KR20190050436A - Method for producing catalyst composition for polymerization of high density polyolefin - Google Patents

Abstract

The present invention provides a method for manufacturing a catalyst composition for olefin polymerization, the catalyst composition for olefin polymerization, and a method for polymerizing olefins comprising a use of the catalyst composition. The catalyst composition of the present invention comprises a magnesium compound, a transition metal compound, and dialkoxybenzene. The catalyst has a constant shape, a small particle size, and a narrow particle size distribution. In addition, an olefin polymer obtained after polymerization is also highly active, has a narrow molecular weight distribution, and has a low generation of fine powder.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a catalyst composition for polymerization of a high-density polyolefin,

The present invention relates to a method for preparing a catalyst composition for polymerization of a high-density polyolefin having a narrow molecular weight distribution, and to a catalyst composition prepared thereby. More specifically, the present invention relates to a process for producing a high-density polyolefin which comprises a dialkoxybenzene as an internal electron donor and which has a small catalyst particle size, a uniform shape, high activity in polyolefin polymerization reaction, narrow molecular weight distribution, And to a catalyst composition prepared thereby.

Ziegler-Natta catalysts have been used to polymerize olefins such as ethylene and propylene. The shape and size of the polymers polymerized using a Ziegler-Natta catalyst are determined by the shape and performance of the catalyst used. Therefore, the particle size and distribution of the catalyst are very important in order to increase the productivity, uniform the particle size of the polymer, and produce a polymer favorable for product molding. In addition, polymer properties produced after polymerization are mostly determined according to the structure constituting the catalyst.

The catalyst for high density polyolefin polymerization is a catalyst which is highly active, and has a high apparent density and a low generation of fine powder of the resulting polymer. Also, the polymer produced after polymerization may have a narrow or wide molecular weight distribution. The present invention relates to a catalyst composition for high-density polyolefin polymerization having a narrow molecular weight distribution.

Polymer rich in fine particles accumulates in the polymerization equipment in the olefin polymerization process, causing many problems. Specifically, the pores for the flow of the drying apparatus used when drying the polymer obtained in the slurry process are likely to be clogged by the fine particles and cause various problems such as deteriorating the ability to transport the polymer product.

As a method of producing such a catalyst, a recrystallization method has been widely used. A catalyst preparation method using a precursor is also known. Catalysts using such precursors are described in Patent Registration No. 10-1716507. The catalyst is a catalyst composition comprising an internal electron donor (dialkoxybenzene) in a precursor consisting of magnesium and a titanium compound, and the use of the catalyst composition for propylene polymerization is disclosed. A catalyst having such a precursor can produce a polymer having a narrow molecular weight distribution upon polymerization of propylene, but has a low catalytic activity.

In addition, in Japanese Patent Application Laid-Open No. 10-2012-0051673, a catalyst is synthesized from a spherical support made of MgCl ₂ / EtOH, and an external electron donor (dialkoxybenzene) is added during polymerization to polymerize ethylene to obtain a polymer having a narrow molecular weight distribution ≪ / RTI > However, the catalyst using the spherical carrier has a very low activity in the polymerization of ethylene, and the catalyst cost is too high, which makes it difficult to commercialize it.

Therefore, there is a need for a recrystallization catalyst that exhibits high activity during polyolefin polymerization and can produce a polymer having a high molecular weight distribution and a high bulk density, and a small molecular weight distribution.

Korean Patent No. 10-1716507 Korean Patent Publication No. 10-2012-0051673

The present invention provides a method for producing a catalyst composition for high density polyolefin polymerization, which is capable of synthesizing an ethylene polymer having a constant shape, a narrow particle size distribution and a small particle diameter, as well as a high apparent density and a narrow molecular weight distribution .

The present invention also provides a catalyst composition for high-density polyolefin polymerization.

The present invention also provides a process for producing a polyolefin comprising the step of polymerizing or copolymerizing an olefin monomer in the presence of the catalyst for polymerizing a high-density polyolefin.

The present invention

(A) dissolving a magnesium compound in a solvent containing an alcohol and a first hydrocarbon solvent having 5 to 25 carbon atoms to prepare a magnesium compound solution;

(B) reacting the magnesium compound solution with dialkoxybenzene; And

(C) reacting the product of the step (B) with a transition metal compound in the presence of a second hydrocarbon solvent having 6 to 25 carbon atoms. The present invention also provides a method for producing a catalyst composition for high density polyolefin polymerization.

The present invention provides a catalyst composition for high-density polyolefin polymerization comprising a magnesium compound, a transition metal compound, and an internal electron donor.

The catalyst composition according to an embodiment of the present invention is a catalyst composition containing a dialkoxybenzene as an internal electron donor and having a small catalyst particle size and a uniform shape. The high-density olefin polymer obtained by polymerization using such a catalyst composition is characterized in that it has a narrow molecular weight distribution and low generation of fine powder. Therefore, such a high density olefin polymer has a narrow molecular weight distribution, which is advantageous for molding an injection product, and has a low fine powder content, so that the product surface after film and blow molding provides excellent results.

1 is an SEM image of the catalyst composition synthesized in Example 1. Fig.

Any numerical ranges listed herein include all values between a low value and a high value, increasing by one unit, under the condition that there is a difference of at least two units between any low value and any high value.

The term "composition" as used herein includes compositions as well as mixtures of materials comprising the degradation products and reaction products formed from the materials of the compositions.

The term " polymer " as used herein is a polymeric compound prepared by polymerization of the same or different types of monomers. The term " polymer " as used herein includes homopolymers and copolymers.

The present invention

(A) dissolving a magnesium compound in a solvent containing an alcohol and a first hydrocarbon solvent to prepare a magnesium compound solution;

(B) reacting the magnesium compound solution with an inner electron donor; And

(C) reacting the product of the step (B) with a transition metal compound in the presence of a second hydrocarbon solvent having 6 to 25 carbon atoms. The present invention also provides a process for producing a catalyst composition for high-density polyolefin polymerization.

The present invention relates to a process for producing a polymer electrolyte membrane, which comprises obtaining a homogeneous solution containing a magnesium compound, an alcohol, a first hydrocarbon solvent and an internal electron donor by charging a transition metal compound in the presence of a second hydrocarbon solvent and reacting, The present invention provides a catalyst composition for high density polyolefin polymerization.

In one embodiment of the invention, the internal electron donor is a compound represented by the formula:

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² are each independently linear C ₁ -C ₁₀ alkyl, branched C ₃ -C ₁₀ alkyl or cyclic C ₃ -C ₁₀ alkyl.

Specifically, the internal electron donor may have a structure in which R ¹ and R ² in Formula 1 are the same as or different from each other, and are each independently methyl, ethyl, propyl, isopropyl, butyl, sec- ≪ / RTI >

More specifically, the internal electron donor is selected from the group consisting of 1,2-di-methoxybenzene, 1,2-di-ethoxybenzene, 1,2-dibutoxybenzene Di-sec-butoxybenzene, 1,2-di-butoxybenzene, 1,2-di-sec- -tert-butoxybenzene). < / RTI >

In one embodiment of the present invention, the internal electron donor is used in an amount of 0.01 to 0.3 mol based on 1 mol of the magnesium compound. If it is out of the above range, the activity of the catalyst may be lowered by interfering with the formation of transition metal particles to be supported on the produced catalyst.

Specific examples of the magnesium compound include magnesium halide, dialkoxymagnesium, alkylmagnesium halide, alkoxymagnesium halide or aryloxymagnesium halide, and magnesium halide is more preferable because it increases the activity of the catalyst. In one embodiment, the magnesium compound is selected from the group consisting of magnesium halide, dialkoxymagnesium, alkyl magnesium halides of 1 to 20 carbon atoms, alkoxy magnesium halides of 1 to 20 carbon atoms, and aryloxy magnesium halides of 6 to 20 carbon atoms. Or more.

Specifically, the magnesium halide compound may be a compound that does not have reducibility such as magnesium chloride, magnesium dichloride, magnesium fluoride, magnesium bromide, magnesium iodide, phenoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, Among them, use of magnesium dichloride is preferred because it exhibits stable and high activity in terms of structure and coordination with the transition metal compound, which is the main active metal.

In the present invention, the alcohol can be used without limitation as long as it is an alcohol known to be used in the production of a Ziegler-Natta catalyst for polyethylene polymerization. Specific examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, neopentanol, cyclopentanol, Aliphatic or alicyclic alcohols such as decanol, dodecanol, 2-methylpentanol, 2-ethylbutanol and 2-ethylhexanol; Aromatic alcohols such as cyclohexanol, methylcyclohexanol, and alpha -methylbenzyl alcohol can be used. Of these, aliphatic or alicyclic alcohols or alcohols having 2 or more carbon atoms are preferably used, and 2-ethyl 1-hexanol It is more preferable to use it.

In the present invention, the alcohol plays a role of improving the catalytic performance by dissolving the magnesium compound and bonding with the magnesium compound in the catalyst to form suitable pores. In one embodiment of the invention, the alcohol is used in an amount of 3 to 4 moles per mole of the magnesium compound. When the alcohol is used in an amount less than 3 mol based on 1 mol of the magnesium compound, the activity is low when the alcohol is added. When the alcohol is used in an amount exceeding 4 mol, the supporting ratio of the transition metal compound decreases and the catalyst particle size becomes large.

In the present invention, the first hydrocarbon solvent serves to facilitate the dispersion of the magnesium compound. When the first hydrocarbon solvent is not used, the magnesium compound may form a hard lump on contact with the alcohol and may be difficult to dissolve.

Specific examples of the first hydrocarbon solvent include aliphatic or alicyclic hydrocarbons having 5 to 25 carbon atoms, and most preferred are aliphatic or alicyclic hydrocarbon solvents having 6 to 17 carbon atoms. More specific examples include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, tetradecane, and mineral oils having 5 to 25 carbon atoms (e.g., Cas No. 8042-47-5); Alicyclic hydrocarbons such as cyclic hexane, cyclic octane, methyl cyclic pentane and methyl cyclic hexane; And aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene.

If the amount of the first hydrocarbon solvent is too small or too large, it is difficult to control the catalyst particle size, and it may be difficult to control the transition metal compound and the donor supporting ratio. Accordingly, it is appropriate that the first hydrocarbon solvent is used in an amount of 2 to 4 mol based on 1 mol of the magnesium compound. The amount of the first hydrocarbon solvent used is less than 2 mol based on 1 mol of the magnesium compound and the magnesium compound is not well dispersed. On the other hand, when the amount of the first hydrocarbon solvent is more than 4 mol, the catalyst particle diameter and the transition metal compound- .

In an embodiment of the present invention, specific examples of the second hydrocarbon solvent having 6 to 25 carbon atoms include aliphatic or alicyclic hydrocarbons having 5 to 25 carbon atoms. Among them, aliphatic or alicyclic hydrocarbons having 6 to 17 carbon atoms Lt; / RTI > hydrocarbon solvents are preferred. More specific examples include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, tetradecane, and mineral oils having 5 to 25 carbon atoms (e.g., Cas No. 8042-47-5); Alicyclic hydrocarbons such as cyclic hexane, cyclic octane, methyl cyclic pentane and methyl cyclic hexane; And aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene. In one embodiment, the second hydrocarbon solvent is hexane.

In one embodiment of the process of the invention, dilution with a second hydrocarbon solvent is used to adjust the particle size of the resulting catalyst. When the second hydrocarbon solvent is not added, the catalyst particle diameter may be as small as 1 占 퐉 or less, and when the second hydrocarbon solvent is excessively added, the catalyst particle size may increase and the catalyst performance may deteriorate. The second hydrocarbon solvent used in the reaction is used in an amount of 3 to 20 mol or 5 to 10 mol based on 1 mol of the magnesium compound. When the amount of the second hydrocarbon solvent is more than 20 mol, the catalyst particle size is increased. In general, in the case of recrystallization catalyst, the transition metal distribution acting as pore volume (pore volume) and active point varies depending on the catalyst particle size, and the apparent density of the polymer and the activity changes. As a result, the activity is lowered when the catalyst particle size is increased. Further, when the second hydrocarbon solvent is not used or when it is used in an amount of less than 3 mol, the catalyst is difficult to produce due to a small particle size of the catalyst and too many fine particles are formed after the production of the polymer.

In one embodiment of the present invention, the transition metal compound may include a compound of the following formula (2).

(2)

MX _n (OR ³ ) _{4 -n}

In Formula 2,

M is selected from the group consisting of transition metal elements of groups IVB, VB and VIB of the periodic table,

X is halogen,

R ³ is an alkyl group having 1 to 10 carbon atoms,

n is from 0 to 4;

In one embodiment, the transition metal compound is _{TiCl 4, TiBr 4, TiCl 3} , Ti (OC 2 H 5) 3 Cl, Ti (OC 2 H 5) 3 Br, Ti (OC 3 H 7) 2 Cl ₂ , Ti (OC ₆ H ₅ ) ₂ Cl ₂ , and Ti (OC ₂ H ₅ ) Cl ₃ . Mixtures of such transition metal compounds may also be used.

The transition metal compound may be used in an amount of 3 to 10 mol based on 1 mol of the magnesium compound. When the amount of the transition metal compound used is less than 3 mol based on 1 mol of the magnesium compound, the activity of the transition metal compound may be lowered, and if the amount of the transition metal compound is more than 10 mol, Thereby reducing the pores in the catalyst, decreasing the activity, increasing the metal residual ratio in the polymer, and increasing the human hazard and environmental pollution.

In one embodiment of the invention, step (B) of the process may be carried out at from 70 to 130 < 0 > C. In another embodiment of the present invention, the step (B) is carried out at 110 to 130 占 폚.

In one embodiment of the invention, step (C) of the process can be carried out at from -20 to 0 < 0 > C. In other embodiments, the temperature may be between -15 and 0 ° C. The transition metal compound may be added to the magnesium mixture maintained at the temperature. That is, the transition metal compound is introduced at -20 to 0 ° C, and the catalyst particle size varies depending on the temperature at which the transition metal compound is introduced. When the transition metal compound is added at a temperature of 0 ° C or higher, the catalyst particle size is small, the catalyst particle size distribution is widened, the catalyst hardness is lowered, the apparent density is lowered, and the generation of fine particles may be increased. On the other hand, when the transition metal compound is added at -20 ° C or lower, the catalyst particle size may be large and the catalyst particle size distribution may be narrowed.

In one embodiment of the present invention, the dropping time of the transition metal compound is suitably 1 to 4 hours. If the addition time of the transition metal compound is less than 1 hour, the temperature rises due to a violent reaction, thereby widening the catalyst particle size distribution. If the addition time exceeds 4 hours, the catalyst particle size becomes large. When the particle size distribution of the catalyst is widened, the particle size distribution of the polymer produced after the polymerization is widened, the apparent density is lowered, and the operation conditions are difficult to form in the product molding, which leads to a disadvantage that the productivity is poor.

In one embodiment of the invention, the addition of the transition metal compound is carried out for 1 to 4 hours under agitation at a stirring rate of 40 to 600 rpm. If the stirring speed is too low, the catalyst particles produced after bonding with the transition metal compound may agglomerate to increase the particle size. Also, if the stirring speed is too high, the catalyst particles may become smaller than the target size, which is not preferable.

In one embodiment of the present invention, the introduction of the transition metal compound takes place slowly because it can prevent temperature build-up and catalyst aggregation. In addition, the temperature may be gradually increased for a certain period of time, for example, for 30 to 90 minutes, for example, in consideration of the temperature rise after completion of the addition of the transition metal compound. Normally, it is appropriate to raise the temperature to 0.1 to 0.5 占 폚 / min. If the temperature suddenly rises suddenly, the catalyst may break or clump and the shape of the catalyst may change. Thereafter, the temperature is gradually raised to 1 deg. C / min to reach 70 deg. C to 80 deg. At this time, if the temperature is raised gradually, the catalyst can be prevented from breaking or aggregation, and the rapid reaction due to temperature rise can be controlled. Thereafter, the material in the catalyst is maintained for 2 to 3 hours (for example, maintaining the reaction at 70 to 80 DEG C) so that stable bonding and reaction can be performed.

According to one embodiment of the present invention, when a transition metal compound is added to a homogeneous mixture containing magnesium, a catalyst having excellent catalyst shape, particle size, and polymerization activity is produced. On the other hand, when a homogeneous mixture containing magnesium is added to a transition metal compound, a catalyst having poor catalyst shape and particle size and low activity is produced.

The present invention further provides, in addition to the above steps (A) to (C), a process for producing a catalyst composition for high-density polyolefin polymerization, which comprises reacting (D) an alkylaluminium compound represented by the following formula .

(3)

R ⁴ _n AlX _{3 -n}

In Formula 3,

R ⁴ is an alkyl group having 1 to 8 carbon atoms,

X is halogen,

n is from 0 to 3;

The alkylaluminium compound can act as a cocatalyst and can form active sites by reducing the transition metal compound, thereby enhancing catalytic activity. In particular, when the transition metal compound is first reacted and the alkylaluminium compound is reacted, transition metal active sites can be more evenly distributed, so that polyethylene having a higher catalytic activity and a broad molecular weight distribution and improved processability can be produced.

Specific examples of such alkylaluminium compounds include triethylaluminium, trimethylaluminium, triisopropylaluminium, trioctylaluminium, diethylaluminium chloride, diethylaluminium bromide, diethylaluminium iodide, di Ethylaluminium fluoride, ethylaluminium dichloride, dimethylaluminium chloride, methylaluminum dichloride and the like can be used.

The process for preparing the polyolefin of the present invention does not use additional external electron donors.

The present invention also provides a catalyst composition for high-density polyolefin polymerization.

The present invention relates to a process for the preparation of an internal electron donor which is obtained by heating a homogeneous solution comprising a magnesium compound, an alcohol, a first hydrocarbon solvent and an internal electron donor in the presence of a second hydrocarbon solvent and then reacting with a transition metal compound at a low temperature, By weight based on the total weight of the polyolefin composition.

The catalyst composition according to the present invention may comprise a magnesium compound, a transition metal compound and an internal electron donor. In one embodiment, the catalyst composition according to the present invention comprises a magnesium compound, a transition metal compound and a dialkoxybenzene.

The internal electron donor has a direct influence on the molecular weight distribution, the catalyst particle size, the activity and the hydrogen reactivity, so an appropriate content in the catalyst is required.

In one embodiment, the catalyst composition may include an internal electron donor in an amount of 2.0 to 5.0 wt% based on the total weight of the composition. If the content is less than 2.0% by weight, a polymer having a broad molecular weight distribution is produced. If the content is more than 5.0% by weight, the catalyst particle size is increased, the catalytic activity is low, and hydrogen reactivity is poor.

In one embodiment, the catalyst composition may comprise from 9.0 to 25.0% by weight of magnesium. If the magnesium content is less than 9.0 wt%, the shape of the catalyst moves away from the spherical shape, and the supporting ratio of the transition metal becomes relatively high, resulting in an excessively high activity. When the activity is excessively high, there is a disadvantage that the produced polymer particle size increases and the apparent density becomes low. On the other hand, when the magnesium content exceeds 25.0% by weight, the supporting ratio of the transition metal compound may be lowered and the activity may be lowered.

Also, the catalyst composition may contain 3.0 to 7.0% by weight of transition metal. When the transition metal in the catalyst composition is contained in an amount of 3.0 wt% or less, ethylene polymerization activity is lowered, and when the transition metal is contained in an amount of 7.0 wt% or more, the polymer apparent density is lowered and the productivity is lowered.

In one embodiment, the catalyst composition may comprise from 10.0 to 16.0% by weight of an alcohol compound. When the amount of the alcohol compound in the catalyst composition is less than 10.0 wt%, the support ratio of the transition metal in the catalyst is lowered. When the amount of the alcohol compound is more than 16.0 wt%, the catalyst particle size becomes larger and the catalyst hardness becomes lower.

In addition, the catalyst composition may contain 1.0 to 10.0 wt% of the second hydrocarbon solvent. If the amount of the second hydrocarbon solvent in the catalyst composition is less than 1.0% by weight, the performance of the catalyst is deteriorated when stored for a long period of time. When the amount of the second hydrocarbon solvent is more than 10.0% by weight, handling of the catalyst may be difficult.

The catalyst composition according to the present invention is a catalyst composition having a constant shape with an average particle size of 3 to 8 탆 and a particle size distribution index of 0.5 to 1.5. In one embodiment, the catalyst has an average particle size of 4 to 6 占 퐉 or 4 to 5 占 퐉. The catalyst particle size and shape are determined according to the catalyst preparation reaction conditions.

In one embodiment of the present invention, a transition metal compound is slowly added dropwise to a mixture obtained by diluting a magnesium compound, an internal electron donor and an alcohol in a second hydrocarbon solvent to bring an average particle size of 3 to 8 占 퐉 and a particle size distribution index of 0.5 to 1.5 Lt; RTI ID = 0.0 > catalyst < / RTI > However, when the mixture containing the magnesium compound is reversed to titanium, the catalyst particle size can be increased, the activity after polymerization is low, and a polymer having a low bulk density is produced.

The catalyst composition of the present invention may have an apparent shape having a small catalyst particle size and a constant shape while containing an internal electron donor.

According to another embodiment of the present invention, there is provided a process for producing a high-density polyolefin polymer composition comprising the steps of polymerizing or copolymerizing an olefin monomer in the presence of a catalyst composition prepared by the above- A process for producing a polyolefin can be provided.

The olefin-based monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-tetradecene, 1-hexadecene, 1-aidocene, norbornene, norbornian, ethylidene norbornene, phenyl novodene, vinyl novodene, dicyclopentadiene, - pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, or mixtures thereof.

In one embodiment of the present invention, the olefin polymer polymerized by the catalyst composition exhibits a molecular weight distribution MwD (Mw / Mn) of 6 or less, such as 3 to 6, and a melt flow index (MFRR) of 35 or less. In one embodiment, the melt flow ratio (MI21.6 / MI2.16) of the olefin polymer is from 20 to 35. In addition, the olefin polymer is characterized by high bulk density and low generation of fine powder. In one embodiment, the olefin polymer is high density polyethylene.

The individual component content of the catalyst composition herein is based on the total weight of the catalyst composition.

Example

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. However, this is provided as an example of the invention, and the scope of the invention is not limited thereto in any sense.

Example  1: Preparation of Catalyst Composition and Polyethylene

One) Preparation of catalyst composition

3.0 g of magnesium dichloride, 16 ml of 2-ethyl-hexanol and 15 ml of decane were charged into a 0.5-liter pressure-resistant glass reactor equipped with a stirrer and an oil circulation heater under nitrogen atmosphere, and stirred at 80 rpm at 300 rpm Respectively. The temperature was raised to 130 ° C to completely dissolve the magnesium dichloride. When the solution became homogeneous, the reaction was maintained for 1 hour and 0.4 ml of 1,2-dimethoxybenzene was added. After the addition, the mixture was kept at the same temperature for 1 hour, cooled to room temperature, and 64 ml of hexane was added. After stirring for 30 minutes, the temperature was lowered to 0 ° C or less. When the temperature was maintained at 0 캜, 16 ml of titanium tetrachloride was slowly added while stirring at 600 rpm. When the addition was completed, the temperature was raised to 70 ° C. and maintained at the same temperature for 1 to 5 hours. Thereafter, the stirring was stopped by lowering the temperature to 45 ° C., and the resulting solid particles were precipitated. Thereafter, the supernatant was removed, washed with 2 liters of hexane five times, and dried to obtain a catalyst composition.

2) Polyethylene manufacture

A 2-liter stainless steel autoclave dried at 120 ° C for 2 hours was purged with nitrogen so that the inside of the reactor was brought to a nitrogen atmosphere. While maintaining the nitrogen atmosphere, the reactor internal temperature was lowered to 25 DEG C and 1 liter of purified hexane was injected. 2.0 mmol of triethylaluminium diluted in hexane was added, and 1 g of the obtained catalyst composition was diluted with 100 ml of decane, and 1 ml of the obtained diluted solution was added. After the addition, the reactor temperature was raised to 75 캜 while stirring at 250 rpm. Then 2.2 bar of H ₂ and 7 bar of ethylene were fed to maintain the pressure. Polymerization usually lasts for 2 hours and ethylene is fed to keep the pressure constant. After completion of the reaction, the solvent was removed by filtration under reduced pressure, and the residual hexane solvent was dried in a vacuum oven at 80 DEG C for 6 hours to obtain a polymer.

Example  2: Preparation of Catalyst Composition and Polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that 42 ml of hexane was added in Example 1.

Example  3: Preparation of Catalyst Composition and Polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that 0.6 ml of 1,2-dimethoxybenzene was added in Example 1.

Example  4: Preparation of Catalyst Composition and Polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that 20 ml of titanium tetrachloride was added in Example 1.

Example  5: Preparation of catalyst composition and polyethylene

The catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that titanium tetrachloride was added at -10 ° C instead of 0 ° C in Example 1.

Example  6: Preparation of catalyst composition and polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that 0.4 ml of 1,2-diethoxybenzene was added instead of 1,2-dimethoxybenzene in Example 1.

Example  7: Preparation of catalyst composition and polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that 0.4 ml of 1,2-dibutoxybenzene was added instead of 1,2-dimethoxybenzene in Example 1.

Example  8: Preparation of Catalyst Composition and Polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that 0.4 ml of 1,2-di-sec-butoxybenzene was added instead of 1,2-dimethoxybenzene in Example 1.

Example  9: Preparation of Catalyst Composition and Polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that 0.4 ml of 1,2-di-tert-butoxybenzene was added instead of 1,2-dimethoxybenzene in Example 1.

Comparative Example  1: Preparation of Catalyst Composition and Polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that hexane was not added in Example 1.

Comparative Example  2: Preparation of Catalyst Composition and Polyethylene

The catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that 19 ml of hexane was added in Example 1.

Comparative Example  3: Preparation of Catalyst Composition and Polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that the temperature was 6 ° C when the titanium tetrachloride was added in Example 1.

Comparative Example  4: Preparation of Catalyst Composition and Polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1, except that 0.7 ml of tetraethoxysilicate was added instead of 1,2-dimethoxybenzene in Example 1.

Comparative Example  5: Preparation of catalyst composition and polyethylene

A catalyst composition and polyethylene were prepared in the same manner as in Example 1 except that 1,2-dimethoxybenzene was added as an external electron donor in the polymerization process without adding 1,2-dimethoxybenzene in the preparation of the catalyst.

Comparative Example  6: Preparation of catalyst composition and polyethylene

Titanium tetrachloride (TiCl ₄ ) was added to the 0.5-liter pressure-resistant glass reactor equipped with a stirrer and an oil circulating heater under a nitrogen atmosphere at 0 ° C and stirred at 300 rpm. It was then added to the spherical support (MgCl ₂ / EtOH) under stirring at the same temperature. After adding 0.5 ml of 1,2-dimethoxybenzene, the temperature was raised to 140 占 폚 within 2 hours and maintained for 1 hour. Stirring was then stopped and the solid product was precipitated. Thereafter, the supernatant was removed, washed with 2 liters of hexane five times, and dried to obtain a catalyst composition. Using the catalyst composition, polyethylene was prepared in the same manner as in Example 1.

Comparative Example  7: Preparation of catalyst composition and polyethylene

6.0 g of Mg ₃ Ti (OC ₂ H ₅ ) ₈ Cl ₂ (precursor described in Example 1 of US 6,825,146) precursor was contacted with 100 ml of TiCl ₄ solution and 0.5 ml of 1,2-dimethoxybenzene. The mixture was heated to 100 < 0 > C and held at that temperature for 60 minutes and then filtered to remove the solvent. The filtration procedure was repeated three times, and then the solid was dried with N ₂ flow to obtain a catalyst composition. Using the catalyst composition, polyethylene was prepared in the same manner as in Example 1.

Experimental Example  1: Evaluation of catalyst particles

The shapes of the catalyst particles prepared according to the above Examples and Comparative Examples were observed with an electron microscope (SEM: Scanning Electron Microscope).

The particle size of the catalyst particles suspended in hexane was measured with a laser particle analyzer (Mastersizer X, manufactured by Malvern Instruments) by a light transmission method. As a result, a cumulative distribution of the particle size was obtained, and the average particle size and the particle size distribution index of the particles were obtained as follows.

(One) Average particle size (D ₅₀ ): the particle size corresponding to the cumulative weight of 50%

(2) Particle size distribution index (P): P = (D ₉₀ -D ₁₀ ) / D ₅₀

In the above, D ₉₀ is the particle size corresponding to the cumulative weight of 90%, and D ₁₀ is the particle size corresponding to the cumulative weight 10%

Experimental Example  2: Analysis of molecular weight distribution (Mw / Mn) of polyethylene

The molecular weight distribution was measured by gel permeation chromatography according to the method according to DIN 55672 under the following conditions: solvent: 1,2,4-trichlorobenzene, flow rate: 1 ml / min, temperature: Calibration using.

Experimental Example  3: Polyethylene Melt Index Analysis

The melt index (MI) was measured at 190 캜 according to ASTM D-1238 at the following load: MI _{2. 16} : 2.16 kg, MI _{21. 6} : 21.6 kg. MI _{21 .6} / MI _{2. 16} is defined as the melt flow ratio (MFRR).

division catalyst
Average particle diameter
(탆) catalyst
Particle size distribution index catalyst
activation
(kg-PE / g-Cat.) polymer
Apparent density
(g / cm ³⁾ Differential wt%
(<125 μm) MwD
(Mw / Mn) MFRR Example 1 4.5 0.8 21 0.30 0.1 4.1 25 Example 2 4.0 0.9 22 0.31 0.3 4.2 30 Example 3 4.2 0.9 20 0.32 0.5 4.0 29 Example 4 4.7 0.8 25 0.30 0.2 4.4 31 Example 5 4.2 1.0 21 0.31 0.4 4.6 28 Example 6 4.0 0.7 22 0.33 0.1 4.0 25 Example 7 4.2 0.8 21 0.35 0.8 4.1 24 Example 8 4.1 0.9 23 0.32 0.9 4.3 26 Example 9 4.4 0.9 25 0.35 1.2 4.2 27 Comparative Example 1 1.0 1.6 14 0.21 74 4.9 35 Comparative Example 2 1.9 1.8 12 0.23 49 5.3 36 Comparative Example 3 2.7 2.0 14 0.21 41 4.6 36 Comparative Example 4 2.8 1.8 13 0.28 18 7.7 42 Comparative Example 5 10 1.9 18 0.23 26 8.6 46 Comparative Example 6 45 1.9 5 0.27 0 6.8 37 Comparative Example 7 26 1.2 8 0.28 0 7.2 38

As shown in Table 1, it was confirmed that the catalyst composition according to an embodiment of the present invention is highly active and has an average particle size of 4 to 5 탆 and a narrow particle size distribution. Also, it is confirmed that the synthesized polymer greatly reduces the amount of fine powder to improve physical properties and appearance characteristics of the final product, and can prevent malfunction of the process machine and errors in the manufacturing process that may be caused by the fine particles .

Also, it can be seen that the polymer synthesized using the catalyst composition according to the embodiment of the present invention has a high apparent density and a narrow molecular weight distribution.

Claims (13)

(A) dissolving a magnesium compound in a solvent containing a first hydrocarbon solvent having 5 to 25 carbon atoms and an alcohol to prepare a magnesium compound solution;
(B) reacting the magnesium compound solution with an internal electron donor represented by the following formula (1); And
(C) a step of reacting the product of step (B) with a transition metal compound in the presence of a second hydrocarbon solvent having 6 to 25 carbon atoms. The method for producing a catalyst composition for high density polyolefin polymerization according to claim 1,
[Chemical Formula 1]

In Formula 1,
R ¹ and R ² are each independently linear C ₁ -C ₁₀ alkyl, branched C ₃ -C ₁₀ alkyl or cyclic C ₃ -C ₁₀ alkyl. The organic electroluminescent device according to claim 1, wherein the internal electron donor represented by Formula 1 is 1,2-di-methoxybenzene, 1,2-di-ethoxybenzene, , 1,2-di-butoxybenzene, 1,2-di-sec-butoxybenzene and 1,2-di-tert-butoxybenzene Is at least one dialkoxybenzene selected from the group consisting of 1,2-di-tert-butoxybenzene. The method for producing a catalyst composition for high density polyolefin polymerization according to claim 1, wherein the transition metal compound comprises a compound represented by the following formula (2)
(2)
MX _n (OR ³ ) _{4 -n}
In Formula 2,
M is selected from the group consisting of transition metal elements of groups IVB, VB and VIB of the periodic table,
X is halogen,
R ³ is an alkyl group having 1 to 10 carbon atoms,
n is from 0 to 4; The method of claim 1, wherein the first hydrocarbon solvent and the second hydrocarbon solvent are each independently selected from the group consisting of hexane, heptane, octane, decane, dodecane, tetradecane, mineral oil, cyclic hexane, cyclic octane, Wherein the at least one compound is at least one compound selected from the group consisting of methylcyclohexane, benzene, toluene, xylene, ethylbenzene and cumene. The magnesium compound according to claim 1, wherein the magnesium compound is selected from the group consisting of magnesium halide, dialkoxymagnesium, alkyl magnesium halide having 1 to 20 carbon atoms, alkoxy magnesium halide having 1 to 20 carbon atoms, and aryloxy magnesium halide having 6 to 20 carbon atoms Lt; RTI ID = 0.0 &gt; polyolefin &lt; / RTI &gt; The process of claim 1, wherein the molar ratio of the magnesium compound and the first hydrocarbon solvent is 1: 2 to 1: 4. The method for producing a catalyst composition for high-density polyolefin polymerization according to claim 1, wherein the molar ratio of the magnesium compound and the alcohol is 1: 3 to 1: 4. The process for producing a catalyst composition for high density polyolefin polymerization according to claim 1, wherein the molar ratio of the magnesium compound and the internal electron donor is 1: 0.01 to 1: 0.3. The process for producing a catalyst composition for high-density polyolefin polymerization according to claim 1, wherein the molar ratio of the magnesium compound and the transition metal compound is 1: 3 to 1:10. The method for producing a catalyst composition for high density polyolefin polymerization according to claim 1, wherein the molar ratio of the magnesium compound and the second hydrocarbon solvent is 1: 3 to 1:20. The process for producing a catalyst composition for high density polyolefin polymerization according to claim 1, wherein the step (C) is carried out at -20 to 0 占 폚. The method according to claim 1, further comprising a step (D) of reacting with an alkylaluminium compound represented by the following formula (3):
(3)
R ⁴ _n AlX _{3 -n}
In Formula 3,
R ⁴ is an alkyl group having 1 to 8 carbon atoms,
X is halogen,
n is from 0 to 3; The method of claim 12, wherein the alkylaluminium compound is selected from the group consisting of triethylaluminium, trimethylaluminium, triisopropylaluminium, trioctylaluminium, diethylaluminium chloride, diethylaluminium bromide, diethylaluminium iodide Wherein the at least one compound is at least one compound selected from the group consisting of diethylaluminium fluoride, ethylaluminium dichloride, dimethylaluminium chloride and methylaluminum dichloride.

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