KR102554325B1 - Method of removing an inorganic material in a catalytic composition - Google Patents

Abstract

The present invention comprises (1) firstly filtering a mixture including a catalyst composition including a transition metal compound represented by Chemical Formula 1 and an inorganic material, and a solvent; (2) reacting by adding two or more halogen-substituted silane compounds to the filtration mixture obtained in the primary filtration step; and (3) drying the reaction mixture after completion of the reaction in step (2), mixing it with a solvent for filtration, and then performing secondary filtration.

Description

Method for removing inorganic substances in catalyst composition {METHOD OF REMOVING AN INORGANIC MATERIAL IN A CATALYTIC COMPOSITION}

The present invention relates to a method for removing inorganic substances included in a catalyst composition, particularly a metallocene catalyst composition such as a transition metal compound.

In general, olefin polymers such as ethylene copolymers are useful polymeric materials used as materials for hollow molded products, extruded products, films, sheets, and the like, and have been produced in the presence of a Ziegler-Natta catalyst system.

The Ziegler-Natta catalyst is a heterogeneous catalyst and is used in systems in which the phases of reactants and catalysts are not the same, such as a liquid phase reactant-solid catalyst. These Ziegler-Natta catalysts are composed of two components, usually halogen compounds such as transition metals titanium (Ti), vanadium (V), chromium (Cr), molybdenum (Mo), zirconium (Zr) (for example, , TiCl ₄ ), alkyllithium, and alkylaluminum.

However, the Ziegler-Natta catalyst has a disadvantage in that it cannot overcome limitations as a heterogeneous catalyst because most of the transition metal atoms do not perform their function, since the concentration of the active species is in the range of several to several tens of % relative to the transition metal atoms.

Recently, as a next-generation catalyst capable of overcoming these disadvantages, metallocene compounds have been attracting attention. The metallocene compounds are homogeneous catalysts containing Group 4 metals and are known to exhibit desirable polymerization activity in olefin polymerization.

The Dow Company announced [Me ₂ Si(Me ₄ C ₅ )N t Bu]TiCl ₂ (Constrained-Geometry Catalyst, hereinafter abbreviated as CGC) in the early 1990s (U.S. Patent Registration No. 5,064,802), ethylene In the copolymerization reaction between alpha-olefin and CGC, the superior aspects of the CGC compared to conventionally known metallocene catalysts can be largely summarized as follows: (1) High activity even at high polymerization temperature and high molecular weight (2) It has excellent copolymerizability with alpha-olefins with high steric hindrance, such as 1-hexene and 1-octene. In addition, as various properties of CGC are gradually known during polymerization, efforts to synthesize its derivatives and use them as polymerization catalysts have been actively made in academia and industry.

Most metallocene catalysts used in polymerization use Group 4 metal elements such as titanium, zirconium, and hafnium (Hf) and supporting ligands as precursors, and are composed of two aromatic five-membered rings and two halogen compounds as leaving groups. Among these, the supporting ligand coordinating to the central metal is generally an aromatic cyclopentadienyl group.

Meanwhile, the above metallocene catalysts are generally used after methylation, and the methylation is attempted in various ways. However, impurities generated in the methylation process are adsorbed on the active site of the catalyst to greatly reduce the activity of the catalyst, or increase the frequency of washing due to solidification in the reactor or inside the heat exchanger at the front and rear of the reactor. that is causing it. In particular, inorganic substances included in the preparation process of the catalyst composition not only affect the polymerization activity but also affect the molecular weight of the prepared polymer.

Due to these problems, it is necessary to study a method capable of maintaining high purity without denaturing the metallocene catalyst while minimizing or removing impurities in the methylation process.

US Patent Registration No. 5,064,802

The present invention has been made to solve the problems of the prior art, and removes at a high removal rate by-products such as inorganic substances generated during the alkylation process that is essentially accompanied when preparing a metallocene catalyst such as a transition metal compound. It is to provide a method for removing inorganic substances with an excellent recovery rate.

In order to solve the above problems, the present invention provides (1) a catalyst composition comprising a transition metal compound represented by Chemical Formula 1 and an inorganic material, and firstly filtering a mixture including a solvent; (2) reacting by adding two or more halogen-substituted silane compounds to the filtration mixture obtained in the primary filtration step; and (3) drying the reaction mixture after completion of the reaction in step (2), mixing it with a solvent for filtration, and then performing secondary filtration.

[Formula 1]

In Formula 1,

Cp is an organic compound in which the number of coordination sites capable of coordinating with a transition metal is 1;

A is Si or C;

Z is -O-, -S-, -NB ₁ - or -PB ₁ -, and B ₁ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a carbon number 1 to 20 silylhydrocarbyl groups;

M is a Group 4 transition metal;

Q ₁ and Q ₂ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a silyl hydrocarbyl group having 1 to 20 carbon atoms;

Y ₁ and Y ₂ are each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms.

The method for removing inorganic substances in the catalyst composition according to the present invention can remove by-products such as inorganic substances generated during the alkylation process, which is essentially accompanied when preparing a metallocene catalyst such as a transition metal compound, with a high removal rate, and the recovery rate of the transition metal compound It is excellent and can maintain high purity because denaturation does not occur.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

Terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

As used herein, the term 'hydrocarbyl group', unless otherwise specified, is a hydrocarbon consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl, or arylalkyl. means gear.

As used herein, the term 'halogen' means fluorine, chlorine, bromine or iodine, unless otherwise specified.

As used herein, unless otherwise specified, the term 'alkyl' refers to a straight-chain, cyclic or branched hydrocarbon moiety, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , t-butyl, n-pentyl, isopentyl and hexyl.

As used herein, unless otherwise specified, the term 'cycloalkyl' refers to a non-aromatic cyclic hydrocarbon radical composed of carbon atoms. 'Cycloalkyl' includes, by way of non-limiting examples, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

As used herein, the term 'aryl', unless otherwise indicated, refers to an optionally substituted benzene ring or to a ring system that may be formed by fusing one or more optional substituents. Exemplary optional substituents are substituted C _l-3 alkyl, substituted C _2-3 alkenyl, substituted C _2-3 alkynyl, heteroaryl, heterocyclic, aryl, optionally having 1 to 3 fluorine substituents. Alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, carboxamide, amino carbonyl, carboxy, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen or ureido. Such rings or ring systems may optionally be fused to aryl rings (eg, benzene rings), carbocyclic rings or heterocyclic rings optionally bearing one or more substituents. Examples of 'aryl' groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl or phenanthryl, and substituted derivatives thereof.

As used herein, the term 'alkenyl' refers to a straight-chain or branched-chain hydrocarbon radical having one or more carbon-carbon double bonds. Examples of 'alkenyl' as used herein include, but are not limited to, ethenyl and propenyl.

As used herein, the term 'alkoxy' refers to the group -OR _a , where R _a is an alkyl as defined above. 'Alkoxy' includes, but is not limited to, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and t-butoxy.

In the present specification, 'silyl' means unsubstituted silyl or a silyl group substituted with one or more substituents. 'Silyl' includes, but is not limited to, silyl, trimethylsilyl, triethylsilyl, isopropyldimethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, hexyldimethylsilyl, methoxymethylsilyl, (2-methoxyethoxy ) Includes methylsilyl, trimethoxysilyl, and triethoxysilyl.

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group refers to an alkyl group substituted by the aryl group.

A method for removing inorganic substances in a catalyst composition of the present invention includes (1) firstly filtering a mixture including a catalyst composition including a transition metal compound represented by Chemical Formula 1 and an inorganic substance, and a solvent; (2) reacting by adding two or more halogen-substituted silane compounds to the filtration mixture obtained in the primary filtration step; and (3) drying the reaction mixture after completion of the reaction in step (2), mixing it with a solvent for filtration, and then performing secondary filtration.

[Formula 1]

In Formula 1,

Cp is an organic compound in which the number of coordination sites capable of coordinating with a transition metal is 1;

A is Si or C;

Z is -O-, -S-, -NB ₁ - or -PB ₁ -, and B ₁ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a carbon number 1 to 20 silylhydrocarbyl groups;

M is a Group 4 transition metal;

Q ₁ and Q ₂ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a silyl hydrocarbyl group having 1 to 20 carbon atoms;

Y ₁ and Y ₂ are each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms.

The method for removing inorganic substances in the catalyst composition according to an example of the present invention can overcome the problem of removal using a conventional filter aid or removal by recrystallization.

Specifically, the removal of inorganic substances using the filter aid may be a relatively simple method of performing filtration by placing a filter aid such as celite on a filter, but the removal efficiency of inorganic substances is low when removed in this way.

A method for removing inorganic substances in a catalyst composition according to the present invention is a method for solving the above problems, and includes adding a silane compound substituted with two or more halogens to a primarily filtered filtration mixture, and drying the silane compound. Since it includes the step of secondary filtration after mixing with a solvent, by-products such as inorganic substances can be removed with a high removal rate.

(1) firstly filtering a mixture including a catalyst composition including a transition metal compound represented by Chemical Formula 1 and an inorganic material and a solvent;

In step (1), a mixture including a catalyst composition including a transition metal compound represented by Formula 1 and an inorganic material and a solvent is firstly filtered.

[Formula 1]

In Formula 1,

Cp is an organic compound in which the number of coordination sites capable of coordinating with a transition metal is 1;

A is Si or C;

Z is -O-, -S-, -NB ₁ - or -PB ₁ -, and B ₁ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a carbon number 1 to 20 silylhydrocarbyl groups;

M is a Group 4 transition metal;

Q ₁ and Q ₂ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a silyl hydrocarbyl group having 1 to 20 carbon atoms;

Y ₁ and Y ₂ are each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms.

In Formula 1, Cp may be any one of ligands represented by Formulas 2 to 5 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,

R ₁ to R ₆ are each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbyloxy group having 1 to 30 carbon atoms.

In one example of the present invention, the R ₁ to R ₄ may each independently be hydrogen or a hydrocarbyl group having 1 to 10 carbon atoms;

The R ₅ and R ₆ may each independently be a hydrocarbyl group having 1 to 10 carbon atoms.

Further, in one example of the present invention, in Chemical Formula 1, Z may be -NB ₁ -, and B ₁ may be a hydrocarbyl group having 1 to 10 carbon atoms.

The hydrocarbyl group is a monovalent functional group obtained by removing a hydrogen atom from a hydrocarbon, and includes an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, and It may contain an alkynyl aryl group and the like. The hydrocarbyl group having 1 to 30 carbon atoms may be specifically a hydrocarbyl group having 1 to 20 carbon atoms, and more specifically, a hydrocarbyl group having 1 to 10 carbon atoms. For example, the hydrocarbyl group having 1 to 30 carbon atoms is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, straight-chain, branched-chain or cyclic alkyl groups such as n-heptyl group and cyclohexyl group; or an aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group.

The hydrocarbyloxy group is a functional group in which the hydrocarbyl group is bonded to oxygen. The hydrocarbyloxy group having 1 to 30 carbon atoms may be specifically a hydrocarbyloxy group having 1 to 20 carbon atoms, and more specifically, a hydrocarbyloxy group having 1 to 10 carbon atoms. For example, the hydrocarbyloxy group having 1 to 30 carbon atoms is methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group, n - a straight-chain, branched-chain or cyclic alkoxy group such as a hexahoxy group, n-heptoxy group, or cyclohexoxy group; or an aryloxy group such as a phenoxy group or a naphthalenoxy group.

The hydrocarbyloxyhydrocarbyl group is a functional group in which one or more hydrogens of the hydrocarbyl group are substituted with one or more hydrocarbyloxy groups. The hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms may be specifically a hydrocarbyloxyhydrocarbyl group having 2 to 20 carbon atoms, and more specifically, a hydrocarbyloxyhydrocarbyl group having 2 to 15 carbon atoms. For example, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms is a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group , tert-butoxyethyl group, tert-butoxyhexyl group or phenoxyhexyl group.

The hydrocarbyl (oxy)silyl group is a functional group in which 1 to 3 hydrogens of -SiH ₃ are substituted with 1 to 3 hydrocarbyl groups or hydrocarbyloxy groups. The hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms may be specifically a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms or 1 to 10 carbon atoms, and more specifically, a hydrocarbyl group having 1 to 5 carbon atoms. It may be an (oxy)silyl group. For example, a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms is an alkylsilyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group, and a dimethylpropylsilyl group. ; Alkoxysilyl groups, such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group, and a dimethoxyethoxysilyl group; and an alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, and a dimethoxypropylsilyl group.

The silyl hydrocarbyl group is a functional group in which one or more hydrogens of the hydrocarbyl group are substituted with a silyl group. The silyl group may be -SiH ₃ or a hydrocarbyl (oxy)silyl group. The silyl hydrocarbyl group having 1 to 20 carbon atoms may be specifically a silyl hydrocarbyl group having 1 to 15 carbon atoms, and more specifically, a silyl hydrocarbyl group having 1 to 10 carbon atoms. For example, the silylhydrocarbyl group having 1 to 20 carbon atoms may be -CH ₂ -SiH ₃ , a methylsilylmethyl group, or a dimethylethoxysilylpropyl group.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

In one example of the present invention, the transition metal compound represented by Formula 1 may be a compound represented by Formula 6 below.

[Formula 6]

R ₁ to R ₆ are each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbyloxy group having 1 to 30 carbon atoms;

A is Si or C;

M is a Group 4 transition metal;

Q ₁ and Q ₂ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a silylhydrocarbyl group having 1 to 20 carbon atoms;

Y ₁ and Y ₂ are each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms;

B ₁ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a silyl hydrocarbyl group having 1 to 20 carbon atoms.

Further, in one example of the present invention, the R ₁ to R ₄ may each independently be hydrogen or a hydrocarbyl group having 1 to 10 carbon atoms;

The R ₅ and R ₆ may each independently be a hydrocarbyl group having 1 to 10 carbon atoms.

Also, in one example of the present invention, B ₁ may be a hydrocarbyl group having 1 to 10 carbon atoms.

In addition, in Formula 6, the A, B ₁ , Y ₁ , Y _{2 ,} Q ₁ and Q ₂ is as defined in Formula 1 above.

Further, in one example of the present invention, in Formula 6, the R ₁ to R ₄ may be hydrogen;

The R ₅ and R ₆ may be alkyl having 1 to 10 carbon atoms;

The Y ₁ and Y ₂ are each independently may be an alkyl having 1 to 10 carbon atoms or an alkoxyalkyl having 2 to 20 carbon atoms;

The Q ₁ and Q ₂ may each independently be an alkyl having 1 to 10 carbon atoms;

The B ₁ may be an alkyl having 1 to 10 carbon atoms.

The inorganic material may be a product that has not been purified or a product that has undergone only primary purification in the manufacturing process of the transition metal compound represented by Formula 1.

The inorganic material may be a by-product generated in the alkylation process during the process of preparing the transition metal compound represented by Formula 1, for example, an alkyl brominated metal compound (where alkyl may be methyl, ethyl or isopropyl, and the metal is may be Mg). In one example of the present invention, the inorganic material may be Mg.

As described above, the inorganic material is introduced as a reactant in the process of alkylating the transition metal compound represented by Formula 1 and is included as an impurity, and a reaction such as copolymerization is performed using a metallocene catalyst such as the transition metal compound. It is a compound that is essential to be removed because it can adsorb to the active site of the catalyst to inhibit the catalyst activity or have a great effect on the molecular weight of the polymer produced.

In the step (1), the catalyst composition is first filtered after being mixed with the solvent, and before mixing the transition metal compound and the inorganic material with the solvent, the ether-based solvent that may be included in the catalyst composition is removed. A drying process may additionally be performed.

The ether-based solvent may be a reaction solvent used in the preparation process of the transition metal compound, and may be, for example, a compound such as methyl t-butyl ether, diethyl ether, or tetrahydrofuran.

Through the drying, the ether-based solvent may be removed to be 0.01% by weight or less based on the total weight of the catalyst composition.

As a method of removing the ether-based solvent, various methods may be applied, and in general, a method of evaporating by heating in a vacuum condition in the range of 0.1 to 400 torr may be applied. In this case, the heating may be performed at a temperature of 10 to 80° C., and the ether-based solvent may be heated for 1 hour to 24 hours to evaporate to a target content. When the above temperature range and pressure range are satisfied, the solvent can be smoothly removed, and it can be removed to a level of 0.01% by weight or less, that is, to a level that is not detected.

The catalyst composition is mixed with a solvent and filtered first in the form of a mixture.

The solvent may be a hydrocarbon solvent, for example, a non-polar solvent, specifically, hexane, heptane, 2-methylpentane or pentane, etc., a solvent capable of selectively dissolving the transition metal compound represented by Formula 1 If so, it can be applied without particular limitation.

The solvent may be mixed in an amount of 15 to 50 times, specifically, 20 to 25 times the total weight of solids in the catalyst composition. When the mixed amount of the solvent is insufficient, the transition metal compound cannot be sufficiently dissolved, and thus the transition metal compound may be removed from the filter together during inorganic removal, and thus the recovery rate of the actual catalyst component may be considerably lowered. In addition, when the mixing amount of the solvent is excessive, economic loss may occur due to the input of an unnecessary amount.

The primary filtration may be performed using a glass filter, and the glass filter may have a lattice size of 10 μm to 30 μm, specifically, 20 μm to 30 μm.

The mixture containing the catalyst composition and the solvent may include a transition metal compound, most of which is in a dissolved state, and an inorganic material, of which most of it is in an undissolved solid state. In this way, inorganic substances may be removed by first filtering solids remaining without inorganic substances dissolved through a filter.

(2) reacting by adding two or more halogen-substituted silane compounds to the filtration mixture obtained in the primary filtration step.

The method for removing inorganic substances in the catalyst composition of the present invention is characterized in that it comprises adding two or more halogen-substituted silane compounds to the firstly filtered filtration mixture and reacting thereto. The process of reacting by adding a silane-based compound to the filtration mixture of step (2) may be performed in a temperature range of -20 ° C to 60 ° C, specifically -10 ° C to 50 ° C, more specifically 0 ° C to 40 ° C It can be made in the temperature range of.

The silane compound substituted with two or more halogens may include a compound represented by Formula 7 below.

[Formula 7]

In Formula 7,

R ₇ and R ₈ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyloxy group having 1 to 20 carbon atoms;

X ₁ and X ₂ are each independently halogen.

In addition, R ₇ and R ₈ may each independently be hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbyloxy group having 1 to 10 carbon atoms.

In addition, the R ₇ and R ₈ may each independently be an alkyl having 1 to 10 carbon atoms.

Also, in one example of the present invention, the silyl compound substituted with two or more halogens may include dimethyldichlorosilane.

The two or more halogen-substituted silane compounds are added to the filtration mixture to react with inorganic substances dissolved in a solvent so that the inorganic substances can be removed by a filter, and the silane-based compound after the reaction is vacuum dried, etc. can be removed through the

When the silane compound substituted with two or more halogens is added to the filtration mixture in the above temperature range, a reaction with the inorganic material may be appropriately performed.

(3) drying the reaction mixture after completion of the reaction in step (2), mixing it with a solvent for filtration, and then performing secondary filtration

The filtration mixture to which the silane-based compound is added in step (2) is reacted with the inorganic material contained as the impurity, and when the reaction is completed, it is preferentially dried, and then mixed with a solvent for filtration and subjected to secondary filtration.

Various methods may be applied to the drying, for example, a method of evaporating by heating in a vacuum condition in the range of 0.1 to 400 torr may be applied. In this case, heating may be performed at a temperature of 10 to 80° C. and may be heated for 1 hour to 24 hours.

The solvent for the filtration may be a hydrocarbon solvent, for example, a non-polar solvent, specifically, hexane, heptane, 2-methylpentane or pentane, etc., which can selectively dissolve the transition metal compound represented by Formula 1. Any solvent that can be used may be applied without particular limitation.

The solvent may be mixed in an amount of 15 to 50 times, specifically, 20 to 25 times the total weight of solids in the catalyst composition. When the mixed amount of the solvent is insufficient, the transition metal compound cannot be sufficiently dissolved, and thus the transition metal compound may be removed from the filter together during inorganic removal, and thus the recovery rate of the actual catalyst component may be considerably lowered. In addition, when the mixing amount of the solvent is excessive, economic loss may occur due to the input of an unnecessary amount.

The secondary filtration may be performed using a glass filter or a celite filter, and may be specifically performed using a glass filter.

The glass filter may have a lattice size of 10 μm to 30 μm, specifically may have a lattice size of 20 μm to 30 μm, and the celite filter may have a lattice size of 0.1 μm to 10 μm It may be, specifically, it may have a lattice size of 0.1 μm to 1 μm.

Meanwhile, in one example of the present invention, the transition metal compound represented by Chemical Formula 1 may be prepared by (a) reacting a ligand compound represented by Chemical Formula 8 with an organolithium compound in a reaction solvent; (b) adding an alkyl bromide metal compound dropwise, then adding MX ₂ compound and then stirring (M is a Group 4 transition metal and X is a halogen); and (c) preparing the transition metal compound represented by Chemical Formula 1 by a method comprising sequentially drying the product of step (b) and then mixing it with a solvent. may have been

[Formula 8]

In Formula 8,

Cp is an organic compound in which the number of coordination sites capable of coordinating with a transition metal is 1;

A is Si or C;

Z is -O-, -S-, -NB ₁ - or -PB ₁ -, and B ₁ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a carbon number 1 to 20 silylhydrocarbyl groups;

H is hydrogen;

Y ₁ and Y ₂ are each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms.

In Formula 8, Cp, A, Z, Y ₁ and Y ₂ are as defined in Formula 1 above.

The alkyl bromide metal compound may be at least one selected from the group consisting of methyl magnesium bromide, ethyl magnesium bromide, and isopropyl magnesium bromide.

Example

Hereinafter, the present invention will be described in more detail based on the following examples. These examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1

1) Preparation of catalyst composition

(1) Preparation of ligand A

A 1-benzothiophene solution was prepared by dissolving 4.0 g (30 mmol) of 1-benzothiophene in THF. Then, 14 mL (36 mmol, 2.5 M in hexane) of n-BuLi solution and 1.3 g (15 mmol) of CuCN were added to the 1-benzothiophene solution. Subsequently, 3.6 g (30 mmol) of tigloyl chloride was slowly added to the solution at -80°C, and the resulting solution was stirred at room temperature for about 10 hours.

Then, the reaction was quenched by pouring 10% HCl into the solution, and the organic layer was separated with dichloromethane to form a beige solid (2E)-1-(1-benzothien-2-yl)-2- This gave methyl-2-buten-1-one.

¹ H NMR (CDCl ₃ ): 7.85-7.82 (m, 2H), 7.75 (m, 1H), 7.44-7.34 (m, 2H), 6.68 (m, 1H), 1.99 (m, 3H), 1.92 (m , 3H)

A solution of 5.0 g (22 mmol) of (2E)-1-(1-benzothien-2-yl)-2-methyl-2-buten-1-one prepared above in 5 mL of chlorobenzene was stirred vigorously. While gently stirring, 34 mL of sulfuric acid was slowly added to the solution. Then, the solution was stirred at room temperature for about 1 hour. Thereafter, ice water was poured into the solution, and the organic layer was separated with an ether solvent to obtain 1,2-dimethyl-1,2-dihydro-3H-benzo[b]cyclopenta[d]thiophen-3-one as a yellow solid. 4.5 g (91% yield) was obtained.

¹ H NMR (CDCl ₃ ): 7.95-7.91 (m, 2H), 7.51-7.45 (m, 2H), 3.20 (m, 1H), 2.63 (m, 1H), 1.59 (d, 3H), 1.39 (d , 3H)

Dissolve 2.0 g (9.2 mmol) of 1,2-dimethyl-1,2-dihydro-3H-benzo[b]cyclopenta[d]thiophen-3-one in a mixed solvent of 20 mL of THF and 10 mL of methanol. To the solution was added 570 mg (15 mmol) of NaBH ₄ at 0°C. Then, the solution was stirred at room temperature for about 2 hours. Thereafter, HCl was added to the solution to adjust the pH to 1, and the organic layer was separated with an ether solvent to obtain an alcohol intermediate.

A solution was prepared by dissolving the alcohol intermediate in toluene. Then, 190 mg (1.0 mmol) of p-toluenesulfonic acid was added to the solution, and the mixture was refluxed for about 10 minutes. The obtained reaction mixture was separated by column chromatography to give an orange-brown color, and 1.8 g (9.0 mmol, 98 g of liquid 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (ligand A) % yield) was obtained.

^1H NMR (CDCl ₃ ): 7.81 (d, 1H), 7.70 (d, 1H), 7.33 (t, 1H), 7.19 (t, 1H), 6.46 (s, 1H), 3.35 (q, 1H), 2.14 (s, 3H), 1.14 (d, 3H)

(2) Preparation of ligand B

Put 13 mL (120 mmol) of t-butylamine and 20 mL of ether solvent in a 250 mL Schlenk flask, and (6-tert-butoxyhexyl) dichloro ( 16 g (60 mmol) of methyl)silane and 40 mL of ether solvent were added to prepare a t-butylamine solution and a (6-tert-butoxyhexyl)dichloro(methyl)silane solution, respectively. Then, after cooling the t-butylamine solution to -78 ° C, (6-tert-butoxyhexyl) dichloro (methyl) silane solution was slowly injected into the cooled solution, and stirred at room temperature for about 2 hours did The resulting white suspension is filtered to give an ivory color, and the liquid 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methyl Silanamine (ligand B) was obtained.

^1H NMR (CDCl ₃ ): 3.29 (t, 2H), 1.52-1.29 (m, 10H), 1.20 (s, 9H), 1.16 (s, 9H), 0.40 (s, 3H)

(3) cross-linking of ligands A and B

A Ligand A solution was prepared by adding 1.7 g (8.6 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (ligand A) to a 250 mL Schlenk flask and adding 30 mL of THF. did After cooling the Ligand A solution to -78°C, 3.6 mL (9.1 mmol, 2.5 M in hexane) of an n-BuLi solution was added to the Ligand A solution, and stirred overnight at room temperature to obtain a purple-brown color. A brown) colored solution was obtained. Solution A was prepared by replacing the purple-brown solution with toluene as a solvent and injecting a solution in which 39 mg (0.43 mmol) of CuCN was dispersed in 2 mL of THF was added to the solution.

Meanwhile, a solution prepared by injecting 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilanamine (ligand B) and toluene into a 250 mL Schlenk flask B was cooled to -78 °C. Solution A previously prepared was slowly injected into the cooled solution B. And the mixture of solutions A and B was stirred overnight at room temperature. And, by filtering and removing the produced solid, 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2 -Dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1-methylsilanamine (a cross-linked product of ligands A and B) yielded 4.2 g (>99% yield).

In order to confirm the structure of the cross-linked product of ligands A and B, the cross-linked product was lithiated at room temperature, and then a H-NMR spectrum was obtained using a sample dissolved in a small amount of pyridine-D5 and CDCl ₃ .

¹ H NMR (pyridine-D5 and CDCl ₃ ): 7.81 (d, 1H), 7.67 (d, 1H), 7.82-7.08 (m, 2H), 3.59 (t, 2H), 3.15 (s,6H), 2.23 -1.73 (m, 10H), 2.15 (s, 9H), 1.91 (s, 9H), 1.68 (s, 3H)

(4) Preparation of transition metal compounds

The ligand compound (3.47 g, 7.354 mmol) prepared in step (3) and 25 mL of toluene were put in a 250 mL Schlenk flask and stirred first. At -40 °C, n-BuLi (6.0 mL, 15.08 mmol, 2.5 M in THF) was added and stirred at room temperature overnight. Thereafter, MeMgBr (6.13 mL, 18.39 mmol, 3.0 M in diethyl ether) was slowly added dropwise at -40 °C, and then TiCl ₄ (THF) ₂ (7.35 mL, 7.354 mmol, 1.0 M in toluene) was added sequentially to room temperature. was stirred overnight.

Example 1

The reaction mixture stirred in (4) of Preparation Example was dried under vacuum and then filtered through a filter (G3) in the presence of a solvent of hexane (0.1 M). 3.0 equivalent of SiMe ₂ Cl ₂ based on the transition metal compound was added to the mixture filtered at 25 °C, and the solvent was removed by vacuum drying, and then filtered through a filter (G3) under a hexane (0.1 M) solvent for a second time. Then, the solvent was dried to obtain a sticky liquid product.

Example 2

A liquid product was obtained in the same manner as in Example 1, except that 1.0 equivalent of SiMe ₂ Cl ₂ was added at 0 °C in Example 1.

Comparative Example 1

The reaction mixture stirred in (4) of Preparation Example was dried under vacuum and then filtered through a filter (G3) in the presence of a solvent of hexane (0.1 M) to obtain a product.

Comparative Example 2

The product (filtered mixture) obtained in Comparative Example 1 was mixed with a hexane (0.1 M) solvent, filtered through a celite filter, and then the product was dried through solvent drying.

Comparative Example 3

A liquid product was obtained in the same manner as in Example 1, except that 3.0 equivalents of trimethylsilylchloride (TMSCl) was added at 25° C. in place of SiMe ₂ Cl ₂ in Example 1.

Comparative Example 4

A liquid product was obtained in the same manner as in Example 1, except that 3.0 equivalents of trimethylsilylchloride (TMSCl) was added at 40 ° C instead of SiMe ₂ Cl ₂ in Example 1.

Comparative Example 5

A liquid product was obtained in the same manner as in Example 1, except that 3.0 equivalents of trimethylsilyl bromide (TMSBr) was added at 25° C. in place of SiMe ₂ Cl ₂ in Example 1.

Comparative Example 6

A liquid product was obtained in the same manner as in Example 1, except that 1.0 equivalent of TMSBr was added at 40° C. in place of SiMe ₂ Cl ₂ in Example 1.

Experimental Example: Measurement of Inorganic Content

Inorganic content (Ti, Mg) was measured using ICP-OES (Optima 7300DV), and measured according to the following procedure.

1) Accurately measure about 0.01 g of sample into the vial.

2) Add 2 mL of concentrated sulfuric acid to the vial containing the sample.

3) Carbonize the sample by heating it on a hot plate.

4) Add 0.02 g of concentrated nitric acid in a hot state.

5) Repeat this process until the color of the solution becomes pale yellow.

6) When white smoke is no longer present in the sample, dry it.

7) After adding 1 mL of nitric acid/0.02 g of hydrogen peroxide 10 times, heat to decompose.

8) When the sample is clearly and completely decomposed, add 300 μL of 1000 mg/kg internal standard Sc, dilute with 30 mL of ultrapure water, and filter.

9) Measured by ICP-OES (Perkin Elmer).

- Create a calibration curve with standard solutions STD1 (Ti 50 μg/mL, Mg 1 μg/mL) and STD2 (Ti 100 μg/mL, Mg 5 μg/mL).

- Analysis conditions: Plasma gas 10 L/min, Auxiliary gas 0.2 L/min, Nebulizer gas 0.8 L/min

RF power is 1300 WATTS, sample flow rate is 1.50 mL/min, measured by radial view

Solvent (M) Additives (Equivalents) T (℃) reaction time
(h) Ti
(weight%) Mg
(weight%) Example 1 Hexane (0.1M) SiMe ₂ Cl ₂ (3) 25 20 6.6 0.02 Example 2 Hexane (0.1M) SiMe ₂ Cl ₂ (1) 0 20 6.9 0.04 Comparative Example 1 - - - 7.4 1.7 Comparative Example 2 Hexane (0.1M) - 25 20 6.6 0.41 Comparative Example 3 Hexane (0.1M) TMSCl (3) 25 20 7.0 0.38 Comparative Example 4 Hexane (1.0M) TMSCl (3) 40 20 7.8 0.45 Comparative Example 5 Hexane (0.1M) TMSBr (3) 25 20 6.9 0.26 Comparative Example 6 Hexane (1.0M) TMSBr (1) 40 20 7.2 0.40

In Table 1, the content of Ti represents the content of Ti included in the transition metal compound, and the content of Mg represents the content of inorganic substances as impurities. As can be seen from Table 1, it can be confirmed that Examples 1 and 2 show a lower inorganic content than Comparative Examples 1 to 6, thereby effectively reducing inorganic substances included in the catalyst composition.

Claims (16)

(1) firstly filtering a mixture including a catalyst composition including a transition metal compound represented by Chemical Formula 1 and an inorganic material, and a solvent;
(2) adding two or more halogen-substituted silane compounds to the filtration mixture obtained in the primary filtration step and reacting at a temperature range of -20 ° C to 60 ° C; and
(3) drying the reaction mixture after completion of the reaction in step (2), mixing it with a solvent for filtration, and then performing secondary filtration;
Method for removing inorganics in the catalyst composition, wherein the solvent and the solvent for filtration are mixed in an amount of 15 to 50 times the total weight of the solid content in the catalyst composition, respectively:
[Formula 1]

In Formula 1,
Cp is an organic compound in which the number of coordination sites capable of coordinating with a transition metal is 1;
A is Si or C;
Z is -O-, -S-, -NB ₁ - or -PB ₁ -, and B ₁ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a carbon number 1 to 20 silylhydrocarbyl groups;
M is a Group 4 transition metal;
Q ₁ and Q ₂ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a silyl hydrocarbyl group having 1 to 20 carbon atoms;
Y ₁ and Y ₂ are each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms.
According to claim 1,
A method for removing inorganic substances in a catalyst composition, wherein Cp is any one of ligands represented by Formulas 2 to 5:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,
R ₁ to R ₆ are each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbyloxy group having 1 to 30 carbon atoms.
According to claim 2,
R ₁ to R ₄ are each independently hydrogen or a hydrocarbyl group having 1 to 10 carbon atoms;
Wherein R ₅ and R ₆ are each independently a hydrocarbyl group having 1 to 10 carbon atoms, a method for removing inorganic substances in the catalyst composition.
According to claim 1,
Wherein Z is -NB ₁ -, and B ₁ is a hydrocarbyl group having 1 to 10 carbon atoms.
According to claim 1,
Method for removing inorganics in a catalyst composition, wherein the transition metal compound represented by Formula 1 is a compound represented by Formula 6 below:
[Formula 6]

R ₁ to R ₆ are each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbyloxy group having 1 to 30 carbon atoms;
A is Si or C;
M is a Group 4 transition metal;
Q ₁ and Q ₂ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a silylhydrocarbyl group having 1 to 20 carbon atoms;
Y ₁ and Y ₂ are each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms;
B ₁ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a silyl hydrocarbyl group having 1 to 20 carbon atoms.
According to claim 5,
R ₁ to R ₄ are hydrogen;
R ₅ and R ₆ are alkyl having 1 to 10 carbon atoms;
The Y ₁ and Y ₂ are each independently an alkyl having 1 to 10 carbon atoms or an alkoxyalkyl having 2 to 20 carbon atoms;
The Q ₁ and Q ₂ are each independently an alkyl having 1 to 10 carbon atoms;
Wherein B ₁ is an alkyl having 1 to 10 carbon atoms, a method for removing inorganic substances in a catalyst composition.
According to claim 1,
The primary filtration is performed using a glass filter, a method for removing inorganic substances in the catalyst composition.
According to claim 1,
The secondary filtration is performed using a glass filter or a celite filter, a method for removing inorganic substances in the catalyst composition.
According to claim 1,
The process of adding a silane-based compound to the filtration mixture of step (2) is made in the temperature range of 0 ℃ to 25 ℃, method for removing inorganics in the catalyst composition.
According to claim 1,
The method of removing inorganics in the catalyst composition, wherein the solvents in step (1) and step (3) are each independently a hydrocarbon solvent.
According to claim 10,
Wherein the hydrocarbon solvent is at least one selected from the group consisting of hexane, heptane, 2-methylpentane and pentane.
According to claim 1,
A method for removing inorganics in the catalyst composition, wherein the inorganics are Mg.
According to claim 1,
The silane compound substituted with two or more halogens includes a compound represented by Formula 7 below, a method for removing inorganic substances in a catalyst composition.
[Formula 7]

In Formula 7,
R ₇ and R ₈ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyloxy group having 1 to 20 carbon atoms;
X ₁ and X ₂ are each independently halogen.
According to claim 1,
The method of removing inorganic substances in the catalyst composition, wherein the silane compound substituted with two or more halogens includes dimethyldichlorosilane.
According to claim 1,
(a) reacting a ligand compound represented by Formula 8 with an organolithium compound in a reaction solvent;
(b) adding an alkyl bromide metal compound dropwise, then adding MX ₂ compound and then stirring (M is a Group 4 transition metal and X is a halogen); and
(c) in a catalyst composition further comprising the step of preparing the transition metal compound represented by Formula 1 by a manufacturing method comprising sequentially mixing the product of step (b) with a solvent after drying the product. Mineral Removal Methods:
[Formula 8]

In Formula 8,
Cp is an organic compound in which the number of coordination sites capable of coordinating with a transition metal is 1;
A is Si or C;
Z is -O-, -S-, -NB ₁ - or -PB ₁ -, and B ₁ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, or a carbon number 1 to 20 silylhydrocarbyl groups;
H is hydrogen;
Y ₁ and Y ₂ are each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms.
According to claim 15,
Wherein the alkyl brominated metal compound is at least one selected from the group consisting of methyl magnesium bromide, ethyl magnesium bromide and isopropyl magnesium bromide.