KR102028736B1

KR102028736B1 - Method for preparing supported hybrid metallocene catalyst, and supported hybrid metallocene catalyst using the same

Info

Publication number: KR102028736B1
Application number: KR1020150038137A
Authority: KR
Inventors: 전만성; 이기수; 조민석; 이승미
Original assignee: 주식회사 엘지화학
Priority date: 2015-03-19
Filing date: 2015-03-19
Publication date: 2019-10-04
Also published as: KR20160112424A

Abstract

The present invention provides a method for preparing a hybrid supported metallocene catalyst that can be used to prepare a polyolefin, a hybrid supported metallocene catalyst prepared using the same, and a method for preparing a polyolefin using the hybrid supported metallocene catalyst. According to the present invention, a hybrid supported metallocene catalyst which exhibits high polymerization activity and can be used for polymerization of an olefin polymer having ultra high molecular weight can be prepared.

Description

Method for preparing hybrid supported metallocene catalyst, and hybrid supported metallocene catalyst prepared using the same {METHOD FOR PREPARING SUPPORTED HYBRID METALLOCENE CATALYST, AND SUPPORTED HYBRID METALLOCENE CATALYST USING THE SAME}

The present invention relates to a method for preparing a hybrid supported metallocene catalyst, a hybrid supported metallocene catalyst prepared using the same, and a method for producing a polyolefin using the hybrid supported metallocene catalyst.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to the existing commercial processes since the invention in the 50s, but is characterized by a wide molecular weight distribution of the polymer because it is a multi-site catalyst having multiple active sites. There is a problem that there is a limit in securing the desired physical properties because the composition distribution is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed mainly of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a single site catalyst as a homogeneous complex catalyst. The polymer has a narrow molecular weight distribution according to the characteristics of a single active site, and a polymer having a uniform composition of the comonomer is obtained, and the stereoregularity, copolymerization characteristics, molecular weight, It has the property to change the crystallinity.

U. S. Patent No. 5,032, 562 describes a process for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. It is a method of producing a bimodal distribution polymer by supporting a titanium (Ti) -based Ziegler-Natta catalyst that generates a high molecular weight and a zirconium (Zr) -based metallocene catalyst that produces a low molecular weight on one support As a result, the supporting process is complicated, and the morphology of the polymer is degraded due to the promoter.

US Pat. No. 5,525,678 describes a method of using a catalyst system for olefin polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a nonmetallocene compound on a carrier. This has the disadvantage that the metallocene compound and the non-metallocene compound must be separately supported, and the carrier must be pretreated with various compounds for the supporting reaction.

U. S. Patent No. 5,914, 289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used and the time required for preparing the supported catalyst are high. The hassle of having to support the metallocene catalyst to be used on the carrier, respectively.

Korean Patent Laid-Open Publication No. 2004-0076965 discloses a method of controlling molecular weight distribution by supporting a dual-nuclear metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reactor. have. However, this method is limited in realizing the characteristics of each catalyst at the same time, and also has the disadvantage of freeing the metallocene catalyst portion in the carrier component of the finished catalyst, causing fouling in the reactor.

Therefore, in order to solve the above disadvantages, there is a continuous need for a method of preparing an olefin polymer having a desired physical property by preparing a hybrid supported metallocene catalyst having excellent activity.

U.S. Patent 5,032,562 U.S. Patent No. 5,525,678 U.S. Patent Registration 5,914,289 Korean Patent Publication No. 2004-0076965

Accordingly, the present invention provides a method for preparing a hybrid supported metallocene catalyst having excellent activity and capable of producing an olefin polymer having a high molecular weight and desired physical properties, a hybrid supported metallocene catalyst prepared using the same, and the hybrid supported metal. An object of the present invention is to provide a method for preparing polyolefin using a Rosene catalyst.

The present invention, the step of supporting the first cocatalyst on the carrier; Supporting the first metallocene compound on the carrier on which the first cocatalyst is supported; Supporting a second cocatalyst on a carrier on which the first cocatalyst and the first metallocene compound are supported; And supporting a second metallocene compound that polymerizes an olefinic monomer with a lower polymerization degree than the first metallocene compound on a carrier on which the first cocatalyst, the first metallocene compound, and the second cocatalyst are supported; It provides a method for producing a hybrid supported metallocene catalyst comprising a.

The present invention also provides a hybrid supported metallocene catalyst prepared by the above method.

In addition, the present invention provides a method for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported metallocene catalyst.

Hereinafter, a method for preparing a hybrid supported metallocene catalyst and a hybrid supported metallocene catalyst according to a specific embodiment of the present invention will be described.

According to one embodiment of the invention, the step of supporting the first promoter on the carrier; Supporting the first metallocene compound on the carrier on which the first cocatalyst is supported; Supporting a second cocatalyst on a carrier on which the first cocatalyst and the first metallocene compound are supported; And supporting a second metallocene compound that polymerizes an olefinic monomer with a lower polymerization degree than the first metallocene compound on a carrier on which the first cocatalyst, the first metallocene compound, and the second cocatalyst are supported; It can be provided a method for producing a hybrid supported metallocene catalyst comprising a.

In addition, the first metallocene compound may be represented by Formula 1, and the second metallocene compound may be represented by Formula 2:

[Formula 1]

(Cp ¹ R ^a ) B ¹ (J) M ¹ Z ¹ ₂

In Chemical Formula 1,

M ¹ is a Group 4 transition metal;

Cp ¹ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms Can be;

R ^a is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkynyl;

Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

B ¹ is one or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp ¹ R ^a ring and J;

J is any one selected from the group consisting of NR ^f , O, PR ^f and S, wherein R ^f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl,

[Formula 2]

(Cp ² R ^b ) _n (Cp ³ R ^c ) M ² Z ² ₃ _-n

In Chemical Formula 2,

M ² is a Group 4 transition metal;

Cp ² and Cp ³ are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;

R ^b and R ^c are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To alkenyl of C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

Z ² is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

n is 1 or 0.

In the hybrid supported metallocene catalyst according to the present invention, the substituents of Chemical Formulas 1 and 2 will be described in detail below.

The alkyl group of C1 to C20 includes a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, An octyl group etc. are mentioned, but it is not limited to this.

The alkenyl group of C2 to C20 includes a straight or branched alkenyl group, and specifically, may include an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto.

The C6 to C20 aryl groups include monocyclic or condensed aryl groups, and specifically include phenyl groups, biphenyl groups, naphthyl groups, phenanthrenyl groups, and fluorenyl groups, but are not limited thereto.

The C5 to C20 heteroaryl group includes a monocyclic or condensed heteroaryl group, and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl group , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.

Examples of the alkoxy group for C1 to C20 include a methoxy group, an ethoxy group, a phenyloxy group, a cyclohexyloxy group, and the like, but are not limited thereto.

Examples of the Group 4 transition metal include titanium, zirconium, and hafnium, but are not limited thereto.

The inventors of the present invention, in the preparation of a hybrid supported metallocene catalyst, proceed with a study on a method of supporting on a carrier so that the characteristics of the metallocene compound that polymerizes the olefin monomer with a high polymerization degree can be well expressed, In the case where the Rosene compound and two cocatalysts were supported in a specific order, the above-described characteristics were expressed to confirm that an ultra high molecular weight polyolefin could be prepared through experiments and completed the invention.

The hybrid supported metallocene catalyst of the embodiment may be a combination of one or more kinds of the first metallocene compound represented by Formula 1 and one or more kinds of the second metallocene compound represented by Formula 2; It is hybridly supported on a carrier together with a catalyst compound.

The first metallocene compound has different properties from the second metallocene compound, that is, when (co) polymerized an olefinic monomer (for example, ethylene and an alpha olefin having 3 or more carbon atoms) using them as a catalyst, The second metallocene compound may exhibit a property of polymerizing the olefinic monomer with a lower polymerization degree (ie, a property of polymerizing a lower molecular weight polyolefin) than the first metallocene compound. More specifically, when copolymerizing ethylene and an alpha olefin having 3 or more carbon atoms using the first and second metallocene compounds as catalysts, the polyolefin prepared using the first metallocene compound has a relatively high molecular weight, The alpha olefin comonomer is included in the polymer chain to exhibit low crystallinity. The polyolefin prepared using the second metallocene compound has a relatively low molecular weight, and the alpha olefin comonomer is included in the polymer chain in a small amount. It can exhibit high crystallinity.

Specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by one of the following structural formulas, but is not limited thereto.

In addition, specific examples of the second metallocene compound represented by Chemical Formula 2 may include a compound represented by one of the following structural formulas, but is not limited thereto.

In the method for preparing the hybrid supported metallocene catalyst of the embodiment, the first and second cocatalysts may be selected from the group consisting of compounds represented by the following Chemical Formulas 3 and 4:

[Formula 3]

-[Al (R ₁ ) -O-] _k-

In Formula 3, each R ₁ is independently a halogen, halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,

[Formula 4]

T ⁺ [BG ₄ ] ^-

In formula (4), T ⁺ is a + monovalent polyatomic ion, B is boron in the +3 oxidation state, G is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, hydro Selected from the group consisting of carbyl groups, halocarbyl groups and halo-substituted hydrocarbyl groups, wherein G has up to 20 carbons, but at up to one position G is a halide group.

More specifically, the compound represented by Chemical Formula 3 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular, or reticular form. Specific examples of such cocatalysts include methylaluminoxane (MAO) and ethyl. Aluminoxane, isobutyl aluminoxane, butyl aluminoxane, etc. are mentioned.

In addition, the promoter of Formula 4 may be a borate-based compound in the form of trisubstituted ammonium salt, or dialkyl ammonium salt, trisubstituted phosphonium salt. Specific examples of such cocatalysts include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, methyl Tetradecyclooctadecylammonium tetraphenylborate, N, N-dimethylaninium tetraphenylborate, N, N-diethylaninium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylaninynium) tetra Phenylborate, trityltetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluoro Rophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pen Fluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetra Kis (pentafluorophenyl) borate, N, N-diethylaninynium tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylaninynium) tetrakis (pentafluorophenyl Borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis ( 2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-, tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylaninium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N- Diethylaninynium tetrakis (2,3,4,6-tetrafluorophenyl) borate or N, N-dimethyl- (2,4,6-trimethylaninynium) tetrakis- (2,3,4,6 Borate compounds in the form of trisubstituted ammonium salts such as -tetrafluorophenyl) borate; Borates in the form of dialkylammonium salts such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl And a borate compound in the form of a trisubstituted phosphonium salt such as) borate.

The hybrid supported metallocene catalyst as described above is prepared by sequentially supporting a first cocatalyst, a first metallocene compound, a second cocatalyst, and a second metallocene compound on a carrier.

That is, the first cocatalyst is first supported on the carrier, the first metallocene compound is sequentially supported, and then the olefinic monomer is prepared at a lower polymerization degree than the second cocatalyst and the first metallocene compound different from the cocatalyst. The second metallocene compound to be polymerized is sequentially supported. In this case, when the first metallocene compound that polymerizes the olefinic monomer with high polymerization degree is first supported on the carrier, the first metallocene compound is activated by the first and second cocatalysts. It is possible to maximize the polymerization activity of, through which a high molecular weight polyolefin excellent in mechanical strength and physical properties can be prepared. In addition, the catalyst prepared by the above method can control the molecular weight distribution by adjusting the input amount of hydrogen when applied to a commercial polymerization process, in particular, by increasing the hydrogen input amount to prepare a polyolefin having a wide molecular weight distribution excellent in processability can do.

On the other hand, the supporting order of the promoter is not limited, and the first promoter may be supported first or the second promoter may be supported first. However, the cocatalyst represented by Chemical Formula 3, which is an alkylaluminoxane-based compound, has a carbon methane reaction between a methyl group bonded to aluminum of the alkylaluminoxane-based compound and a hydroxy group of silica, and thus is chemically fixed so that the cocatalyst is well supported. However, since the cocatalyst represented by Chemical Formula 5, which is a borate compound, is only physically fixed with silica, the cocatalyst represented by Chemical Formula 3, which is an alkylaluminoxane compound, is used as the first cocatalyst to react with silica, and the borate It is preferable to use a cocatalyst represented by the above formula (4) as a second compound as a second cocatalyst in terms of supporting efficiency.

In addition, as described above, in the order of the cocatalyst compound-> metallocene compound, the previously supported cocatalyst compound reacts with the hydroxy group on the surface of the carrier in advance, and the scavenger for impurities such as moisture and catalyst foreign substances By acting as a scavenger it can help to prepare a uniform catalyst. Accordingly, the possibility of deactivation of the first and second metallocene compounds supported after the support of the promoter compound can be reduced, thereby preparing a supported catalyst with high activity.

At this time, supporting the first and second cocatalyst on the carrier; And each step of supporting the first and second metallocene compounds may be performed at about 20 to 150 ° C, preferably about 30 to 100 ° C.

Meanwhile, the mass ratio of the total transition metal to the carrier included in the first metallocene compound represented by Formula 1 and the second metallocene compound represented by Formula 2 may be about 1: 10 to 1: 1,000. In addition, the mass ratio of the first and second cocatalyst compounds to the carrier may be about 1: 1 to 1: 100. When the cocatalyst and the metallocene compound are included in the mass ratio, the active and polymer microstructures can be optimized.

In the method for preparing the hybrid supported metallocene catalyst of the embodiment, a carrier containing a hydroxyl group on the surface may be used. Preferably, the carrier is dried to remove moisture on the surface. The carrier which has a hydroxyl group and a siloxane group can be used.

For example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, which are typically oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. When the drying temperature of the carrier is less than 200 ° C., the moisture is too much to react with the surface of the carrier and the promoter reacts. When the carrier temperature exceeds 800 ° C., the pores on the surface of the carrier are combined to reduce the surface area, and more hydroxyl groups are present on the surface. It is not preferable because it disappears and only siloxane groups remain and the reaction site with the promoter decreases.

The amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 5 mmol / g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxy group is less than 0.1 mmol / g, the reaction site with the promoter is small, and if the amount of the hydroxy group is more than 10 mmol / g, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not.

According to another embodiment of the invention, there is provided a hybrid supported metallocene catalyst prepared by the above-described method.

In addition, according to another embodiment of the invention, there is provided a method for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of a hybrid supported metallocene catalyst prepared by the above-described method.

In the method for producing a polyolefin, preparing a hybrid supported metallocene catalyst according to the embodiment described above; And under the hybrid supported metallocene catalyst, it is possible to produce a polyolefin by a method comprising the step of polymerizing an olefin monomer.

In the method for producing such polyolefin, the hybrid supported metallocene catalyst can be used for polymerization of olefin monomers as such. In addition, the catalyst may be prepared as a catalyst which has been reacted with the olefinic monomer to be prepolymerized and used as a catalyst, for example, by separately contacting the catalyst with an olefinic monomer such as ethylene, propylene, 1-butene, 1-hexene or 1-octene It can also be prepared and used as a prepolymerized catalyst.

Examples of the olefin monomer that can be polymerized using the hybrid supported metallocene catalyst include ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds. More specifically, examples of the olefin monomers include ethylene, 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-aitocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1, 4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, or 3-chloromethylstyrene, and the like. It may be.

In the step of polymerizing the olefin monomer under the hybrid supported metallocene catalyst, it is preferable to polymerize the olefin monomer at a temperature of 50 to 150 ℃.

The olefin polymerization process using the catalyst can proceed according to a slurry, a gas phase process or a mixing process of a slurry and a gas phase, and a slurry or a gas phase process is preferable.

In the method for preparing the polyolefin, the hybrid supported metallocene catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, or an isomer thereof; Aromatic hydrocarbon solvents such as toluene, benzene; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; It can be dissolved or diluted and injected into the back. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.

According to the present invention, a method of preparing a hybrid supported metallocene catalyst capable of improving the mechanical properties of a polyolefin by increasing the molecular weight during polymerization of an olefin while showing high catalytic activity and a method of preparing a polyolefin using the same can be provided.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

The organic reagents and solvents necessary for the preparation and polymerization of the catalyst were purified by Aldrich's standard method, and ethylene was passed through a high-purity product from Applied Gas Technology through a water and oxygen filtration device. Used.

In addition, the reproducibility of the experiment was improved by blocking contact between air and water at all stages of catalyst synthesis, loading, and olefin polymerization, and spectra were obtained using 300 MHz NMR (Bruker) to prove the structure of the catalyst.

Production Example One

At room temperature, 50 g of Mg (s) was added to a 10 L reactor, followed by 300 ml of THF. After adding 0.5 g of I ₂ , the reactor temperature was maintained at 50 ° C. After the reactor temperature was stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a rate of 5 ml / min using a feeding pump. As the 6-t-butoxyhexyl chloride was added, it was observed that the reactor temperature was increased by 4-5 ° C. It was stirred for 12 hours while adding 6-t-butoxyhexyl chloride. After 12 hours of reaction, a black reaction solution was obtained. After taking 2 ml of the resulting black solution, water was added to obtain an organic layer, and 6-t-butoxy hexane was confirmed by ¹ H NMR, and the Grignard reaction proceeded well from 6-t-butoxyhexane. there was. Thus 6-t-butoxyhexyl magnesium chloride was synthesized. 500 g of MeSiCl ₃ and 1 L of THF were added to the reactor, and the reactor temperature was cooled to -20 ° C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 ml / min using a feed pump. After supplying the Grigard Reagent, the reaction mixture was stirred for 12 hours while slowly raising the temperature of the reactor. After 12 hours, it was confirmed that a white MgCl ₂ salt was produced. 4 L of hexane was added to remove the salt through labdori to obtain a filter solution. After the filter solution was added to the reactor, hexane was removed at 70 ° C. to obtain a pale yellow liquid. The obtained liquid was confirmed to be a desired methyl (6-t-butoxyhexyl) dichlorosilane (methyl (6-t-butoxy hexyl) dichlorosilane) compound through ¹ H NMR.

¹ H NMR (300 MHz, CDCl ₃ ): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H)

Tetramethylcyclopentadiene (1.2 mole, 150 g) and 2.4 L of THF were added to the reactor, and the reactor temperature was cooled to -20 ° C. 480 ml of n-BuLi was added to the reactor at a rate of 5 ml / min using a feed pump. After n-BuLi was added, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent of methyl (6-t-butoxyhexyl) dichlorosilane (326 g, 350 ml) was quickly added to the reactor. After stirring for 12 hours while slowly raising the reactor temperature to room temperature, the reactor temperature was further cooled to 0 ° C., and then 2 equivalents of t-BuNH ₂ was added thereto. Stirring for 12 hours while slowly raising the reactor temperature to room temperature. After 12 hours of reaction, THF was removed, and 4 L of hexane was added to obtain a filter solution from which salt was removed through labdori. After adding the filter solution to the reactor again, the hexane was removed at 70 ℃ to obtain a yellow solution. The yellow solution may be identified as methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane (methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane) compound through ¹ H NMR. there was.

-78 synthesized in THF solution from n-BuLi and the ligand methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane (methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane) TiCl ₃ (THF) ₃ (10 mmol) was quickly added to the dilithium salt of the ligand at ° C. The reaction solution was slowly stirred at -78 ° C to room temperature for 12 hours. After stirring for 12 hours, the equivalent of PbCl ₂ at room temperature (10 mmol) was added to the reaction solution, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution was obtained. After removing THF from the reaction solution, hexane was added to filter the product. After hexane was removed from the filter solution, it was confirmed by ¹ H NMR that the desired [methyl (6-t-butoxyhexyl) silyl (η5-tetramethylCp) (t-butylamino) TiCl ₂ ] compound.

¹ H NMR (300 MHz, CDCl ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H ), 0.7 (s, 3H)

Production Example 2

Using 6-chlorohexanol, t-Butyl-O- (CH ₂ ) ₆ -Cl was prepared by the method shown in Tetrahedron Lett. 2951 (1988), and reacted with NaCp. t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80 ° C./0.1 mmHg).

Further, t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C, and normal butyllithium (n-BuLi) was slowly added, and the temperature was raised to room temperature, followed by reaction for 8 hours. . The solution was added slowly to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 mL) at −78 ° C., followed by slowly adding a lithium salt solution. The reaction was further reacted for 6 hours.

All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of hexane solvent. The filtered solution was dried in vacuo and hexane was added to induce precipitate at low temperature (-20 ° C). The obtained precipitate was filtered at low temperature to give [tBu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl _{2 as a} white solid. The compound was obtained (yield 92%).

¹ H NMR (300 MHz, CDCl ₃ ): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 ( t, J = 8 Hz), 1.7-1.3 (m, 8 H), 1.17 (s, 9 H).

Example One

Silica was prepared by dehydrating Grace Davison's SYLOPOL 948 under vacuum at 600 ° C. for 12 hours. Then, 100 ml of toluene solution was added to the glass reactor, and 10 g of prepared silica was added thereto, followed by stirring while raising the reactor temperature to 40 ° C. After sufficiently dispersing the silica, 57 ml of 10 wt% methylaluminoxane (MAO) / toluene solution was added thereto, and the mixture was stirred at 200 rpm for 16 hours while raising the temperature to 60 ° C. The temperature was lowered back to 40 ° C. and washed with a sufficient amount of toluene to remove unreacted aluminum compounds. After 50 ml of toluene was added again, 0.706 mmol of the metallocene compound prepared in Preparation Example 1 was dissolved in 50 ml of toluene, brought into a solution state, and put into a reactor, followed by stirring for 2 hours. Then, 1.12 mmol (0.90 g) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was dissolved in 50 ml of toluene, and then charged into a reactor including a supported catalyst, followed by stirring at 200 rpm for 2 hours at 40 ° C. . After the reaction was completed, 0.413 mmol of the metallocene compound prepared in Preparation Example 2 was dissolved in 50 ml of toluene to make a solution, and then stirred in the reactor for 2 hours. Subsequently, the catalyst was settled, the toluene layer was separated and removed, and then substituted with hexane. The catalyst was further settled, the hexane layer was separated and removed, and the remaining hexane was removed at 40 ° C. to prepare a supported catalyst for olefin production.

Example 2

Silica was prepared by dehydrating Grace Davison's SYLOPOL 948 under vacuum at 600 ° C. for 12 hours. Then, 100 ml of toluene solution was added to the glass reactor, and 10 g of prepared silica was added thereto, followed by stirring while raising the reactor temperature to 40 ° C. After sufficiently dispersing the silica, 57 ml of a 10 wt% methylaluminoxane (MAO) / toluene solution was added thereto, followed by stirring at 200 rpm for 16 hours while raising the temperature to 95 ° C. The temperature was lowered back to 80 ° C. and washed with a sufficient amount of toluene to remove unreacted aluminum compounds. After 50 ml of toluene was added again, 0.706 mmol of the metallocene compound prepared in Preparation Example 1 was dissolved in 50 ml of toluene, brought into a solution state, and put into a reactor, followed by stirring for 2 hours. Then, 1.12 mmol (0.90 g) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was dissolved in 50 ml of toluene, and then charged into a reactor including a supported catalyst, followed by stirring at 200 rpm for 2 hours at 80 ° C. . After the reaction was completed, 0.413 mmol of the metallocene compound prepared in Preparation Example 2 was dissolved in 50 ml of toluene to make a solution, and then stirred in the reactor for 2 hours. Subsequently, the catalyst was settled, the toluene layer was separated and removed, and then substituted with hexane. The catalyst was further settled, the hexane layer was separated and removed, and the remaining hexane was removed at 40 ° C. to prepare a supported catalyst for olefin production.

Example 3

Silica was prepared by dehydrating Grace Davison's SYLOPOL 948 under vacuum at 600 ° C. for 12 hours. Then, 100 ml of toluene solution was added to the glass reactor, and 10 g of prepared silica was added thereto, followed by stirring while raising the reactor temperature to 40 ° C. After sufficiently dispersing the silica, 28.5 ml of a 10 wt% methylaluminoxane (MAO) / toluene solution was added and stirred at 200 rpm for 16 hours while raising the temperature to 60 ° C. The temperature was lowered back to 40 ° C. and washed with a sufficient amount of toluene to remove unreacted aluminum compounds. After 50 ml of toluene was added again, 0.706 mmol of the metallocene compound prepared in Preparation Example 1 was dissolved in 50 ml of toluene, brought into a solution state, and put into a reactor, followed by stirring for 2 hours. Then, 1.12 mmol (0.90 g) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was dissolved in 50 ml of toluene, and then charged into a reactor including a supported catalyst, followed by stirring at 200 rpm for 2 hours at 40 ° C. . After the reaction was completed, 0.413 mmol of the metallocene compound prepared in Preparation Example 2 was dissolved in 50 ml of toluene to make a solution, and then stirred in the reactor for 2 hours. Subsequently, the catalyst was settled, the toluene layer was separated and removed, and then substituted with hexane. The catalyst was further settled, the hexane layer was separated and removed, and the remaining hexane was removed at 40 ° C. to prepare a supported catalyst for olefin production.

Comparative example One

For preparing olefins in the same manner as in Example 1, except that N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate was dissolved in toluene and then added to a reactor containing a supported catalyst and stirred. A supported catalyst was prepared.

Comparative example 2

For preparing olefins in the same manner as in Example 2, except that N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate was dissolved in toluene and then added to a reactor containing a supported catalyst and stirred. A supported catalyst was prepared.

Comparative example 3

For preparing olefins in the same manner as in Example 3, except that N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate was dissolved in toluene, and then added to a reactor containing a supported catalyst and stirred. A supported catalyst was prepared.

Comparative example 4

Silica was prepared by dehydrating Grace Davison's SYLOPOL 948 under vacuum at 600 ° C. for 12 hours. Then, 100 ml of toluene solution was added to the glass reactor, and 10 g of prepared silica was added thereto, followed by stirring while raising the reactor temperature to 40 ° C. After sufficiently dispersing the silica, 57 ml of 10 wt% methylaluminoxane (MAO) / toluene solution was added thereto, and the mixture was stirred at 200 rpm for 16 hours while raising the temperature to 60 ° C. The temperature was lowered back to 40 ° C. and washed with a sufficient amount of toluene to remove unreacted aluminum compounds. After 50 ml of toluene was added again, 0.706 mmol of the metallocene compound prepared in Preparation Example 1 was dissolved in 50 ml of toluene, brought into a solution state, and put into a reactor, followed by stirring for 2 hours. After the reaction was completed, 0.413 mmol of the metallocene compound prepared in Preparation Example 2 was dissolved in 50 ml of toluene to make a solution, and then stirred in the reactor for 2 hours. Then, 1.12 mmol (0.90 g) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was dissolved in 50 ml of toluene, and then charged into a reactor including a supported catalyst, followed by stirring at 200 rpm for 2 hours at 80 ° C. . Subsequently, the catalyst was settled, the toluene layer was separated and removed, and then substituted with hexane. The catalyst was further settled, the hexane layer was separated and removed, and the remaining hexane was removed at 40 ° C. to prepare a supported catalyst for olefin production.

Comparative example 5

Silica was prepared by dehydrating Grace Davison's SYLOPOL 948 under vacuum at 600 ° C. for 12 hours. Then, 100 ml of toluene solution was added to the glass reactor, and 10 g of prepared silica was added thereto, followed by stirring while raising the reactor temperature to 40 ° C. 0.706 mmol of the metallocene compound prepared in Preparation Example 1 was dissolved in 50 ml of toluene, brought into a solution state, and charged into the reactor, followed by stirring for 2 hours. Then, 1.12 mmol (0.90 g) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was dissolved in 50 ml of toluene, and then charged into a reactor including a supported catalyst, followed by stirring at 200 rpm for 2 hours at 40 ° C. . After the reaction was completed, 0.413 mmol of the metallocene compound prepared in Preparation Example 2 was dissolved in 50 ml of toluene to make a solution, and then stirred in the reactor for 2 hours. Subsequently, the catalyst was settled, the toluene layer was separated and removed, and then substituted with hexane. The catalyst was further settled, the hexane layer was separated and removed, and the remaining hexane was removed at 40 ° C. to prepare a supported catalyst for olefin production.

Comparative example 6

Instead of adding 57 ml of 10 wt% methylaluminoxane (MAO) / toluene solution, a supported catalyst for preparing olefin was prepared in the same manner as in Example 1 except that 37.5 ml of 2M trimethylaluminum (TMA) toluene solution was added.

Comparative example 7

For preparing olefins in the same manner as in Comparative Example 6, except that N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate was dissolved in toluene and then added to a reactor containing a supported catalyst and stirred. A supported catalyst was prepared.

In Examples 1 to 3 and Comparative Examples 1 to 7, the supported amounts of the metallocene compound and the cocatalyst are summarized in Table 1 below.

Article 1 Catalyst Preparation Example 1
Metallocene compound Article 2 Catalyst Preparation Example 2
Metallocene compound mmol / gSiO ₂ wt% / gSiO ₂ mmol / gSiO ₂ wt% / gSiO ₂ Example 1 7.5 3.5 0.112 2.5 Example 2 7.5 3.5 0.112 2.5 Example 3 3.75 3.5 0.112 2.5 Comparative Example 1 7.5 3.5 0 2.5 Comparative Example 2 7.5 3.5 0 2.5 Comparative Example 3 3.75 3.5 0 2.5 Comparative Example 4 7.5 3.5 0.112 2.5 Comparative Example 5 0 3.5 0.112 2.5 Comparative Example 6 7.5 3.5 0.112 2.5 Comparative Example 7 7.5 3.5 0 2.5

Experimental Example

20 mg of the mixed supported metallocene catalyst prepared in Examples 1 to 3 and Comparative Examples 1 to 7 were quantified in a dry box, respectively, placed in a 50 ml glass bottle, sealed with a rubber diaphragm, and taken out of the dry box to prepare a catalyst for injection. It was. The polymerization was carried out in a 2 L metal alloy reactor with temperature control and high pressure, equipped with a mechanical stirrer.

Into this reactor, 1 L of hexane and 1-hexene (10 ml) containing 0.5 mmol of triethylaluminum were injected, and each of the supported catalysts was introduced into the reactor without air contact, and then gas ethylene monomer was added at 80 ° C. The polymerization was continued for 1 hour while continuously applying a pressure of 40 gf / cm 2. Termination of the polymerization was completed by first stopping stirring and then doubling and removing ethylene. The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried in an oven at 70 ° C. for 4 hours.

Activity and molecular weight were then measured for each polymer obtained, and the results are shown in Table 2 below.

Active (kgPE / g-Cat) Molecular Weight (Mw) Example 1 10.3 851,000 Example 2 15.5 907,000 Example 3 7.0 821,000 Comparative Example 1 5.0 503,000 Comparative Example 2 8.0 534,000 Comparative Example 3 3.0 453,000 Comparative Example 4 13.2 358,000 Comparative Example 5 0 - Comparative Example 6 6.2 512,000 Comparative Example 7 1.0 475,000

As shown in Table 2, the mixed supported metallocene catalyst prepared by using two kinds of metallocene compounds and two types of cocatalysts and specifying their supporting order as in Examples 1 to 3 is one It was confirmed that only the cocatalyst was used or the catalytic activity was significantly higher than that of Comparative Examples 1 to 4, in which the supporting order was different.

More specifically, Example 2 is to increase the supporting temperature of the first cocatalyst, the metallocene compound of Preparation Example 1, the second cocatalyst, the metallocene compound of Preparation Example 2 compared to Example 1, through When increasing the supporting temperature, it was confirmed that there is an additional effect of increasing the activity while maintaining the high molecular weight.

In Comparative Example 4, a second cocatalyst was supported after supporting the metallocene compound of Preparation Example 2. In this case, Preparation Example 2 metallocene compound forming a low molecular weight polymer was prepared as the metal of Preparation Example 1. It is more activated than a sen compound, and the molecular weight of the polymer prepared in comparison with Example 1 is lower than 1/2, which causes a problem in the commercial process.

In Comparative Example 5, the first cocatalyst was not applied. In this case, it was confirmed that there was no polymerization activity.

Comparative Example 6 is a case where TMA (trimethylaluminum) is applied instead of MAO (methylaluminoxane) as the first cocatalyst, and in this case, the activity is lower and the molecular weight is lower than that of Example 1 to which MAO is applied. There was a limit.

In Comparative Example 7, TMA (trimethylalluminium) was used instead of MAO (methylaluminoxane) as the first cocatalyst, and the second cocatalyst was not applied. In this case, the polymerization activity was extremely low.

In sum, the catalytic activity of the hybrid supported metallocene catalyst prepared by using two kinds of metallocene compounds and two types of promoters and specifying their supporting order as in Examples 1 to 3 was not. This remarkably high, high molecular weight polymer can be prepared and found to be applicable to commercial processes.

Claims

Supporting the first cocatalyst on the carrier;
Supporting the first metallocene compound on the carrier on which the first cocatalyst is supported;
Supporting a second promoter on a carrier on which the first promoter and the first metallocene compound are supported; And
Supporting a second metallocene compound that polymerizes an olefinic monomer at a lower polymerization degree than the first metallocene compound on a carrier on which the first promoter, the first metallocene compound, and the second promoter are supported; Include,
The first cocatalyst is a compound represented by the following formula (3), the second cocatalyst is a compound represented by the formula (4), a method for producing a hybrid supported metallocene catalyst:
[Formula 3]
-[Al (R ₁ ) -O-] _k-
In Formula 3, each R ₁ is independently a halogen, halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,
[Formula 4]
T ⁺ [BG ₄ ] ^-
In formula (4), T ⁺ is a + monovalent polyatomic ion, B is boron in the +3 oxidation state, G is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, hydro Selected from the group consisting of carbyl groups, halocarbyl groups and halo-substituted hydrocarbyl groups, wherein G has up to 20 carbons, but at up to one position G is a halide group.

The method of claim 1,
The first metallocene compound is represented by the following formula (1), the second metallocene compound is a method of producing a hybrid supported metallocene catalyst represented by the formula (2):
[Formula 1]
(Cp ¹ R ^a ) B ¹ (J) M ¹ Z ¹ ₂
In Chemical Formula 1,
M ¹ is a Group 4 transition metal;
Cp ¹ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms Can be;
R ^a is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkynyl;
Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
B ¹ is one or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp ¹ R ^a ring and J;
J is any one selected from the group consisting of NR ^f , O, PR ^f and S, wherein R ^f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl,
[Formula 2]
(Cp ² R ^b ) _n (Cp ³ R ^c ) M ² Z ² ₃ _-n
In Chemical Formula 2,
M ² is a Group 4 transition metal;
Cp ² and Cp ³ are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;
R ^b and R ^c are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To alkenyl of C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
Z ² is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
n is 1 or 0.

The method of claim 2,
Method for preparing a hybrid supported metallocene catalyst of the first metallocene compound represented by Formula 1 is one of the following structural formulas:

The method of claim 2,
Method for producing a hybrid supported metallocene catalyst of the second metallocene compound represented by Formula 2 is one of the following structural formulas:

delete

The method of claim 1,
The mass ratio of the transition metal to the carrier of the first metallocene compound and the second metallocene compound is 1: 10 to 1: 1,000 method for producing a hybrid supported metallocene catalyst.

The method of claim 1,
Wherein the mass ratio of the first and second cocatalyst compounds to the carrier is from 1: 1 to 1: 100.

The method of claim 1,
The carrier is a method for producing a hybrid supported metallocene catalyst comprising at least one selected from the group consisting of silica, silica-alumina and silica-magnesia.

A mixed supported metallocene catalyst prepared by the method of any one of claims 1 to 4 and 7 to 9.

A process for producing a polyolefin comprising polymerizing an olefinic monomer in the presence of the hybrid supported metallocene catalyst of claim 10.