WO2015186970A1 - Method of preparing polyolefin and polyolefin prepared by said method - Google Patents

Abstract

The present invention relates to a method capable of more easily and effectively preparing polyolefin, and polyolefin prepared by the same, wherein the method is for preparing polyolefin having a high molecular weight and various molecular weight distributions, which is difficult to prepare through a typical metallocene catalyst. The method for preparing polyolefin includes a step of polymerizing olefin-based monomers in the presence of hydrogen gas and a metallocene-containing catalyst in which a carrier contains a metallocene compound having a certain chemical structure.

Description

 【Specification】

 [Name of invention]

 Process for preparing polyolefin and polyolefin produced therefrom

 [Cross Citation with Related Application (s)]

 This application is the Korean patent application No. 10-2014-0067697 dated June 3, 2014 and

Claiming the benefit of priority based on Korean Patent Application No. 10-2015-0078104, issued June 2, 2015, all contents disclosed in the literature of the Korean patent applications are incorporated as part of this specification.

 Technical Field

The present invention ^'relates to a high molecular weight and the polyolefin production polrieul from the production method and this the repin which can be easily than polyolefins manufactured effectively with a wide range of molecular weight distribution.

 Background Art

 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 due to its multi-site catalyst having many active sites. There is a problem that there is a limit in securing the desired physical properties because the composition distribution is not uniform.

 In particular, when preparing ultra-high molecular weight polyolefins with a weight average molecular weight of 1 million or more using a Ziegler-Natta catalyst, the catalyst residues (C1 components, etc.) are high, so that polyolefins may be decomposed during molding at a high temperature, which is a molecular weight of the polyolefin. May involve degradation. For this reason, there exists a disadvantage that the outstanding physical property as an ultra high molecular weight polyolefin cannot express correctly.

 In comparison, when a high molecular weight polyolefin is obtained using a metallocene catalyst, the molecular weight distribution is relatively small, and thus, the layer resistance may be improved. In addition, since the C1 component of the catalyst residue is small, decomposition of polyolefin can be greatly suppressed during molding. However, polyolefin produced using a metallocene catalyst has a problem of poor workability due to a narrow molecular weight distribution.

In general, the wider the molecular weight distribution, the lower the viscosity according to the shear rate. As the degree is increased, it shows excellent processability in the processing area. Due to the relatively narrow molecular weight distribution, the polyolefin made of the metallocene catalyst has a high viscosity at high shear rate, so that a lot of load or pressure is extruded at the time of extrusion, thereby reducing the extrusion productivity. ， The bubble stability during blow molding process is greatly reduced, there is a disadvantage that the surface of the produced molded article is uneven, leading to a decrease in transparency.

 In addition, in the process of obtaining a high molecular weight polyolefin by using a metallocene catalyst, it is usually possible to control the molecular weight by adjusting the input amount of hydrogen gas, the molecular weight of the polyolefin decreases as the amount of the hydrogen gas is increased. Furthermore, even if the polymerization is carried out without hydrogen gas, it is difficult to obtain ultra high molecular weight polyolefin having a weight average molecular weight of 1 million or more due to the excellent beta hydrogen removal reaction due to the nature of the metallocene catalyst.

 Accordingly, attempts have been made to obtain polyolefins which simultaneously stratify a broader molecular weight distribution and a larger molecular weight.

 However, due to the large reactivity of the metallocene catalyst and the like, it is true that there was a limit in producing a polyolefin that simultaneously satisfies a sufficiently large molecular weight and a wider molecular weight distribution. As a result of having a large molecular weight and a wider molecular weight distribution, there is a continuous demand for the development of a technology that can more efficiently produce polyolefins that can satisfy mechanical properties and processability and can be preferably used for large products. have.

 [Contents of the Invention]

 [Problem to solve]

 Accordingly, the present invention provides a method for preparing polyolefin and a polyolefin produced from the same, which makes it easier and more efficient to prepare polyolefin having a high molecular weight and various molecular weight distributions, which are difficult to manufacture through a conventional metallocene catalyst. will be.

 [Measures of problem]

 The present invention provides a polyolefin comprising a step of polymerizing at least one first metallocene compound represented by the following Chemical Formula 1 and a supported metallocene catalyst having a promoter supported on a carrier and hydrogen gas in the presence of hydrogen gas; Provide the manufacturing method:

[Formula 1]

 In Chemical Formula 1,

 A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 A C20 alkoxyalkyl group, C3 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl group;

 D is -0-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20;

 L is a C1 to C10 straight or branched chain alkylene group;

 B is carbon, silicon or germanium;

 Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;

 M is a Group 4 transition metal;

X ¹ and X ² are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ¹ and C ² are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c, except that both C ¹ and C ² are Chemical Formula 2c;

[Formula 2a]

 In Chemical Formulas 2a, 2b, and 2c,

 R1 to R17 and R1 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group , C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, two of R10 to R17 adjacent to each other The foregoing can be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

 The present invention also provides a polyolefin produced according to the polyolefin production method.

 【Effects of the Invention】

According to the production method of the present invention, the conventional metallocene catalyst was difficult to manufacture Polyolefins with high molecular weight and broad molecular weight distribution can be produced very effectively. Since the high molecular weight polyolefin has a small amount of catalyst residue due to the nature of the polyolefin made of the metallocene catalyst, it is possible to suppress decomposition of polyolefin in the high temperature molding process. Therefore, it is possible to express excellent properties according to high molecular weight and wide molecular weight distribution, and to use for large blow molding products, next-generation pipe products requiring excellent pressure resistance and heat resistance properties, or injection products having good stress cracking properties. Very preferably.

 In addition, according to the combination of the metallocene compound included in the metallocene catalyst of the present invention, the interaction with the molecular weight modifier, and the reaction properties against hydrogen, it is possible to prepare a polyolefin having various weight average molecular weight and molecular weight distribution. . Accordingly, the polyolefin having the desired physical properties can be easily prepared according to the specific combination of the metallocene compound and the selective use of hydrogen and the molecular weight modifier.

 [Specific contents for implementation of the invention]

 Hereinafter, a method for preparing a polyolefin and a polyolefin produced therefrom according to a specific embodiment of the present invention will be described.

 According to an embodiment of the present invention, polymerizing an olefinic monomer in the presence of hydrogen gas and a supported metallocene catalyst having at least one first metallocene compound represented by Formula 1 and a promoter supported on a carrier Provided is a method for preparing a polyolefin, including:

 [

 In Chemical Formula 1,

 A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 A C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

D is -0-, -S-, -N (R)-or -Si (R) (R ')-, where R and R' are The same or different, each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, or C6 to C20 aryl group;

 L is a C1 to C10 straight or branched chain alkylene group;

 B is carbon, silicon or germanium;

 Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;

 M is a Group 4 transition metal;

X ¹ and X ² are the same as or different from each other, and each independently halogen, C 1 to C 20 alkyl group, C 2 to C 20 alkenyl group, C 6 to C 20 aryl group, nitro group, amido group, C 1 to C 20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ¹ and C ² are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c, except that both C ¹ and C ² are Chemical Formula 2c;

[Formula 2c]

 In Chemical Formulas 2a, 2b and 2c,

 R1 to R17 and R1 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group , C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, two of R10 to R17 adjacent to each other The foregoing can be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring. .

 In the method for preparing a polyolefin according to one embodiment, the agent represented by Chemical Formula 1

A polyolefin is prepared by polymerizing a supported metallocene catalyst having at least one metallocene compound and a cocatalyst supported on a carrier, and an olefinic monomer in the presence of hydrogen gas.

 In this manufacturing method, the first metallocene compound of Formula 1 forms a structure in which an indeno indole derivative and / or a fluorene derivative is crosslinked by a bridge, and forms a Lewis base in the ligand structure. By having a non-covalent electron pair which can act, it can be supported on the surface having the Lewis acid characteristics of the carrier to exhibit higher polymerization activity. In addition, it is possible to maintain high activity due to the high activity, including the electronically rich indeno indole group and / or fluorene group, due to the appropriate steric hindrance and the electronic effect of the ligand. In addition, since the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative is grown can be stabilized by hydrogen bonding, beta-hydrogen elimination can be suppressed, thereby enabling the production of a higher molecular weight polyolefin. In addition, since the hydrogen reactivity is low, polyolefins having high weight average molecular weight and wide molecular weight distribution can be prepared.

Furthermore, in addition to the first metallocene compound of Formula 1 and hydrogen gas, a second to selectively prepare a medium or low molecular weight polyolefin, By properly using a metallocene compound and a molecular weight modifier, the present invention was completed by confirming that polyolefins having a high molecular weight and various molecular weight distributions, which were difficult to prepare using a metallocene catalyst, could be prepared.

 Meanwhile, in the first metallocene compound of Formula 1, the substituents will be described in more detail as follows.

 The C1 to C20 alkyl group includes a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nuclear group, heptyl group, Octyl group etc. can be mentioned, 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, and pentenyl group, but is not limited thereto.

 The C6 to C20 aryl group includes a monocyclic or condensed aryl group, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but is 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 And 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 cyclonuxyloxy group, and the like, but are not limited thereto.

 The Group 4 transition metal may include titanium, zirconium, hafnium, and the like, but is not limited thereto.

 In addition, in Formulas 2a, 2b and 2c, which are ligand-derived structures included in Formula 1, R1 to R17 and R1 'to R9' are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, and n-butyl. Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, phenyl group, halogen group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, trimethyl It is more preferable that it is a silyl methyl group, a meso group, or an ethoxy group, but it is not limited to this.

In addition, L in Formula 1 is a C4 to C8 linear or branched alkylene group More preferably, but is not limited thereto. In addition, the alkylene group may be unsubstituted or substituted with an alkyl group of C1 to C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20.

 In addition, in Formula 1, A, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, methoxymethyl, tert-butoxymethyl, 1-ethoxyethyl, 1-methyl It is preferable that it is a 1- methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, but it is not limited to this.

 And, it is preferable that B of Formula 1 is silicon, but is not limited thereto.

 According to an embodiment of the present invention, specific examples of the structure represented by Chemical Formula 2a may include a structure represented by one of the following structural formulas, but is not limited thereto.

 A specific example of the structure represented by Chemical Formula 2b may include a structure represented by one of the following structural formulas, but is not limited thereto.

 In addition, specific examples of the structure represented by Formula 2c may include a group as one of the following structural formulas, but is not limited thereto.

 In addition, 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.

_// u O _S S2M12 _/ .698sszA

 The first metallocene compound of Formula 1 described above has excellent activity and high molecular weight

^■ Polyolefin can be produced. In particular, even when used on a carrier, it shows a high polymerization activity, thereby enabling the production of high molecular weight or ultra high molecular weight polyolefin. In addition, even when the polymerization reaction is performed including hydrogen gas to prepare an olefin polymer having a high molecular weight and a wide molecular weight distribution, the metallocene compound according to the present invention exhibits low hydrogen reactivity and still has high activity. Polymerization of the olefin based polymer of molecular weight to ultra high molecular weight is possible. Therefore, even when used on a carrier in common with a catalyst having different properties, it is possible to produce an eleupine-based polymer that satisfies high molecular weight properties without degrading the activity, thereby providing a wide molecular weight distribution while including an olefinic polymer of the polymer. It is possible to easily produce the olefin polymer having.

 The first metallocene compound of Chemical Formula 1 may be prepared by connecting an indenoindole derivative and / or fluorene derivative with a bridge compound to prepare a ligand compound, and then performing metallation by introducing a metal precursor compound. Can be. The manufacturing method of the said 1st metallocene compound is concretely demonstrated to the Example mentioned later.

Meanwhile, according to one embodiment of the present invention, the supported metallocene catalyst may be a single supported metallocene catalyst including at least one first metallocene compound represented by Chemical Formula 1, a cocatalyst compound and a carrier, Or a common supported metallocene catalyst including at least one first metallocene compound represented by Formula 1, at least one second metallocene compound, a cocatalyst compound, and a carrier. That is, in the specification of the present invention, the supported metallocene catalyst or the metallocene supported catalyst is the first metallocene. A single supported metallocene catalyst carrying only one or more compounds alone and a hybrid supported metallocene catalyst carrying at least one first metallocene compound and at least one second metallocene compound shall be included. .

 The second metallocene compound may be selected from compounds represented by the following Chemical Formulas 3 to 5.

 [Formula 3]

 In Chemical Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² 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 ^a and R ^b 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 Alkenyl to C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

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;

 n is 1 or 0;

[Formula ⁴ ]

 In Chemical Formula 4,

M ² is a Group 4 transition metal;

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

R ^c and R ^d 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 C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ² is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C ₄₀ alkyl aryl, C7 to aryl C40 alkyl, C6 to aryl C20, a substituted or unsubstituted C1 to C20 alkyl for the Lidene, a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

B ¹ is one or more of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp ³ R ^c ring and the Cp ⁴ R ^d ring or crosslink one Cp ⁴ R ^d ring to M ² Or a combination thereof;

 m is 1 or 0;

 [Formula 5]

(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂

 In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁵ 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 ^e 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 Arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

Z ³ 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 , Substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

B ² is R ^{5 e} Cp carbon, germanium, silicon, phosphorus, or of cross-linking the ring and J At least one or a combination of nitrogen atom containing radicals;

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.

In Formula 4, when m is 1, it means that a Cp ³ R ^c ring and a Cp ⁴ R ^d ring or a Cp ⁴ R ^d ring and M ² are bridge compound structures cross-linked by B ¹ , and in is 0. In the case of, it means a non-crosslinked compound structure.

 As the second metallocene compound represented by Formula 3, for example,

As the second metallocene compound represented by Formula 4, for example

In addition, the second metallocene compound represented by Chemical Formula 5 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

The common supported metallocene catalyst may include at least one of the first metallocene compound represented by Formula 1 and at least one of the second metallocene compound selected from the compounds represented by Formulas 3 to 5. It is commonly supported on a carrier together with a promoter catalyst.

The first metallocene compound represented by Formula 1 of the common supported metallocene catalyst mainly contributes to making a high molecular weight copolymer having a high SCB (short chain branch) content, and is represented by the second metal represented by Formula 3 Sen compounds may contribute primarily to making low molecular weight copolymers with low SCB content. Also, The second metallocene compound represented by Formula 4 or 5 may contribute to making a low molecular weight copolymer having a moderate SCB content.

 In the common supported metallocene catalyst, the first metallocene compound has a ligand structure in which an indeno indole derivative and a fluorene derivative are crosslinked by a bridge compound, and a non-covalent electron pair capable of acting as a Lewis base to the ligand structure. By having a supported on the surface having the Lewis acid characteristics of the carrier it shows a high polymerization activity even when supported. In addition, due to the electronically rich indeno indole and / or fluorene group, the activity is high, and due to the proper steric hindrance and the electronic effect of the ligand, the reaction is not only low but also maintains high activity even in the presence of hydrogen. . Therefore, in the case of making a common supported metallocene catalyst using such a transition metal compound, the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative is grown is stabilized by hydrogen bonding to polymerize an ultrahigh molecular weight olepin-based polymer. Can be.

In addition, the common supported betalocene catalyst of the present invention includes a first metallocene compound represented by Chemical Formula 1 and a second metallocene compound selected from ^' compounds represented by Chemical Formulas 3 to 5, By containing at least two or more metallocene compounds, a high molecular weight olefin-based copolymer having a high SCB content and at the same time a wide molecular weight distribution, it is possible to prepare a leupine polymer having excellent physical properties and excellent processability.

 In the method for preparing polyolefin according to the present invention, the cocatalyst supported on the carrier for activating the first and the crab 2 metallocene compounds is an organometallic compound containing a Group 13 metal, and generally a metallocene. It will not be specifically limited if it can be used when polymerizing an olefin under a catalyst.

 According to an embodiment of the present invention, in particular, the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst of Formula 6 and a borate-based second cocatalyst of Formula 7 below.

 [Formula 6]

-[Al (R ₁₈ ) -0-] _k -In formula (6), R ₁₈ is each independently a halogen, halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more, [Formula 7]

T ⁺ [BG ₄ ] ^"

In formula 7, T ⁺ is a + monovalent polyatomic ion, Β is boron in +3 oxidation state _:

Each G is independently selected from the group consisting of a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, a hydrocarbyl group, a halocarbyl group and a halo-substituted hydrocarbyl group, wherein G is 20 It has up to 5 carbons, but at less than one position G is a halide group.

 By the use of the first and second cocatalysts, the molecular weight distribution of the finally produced polyolefin can be more uniform, and the polymerization activity can be improved.

 The first cocatalyst of Chemical Formula 6 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular or reticulated form, and specific examples of the first cocatalyst include methylaluminoxane (ΜΑΟ) and ethylalumina. Noxic acid, isobutyl aluminoxane, or butyl aluminoxane etc. are mentioned.

 In addition, the second cocatalyst of Formula 7 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt. Specific examples of such a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (η-butyl) ammonium tetraphenylborate , Methyltetracyclooctadecylammonium tetraphenylborate, Ν, Ν-dimethylaniline tetraphenylborate, Ν, Ν-diethylaninium tetraphenylborate, Ν, Ν-dimethyl (2,4,6-trimethylaninium Tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium, tetra Kiss (pentafluorophenyl) borate,

Tripropylammonium tetrakis (pentafluorophenyl) borate tri (η-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, Ν-dimethylaninium tetrakis (pentafluorophenyl) borate, Ν, Ν-diethylaninium tetrakis (pentafluorophenyl) borate, Ν, Ν-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, Ν, Ν-dimethylaninynium tetrakis (2,3,4,6-tetrafluorophenyl) borate, Ν, Ν-diethylaninynium tetrakis (2 , 3,4,6-tetrafluorophenyl) borate or Ν, Ν-dimethyl- (2,4,6-trimethylaninynium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate Borate compounds in the form of trisubstituted ammonium salts; Borate type in the form of dialkylammonium salt, such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetradecyl ammonium tetrakis (pentafluorophenyl) borate, or dicyclonuclear ammonium 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.

 In the single supported metallocene catalyst or the common supported metallocene catalyst, the mass ratio of the total transition metal to the carrier included in the first and second metallocene compounds may be 1:10 to 1: 1,000. When including the carrier and the metallocene compound in the mass ratio, it can exhibit an optimal shape.

 In addition, the mass ratio of the promoter compound to the carrier may be from 1: 1 to 1: 100. The mass ratio of the first and second metallocene compounds may be 10: 1 to 1:10, preferably 5: 1 to 1: 5. 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 producing the polyolefin, the carrier may be a carrier containing a hydroxy group on the surface, and preferably, a carrier having a semi-aromatic hydroxyl group and a siloxane group, which is dried to remove moisture from the surface. Can be used.

For example, silica dried at high temperature, silica-alumina, and silica-magnesia Etc. may be used, and they may typically contain oxides, carbonates, sulfates, and nitrate components, such as Na ₂ O, K ₂ CO ₃ , BaS0 ₄ , and Mg (N0 ₃ ) ₂ .

The drying temperature of the carrier is preferably about 200 to 800 ^° C., more preferably about 300 to 600 ^° C., and most preferably about 300 to 400 ^° C. If the drying temperature of the carrier is less than about 200 ^° C, the moisture is too much and the surface of the carrier reacts with the promoter, and if it exceeds about 800 ^° C, pores on the surface of the carrier are combined to reduce the surface area, It is not preferable because many hydroxyl groups are lost and only siloxane groups are left, resulting in a decrease in reaction space with the promoter.

 The amount of hydroxy groups on the surface of the carrier is preferably about 0.1 to 10 mmol / g, more preferably about 5 to 1 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 hydroxyl group is less than about 0.1 mmol / g, the reaction site with the cocatalyst is small. If the amount of the hydroxyl group is greater than about 10 mmol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. Not desirable

 In the single supported metallocene catalyst or the common supported metallocene catalyst, the mass ratio of the total transition metal: carrier included in the first and second metallocene compounds may be about 1: 10 to 1: 1,000. When the carrier and the metallocene compound are included in the mass ratio, an optimal shape can be exhibited.

 On the other hand, in the method for producing a polyolefin of one embodiment, in addition to the supported metallocene catalyst and hydrogen gas described above, it is possible to selectively produce a polyolefin by polymerizing the olefinic monomer in the presence of a molecular weight regulator.

 According to an embodiment of the present invention, the molecular weight modifier may include a mixture of a cyclopentadienyl metal compound of Formula 8 and an organoaluminum compound of Formula 9 or a reaction product thereof.

 [Formula 8]

Cp ⁶ Cp ⁷ M ⁴ X ' ₂

 In Chemical Formula 8,

Cp ⁶ and Cp ⁷ each independently include a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, or a substituted or unsubstituted fluorenyl group A ligand, Μ 'is a Group 4 transition metal element, X' is a halogen;

 [Formula 9]

R ^f R ^g R ^h Al

 In Chemical Formula 9,

R ^f , R ^g , and R ^h are each independently an alkyl group having 4 to 20 carbon atoms or a halogen, and at least one of R ^f , R ^g , and R ^h is an alkyl group having 4 to 20 carbon atoms.

 The molecular weight modifier itself does not exhibit activity as an olephine polymerization catalyst, and its mechanism of action is not specifically identified, but assists the activity of the metallocene catalyst to support the activity of the polyolefin having a larger molecular weight and a wider molecular weight distribution. It has been confirmed that it allows for manufacture.

 It has been confirmed that due to the interaction with such a molecular weight modifier, hydrogen gas, and the first and second metallocene catalysts, polyolefins having a larger weight average molecular weight and a wider molecular weight distribution can be produced.

 In addition, the polymerization reaction for producing the polyolefin for blow molding and the like may be mainly carried out in a slurry phase polymerization or the like in an aliphatic hydrocarbon-based organic solvent such as nucleic acid. However, as the molecular weight modifier is formed from an organoaluminum compound of formula 9 having an alkyl group having 4 or more carbon atoms, it may exhibit more excellent solubility in aliphatic hydrocarbon-based organic solvents such as the nucleic acid. Therefore, such a molecular weight modifier can be stably dissolved in an organic solvent used as a reaction medium or a diluent and supplied to the reaction system, and its action and effect can be more uniformly and excellently expressed during the polymerization process. In addition, even when the aliphatic hydrocarbon-based organic solvent such as nucleic acid is used as a reaction medium, polyolefin of excellent physical properties can be produced, so that there is no necessity of using an aromatic hydrocarbon-based organic solvent, and the aromatic hydrocarbon-based organic solvent is polyolefin or There is no problem in smell or taste due to remaining in the product, and as a result, the polyolefin prepared according to one embodiment can be used very suitably for a large product.

As a result, according to one embodiment, by having a larger molecular weight and a broader polymodal molecular weight distribution, it is possible to exhibit excellent mechanical properties and processability, and to more effectively prepare polyolefin, which is preferably used for a large product. . Therefore, in the method for producing a polyolefin of one embodiment, the ultra-high molecular weight polyolefin can be more effectively produced using such a molecular weight modifier and hydrogen, and the previously supported single supported metallocene catalyst or common supported metallocene catalyst.

 In the molecular weight modifier, specific examples of the cyclopentadienyl metal compound of Formula 8 include biscyclopentadienyl titanium dichloride, biscyclopentadienyl zirconium dichloride, biscyclopentadienyl hafnium dichloride, and bis indenyl titanium Dichloride or bisflorenyl titanium dichloride and the like. In addition, specific examples of the organoaluminum compound of the formula (8) include triisobutyl aluminum, trinuclear aluminum, trioctyl aluminum, diisobutyl aluminum chloride, dinuxyl aluminum chloride, isobutyl aluminum dichloride, and the like.

In addition, the compound of Formula 8 and the compound of Formula 9 are about 1: 0.1 to 1: 100 based on the molar ratio of the metal element (M ⁴ ) included in Formula 8 and aluminum (A1) included in Formula 9 Black is preferably used in a molar ratio of about 1: 0.5 to 1:10.

The molecular weight modifier may be used in an amount of about 10 ⁻⁷ to about ¹ parts by weight, or about 10 ⁻⁵ to 10 · ² parts by weight based on the total loo parts by weight of the first and second olefinic monomers. As it is used in this content range, the action and effect due to the addition of the molecular weight regulator is optimized, the polymer melt index is low, the molecular weight distribution is wide, the molecular weight is large, and the stress cracking resistance is improved more than the density or polymer melt index. Polyolefins can be obtained.

 On the other hand, the above-described molecular weight modifier may be used in a state supported on the carrier together with the above-described first and second metallocene compounds, it may be added to and mixed with the semi-ungung system separately from the supported metallocene catalyst.

The molecular weight modifier described above is an amount such that the molar ratio of the transition metal contained in the first and second metallocene compounds: the molecular weight modifier is about 1: 0.1 to 1: 2, or about 1: 0.2 to 1: 1.5. Can be used as If the amount of the molecular weight modifier is too small, ultra high molecular weight polyolefin may be difficult to prepare properly. On the contrary, if the amount of the molecular weight modifier is excessively large, it is possible to produce a polyolefin having a higher molecular weight, but the catalyst activity may be lowered. The supported metallocene catalyst as described above may be prepared by supporting a cocatalyst on a carrier, and further supporting the first and second metallocene compounds, and optionally, the molecular weight modifier is added to the first and second It may be prepared by supporting the metallocene compound together or before or after supporting the first and second metallocene compounds. Since the supporting method of each component depends on the manufacturing process and conditions of the conventional metallocene supported catalyst, further description thereof will be omitted.

 Polymerization may be performed by supplying an olefinic monomer in the above-described single supported metallocene catalyst or common supported metallocene catalyst and optionally, a semi-unggi group containing a molecular weight regulator.

 In this case, according to one embodiment of the present invention, the polymerization may proceed by supplying an olefinic monomer in the presence of hydrogen gas.

 At this time, the hydrogen gas serves to suppress the rapid reaction of the metallocene catalyst at the beginning of the polymerization so that a high molecular weight polyolefin can be produced in a larger amount. Polyolefins having a wide molecular weight distribution can be obtained effectively.

 The hydrogen gas may be introduced such that the molar ratio of such hydrogen gas: olefin monomer is about 1: 100 to 1: 1,000. When the amount of hydrogen gas used is too small, the catalyst activity may not be sufficiently realized, making it difficult to prepare a polyolefin having a desired molecular weight and molecular weight distribution, and when the amount of hydrogen gas is added, the activity of the catalyst is not sufficiently realized. You may not.

On the other hand, in the counterunggi, the organoaluminum compound for removing the water in the counterunggi is further added, the polymerization reaction may proceed in the presence thereof. Specific examples of such an organoaluminum compound include trialkylaluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesqui halide, and more specific examples thereof include A1 (C _2). H ₅ ) ₃ , A1 (C ₂ H ₅ ) ₂ H, A1 (C ₃ H ₇ ) ₃ , A1 (C ₃ H ₇ ) ₂ H, Al (iC ₄ H ₉ ) ₂ H, A1 (C ₈ H ₁₇ ) ₃ , A1 (C _I2 H ₂₅ ) ₃ , Al (C ₂ H ₅ ) (Ci ₂ H ₂₅ ) ₂ , Al (iC ₄ H ₉ ) (Ci ₂ H ₂₅ ) ₂ , Al (iC ₄ H ₉ ) ₂ H, Al (iC ₄ H ₉ ) ₃ , (C ₂ H ₅ ) ₂ A1C1, (i-C ₃ H ₉ ) ₂ A1C1 or (C ₂ H ₅ ) ₃ A1 ₂ C1 ₃ , and the like. Such organoaluminum compounds may be continuously introduced into the reactor and may be introduced at a rate of about 0.1 to 10 moles per kilogram of reaction medium introduced into the reactor for proper water removal. On the other hand, in the method for producing a polyolefin of one embodiment, the olefin monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds.

 Specific examples of the olefinic 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-nucleodecene, 1-eicosene, norbornene, norbonadiene, ethylidene norbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-nuxadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc. are mentioned, These monomers can also be mixed and copolymerized 2 or more types.

 The polymerization reaction can be carried out by homopolymerization with one olefinic monomer or copolymerization with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor or a gas phase reaction reactor.

 In addition, the supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane and chloro It may be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom such as benzene and injected into the reaction system. The solvent used herein is preferably used by removing a small amount of water, air, or the like acting as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter.

 The polyolefin obtained according to the preparation method of the above-described embodiment may be a high molecular weight or ultra high molecular weight polyolefin having a weight average molecular weight of about 100,000 to about 2,000,000 g / mol, or about 400,000 to about 1,500,000 g / m, The distribution (Mw / Mn) is about 2.0 to about 25, or about 2.2 to about 10, and may have various molecular weight distributions.

In addition, the weight average molecular weight and molecular weight distribution can be variously changed by adjusting the type and content of the first and second metallocene compounds, the amount of hydrogen gas, the amount of molecular weight control agent, etc. within the above-described range, It is very useful for preparing physical polyolefins. That is, since the reaction properties to the hydrogen and the molecular weight regulator of the first and second metallocene compounds are different, the selective combination of the metallocene compound and the amount of hydrogen gas and the molecular weight regulator are added in one reactor. Polyolefins having relatively small weight average molecular weight and narrow molecular weight distribution, polyolefins having small weight average molecular weight and wide molecular weight distribution, polyolefins having large weight average molecular weight and narrow molecular weight distribution, large weight average within the above-mentioned range Both the molecular weight and the production of polyolefins with a broad molecular weight distribution are possible.

 In addition, the polyolefin produced by the production method of the present invention has a relatively wide molecular weight distribution and a very high molecular weight, and due to the nature of the polyolefin made of a metallocene catalyst, the amount of catalyst residue is small, so that decomposition of the polyolefin can be suppressed during high temperature molding processing. Can be.

 In particular, it can exhibit excellent physical properties according to high molecular weight, and is very preferably used for applications such as large blow molding products, next generation pipe products requiring excellent pressure resistance and heat resistance properties, or injection products having good stress cracking properties. Can be.

 Hereinafter, the present invention will be described in detail with reference to Examples. However, these embodiments may be modified in various forms, and the scope of the present invention should not be construed as being limited by the embodiments described below.

<Example>

 Synthesis Example of First Metallocene Compound

Preparation of 1-1 Ligand Compound

2 g of fluorene was dissolved in 5 mL MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, followed by stirring at room temperature overnight. (6- (tert- 3.6 g of butoxy) hexyl) dic loro (methyl) silane was dissolved in 50 mL of nucleic acid (hexane), and the fluorene-Li slurry was transferred for 30 minutes in a dry ice / acetone bath and stirred at room temperature overnight. At the same time, ^{5, 8-dimethyl-5,10-} dihydroindeno [l, 2-b] indoIe (12 mmol, 2.8 g) addition of 2.5M n-BuLi hexane solution 5.5 mL dissolved in 60 mL THF in a dry ice / acetone bath It was added dropwise and stirred overnight at room temperature. NMR sample reaction solution of fluorene with (6- (tert-butoxy) hexyl) dichloro (methyl) silane was confirmed by NMR sampling to confirm the completion of the reaction, followed by dihydroindeno [1, 2-b] indole- as 5,8-dimethyl-5, l. Li solution was transferred under dry ice / acetone bath. Stir overnight at room temperature. After reaction, the organic layer was extracted with ether / water, and the remaining moisture of the organic layer was removed with MgS0 ₄ to obtain a ligand compound (Mw 597.90, 12 mmol), and two isomers were formed in 1H-NMR.

 1 H NMR (500 MHz, d6-benzene): -0.30 to -0.18 (3H, d), 0.40 (2H, m), 0.65 to 1.45 (8H, m), 1.12 (9H, d), 2.36 to 2.40 (3H , d), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38 (1H, d), 6.90-7.80 (15H, m)

 Preparation of 1-2 metallocene compound

7.2 g (12 mmol) of the ligand compound synthesized in 1-1 was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, followed by stirring at room temperature overnight. Drying in vacuo gave a brown colored sticky oil. It was dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared, and 50 mL of toluene was added to prepare a slurry. 50 mL of ZrCl ₄ (THF) ₂ was transferred to a luene slurry in a dry ice / acetone bath. The solution was changed to violet color at room temperature overnight. The reaction solution was filtered to remove LiCl. The toluene of the filtrate was removed by vacuum drying, and the nucleic acid was added and sonicated for 1 hour. The slurry was filtered to obtain 6 g of a dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol%). Two isomers were observed on 1 H-NMR.

1 H NMR (500 MHz, CDC1 ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m), 1.79 (2H, m), 1.98-2.19 (4H, m), 2.58 (3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m) Preparation Example of Second Metallocene Compound Synthesis Example 2

itBu-O— (CH ₂ ½) (CH ^> Si (C5 (CH3) ₄ ¥ tBu-N) TiCb Preparation

50 g of Mg (s) was added to a 10 L reactor at room temperature, and then 300 mL of THF was added. 1 ₂ After adding 0.5 g, the reaction temperature was maintained at 50 ^° C. After the reaction temperature was stabilized, 250 g of 6-t-butthoxyhexyl chloride was added to the reaction vessel at a rate of 5 mL / min using a feeding pump. It was observed that the reaction temperature increased by about 4 to 5 ^° C. with the addition of 64-subspecialty chloride. The mixture was stirred for 12 hours while adding 6-t-butoxynuxyl chloride. After 12 hours of reaction, a black reaction solution was obtained. 2 mL of the resulting black solution was taken, water was added thereto, an organic layer was obtained, and 6-t-butoxynucleic acid (6-t-buthoxyhexane) was confirmed by 1 H-NMR. It can be seen that the Gringanrd reaction proceeded well from the 6-t-butoxyhexane. Thus, 6-t-buthoxyhexyl magnesium chloride was synthesized.

After adding 500 g of MeSiCl ₃ and 1 L of THF to the reaction vessel, the reaction temperature was adjusted to -20 ^° C. 560 g of the synthesized 6-t-subsilicate magnesium chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. After feeding the Grignard reagent, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, white MgCl ₂ salt was produced. 4 L of nucleic acid was added to remove the salt through a labdori to obtain a filter solution. After adding the obtained filter solution to the reactor, the nucleic acid was removed at 70 ^° C to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired methyl (6-t-buthoxy hexyl) dichlorosilane} compound through 1H-NMRol.

Ή-NMR (CDC1 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)

 1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4

After adding L of THF to the reactor, the reaction temperature was cooled to -20 ^° C. _The reactor was added at a rate of 5 mL / min using _n- BuLi 480 mL feeding 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-butthoxy hexyl) dichlorosilane (326 g, 350 mL) was added quickly to the reactor. Slowly return the reaction temperature to room temperature After stirring for 12 hours while raising the reaction temperature, the reaction mixture was again cooled to 0 ^° C., and then 2 equivalents of t-BuNH 2 was added thereto. The reaction mixture was stirred for 12 hours while slowly warming to room temperature. After 12 hours of reaction, THF was removed and 4 L of nucleic acid was added to obtain a filter solution from which salts were removed through labdori. After the filter solution was added to the reactor again, the nucleic acid was removed from 7 (C to obtain a yellow solution. The yellow solution obtained was obtained through 1H-NMR in methyl (6-t-butoxynucleus) (tetramethyl c _p H). It was confirmed that the compound is t-butylaminosilane (Methyl (6 ᅳ t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane).

n-BuLi and ligand dimethyl (tetramethyl _Cp H) t-butylaminesilane

TiCl ₃ (THF) ₃ (10 mmol) was quickly added to the dilithium salt of -78 ^° C ligand synthesized in THF solution from (Dimethyl (tetramethylCpH) t-Butylaminosilane). The reaction solution was stirred for 12 hours while slowly raising the temperature to -78 ^° C. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the semi-aqueous solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, the blue vagina obtained a black solution. After removing THF from the resulting semi-aqueous solution, nucleic acid was added to filter the product. After removing the nucleic acid from the resulting filter solution, the desired ([methyl (6-t-buthoxyhexyl) silyl (5-tetramethylCp) (t-

Butylamido)] TiCl ₂ ) (tBu-0- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) (tBu-N) TiCl ₂ was confirmed.

1 H-NMR (CDC1 ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (s, 3H) Synthesis Example 3

 Preparation of tert-Bu-O-fCH lMeSi ^ -CnH '^ ZrCb

L0 mole of a Grignard reagent tert-Bu-0- (CH ₂ ) ₆ MgCl solution was obtained from the reaction between the tert-Bu-0- (CH ₂ ) ₆ Cl compound and Mg (0) in THF solvent. The Grignard compound prepared above was added to a flask containing MeSiCl ₃ compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at −30 ^° C., and stirred at room temperature for 8 hours or more, and the filtered solution was Vacuum drying afforded a compound of tert-Bu-0- (CH ₂ ) ₆ SiMeCl ₂ (yield 92%).

-Add fluorene (3.33 g, 20 mmol), nucleic acid (100 mL) and MTBE (methyl tert-butyl ether, 1.2 mL, 10 mmol) at ² 0 ^° C, and add 8 mL of n-BuLi (2.5). M in Hexane) was added slowly and stirred at room temperature for 6 hours. After stirring is complete, the reaction temperature is- ^ 욷 t yes ^

Itofe jung οε

[： Yb .SL- Ιγ α Loong ^ Yung ΤΓ 4He ^^ Hung {H ^ l 8 '： r ί ^ Yeong ^ l ^^ t ^ Loong (nng

^-u ) ts ^-^ 'ΐΓΐο½ ItoJHI with ¾¾- ⁹ (¾) -0-1-} ty [toa8Z, -¾ ^

^• (g _H ui «i 1Ό / a 08 -dq '% 09 yong ^) b ^ ¾ to ¾¾- ⁹ (¾3) -0- ϊ t BN ((8861) 1S6∑: V3

(P 'H2' H-niJ) Mr OZ

'(p''n-)WL' (pp 09 · '(^' Ht ¾- ι) ςν '(t Ήζ' Η- «υ) 06 ^' 9 Ό

^{'HZ: -niJ) 98 "9} ' 0 'HZ C a - :) J Ke' 0u ¾17 ¾D) 16- 'HP ' ZH) 99 'ΐ' HZ: 'ZHO-IS) 8S' (s ¾ £ ' ! S ^) 9Z \ '(s ¾6' 0 «9-^) 51 ： (9090'z 麵 00S) ¾ 匪 H,

^■ (% S 6 Dragons ^ ' ^§ £)-^ ¾ 륜 ^ ^^ He ^ Hung t Γο 욷 Ϊ t8 t Yes ^

to (l ^m OZ) 9 'Έ ₉ ζτ) ^z (dRl) D ^ Z barrel ^ Yung

i lv8

[YI Rong ^ ^ ΰ geung i ° Y ir {s {[ a ^ t ^ barrel ^(3UBX3 H u ⁱ ςτ) n ⁿ ^ eu gt Melting

C ui oz) 3aLP / (Iouiui 9 '§ gf £) ( ^0I H ^{£ I} -6)! S ³ W ( ⁹ (i) -O-n8-J pan) t-vltoaOZ- OT

^• (P 'm' H-nid) S8

'(ui ¾17' H-nid) 0t ^ '(^' Ht 'H-niJ) S £' («1 'Ht ^' H m) strip '(s ¾S' Η6- ^η υ) θΙ '(J' Ηζ '2H3-Ona-m) l3 £' (ui ¾Z 'ζΗ3) 6 ΐ' (s ¾6 '0 ^-^) /. 11' (^ 'Ht ⁷ ' ZUD) 960 'H

H3) 8Π) '(u ⁱ ' HZ 'Z D-} S) 9Z 0' (s ¾ £ ¾ ³ W) S £ O_ ： (HDaD 'ZHWOOS) ¾PMN HI

^ S Dragon ^ '§ That ^ ¾ great ring ^z ( ⁰¹ H 3-6)! S9 ( ⁹ (

^ HYI LONG ^ Ying BL ^ L ^ f ^ Knee ί ^^ U v ro YONG (louiui ₀₁

08SS00 / ST0ZaM / X3d 0.698T / S10Z OAV Reacted further.

All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of a hexane solvent. After the filtered solution was dried in vacuo, nucleic acid was added to induce precipitate ^at low temperature (-20 ^° C.). The obtained precipitate was filtered at low temperature to give a [tBu-0- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound as a white solid (yield 92%).

1 H NMR (300 MHz, CDC1 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).

¹³ C NMR (CDC1 ₃ ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

<Preparation Example of Supported Catalyst>

 Preparation Example 1

Into a glass reactor at room temperature, toluene 100 mLol was added, 10 g of dried silica was added, and the reaction mixture was stirred while raising the temperature of the reactor to 40 ^° C. After sufficiently dispersing the silica, 60.6 mL of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, the temperature was raised to 80 ^° C., and the mixture was stirred at 200 rpm for 16 hours. Thereafter, the temperature was lowered to 40 ^° C. and then washed with a sufficient amount of toluene to remove unreacted aluminum compounds. Again 100 mL of toluene was added, and 0.5 mmol of the metallocene catalyst prepared in Synthesis Example 1 was added thereto, followed by stirring for 2 hours. After the reaction was completed, the stirring was stopped, the toluene was separated and removed, and then the reduced pressure was removed at 40 ^° C. to remove the toluene, thereby preparing a supported catalyst. Preparation Example 2

100 mL of toluene was added to a glass reaction vessel at room temperature, 10 g of dried silica was added thereto, and the reaction mixture was stirred while raising the reaction temperature to 40 ^° C. After sufficiently dispersing the silica, 60.6 mL of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, the temperature was lowered to 80 ^° C., and the mixture was stirred at 200 rpm for 16 hours. Thereafter, the temperature was lowered to 40 ^° C., and then washed with a sufficient amount of toluene to remove unreacted aluminum compounds. Again 100 mL of toluene was added, and 0.5 mm of the metallocene catalyst prepared in Synthesis Example 1 was added thereto, followed by stirring for 1 hour. Next time 5 mm of the metallocene catalyst prepared in Synthesis Example 2 was further added, followed by stirring for 2 hours. After the reaction was completed, the stirring was stopped, the toluene layer was separated and removed, and the reduced pressure was removed at 40 ^° C. to remove the toluene to prepare a supported catalyst. Preparation Example 3

 In Preparation Example 2, metallocene catalyst of Synthesis Example 3 instead of the metallocene catalyst of Synthesis Example 2

A supported catalyst was prepared in the same manner as in Preparation Example 2, except that 0.5 mm was added thereto. Preparation Example 4

 In Preparation Example 2, the metallocene catalyst of Synthesis Example 4 instead of the metallocene catalyst of Synthesis Example 2

A supported catalyst was prepared in the same manner as in Preparation Example 2, except that 0.5 mm was added thereto. <Production Example of Molecular Weight Control Agent>

 Preparation Example 5

0.83 g of bis (cyclopentadienyl) -titanium dichloride and 50 mL of nucleic acid were sequentially added to a 250 mL round ^' bottom flask, followed by stirring. 6 mL of triisobutylalunium (1M in hexane) was added thereto, stirred at room temperature for 3 days, and then the solvent was removed in vacuo to obtain a green compound, which was oxidized as titanium reduced. Did not change color. In the following the green compound was used as it is without purification.

 1 H NMR (CDC13, 500 MHz): 6.3-6.6 (br m, 10H), 1.2-1.8 (br m, 4H), 0.8 (br s, 18H)

<Ethylene Polymerization Example>

 Example 1

30 mg of the supported catalyst prepared in Preparation Example 1 was quantified in a dry box, placed in a 50 mL glass bottle, sealed with a rubber barrier, and taken out of the dry box to prepare a catalyst for injection. The polymerization is equipped with a mechanical stirrer and temperature controlled It was carried out in a 2 L metal alloy reactor where possible and used at high pressure. 1.2 L of nucleic acid containing 1.0 mm of triethylaluminum was injected into the reactor, and the supported catalyst was introduced into the reactor without air contact, followed by gas at a pressure of 40 Kgf / ctn ² at 80 ^° C. Ethylene monomer and 0.25 mol% of hydrogen relative to ethylene charge were added together with ethylene for polymerization for I hour. Termination of the polymerization was completed by first stopping the reaction and then evacuating and removing the ethylene. The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried in an 80 ^° C. vacuum oven for 4 hours. Example 2

 In Example 1, ethylene polymerization was carried out in the same manner as in Example 1, except that 0.5 mol% of hydrogen was added together with ethylene to polymerize ethylene. Example 3

 In Example 1, ethylene polymerization was carried out in the same manner as in Example 1, except that 30 mg of the supported catalyst of Preparation Example 2 was used instead of the supported catalyst prepared in Preparation Example 1. Example 4

 In Example 1, ethylene polymerization was carried out in the same manner as in Example 1, except that 30 mg of the supported catalyst of Preparation Example 3 was used instead of the supported catalyst prepared in Preparation Example 1. Example 5

In Example 1½, ethylene polymerization was carried out in the same manner as in Example 1, except that 30 mg of the supported catalyst of Preparation Example 4 was used instead of the supported catalyst prepared in Preparation Example 1. Example 6 30 mg of the supported catalyst prepared in Preparation Example 2 was quantified in a dry box, placed in a 50 mL glass bottle, sealed with a rubber barrier, and taken out of the dry box to prepare a catalyst for injection. The polymerization was carried out in a 2 L metal alloy reactor, equipped with a mechanical stirrer, temperature controlled and used at high pressure.

After injecting 1.2 L of nucleic acid containing triethylaluminum of 1.0 mm or less into the reaction vessel, the molecular weight regulator of Preparation Example 5 was introduced without air contact so as to be 0.5 mole with respect to 1 mole of aluminum. After the prepared supported catalyst was introduced into the reactor without air contacting, gas ethylene monomer at a pressure of 40 Kgf / cm ² at 80 ^° C. and 0.25 mol% of hydrogen relative to the ethylene content were continuously added together with ethylene for 1 hour. During the polymerization. Termination of the polymerization was completed by first stopping the reaction and then evacuating and removing the ethylene. The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried for 4 hours in an 80 ^° C vacuum Aubon. Example 1

 In Example 6, ethylene polymerization was carried out in the same manner as in Example 6, except that 30 mg of the supported catalyst of Preparation Example 3 was used instead of the supported catalyst prepared in Preparation Example 2. Example 8

 In Example 6, ethylene polymerization was carried out in the same manner as in Example 6, except that 30 mg of the supported catalyst of Preparation Example 4 was used instead of the supported catalyst prepared in Preparation Example 2. The polymerization conditions of Examples 1 to 8 are collectively shown in Table 1 below. TABLE 1

 Example No. Catalyst precursor hydrogen molecular weight modifier

Example 1 Synthesis Example 1 0.25 mol%-Example 2 Synthesis Example 1 0.5 mol%-Example 3 Synthesis Example 1 + Synthesis Example 2 0. 25 mol%-Example 4 Synthesis Example 1 + Synthesis Example 3 0. 25 mol%- Example 5 Synthesis Example 1 + Synthesis Example 4 0.25 mol%-Example 6 Synthesis Example 1 Synthesis Example 2 0.25 mol% 0.5 mol (relative to 1 mol of Al) Example 7 Synthesis Example 1 + Synthesis Example 3 0 25 mol% 0.5 mol (relative to 1 mol of Al) Example 8 Synthesis Example 1 + Synthesis Example 4 0.25 mol% 0.5 mol (relative to Al lmol) Further, the polymerization activity according to the polymerization of Examples 1 to 8, The weight average molecular weight and molecular weight distribution of the polyolefins are shown in Table 2 below.

 TABLE 2

As can be seen in Table 2, according to the production method of the polyolefin of the present invention, various weight average molecular weight and molecular weight distribution depending on the combination of the metallocene compound, its reactivity to hydrogen, and the interaction with the molecular weight modifier It was possible to prepare polylipin having. Accordingly, it is expected that polyolefins having desired physical properties can be easily produced according to specific combinations of metallocene compounds and selective use of hydrogen and molecular weight modifiers.

Claims

[Patent Claims]

 [Claim 1]

 A method for producing a polyolefin comprising polymerizing an olefinic monomer in the presence of hydrogen gas and a supported metallocene catalyst having at least one first metallocene compound represented by Formula 1 and a promoter supported on a carrier:

 [

 In Chemical Formula 1,

 A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 C20 alkoxyalkyl group, C3 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl group;

 D is -0-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20;

 L is a C1 to C10 straight or branched chain alkylene group;

 B is carbon, silicon or germanium;

 Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;

 M is a Group 4 transition metal;

X ¹ and X ² are the same as or different from each other, and each independently halogen, C 1 to C 20 alkyl group, C 2 to C 20 alkenyl group, C 6 to C 20 aryl group, nitro group, amido group, C 1 to C 20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ¹ and C ² are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c, provided that both C ¹ and C ² are Except for 2c;

 In Chemical Formulas 2a, 2b, and 2c,

 R1 to R17 and R1 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group , C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, two of R10 to R17 adjacent to each other The foregoing can be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

[Claim 2] The method of claim 1, wherein the supported metallocene catalyst further comprises at least one second metallocene compound selected from compounds represented by the following Chemical Formulas 3-5:

[Formula ³ ]

 In Chemical Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and are 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 ^a and R ^b 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 Alkenyl to C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

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;

 n is 1 or 0;

[Claim 3]

The method of claim 1, wherein the production method of the polrieul repin selected from the group in the metallocene compound has the following structural formula as a metal represented the formula _1≤:

 [Formula 4]

 In Chemical Formula 4,

M ² is a Group 4 transition metal;

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

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

Z ² is a halogen atom, C 1 to C 20 alkyl, C 2 to C 10 alkenyl, C 7 to

C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 aryl Alkoxy;

B ¹ is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp ³ R ^c ring and the Cp ⁴ R ^d ring or crosslinks one Cp ⁴ R ^d ring with M ² Or a combination thereof;

 m is 1 or 0;

[Formula ⁵ ]

(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂

 In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁵ 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 ^e 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 Arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

Z ³ 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 , Substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

B ² is one or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp ⁵ R ^e ring and J;

J is any one selected from the group consisting of NR ^f , 0, PR ^f and S, wherein R ^f is Alkyl, aryl, substituted alkyl or substituted aryl of CI to C ² 0

[Claim 5]

I according to I ^2, wherein the metallocene compound to the second metal represented by the general formula ⁽⁴⁾ A method of manufacturing a polyolefin selected from the group consisting of the following structural formula:

[Claim 6]

 The method of claim 2, wherein the second metallocene compound represented by Chemical Formula 5 is selected from the group consisting of the following structural formulas:

[Claim 7]

 The method of claim 1, wherein the carrier is selected from the group consisting of silica, silica-alumina, and silica-magnesia.

[Claim 8]

 The method of claim 1, wherein the promoter comprises an aluminum-containing first promoter of Formula 6 and a borate-based second promoter of Formula 6

[Claim 9]

The method of claim 1, wherein the olefin monomer is ethylene, propylene, 1-butene, 1-nuxene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-decene , 1-undecene, 1-dodecene, norbornene, A method for producing a polyolefin, comprising at least one monomer selected from the group consisting of ethylidene norbornene, styrene, alpha -methyl styrene, and 3-chloromethyl styrene.

[Claim 10]

 The method for producing a polyolefin according to claim 1 or 2, wherein a molecular weight modifier is further added to polymerize the olefinic monomers.

[Claim 1 11]

 The method of claim 10, wherein the molecular weight modifier comprises a cyclopentadienyl metal compound represented by the following Chemical Formula 8 and an organoaluminum compound represented by the following Chemical Formula 9 or a reaction product thereof:

[Claim 12]

 The method for producing a polyolefin according to claim 10, wherein the molecular weight modifier is used so that the molar ratio of transition metal: molecular weight modifier contained in the first and second metallocene compounds is 1: 0.1 to 1: 2.

[Claim 13]

Polyolefin produced according to the polyolefin production method of claim 1.

[Claim 14]

 The polyolefin according to claim 13, wherein the weight average molecular weight is 100,000 to 2,000,000 g / m.

[Claim 15]

 The polyolefin according to claim 13, wherein the molecular weight distribution is from 2.0 to 25.

[Claim 16]

 The polyolefin of claim 13 used for large product.