an ethylene monomer and an alpha-olefin monomer while introducing hydrogen in the presence of a hybrid supported metallocene catalyst according to claim 1. Method for manufacturing polyethylene. In Paragraph 16, The above alpha-olefin monomer is added in an amount of 5 to 20 weight percent based on the total weight of the monomers including the ethylene monomer and the alpha-olefin monomer, and The above hydrogen is introduced at a concentration of 5 to 500 ppm based on the total weight of the monomers, including ethylene monomer and alpha-olefin monomer. Method for manufacturing polyethylene. In Paragraph 16, The above alpha-olefin monomer is 1-butene, Method for manufacturing polyethylene.

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