WO2018101794A2 - Metallocene catalyst system comprising operationally stable composition, and method for producing polyolefin by means of metallocene catalyst system - Google Patents

Abstract

The present invention relates to a metallocene catalyst system comprising an operationally stable composition, and a method for producing polyolefin by means of the metallocene catalyst system. More specifically, by utilizing the metallocene catalyst system comprising: 90-99.9 wt% metallocene compound of one or more types; and 0.1-10 wt% operationally stable composition comprising one or more types of compounds selected from the group consisting of sulfate, sulfonate, phosphate, and carboxylate, and one or more types of white mineral oil, the unique activity of the catalyst is maintained and fouling and agglomeration phenomena are minimized during olefin polymerization to allow the process to be stably carried out, and thus by means of the present invention, a method for producing polyolefin can be provided, and produced polyolefin can be provided.

Description

Metallocene catalyst system comprising a composition for operating stability and polyolefin production method using the same

The present invention relates to a metallocene catalyst system comprising a composition for operating stability and a method for producing polyolefin using the same, and more particularly, stable process operation by maintaining the intrinsic activity of the catalyst during the olefin polymerization and minimizing fouling and aggregation phenomenon It relates to a metallocene catalyst system and a polyolefin production method and polyolefin using the same.

In the polymerization of olefins to produce polyolefins, various polymerization catalysts such as Ziegler-Natta catalysts, chromium catalysts or metallocene catalysts are used depending on the type of the central metal. These polymerization catalysts are selectively used according to each production process and application because of different catalytic activity, molecular weight distribution characteristics of the polyolefins prepared using the same, and reaction characteristics with respect to comonomers.

Among these, metallocene is basically a transition metal or transition metal halogen compound having a coordination bond of a cyclopentadienyl ligand, and has various molecular structures according to changes in ligand form and central metal. In general, the metallocene compound alone is inactive as a polymerization catalyst, is activated as a cation by the action of a promoter such as methylaluminoxane (MAO), and at the same time, the promoter is coordinated as an anion that does not coordinate with the metallocene compound. The unsaturated cationic active species are stabilized to form a catalyst system having activity in various olefin polymerizations.

The characteristics of the metallocene catalyst are that since the polymer has a uniform activity point, the polymer has a narrow molecular weight distribution, is easy to copolymerize, has a uniform distribution of comoners, and can adjust the steric structure of the polymer according to the symmetry of the catalyst. .

As a method of producing a polyene pin using a metallocene catalyst, a solution polymerization process, a slurry polymerization process, and a gas phase polymerization process are known. Among them, the solution polymerization process is polymerization in the state that the polymer is melted in the liquid phase, and the slurry polymerization process is the polymerization in suspension state, in which the polymer produced in the liquid polymerization medium is dispersed in the solid state. In the gas phase polymerization process, a polymer produced in a gas phase polymerization medium is dispersed in a fluidized state.

In general, a slurry polymerization process is a suspension in which a polymer is polymerized and dispersed in a liquid medium, and polymer particles may agglomerate with each other depending on reaction conditions. May cause operability problems. In addition, the gas phase polymerization process is performed at a temperature lower than the melting point of the polymer to be formed, which also causes the polymer particles to soften and agglomerate or stick to the reaction apparatus when the temperature rises above the critical temperature for several reasons. Therefore, in the gas phase polymerization process, fouling may occur frequently on the inner wall of the circulating gas line, the heat exchanger, the inner wall of the cooler, and agglomeration near the softening point of the polyolefin. This phenomenon may be influenced by the polymerization medium, the molecular weight, the concentration of the comonomer, and the like. In addition, this phenomenon may be intensified as the concentration of the polymer particles is higher and the size of the polymer particles is smaller.

As such, when fouling and agglomeration are intensified in the slurry polymerization process or the gas phase polymerization process, heat transfer and heat removal in the reactor become difficult, normal polyolefin transfer is hindered, and smooth control of the polymerization reaction and long-term operation are impossible. Not only will the production efficiency be reduced, but it can also cause premature reactor shutdown.

Accordingly, various attempts have been made to minimize fouling and agglomeration of polyolefins. For example, US Pat. No. 4,650,841 discloses a method of preventing fouling by reducing catalyst activity using an inactivating agent, US Pat. No. 5,733,988 discloses a method of adding alcohol, ether, ammonia, and the like as an antifouling agent. Doing. However, since these methods lower the activity of the catalyst, there is a limit that the activity of the reaction is lowered and the production efficiency is inevitably reduced. In addition, US Pat. No. 5,270,407 discloses a method for preventing fouling by adding polysiloxane to the catalyst system, US Pat. No. 3,956,257 discloses a fouling prevention method using hydrocarbyl aluminum alkoxide. However, these methods also have a limitation in that the catalytic activity is reduced overall.

Therefore, there is an urgent need to study a catalyst system capable of long-term stable operation by minimizing fouling and agglomeration while maintaining the inherent activity of the catalyst.

The present invention aims to solve all the above-mentioned problems.

SUMMARY OF THE INVENTION An object of the present invention is to provide a metallocene catalyst system which enables long-term operation of a more stable operation by minimizing fouling and agglomeration while maintaining the inherent activity of the catalyst during polyolefin polymerization through slurry polymerization or gas phase polymerization. .

Another object of the present invention is to provide a polyolefin production method using the metallocene catalyst system described above.

Another object of the present invention is to provide a polyolefin prepared using the above-described metallocene catalyst system and polyolefin production method.

The characteristic structure of this invention for achieving the objective of this invention mentioned above, and realizing the characteristic effect of this invention mentioned later is as follows.

According to one embodiment of the invention, 100 parts by weight of at least one metallocene compound; And 30 to 300 parts by weight of a composition for operational stabilization comprising at least one compound selected from the group consisting of sulfates, sulfonates, phosphates and carboxylates and at least one white mineral oil. A system is provided.

In addition, according to another embodiment of the present invention at least one or more white mineral oil; And it provides a metallocene catalyst system comprising at least one or more of the first compound represented by the formula (1) as a composition for the operation stability.

[Formula 1]

M ¹ is any one of carbon, sulfur and phosphorus atoms, M ² is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, calcium, strontium, barium and radium, A ¹ is hydrogen, Oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carbon number Is an aryloxy group having 6 to 30, at least one substituent of an acetate group, O represents an oxygen atom, R ¹ is an alkyl or isoalkyl group having 8 to 20 carbon atoms, alkenyl group having 8 to 20 carbon atoms, carbon number Is an alkynyl group having 8 to 20 and an aryl group having 6 to 30 carbon atoms, and at least one is an integer of 1 or 2.

In addition, according to another embodiment of the present invention, a metallocene catalyst system is provided, wherein the first compound includes a second compound represented by Formula 2 below.

[Formula 2]

M ³ is a sulfur atom, M ⁴ is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and francium, A ² is hydrogen, oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, carbon number Any one or more of alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 30 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, and acetate groups O is an oxygen atom, R ² is an alkyl or isoalkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an alkynyl group having 8 to 20 carbon atoms, and an aryl having 6 to 30 carbon atoms. At least one substituent of the group.

In addition, according to another embodiment of the present invention, a metallocene catalyst system including a compound represented by Chemical Formula 5 is provided.

[Formula 5]

M ⁵ is a Group 4 transition metal, Z ¹ and Z ² are each independently a halogen atom or a methyl group, Cp ¹ and Cp ² are the same as or different from each other, and are each independently cyclopentadienyl, indenyl, 4,5 , 6,7-tetrahydro-1-indenyl, and a fluorenyl radical, which may be substituted with one or more hydrocarbon groups having 1 to 20 carbon atoms, and R ³ and R ⁴ are the same as each other Or different and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an alkoxyalkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aryloxy group of 6 to 10 carbon atoms, or carbon atoms An alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an aryl alkenyl group having 8 to 40 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and R ⁵ is (Cp ¹ R ³⁾ and (Cp ² R ⁴⁾ the Sikimyeo crosslinked by the organic bond, a divalent hydrocarbon group containing an element selected from silicon, germanium, phosphorus, and the group consisting of nitrogen, boron or aluminum, m is 0 or 1.

According to another embodiment of the present invention, in the presence of the above-described metallocene catalyst system to the polymerization reactor for the production of polyolefin comprising the step of polymerizing at least one monomer selected from the group consisting of ethylene and olefin monomers A method is provided.

According to another embodiment of the present invention, in the presence of the metallocene catalyst system described above, there is provided a polyolefin prepared using the above-described polyolefin production method with at least one monomer selected from the group consisting of ethylene and olefinic monomers. do.

The present invention is to include a specific operation stability composition in the metallocene catalyst system. By minimizing fouling and agglomeration during polyolefin polymerization, more stable operation can be operated for a long time.

In addition, the present invention, by including a specific operation stability composition in the metallocene catalyst system, the activity inherent to the metallocene catalyst can be maintained without being lowered.

In addition, the present invention has an effect of improving the ease of mixing and flowability in the catalyst system of the composition for operation stability by including a white mineral oil in the composition for operation stability.

1 is a graph comparing the polymerization kinetic when using the catalyst system according to Example 1 and Comparative Example 1 of the present invention.

Figure 2 is a graph measuring the temperature change of the inner wall of the reactor during polyolefin polymerization using the catalyst system according to Example 6 of the present invention.

3 is a graph measuring the temperature change of the inner wall of the reactor during polyolefin polymerization using the catalyst system according to Comparative Example 6 of the present invention.

DETAILED DESCRIPTION The following detailed description of the invention refers to the accompanying drawings that show, by way of illustration, specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. It should be understood that the various embodiments of the present invention are different but need not be mutually exclusive. For example, certain shapes, structures, and characteristics described herein may be embodied in other embodiments without departing from the spirit and scope of the invention with respect to one embodiment. In addition, it is to be understood that the location or arrangement of individual components within each disclosed embodiment may be changed without departing from the spirit and scope of the invention. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope of the present invention, if properly described, is defined only by the appended claims, along with the full range of equivalents to which such claims are entitled. Like reference numerals in the drawings refer to the same or similar functions throughout the several aspects.

As used herein, the meaning of “comprises” or “contains” embodies a particular property, region, integer, step, operation, element, or component, and of other specific properties, region, integer, step, operation, element, or component. It does not exclude the addition.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily implement the present invention.

The metallocene catalyst system according to an embodiment of the present invention may include at least one metallocene compound and an operation stability composition, and the operation stability composition may be selected from the group consisting of sulfate, sulfonate, phosphate, and carboxylate salts. At least one compound selected and at least one white mineral oil.

In this case, the white mineral oil has an effect of facilitating mixing of the catalyst composition and the composition for operation stabilization during polymerization by adding at least one compound selected from the group consisting of sulfate, sulfonate, phosphate and carboxylate. This allows the polymer to be formed uniformly in the polymerization reactor.

Metallocene catalyst system comprising at least one compound selected from the group consisting of sulphate, sulfonate, phosphate and carboxylate salts as one embodiment of the present invention, the polymer particles in the production of polyolefins by gas phase polymerization or slurry polymerization The intrinsic activity of the catalyst can be stably maintained while minimizing the static electricity generated by friction between the liver or friction between the polymer particles and the inner wall of the reactor. It is assumed that this is because the metallocene catalyst system of the above embodiment forms the particle size and bulk density of the polymer present in the reactor in a range in which generation of static electricity due to friction can be minimized.

First, the composition for operating stability according to an embodiment of the present invention may include at least one or more white mineral oil and at least one or more first compounds represented by the following Chemical Formula 1.

In Chemical Formula 1,

M ¹ is any of carbon, sulfur, phosphorus atoms;

M ² is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, calcium, strontium, barium and radium;

A ¹ is hydrogen, oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, and 1 to 10 carbon atoms. A substituent of at least one of an alkoxy group, an aryloxy group having 6 to 30 carbon atoms, and an acetate group;

O means oxygen atom;

R ¹ is a substituent of any one of an alkyl group or isoalkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an alkynyl group having 8 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms;

n is an integer of 1 or 2.

Preferably, the first compound may include a second compound represented by Formula 2 below.

In Chemical Formula 2,

M ³ is a sulfur atom;

M ⁴ is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and francium;

A ² is hydrogen, oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, and 1 to 10 carbon atoms. A substituent of at least one of an alkoxy group, an aryloxy group having 6 to 30 carbon atoms, and an acetate group;

O means oxygen atom;

R ² is a substituent of any one of an alkyl group or isoalkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an alkynyl group having 8 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms.

The second compound is preferably at least one selected from sodium dodecylsuflate (SDS) represented by the following Chemical Formula 3 and sodium lauryl sulfoacetate (SLSA) represented by the following Chemical Formula 4 It may include.

When the stabilizer composition is included in an excessive amount, the effect of improving the stabilization of the operation may be similar after the improvement to a certain limit, but the activity of the catalyst may be reduced by reacting the excess stabilizer composition with the catalyst.

Accordingly, the composition for operation stability comprising at least one or more white mineral oils described above and at least one compound selected from the group consisting of sulfates, sulfonates, phosphates and carboxylates is based on 100 parts by weight of the metallocene catalyst compound. To 300 parts by weight, preferably 30 to 200 parts by weight.

On the other hand, the metallocene catalyst system according to the present invention may include a conventional metallocene compound, the configuration is not particularly limited.

However, according to one embodiment of the present invention, the metallocene compound may be a compound represented by Formula 5 below:

In Chemical Formula 5,

M ⁵ is a Group 4 transition metal;

Z ¹ and Z ² are each independently a halogen atom or a methyl group;

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

R ³ and R ⁴ are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 carbon atoms Aryloxy group having 10 to 10 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, or alkynyl group having 2 to 10 carbon atoms, ;

R ⁵ cross-links (Cp ¹ R ³ ) and (Cp ² R ⁴ ) by a covalent bond, a divalent hydrocarbon containing an element selected from the group consisting of methyl groups or silicon, germanium, phosphorus, nitrogen, boron and aluminum Group;

m is 0 or 1;

According to the present invention, in Formula 5, M ⁵ may be an element such as Ti, Zr, Hf, etc. Group 4 transition metal, R ⁵ is preferably in the methyl group, silicon, germanium, phosphorus, nitrogen, boron and aluminum It may include any one.

In Formula 5, when m is 1, (Cp ¹ R ³ ) and (Cp ² R ⁴ ) mean a bridged compound structure crosslinked by R ⁵ , and when m is 0, non-crosslinking Mean the compound structure.

As a non-limiting example, the metallocene compound is BisIndenylZrCl ₂ , BisIndenylHfCl ₂ , Bis (1-butyl-3-methylcyclopentadienyl) ZrCl ₂ , Bis (cyclopentadienyl) ZrCl ₂ , rac-Ethylene-1,2-bis (1-indenyl ) ZrCl ₂ , rac-Dimethylsilylene-bis (1-indenyl) ZrCl ₂ , (Cyclopentadienyl) IndenylZrCl ₂ , [Dimethylsilyl (η5-tetramethylCyclopentadienyl) (t-butylamido)] TiCl _2, and the like.

On the other hand, the metallocene catalyst system according to the present invention may further include a cocatalyst compound.

The promoter compound may be a conventional compound capable of activating the metallocene compound, preferably at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 9.

In Chemical Formula 6,

Al is aluminum;

R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms;

p is an integer of 2 or more;

In Chemical Formula 7,

M ⁶ is aluminum or boron;

Each R ⁹ is independently hydrogen, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms, or alkoxy having 1 to 20 carbon atoms;

In Chemical Formulas 8 and 9,

L ¹ and L ² are each independently neutral or cationic Lewis bases;

[L ¹ -H] ⁺ or [L ² ] ⁺ is a Bronsted acid;

M ⁷ and M ⁸ are each independently a Group 13 element of the Periodic Table of the Elements;

R ¹⁰ and R ¹¹ each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, unsubstituted or substituted with halogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy or phenoxy radical having 1 to 20 carbon atoms It is a substituted C1-C20 alkyl group.

The compound represented by the formula (6) is aluminoxane, and is not particularly limited as long as it is an ordinary alkylaluminoxane.

For example, methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like can be used, and specifically, methyl aluminoxane can be used. The alkylaluminoxane may be prepared by a conventional method such as adding an appropriate amount of water to trialkylaluminum, or reacting a trialkylaluminum with a hydrocarbon compound or an inorganic hydrate salt containing water, and is generally linear and cyclic. Aluminoxanes are obtained in mixed form.

As the compound represented by the formula (7), for example, a conventional alkyl metal compound can be used.

Specifically, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, Trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron , Tributyl boron, tripentafluorophenylboron and the like can be used, and more specifically, trimethylaluminum, triisobutylaluminum, tripentafluorophenylboron and the like can be used.

Examples of the compound represented by the formula (8) or (9) include methyldioctateylammonium tetrakis (pentafluorophenyl) borate ([HNMe (C18H37) 2] + [B (C6F5) 4]-), trimethylammonium tetrakis ( Phenyl) borate, triethylammonium tetrakis (phenyl) borate, tripropylammonium tetrakis (phenyl) borate, tributylammonium tetrakis (phenyl) borate, trimethylammonium tetrakis (p-tolyl) borate, tripropylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl) borate, triethylammonium tetrakis (o, p-dimethylphenyl) borate, trimethylammonium tetrakis (p-trifluoromethylphenyl) borate, Tributylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (pentafluorophenyl) borate Rate, triphenylphosphonium tetrakis (phenyl) borate, trimethylphosphonium tetrakis (phenyl) borate, N, N-diethylanilinium tetrakis (phenyl) borate, N, N-dimethylanilinium tetrakis (pentafluor Rophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl Borate, trimethylammonium tetrakis (phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, tripropylammonium tetrakis (phenyl) aluminate, tributylammonium tetrakis (phenyl) aluminate, trimethylammonium tetrakis (p-tolyl) aluminate, tripropylammonium tetrakis (p-tolyl) aluminate, triethylammonium tetrakis (o, p-dimethylphenyl) aluminate, Tributylammonium tetrakis (p-trifluoromethylphenyl) aluminate, trimethylammonium tetrakis (p-trifluoromethylphenyl) aluminate, tributylammonium tetrakis (pentafluorophenyl) aluminate, N, N-di Ethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (pentafluorophenyl) aluminate, diethylammonium tetra Keith (pentafluorophenyl) aluminate, triphenylphosphonium tetrakis (phenyl) aluminate, trimethylphosphonium tetrakis (phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, tributylammonium tetrakis ( Phenyl) aluminate, and the like, but is not limited thereto. Specifically, methyldioctateylammonium tetrakis (pentafluorophenyl) borate ([HNMe (C18H37) 2] + [B (C6F5) 4]-), N, N-dimethylanilinium tetrakis (pentafluorophenyl ) Borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, and the like.

Here, the promoter compound is 1: 1 to 1: 10,000, or 1: 1 to 1: 1,000, based on the molar ratio of the metal contained in the promoter compound to 1 mol of the transition metal contained in the metallocene compound. Or 1: 1 to 1: 100.

The metallocene compound, the composition for operation stability, and the cocatalyst compound may be a supported catalyst supported on a carrier. The catalyst may be supported on a carrier to maintain a good dispersion and stability in order to improve catalyst activity and maintain stability.

The carrier is a solid that disperses and retains the catalytically functional material stably, and is usually a porous or large-area material for highly dispersed and supported so as to increase the exposed surface area of the catalytically functional material. The carrier must be mechanically, thermally and chemically stable.

The carrier is not limited in kind, and may include all carriers that can be used as a carrier, and may be, for example, silicon compounds including silica, alumina, titanium compounds, bauxite, zeolite, zinc oxide, starch, synthetic polymers, and the like. Preferably, it may be silica, but is not limited thereto.

The carrier may have an average particle size of 10 to 250 microns, preferably an average particle size of 10 to 150 microns, and more preferably 20 to 100 microns.

The micropore volume of the carrier may be 0.1 to 10 cc / g, preferably 0.5 to 5 cc / g, more preferably 1.0 to 3.0 cc / g.

The specific surface area of the carrier may be 1 to 1000 m ² / g, preferably 100 to 800 m ² / g, and more preferably 200 to 600 m ² / g.

In addition, when the carrier is silica, the silica may be a drying temperature of 200 to 900 ℃. Preferably from 300 to 800 ° C, more preferably from 400 to 700 ° C. If the temperature is less than 200 ° C., there is too much water, and the surface of the surface reacts with the promoter, and if it exceeds 900 ° C., the carrier collapses.

The concentration of the hydroxy group in the dried silica may be 0.1 to 5 mmol / g, preferably 0.7 to 4 mmol / g, more preferably 1.0 to 2 mmol / g. If the amount is less than 0.5 mmol / g, the supported amount of the promoter is low, and if the amount exceeds 5 mmol / g, there are problems in that the catalyst component is inactivated due to many side reactions.

As a non-limiting example, the supported catalyst according to the above embodiment is suspended by stirring silica gel and slowly adding a cocatalyst compound (methyl aluminoxane, etc.), and then adding an operation stability composition and a metallocene compound thereto, and stirring It can be prepared through a washing, drying process.

The metallocene catalyst can be prepared by supporting the metallocene compound and the promoter compound according to the present invention by supporting them on a carrier.

The solvent for the reaction in the preparation of the metallocene catalyst is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, diethyl ether or tetrahydrofuran (THF It may be an organic solvent such as ether solvent, acetone, ethyl acetate, and the like, preferably toluene, hexane, but is not limited thereto.

The metallocene compound can be activated by mixing (contacting) the promoter compound. The mixing can be carried out in the presence of the hydrocarbon solvent, or without the solvent, usually under an inert atmosphere of nitrogen or argon.

When the metallocene compound is activated as a promoter compound, the temperature may be 0 to 100 ° C, preferably 10 to 30 ° C, and a time may be 5 minutes to 24 hours, and preferably 30 minutes to 3 minutes. It can be time.

The metallocene compound may be used as it is, or the catalyst composition in a solution state uniformly dissolved in the hydrocarbon solvent or the like, or in a solid powder state in which the solvent is removed, but is not limited thereto.

The composition for operating stability of the present invention is prepared by stirring the compound represented by the formula (1) and the white mineral oil at a temperature of 500 to 3000 rpm for 30 minutes to 24 hours, preferably 2 to 4 hours at a temperature of room temperature to 90 ℃ can do.

On the other hand, according to another embodiment of the present invention, in the presence of a metallocene catalyst system, the step of polymerizing at least one monomer selected from the group consisting of ethylene and olefinic monomers using gas phase polymerization or slurry polymerization A method for producing a polyolefin is provided.

At this time, the polymerization reactor may use any one or more of a batch reactor, a continuous reactor and a gas phase polymerization reactor.

When the polymerization is carried out in a slurry phase, a solvent or olefin itself can be used as the medium. The solvent includes propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, dichloroethane, chloro Benzene and the like can be exemplified, and these solvents may be mixed and used in a predetermined ratio, but are not limited thereto.

In addition, examples of the olefin monomers include ethylene, α-olefins, cyclic olefins, and the like, and preferably, α-olefins having 2 to 20 carbon atoms, diolefins having 1 to 20 carbon atoms, and 3 carbon atoms. At least one compound selected from the group consisting of cycloolefins having from 20 to 20 and cyclodiolefins having from 3 to 20 carbon atoms. Even more preferably, it may be, but is not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, mixtures thereof.

The α-olefins may have 3 to 12 carbon atoms, for example, include aliphatic olefins having 3 to 8 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, and 3-methyl-1-butene , 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 4,4-dimethyl-1-pentene, 4, 4-diethyl-1-hexene, 3,4-dimethyl-1-hexene and the like can be exemplified, but is not limited thereto.

The α-olefins may be polymerized singly or two or more olefins may be alternating, random, or block copolymerized. Copolymerization of the α-olefins is copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, for example, 3 to 8 (specifically, ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, and ethylene 4-methyl-1-pentene, such as ethylene and 1-octene) and copolymerization of propylene with an α-olefin having 4 to 12 carbon atoms, for example 4 to 8 carbon atoms (specifically, propylene and 1-butene, propylene and 4- Methyl-1-pentene, propylene and 4-methyl-1-butene, propylene and 1-hexene, propylene and 1-octene, and the like. In the copolymerization of ethylene or propylene with other α-olefins, the amount of other α-olefins may be up to 99 mole percent of the total monomers, typically for ethylene copolymers up to 80 mole percent.

In addition to the above α-olefins, 1,3-butadiene, 1,4-pentadiene, and 2-methyl-1,3-butadiene (2-methyl- Diolefin having 1 to 20 carbon atoms including 1,3-butadiene); 3 carbon atoms, including cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbonene, and methyl-2-norbonene Cycloolefin or cyclodiolefin of 20 to 20; Substituted styrene in which an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a halogen group, an amine group, a silyl group, a haloalkyl group, or the like is bonded to a styrene ring or a phenyl ring of styrene; Or mixtures thereof.

In addition, the temperature and pressure during the polymerization is not particularly limited because it may vary depending on the reaction materials, reaction conditions, etc., the polymerization temperature may be 0 to 120 ℃ in the case of slurry or gas phase polymerization, preferably 60 to 100 ℃ Can be.

In addition, the polymerization pressure may be 1 to 150 bar, preferably 5 to 50 bar, more preferably 10 to 20 bar. The pressure may be by injection of an olefin monomer gas (eg ethylene gas).

When the polyolefin is polymerized at the preferred polymerization temperature and pressure, the catalytic activity is superior to other conditions, and fouling and agglomeration are reduced. However, in the case of fouling and agglomeration phenomenon, it is difficult to remarkably fall only by the operating conditions, it is preferable to include the composition for stabilizing the operation according to the present invention in a specific content ratio.

The polymerization can also be carried out in two or more steps with different reaction conditions, and the molecular weight of the final polymer can be controlled by varying the polymerization temperature or by injecting hydrogen into the reactor.

In addition, in the presence of a metallocene catalyst system according to the present invention, there is provided a polyolefin prepared using the above-described method for producing a polyolefin.

When the metallocene catalyst system according to the present invention is applied, fouling and agglomeration phenomenon are minimized by including the composition for operating stability, and at the same time, there is an effect of maintaining or improving the intrinsic activity of the catalyst.

Example

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Preparation Example 1

[Preparation of Supported Metallocene Catalysts]

MAO and metallocene catalyst compounds, which are cocatalysts used in the catalyst, lose their activity when they react with moisture and oxygen in the air. Therefore, all experiments were conducted under nitrogen condition using Glove Box and Schlenk Technique. The 10 L supported catalytic reactor is washed to remove foreign substances and the reactor is vacuumed to remove internal air using a vacuum for at least 10 minutes.

300 g of Grace XPO2410 is introduced into the reactor using vacuum-nitrogen pressure difference and gravity. Fill the reactor with nitrogen until atmospheric pressure is reached. 500 ml of purified Toluene is added and stirred briefly at room temperature at an appropriate speed.

1187 g of 10% MAO in toluene is added to 6.297 g of the metallocene catalyst and stirred at room temperature for 30 minutes. The mixed solution of metallocene catalyst + MAO Pre-Contact 1 hour stirring step is added to a 10 L reactor. After stirring for 3 hours, stirring and heating are stopped.

Stop the agitation and remove the supernatant after approximately 40 minutes of solid / liquid separation. In a glove box, 6.376 g of Al-St and 2.125 g of Statsafe 3000 are placed in a flask and removed while maintaining the sealed condition and added to the 10 L reactor using the appropriate amount of Toluene. Add 500 ml of toluene and stir at room temperature for 1 hour.

Add about 500 mL of toluene, stir for 10 minutes, and remove the supernatant after 10 minutes of precipitation. Add about 1 L of Toluene and use nitrogen pressure while stirring to transfer the entire slurry to the 3 L Flask sealed in advance with Schlenk Line and Septa. Remove the supernatant from the 3 L Flask. Dry under vacuum at 60 ° C in an oil bath for at least 12 hours.

Preparation Example 2

[Production of Operational Stabilization Composition]

Mineral oil and sodium dodecyl sulfate, which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 7.5 g of sodium dodecyl sulfate (CAS.No.151-21-3; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) Stir at 90 ° C. for 3 hours at a speed of rpm.

Preparation Example 3

[Production of Operational Stabilization Composition]

Mineral oil and sodium dodecyl sulfate, which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 10 g of sodium dodecyl sulfate (CAS.No.151-21-3; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) to 1000 Stir at room temperature for 3 hours at rpm.

Preparation Example 4

[Production of Operational Stabilization Composition]

Mineral oil and sodium lauryl sulfoacetate, which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 7.5 g of sodium lauryl sulfoacetate (CAS.No. 1847-58-1; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) Stir at 90 ° C. for 3 hours at 1000 rpm.

Preparation Example 5

[Production of Operational Stabilization Composition]

Mineral oil and sodium lauryl sulfoacetate, components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 10 g of sodium dodecyl sulfate (CAS.No.151-21-3; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) to 1000 Stir at 90 ° C. for 3 hours at a speed of rpm.

Preparation Example 6

[Production of Operational Stabilization Composition]

Mineral oil and sodium lauryl sulfoacetate, components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 0.25 g of sodium lauryl sulfoacetate (CAS.No. 1847-58-1; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) Stir at 90 ° C. for 3 hours at 1000 rpm.

Preparation Example 7

[Production of Operational Stabilization Composition]

Mineral oil and sodium dodecyl sulfate, which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 0.25 g of sodium dodecyl sulfate (CAS.No.151-21-3; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) Stir at 90 ° C. for 3 hours at a speed of rpm.

Preparation Example 8

[Production of Operational Stabilization Composition]

Mineral oil and sodium lauryl sulfoacetate, which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 35 g of sodium lauryl sulfoacetate (CAS.No. 1847-58-1; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) Stir at 90 ° C. for 3 hours at 1000 rpm.

Example 1

[Slurry Phase Polymerization of Polyolefins Using Composition for Operational Stability]

Polymerization experiments were carried out in a 2 L Autoclave slurry reactor. Purge for about 1 hour with nitrogen to remove foreign substances such as water and oxygen. Thereafter, 0.8 L of hexane was introduced into the reactor, followed by stirring at 200 rpm to adjust the polymerization temperature. Then 0.5 ml of 1 M TIBAL (triisobutylaluminum) is injected into the Scavenger. 30 mg of the supported catalyst of Preparation Example 1 and 32 mg of the composition for operation stability of Preparation Example 2 were injected into a reactor together with 0.2 L of hexane. When the temperature of the reactor reaches 80 ° C, nitrogen is injected to 1 kgf / cm ² including hexane vapor pressure, and 14 kgf / cm ² ethylene is injected to adjust the total air pressure to 15 kgf / cm ² . While stirring the reactor at 1,000 rpm, 50 ml of comonomer 1-hexene was added using a Syringe pump to proceed with the reaction. After the polymerization reaction is performed for 1 hour, the reaction gas is removed and the reactor is opened to obtain 214 g of the resulting polyolefin resin. The operating conditions of the polymerization reaction are shown in Table 1 below, and it was confirmed that the polymer coating was not present in the wall and the stirrer.

Also. The resin shape obtained through the polymerization was compared through the Fouling index used in the present specification, and the results are shown in Table 2 together with the catalytic activity. The fouling index categorizes fouling and agglomeration within the polymerization reactor walls and agitators into the resulting polymer form.

Fouling index 0: no fouling and agglomeration

Fouling index 1: Agglomeration of the polymer less than 1 cm (polymer diameter)

Fouling index 2: Agglomeration of the polymer 1-2 cm

Fouling index 3: Agglomeration of the polymer 2 ~ 4 cm

Fouling index 4: Polymer of film form 4 ~ 6 cm

Fouling index 5: 6 ~ 8 cm film polymer

Fouling index 6: Reactor wall sheet formation

And the polymerization kinetic of Example 1 was measured and the result is shown in FIG.

Example 2

[Slurry Phase Polymerization of Polyolefins Using Composition for Operational Stability]

A polyolefin (172 g) was prepared in the same manner as in Example 1 except for injecting 50 mg of the composition for operation stability of Preparation Example 2, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was not present in the wall and the stirrer.

In addition, the catalytic activity and fouling phenomenon in the polyethylene polymerization process were measured and observed, and the results are shown in Table 2.

Example 3

[Slurry Phase Polymerization of Polyolefins Using Composition for Operational Stability]

A polyolefin (206 g) was prepared in the same manner as in Example 1 except that 25 mg of the composition for operating stability of Preparation Example 3 was prepared, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was not present in the wall and the stirrer.

In addition, the catalytic activity and fouling phenomenon in the polyethylene polymerization process were measured and observed, and the results are shown in Table 2.

Example 4

[Slurry Phase Polymerization of Polyolefins Using Composition for Operational Stability]

A polyolefin (168 g) was prepared in the same manner as in Example 1 except that 16 mg of the composition for operating stability in Preparation Example 4 was injected, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was not present in the wall and the stirrer.

In addition, the catalytic activity and fouling phenomenon in the polyethylene polymerization process were measured and observed, and the results are shown in Table 2.

Example 5

[Slurry Phase Polymerization of Polyolefins Using Composition for Operational Stability]

A polyolefin (173 g) was prepared in the same manner as in Example 1 except for injecting 15 mg of the composition for operation stability of Preparation Example 5, and the operating conditions of the polymerization reaction are shown in Table 1 below.

In addition, the catalytic activity and fouling phenomenon in the polyethylene polymerization process were measured and observed, and the results are shown in Table 2.

Example 6

[Gasmic Polymerization of Polyolefins Using Composition for Operational Stability]

2.5 g / hr of the supported catalyst of Preparation Example 1 and 1.5 g / hr of the composition for operation stability of Preparation Example 3 were prepared using a gas phase fluidized bed pilot reactor. Table 3 shows the results of operating the gas phase fluidized bed pilot reactor with the same catalyst. In the polyethylene manufacturing process, the temperature change of the inner wall was measured through a static probe, and the results are shown in FIG. 2. As can be seen from the change in the temperature lines in Figure 2, the reactor wall temperature is kept stable, more than 50 hours of stable operation was possible. At this time, the static average value was measured as -1.21 kV.

Comparative Example 1

[Slurry Phase Polymerization of Polyolefins without Using Operational Stability]

Polyolefin (170 g) was prepared in the same manner as in Example 1, except that the composition for operation stability was not included, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was present on the wall and the stirrer.

In addition, the catalytic activity and fouling phenomenon in the polyethylene polymerization process were measured and observed, and the results are shown in Table 2.

In addition, the polymerization kinetic of Comparative Example 1 was measured, and the results are shown in FIG. 1.

Comparative Example 2

[Slurry Phase Polymerization of Polyolefins Using Composition for Operational Stability]

A polyolefin (154 g) was prepared in the same manner as in Example 1 except for injecting the composition for operating stability of Preparation Example 6, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was present on the wall and the stirrer.

In addition, the catalytic activity and fouling phenomenon in the polyethylene polymerization process were measured and observed, and the results are shown in Table 2.

Comparative Example 3

[Slurry Phase Polymerization of Polyolefins Using Composition for Operational Stability]

A polyolefin (150 g) was prepared in the same manner as in Example 4 except for injecting the composition for operating stability of Preparation Example 7, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was present on the wall and the stirrer.

In addition, the catalytic activity and fouling phenomenon in the polyethylene polymerization process were measured and observed, and the results are shown in Table 2.

Comparative Example 4

[Slurry Phase Polymerization of Polyolefins Using Composition for Operational Stability]

A polyolefin (62 g) was prepared in the same manner as in Example 4 except for injecting the composition for operating stability of Preparation Example 8, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was present on the wall and the stirrer.

In addition, the catalytic activity and fouling phenomenon in the polyethylene polymerization process were measured and observed, and the results are shown in Table 2.

Comparative Example 5

[Slurry Phase Polymerization of Polyolefins Using Composition for Operational Stability]

A polyolefin (74 g) was prepared in the same manner as in Example 1 except that 100 mg of the composition for operation stability of Preparation Example 2 was prepared, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was not present in the wall and the stirrer.

In addition, the catalytic activity and fouling phenomenon in the polyethylene polymerization process were measured and observed, and the results are shown in Table 2.

Comparative Example 6

[Gaseous Polymerization of Polyolefins without Using Operational Stability]

A polyolefin was prepared in the same manner as in Example 6 except that the composition for operation stability was not included.

Temperature change of the inner wall surface was measured through a static probe in the polyethylene manufacturing process, the results are shown in FIG. As can be seen from the change in the temperature line in Figure 3, after about 18 hours after the catalyst injection, the temperature of the reactor wall rapidly rises (hot spot) occurs to produce a sheet and chunk, continuous operation was not possible. At this time, the static average value was measured as -1.899 kV.

division catalyst Operational stability composition Operational stability composition / catalyst content ratio TIBAL (μmol) Polymerization temperature (℃) Polymerization time (min) Ethylene (atm) 1-hexene (mM) Example 1 Preparation Example 1 Preparation Example 2 1.1 2 80 60 14 0.4 Example 2 Preparation Example 1 Preparation Example 2 1.7 2 80 60 14 0.4 Example 3 Preparation Example 1 Preparation Example 3 0.8 2 80 60 14 0.4 Example 4 Preparation Example 1 Preparation Example 4 0.5 2 80 60 14 0.4 Example 5 Preparation Example 1 Preparation Example 5 0.5 2 80 60 14 0.4 Comparative Example 1 Preparation Example 1 - - 2 80 60 14 0.4 Comparative Example 2 Preparation Example 1 Preparation Example 6 1.1 2 80 60 14 0.4 Comparative Example 3 Preparation Example 1 Preparation Example 7 0.5 2 80 60 14 0.4 Comparative Example 4 Preparation Example 1 Preparation Example 8 0.5 2 80 60 14 0.4 Comparative Example 5 Preparation Example 1 Preparation Example 2 3.3 2 80 60 14 0.4

division Active (gPE / gCat) Fouling index Example 1 7133 0 Example 2 5733 0 Example 3 6867 0 Example 4 5600 0 Example 5 5756 0 Comparative Example 1 5667 3 Comparative Example 2 5133 2 Comparative Example 3 5000 2 Comparative Example 4 2067 2 Comparative Example 5 2467 0

Example 6 Comparative Example 6 C2 PP (K / G) 14.2 14.08 Static (kV) -1.21 -1.899 Temp. (℃) 82 85 UBD (g / cc) 0.288 0.239 H2 / C2 (%) 0.13 0.13 C6 / C2 (%) 0.96 0.821 Active (kgPE / kgCat.) 6000 6000 MI (g / min) 1.35 0.925 Bulk Density (g / cm ³ ) 0.479 0.495

As can be seen from the comparison of Comparative Examples 1 and 6 and Examples 1 to 6 shown in Table 2 above, using the composition for operation stability according to the present invention, the wall by the electrostatic charging present in the fluidized bed reactor than when not in use And fouling and agglomeration in the stirrer were surprisingly reduced. Specifically, when the composition for operating stability according to the embodiment of the present invention is included in a metallocene catalyst system in a certain ratio, not only the overall catalytic activity is superior to Comparative Example 1 that does not include the operation stability composition, Example 1 to 6, all of the fouling index (fouling index) is an index for indicating the fouling phenomenon was not observed, especially in the sixth embodiment of the gas phase polymerization, the reactor wall temperature is kept stable Although it can be confirmed that the operation can be performed even for a long time of 50 hours or more, in the case of Comparative Example 1, which does not include the composition for operating stability, the fouling index was found to be 3, and the fouling phenomenon was observed. In Comparative Example 6, the wall temperature of the reactor rapidly increased from about 18 hours after the catalyst injection (hot spot) occurred. It can be confirmed that continuous operation is impossible due to sheet and chunk.

Moreover, when using the composition for operating stability according to the present invention through Figure 1, it can be seen that the polymerization activity was significantly increased and the polymerization kinetic properties were kept constant. This phenomenon is similarly observed in the gas phase polymerization of Example 6.

In addition, when the temperature change of the inner wall surface was measured through a static probe in the polyolefin manufacturing process of Comparative Examples 6 and 6, Example 6 shows that the reactor wall temperature is stably as shown in the change of the temperature lines of FIG. It can be confirmed that stable operation for more than 50 hours is possible.

On the contrary, in Comparative Example 6, as can be seen from the change in the temperature lines of FIG. 3, the temperature of the reactor wall rapidly rises from about 18 hours after the catalyst injection (Hot spot) occurs, and the sheet and the chunk are generated to continuously operate. This was impossible.

Based on the mass of the supported catalyst, the composition for operating stability is preferably 30 to 300, or particularly preferably 30 to 200% by weight. However, depending on the composition of the composition, the appropriate amount of the composition for operation stability is fluid. In the case of using Preparation Example 2 for the operation stability of the catalyst, as the content of the composition for operation stability increases, it is operationally stable without significant change in fouling and agglomeration phenomenon inside the stirrer, but the polymerization activity decreases. This can be confirmed by Comparative Example 5.

Specifically, Comparative Example 5 was included in the stabilizer composition 330% by weight, it was confirmed that the catalyst activity sharply dropped.

Therefore, when the content ratio of the composition for operation stability is present in the reactor at a ratio above the numerical range according to the present invention serves as a polymerization inhibitor to reduce the activity of the catalyst through the reaction with the catalyst. Accordingly, the metallocene supported catalyst is advantageously present in an amount of 1: 2 or less based on the weight of the composition for operating stability.

The composition for operation stability includes a white mineral oil and a composition of Formula 1, wherein the composition of Formula 1 may include 1 to 50% by weight based on the total weight of the operation stability composition. If the composition of Formula 1 is in an amount ratio of 1 to 50% by weight, it may have an optimum operation stability by appropriately adjusting the content ratio of the composition and the supported catalyst for the operation stability, but if it is out of this the content ratio of the composition and the supported catalyst for operation stability Even if control is controlled, operations may become unstable due to problems such as flowability and phase separation.

In particular, when the content ratio of the composition of formula (1) is less than 1% by weight relative to the total weight of the composition for the operation stability, the amount of the composition of the formula (1) required to exhibit the operation stability during polymerization should be added, and accordingly 99% or more of mineral oil The method of using the composition for operational stability of the containing form is wasteful. In addition, a phase separation phenomenon with the white mineral oil occurs, which may cause the input instability in the reactor and adversely affect the polymerization operation stability, which can be confirmed through Comparative Examples 2 and 3.

Specifically, in Comparative Examples 2 and 3, sodium lauryl sulfoacetate and sodium dodecyl sulfate, which are included in the compound represented by Formula 1, were included in less than 1% by weight, respectively, and the fouling index of the polyolefin was 2 with a fouling index of 2. Was observed.

In addition, when the content ratio of the composition of Formula 1 exceeds 50% by weight based on the total weight of the composition for the operation stability, there is a problem that the polymerization cannot proceed uniformly in the reactor because the mixing of the catalyst composition, the composition for operation stability, and the monomer is not easy. . In Comparative Example 4, since sodium lauryl sulfoacetate added a composition exceeding 50% by weight relative to the total composition, and the polymerization was not uniform, the activity was drastically decreased and the fouling index was 2. A fouling phenomenon of was observed. Although the stability of the composition was not improved even though the composition of Formula 1 was added in excess of Example 4, it indicates the importance of balanced dispersion and flow control of the composition for stability of operation.

In addition, the composition for operation stability is preferably produced at a temperature range lower than the melting point of the composition represented by the formula (1), and particularly preferably, can be prepared at a temperature range from room temperature to 90 ℃.

The polyolefin polymerization process according to the invention can be carried out on an industrial scale, no coatings occur and no aggregates are formed, the productivity of the catalysts used is increased and can have good morphology.

Although the present invention has been described by specific embodiments such as specific components and the like, but the embodiments and the drawings are provided to assist in a more general understanding of the present invention, the present invention is not limited to the above embodiments. For those skilled in the art, various modifications and variations can be made from these descriptions.

Accordingly, the spirit of the present invention should not be limited to the above-described embodiments, and all of the equivalents or equivalents of the claims, as well as the appended claims, fall within the scope of the spirit of the present invention. I will say.

Claims (16)

100 parts by weight of at least one metallocene compound; And Metallocene catalyst system comprising 30 to 300 parts by weight of the composition for operation stability comprising at least one compound selected from the group consisting of sulfates, sulfonates, phosphates and carboxylates and at least one white mineral oil . The method of claim 1, The composition for operation stability, At least one white mineral oil; And Metallocene catalyst system comprising at least one first compound represented by the following formula (1). [Formula 1]

In Chemical Formula 1, M ¹ is any of carbon, sulfur, phosphorus atoms; M ² is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, calcium, strontium, barium and radium; A ¹ is hydrogen, oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, and 1 to 10 carbon atoms. A substituent of at least one of an alkoxy group, an aryloxy group having 6 to 30 carbon atoms, and an acetate group; O means oxygen atom; R ¹ is a substituent of any one of an alkyl group or isoalkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an alkynyl group having 8 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms; n is an integer of 1 or 2. The method of claim 2, The first compound is a metallocene catalyst system, characterized in that it comprises a second compound represented by the formula (2). [Formula 2]

In Chemical Formula 2, M ³ is a sulfur atom; M ⁴ is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and francium; A ² is hydrogen, oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, and 1 to 10 carbon atoms. A substituent of at least one of an alkoxy group, an aryloxy group having 6 to 30 carbon atoms, and an acetate group; O means oxygen atom; R ² is a substituent of any one of an alkyl group or isoalkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an alkynyl group having 8 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. The method of claim 3, The second compound is a metallocene catalyst system comprising any one or more of sodium dodecyl sulfate represented by the following formula (3) and sodium lauryl sulfoacetate represented by the following formula (4). [Formula 3]

[Formula 4]

The method of claim 1, The metallocene compound is a metallocene catalyst system is a compound represented by the formula (5). [Formula 5]

In Chemical Formula 5, M ⁵ is a Group 4 transition metal; Z ¹ and Z ² are each independently a halogen atom or a methyl group; 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 one or more hydrocarbon groups of 1 to 20 carbon atoms; R ³ and R ⁴ are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 carbon atoms Aryloxy group having 10 to 10 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, or alkynyl group having 2 to 10 carbon atoms, ; R ⁵ is a divalent hydrocarbon group which crosslinks (Cp ¹ R ³ ) and (Cp ² R ⁴ ) by a covalent bond and contains an element selected from the group consisting of silicon, germanium, phosphorus, nitrogen, boron and aluminum. ; m is 0 or 1; The method of claim 1, A metallocene catalyst system further comprising at least one cocatalyst compound selected from the group consisting of compounds represented by formulas (6) to (9) below. [Formula 6]

In Chemical Formula 6, Al is aluminum; R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms; p is an integer of 2 or more; [Formula 7]

In Chemical Formula 7, M ⁶ is aluminum or boron; Each R ⁹ is independently hydrogen, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms; [Formula 8]

[Formula 9]

In Chemical Formulas 8 and 9, L ¹ and L ² are each independently neutral or cationic Lewis bases; [L ¹ -H] ⁺ or [L ² ] ⁺ is a Bronsted acid; M ⁷ and M ⁸ are each independently a Group 13 element of the Periodic Table of the Elements; R ¹⁰ and R ¹¹ each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, unsubstituted or substituted with halogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy or phenoxy radical having 1 to 20 carbon atoms It is a substituted C1-C20 alkyl group. The method of claim 6, The promoter compound represented by Chemical Formula 4 includes at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, n-butyl aluminoxane and isobutyl aluminoxane; The promoter compound represented by Chemical Formula 5 includes at least one selected from the group consisting of trimethylaluminum, triisobutylaluminum, and tripentafluorophenylboron; The cocatalyst compound represented by Chemical Formula 6 includes dimethylanilinium tetrakis (pentafluorophenyl) borate; The cocatalyst compound represented by Chemical Formula 7 includes a triphenylcarbonium tetrakis (pentafluorophenyl) borate. The method of claim 1, The metallocene catalyst system further comprises a carrier on which the metallocene compound and the composition for operating stability are supported. The method of claim 8, The carrier, At least one or more selected from the group consisting of silica, magnesium and alumina; Average particle size is 10 to 250 microns; Micropore volume is from 0.1 to 10 cc / g; Metallocene catalyst system, characterized in that the specific surface area is 1 to 1000 m ² / g. The method of claim 8, The mass ratio of the transition metal of the metallocene compound and the mass of the carrier is 1:10 to 1: 1000 metallocene catalyst system, characterized in that. (a) adding a solvent to the carrier to prepare a carrier solution; (b) adding a metallocene compound and a cocatalyst compound to the carrier solution to prepare an activated metallocene supported catalyst solution; (c) mixing the compound according to claim 2 and white mineral oil to prepare a composition for operational stability; And (d) adding the operation stability composition to the supported metallocene catalyst solution. The method of claim 11, Method of producing a metallocene catalyst system comprising the step of preparing a solid metallocene supported catalyst solution by removing the supernatant after stirring in step (b). A method for producing a polyolefin, comprising the step of polymerizing to a polymerization reactor by the presence of at least one monomer selected from the group consisting of ethylene and olefin monomers in the presence of the metallocene catalyst system according to claim 1. The method of claim 13, The polymerization can proceed in gas phase or slurry phase; The polymerization reactor is a method for producing a polyolefin, characterized in that any one or more of a batch reactor, a continuous reactor and a gas phase polymerization reactor. The method of claim 13, The olefinic monomer is at least one selected from the group consisting of an alpha olefin having 2 to 20 carbon atoms, a diolefin having 1 to 20 carbon atoms, a cycloolefin having 3 to 20 carbon atoms, and a cyclodiolefin having 3 to 20 carbon atoms. Method for producing a polyolefin, characterized in that it comprises a compound. A polyolefin prepared using the process for producing a polyolefin according to claim 13 with at least one monomer selected from the group consisting of ethylene and olefinic monomers in the presence of a metallocene catalyst system according to claim 1.

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