KR102160452B1 - Method for manufacturing catalyst composition for polymerization of olefin, catalyst composition for polymerization of olefin manufactured by the method and process for polymerization of olefin using the same - Google Patents

Abstract

The present invention relates to: a method for manufacturing a catalyst for olefin polymerization, comprising a step of smoothly modifying a surface of a support by post-treating a surface of a dialkoxymagnesium solid support with a polar solvent when manufacturing a catalyst composition for olefin polymerization; a catalyst for olefin polymerization manufactured thereby; and a method for manufacturing an olefin using the same. According to the catalyst for olefin polymerization manufactured by using the dialkoxymagnesium support according to the present invention, olefins having no fine powder and high apparent density can be manufactured, so that process stability during a polymerization process is excellent and productivity can be increased.

Description

A method for preparing a catalyst composition for olefin polymerization, a catalyst composition for olefin polymerization prepared thereby, and a method for producing olefins using the same. OF OLEFIN USING THE SAME}

The present invention relates to a method for preparing a catalyst composition for olefin polymerization capable of providing a high bulk density of a polymerized olefin, a catalyst composition for olefin polymerization prepared thereby, and a method for producing an olefin using the same.

The catalyst for olefin polymerization refers to a catalyst system comprising a combination of a main catalyst mainly composed of a transition metal such as titanium, chromium, vanadium, etc., a cocatalyst, and an electron donor, and has been extensively studied. In general, it has been developed in the direction of improving polymerization activity and stereoregularity, and when its constituents and manufacturing methods are determined, the properties and particle distribution of the resulting polypropylene are determined.

The catalyst for olefin polymerization must satisfy requirements such as high catalyst activity, appropriate particle size, minimization of fine particles, and high apparent density in order to stably apply to various processes such as slurry polymerization, bulk polymerization, and gas phase polymerization. Until now, the Ziegler-Natta catalyst prepared using a magnesium chloride carrier as a catalyst for olefin polymerization has been most widely used, and recrystallization, precipitation, and spray drying are known as methods for satisfying various requirements of the carrier.

When preparing a catalyst using a dialkoxymagnesium obtained through the reaction of magnesium and alcohol using a chemical reaction as a carrier, it has the advantage that a catalyst having higher activity can be prepared compared to conventional methods. The highly active Ziegler-Natta type catalyst component can be prepared by contacting a titanium compound with a solid support including magnesium halide. Further, it is obtained by reacting titanium tetrachloride and dialkoxy magnesium. At this time, the dialkoxy magnesium is converted into a magnesium chloride support through a reaction with titanium tetrachloride to form an active catalyst component through coordination with titanium.

The manufacturing process of a catalyst for Ziegler-Natta olefin polymerization based on a conventional dialkoxymagnesium support includes a pretreatment step of substituting an alkoxy group with a chlorine group using silicon tetrachloride or titanium tetrachloride on the support; Washing the side reactants; Introducing an internal electron donor to the washed carrier; Introducing titanium tetrachloride at high temperature into the support into which the internal electron donor has been introduced into the support; Re-injecting the secondary titanium tetrachloride into the support at high temperature; And removing the side-reactant by precipitation/supernatant decantation at high temperature and drying the solid catalyst.

In the case of diethoxymagnesium carrier, unlike the recrystallization method and spray drying method in which the carrier is instantaneously prepared, the crystal powders grow in agglomerization form by chemical reaction, so the morphology of the carrier surface is roughened and the appearance of the polymerized powder. It has a disadvantage of low density. When the apparent density of the polymerized powder is low, light polymerized powder is mixed into the heat exchanger through the upper part of the reactor by the reactor cycle gas during gas phase polymerization in the process of fluidizing the polymerized powder, thereby reducing heat exchange efficiency and reducing productivity. .

An object of the present invention is to provide a method for producing a catalyst composition capable of polymerizing olefins exhibiting a high apparent density.

Another object of the present invention is to provide a catalyst composition prepared by the method for preparing the catalyst composition.

One aspect of the present invention for achieving the above object is (a) preparing a dialkoxymagnesium solid support; (b) modifying the surface of the dialkoxymagnesium solid support by post-treating the surface of the dialkoxymagnesium solid support with a polar solvent. Step to do; And (c) it relates to a method for producing a catalyst composition for olefin polymerization comprising the step of preparing an olefin polymerization catalyst by adding titanium tetrachloride.

Another aspect of the present invention for achieving the above object relates to a catalyst composition for olefin polymerization prepared by the method for producing the catalyst for olefin polymerization.

Another aspect of the present invention for achieving the above object relates to a method for producing an olefin polymer comprising the step of polymerizing an olefin-based monomer in the presence of the catalyst composition for olefin polymerization.

The carrier for an olefin polymerization catalyst according to the present invention has a uniform particle size distribution and an apparent density because the surface of dialkoxymagnesium is post-treated with a polar solvent to improve the morphology of the carrier surface, so that it has a large sphericity and can completely remove fine particles. high. When using a catalyst for olefin polymerization prepared using a dialkoxymagnesium carrier whose surface is smoothly modified by post-treatment, olefins with no fine powder and high apparent density can be produced, resulting in excellent process stability and productivity during the polymerization process. Can increase

1 is a graph of particle size distribution of a post-treated dialthoxymagnesium carrier according to an embodiment of the present invention.
2(a) is a 1,000-fold SEM image of a post-treated dialthoxymagnesium carrier according to an embodiment of the present invention.
2(b) is a 10,000-fold SEM image of a post-treated dialthoxymagnesium carrier according to an embodiment of the present invention.
3 is a graph showing the particle size distribution of the dialoxymagnesium carrier according to Comparative Preparation Example 1 of the present invention.
4(a) is a 1,000-fold SEM image of the dialthoxymagnesium carrier according to Comparative Preparation Example 1 of the present invention.
4(b) is a 10,000-fold SEM image of the dialoxymagnesium carrier according to Comparative Preparation Example 1 of the present invention.

The method for preparing the catalyst for olefin polymerization according to the present invention is characterized by improving the rough surface morphology of the diethoxymagnesium carrier by using a polar solvent having solubility in dialoxymagnesium, and using the prepared catalyst, it has high apparent density. It is possible to polymerize the olefin having.

Hereinafter, a method for preparing the catalyst composition for olefin polymerization of the present invention will be described in more detail.

(A) preparing a dialkoxy magnesium solid carrier

In this step, an iodine initiator is added dropwise to a reactor into which alcohol is added to completely dissolve it, and magnesium metal powder is added dropwise to prepare dialkoxymagnesium.

First, iodine (I ₂ ) is completely dissolved in an alcohol having 1 to 10 carbon atoms. After maintaining the internal temperature of the reactor at about 20 to 100°C, magnesium powder is introduced into the reactor and stirred at a speed of 230 to 250 rpm to proceed with the reaction for 10 extra. Magnesium and alcohol were added dropwise and the reaction was repeated for 10 extra, and the reaction was performed for 4 to 6 hours to confirm that no hydrogen was generated, and the reaction was terminated by cooling the reactor temperature to 25°C. After the reaction, ethyl alcohol was added several times to stop stirring and precipitated to remove the supernatant to prepare a dialkoxymagnesium solid carrier.

In the iodine initiator, 0.001 to 0.100 mole fraction of magnesium metal is added, and preferably 0.003 to 0.010 mole fraction is added. When the amount of the initiator used is less than 0.001 mole fraction, the reaction proceeding rate is too slow to generate a coarse carrier, and if the amount of the initiator exceeds 0.100 mole fraction, the reaction rate is too fast and the amount of fine powder generated by excessive aggregation reaction There are many.

The reaction temperature is in the range of 20 to 100°C, preferably in the range of 50 to 80°C. When the reaction temperature is lower than 20°C, a coarse carrier is generated due to a too slow reaction, and when the reaction temperature is higher than 100°C, the reaction rate is too fast and the amount of fine powder generated by excessive aggregation reaction is increased. After completion of the reaction, the residual initiator and the reaction intermediate dissolved in the alcohol are removed by 3 times precipitation/supernatant decantation through alcohol.

(B) Post-treatment of the dialkoxymagnesium solid carrier to modify the surface of the carrier

This step is a step of post-treating the dialkoxymagnesium solid carrier prepared in step (a).

First, the dialkoxymagnesium solid carrier prepared in step (a) is dissolved in a polar solvent to prepare a reactant carrying the solid carrier. Subsequently, a polar solvent corresponding to 5wt% to 40wt% of the weight of the carrier is added dropwise to the reactant, stirred at 0°C to 78°C for several hours, then precipitated and the supernatant is removed. When the polar solvent is added dropwise to less than 5 wt% of the weight of the carrier, the degree of modification of the surface by improving the morphology of the carrier surface is insufficient, and when a polar solvent is added dropwise in excess of 40 wt% of the carrier weight, the carrier is dissolved by the polar solvent There is a problem in that there are many carriers and excessive agglomeration between carriers increases the carrier size and decreases the apparent density. In addition, when the post-treatment reaction temperature of the carrier is less than 0°C or exceeds 78°C, the post-treatment reaction does not occur smoothly, and the degree of modification of the surface by improving the morphology of the carrier surface is insufficient. Particularly, when the post-treatment reaction temperature is less than 0℃, the solubility of the carrier in the polar solvent decreases, making it difficult to dissolve and remove the fine powder. When it exceeds 78℃, the solubility in the polar solvent increases, resulting in excessive aggregation between the carriers. There is a problem that is increased and the apparent density decreases.

Subsequently, after washing with an organic solvent several times, the solvent was completely removed through nitrogen purge after washing several times with normal hexane. The organic solvent used for cleaning may include a polar solvent and a non-polar solvent whose dielectric constant does not exceed 24.7.

In the process of modifying the surface of the prepared diethoxymagnesium, when post-treatment is performed for a certain period of time by adding an appropriate amount of a polar solvent, the rough surface morphology of the resulting carrier is improved and the surface is smoothly modified. The polar solvent used in the present invention preferably has a dielectric constant (ε) in the range of 30 to 46.7. The dielectric constant is a measure of the polarity of a polar solvent. If the dielectric constant is less than 30, the polarity is low, so solubility in the carrier is lowered, and when it is greater than 46, the solubility in the carrier increases and excessive aggregation may occur.

Polar solvents that can be used include ether solvents having 1 to 20 carbon atoms, ester solvents, sulfone solvents, amine solvents, nitrile solvents, alcohol solvents, organic halogen solvents and organic peroxide solvents having solubility in diethoxymagnesium. It may be one or more selected from the group consisting of.

The alcohol-based solvent may be at least one selected from methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, ethylene glycol, and propylene glycol, but is not limited thereto.

The ether solvent may be at least one selected from tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl ether, and dibutyl ether, but is not limited thereto.

The ester-based solvent is ethyl acetate, butyl acetate, amyl acetate, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, γ- Selected from caprolactone, δ-valerolactone and ε-caprolactone, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, methyl acetate, ethyl acetate, methyl hexanoate and methyl formate There may be more than one, but is not limited thereto.

The sulfone solvents include dimethyl sulfoxide, tetramethylene sulfone, ethylnethyl sulfone, dibutyl sulfone, butadiene sulfone, diethyl sulfone and dimethyl sulfone. It may be one or more selected from (dimethyl sulfone), but is not limited thereto.

The amine solvent may be one or more selected from hexamethylphosphoramide, ethylamine, propylamine, and cyclohexylamine, but is not limited thereto.

The nitrile solvent is valeronitrile, caprylonitrile, heptanenitrile, cyclohexane carbonnitrile, acetonitrile, heptyl cyanide, 2-fluorobenzonitrile, 4-fluorobenzonitrile, phenylacetonitrile, 2-fluoro It may be one or more selected from phenylacetonitrile and 4-fluorophenylacetonitrile, but is not limited thereto.

The organic peroxide solvent is isobutyl peroxide, lauroyl peroxide, benzoyl peroxide, m-toluoyl peroxide, t-butyl peroxy-2-ethyl hexa Noate, t-butyl peroxy bivalate, t-butyloxyneodecanate, diisopropyl peroxy dicarbonate, diethoxy peroxy dicarbonate, bis-(4-t-butylcyclohexyl) peroxy di It may be one or more selected from carbonate, dimethoxy isopropyl peroxy dicarbonate, dicyclohexylperoxy dicarbonate, and 3,3,5-trimethylhexanoyl peroxide, but is not limited thereto.

The organic halogen-based solvent may be at least one selected from chloroform and chlorobenzene, but is not limited thereto.

The carrier according to the present invention thus prepared has an apparent density of 0.29 g/ml or more, a particle size distribution (D90-D10)/D50 of 0.69 g/ml or less, and a sphericity (Mv/Ma) of 0.82 or more.

In one embodiment of the present invention, the dialkoxy magnesium may be represented by the following formula (1).

[Formula 1]

Mg(OR ¹ ) ₂

In Formula 1, R ¹ is selected from primary, secondary and tertiary alkyl groups including C1-20 linear and branched aliphatic structures.

(C) adding titanium tetrachloride dropwise, removing side-reactants at high temperature, and obtaining a solid catalyst

After raising the temperature of the reactor containing the mixture obtained from step (b) to 60 to 80°C over 3 to 5 hours, titanium tetrachloride is added. The inner temperature of the reactor was raised to 110°C and reacted at 110°C for several hours. After the reaction, the stirring was stopped, the supernatant was removed, and an organic solvent and titanium tetrachloride were additionally added to react for an additional 30 minutes to 2 hours. At this time, titanium tetrachloride is added in an amount of 1 to 10 moles relative to each support. Preferably, 1.5 to 3.0 mole fraction is added. If the amount is less than 1 mole fraction, the activity of the prepared catalyst is low, and if the amount exceeds 10 mole fraction, the catalyst activity is lowered, which is not preferable. After stopping the agitation, titanium chloride alcoholate and unreacted dihalogenated organic compounds are removed by 3 times precipitation/supernatant decantation using a hydrocarbon solvent having a boiling point higher than 100°C at a high temperature of about 100°C. After washing the solid component with a solution of toluene and normal hexane at a temperature of 60° C., purging with nitrogen at a temperature of about 70° C. to completely remove the solvent, a solid catalyst is obtained.

According to the present invention, the morphology of the carrier surface is improved by post-treating the surface of dialkoxymagnesium with a polar solvent, so that the sphericity is large and fine powder is removed, thereby improving the particle size distribution and increasing the apparent density. The catalyst for olefin polymerization prepared by using such a support has an advantage that it has excellent process stability in the polymerization process and can increase productivity because it is possible to produce olefins having a high apparent density without fine powder.

The method of preparing the catalyst composition for olefin polymerization may further include a step commonly employed in the technical field to which the present invention pertains, in addition to the steps described above. The olefin-based monomer is polymerized using the thus prepared catalyst composition for olefin polymerization.

The catalyst composition for olefin polymerization according to the present invention may further include a cocatalyst. The cocatalyst can reduce the transition metal compound to form an active point, thereby increasing catalytic activity. There is no particular limitation on the cocatalyst, and any organometallic compound known to be used in the production of a general catalyst for olefin polymerization may be used without limitation. Among them, it is preferable to use an alkyl aluminum compound represented by the following formula (2).

[Formula 2]

R ² _n AlX _3-n

In Formula 2, R ² is an alkyl group having 1 to 8 carbon atoms, X is halogen, and n is 0 to 3.

Specific examples of the cocatalyst are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tributyl aluminum, diethyl aluminum dichloride, ethyl aluminum dichloride, ethyl aluminum sesq chloride, tripropyl aluminum, tributyl aluminum, tripentyl aluminum , Trihexyl aluminum, trioctyl aluminum, and the like, and one or more of them may be selected and used.

In addition, the catalyst composition for olefin polymerization may further include an external electron donor. As the transition metal compound is reduced in the catalyst composition for olefin polymerization, a part of the internal electron donor is removed, and the vacancy is bonded to the external electron donor, so that the polymerization reaction may proceed. Accordingly, the role of the external electron donor in the catalyst composition for olefin polymerization is similar to the role of the internal electron donor described above. That is, it is possible to increase the activity of the catalyst more effectively in the olefin polymerization reaction, and increase the stereoregularity during the olefin polymerization.

The external electron donor can be used without any particular limitation as long as it is an external electron donor commonly used for olefin synthesis, but it is particularly preferable to use a silane-based compound represented by the following formula (3).

[Formula 3]

R ³ _n Si(OR ⁴ ) _4-n

In Formula 3, R ³ and R ⁴ are each independently hydrogen, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an amino having 1 to 10 carbon atoms. It is a functional group selected from the group consisting of an alkyl group and an alkoxyalkyl group having 2 to 10 carbon atoms.

Specific examples of the external electron donor include cyclic hexylmethyldimethoxysilane, dicyclic pentyldimethoxysilane, diisopropyldimethoxysilane, vinyl triethoxysilane, triethylmethoxysilane, trimethylethoxysilane, dicyclo Pentyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, diphenyldiethoxysilane, phenylpropyldimethoxysilane, fenyltrimethoxysilane, tertiarybutyltrimethoxysilane, cyclic hexylethyldimethoxysilane , Cyclic hexylmethyldimethoxysilane, cyclic pentyltriethoxysilane, diisobutyldiethoxysilane, isobutyltriethoxysilane, normal propyltrimethoxysilane, isopropyltrimethoxysilane, cyclicheptylmethyldiethoxy Silane, dicycloheptyldiethoxysilane, and the like, and one or more of them may be selected and used.

The external electron donor is used together with a cocatalyst during polymerization, and may be selectively used if necessary. The concentration of the external electron donor and the cocatalyst may include 0.01 to 10 moles, preferably 0.1 to 10 moles per mole of the transition metal compound, respectively.

The catalyst composition for olefin polymerization according to the present invention may further include various previously known internal electron donor compounds, such as a succinate compound, a silane compound, or a fluorene compound.

In addition, the catalyst composition for olefin polymerization may be a solid catalyst, and may have an average diameter of 5 μm to 100 μm, or 5 μm to 70 μm. The average diameter of the catalyst for olefin polymerization means the average diameter of a plurality of solid particles of the catalyst composition for olefin polymerization.

When the average diameter of the catalyst composition for olefin polymerization decreases to less than 5 μm, the size of the catalyst for olefin polymerization is not sufficiently secured, so it is difficult to generate smooth flow in a fluidized bed reactor (gas phase reactor), and catalyst particles in the form of small fine powders Goes to the top of the reactor, deteriorating the operational stability of the reactor, and reducing catalyst mileage.

The catalyst composition for olefin polymerization may further include excipients or additives commonly employed in the technical field to which the present invention pertains, in addition to the internal electron donor, transition metal compound, support, cocatalyst, external electron donor, and the like as described above. have.

The polymerizable olefinic monomer in the present invention is not necessarily limited thereto, but is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -Decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, nobornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclo It may be one or more selected from the group consisting of pentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene have.

In addition, the olefin prepared by using the catalyst composition of the embodiment may further include additives such as a heat stabilizer, a light stabilizer, a flame retardant, carbon black, a pigment, an antioxidant, and the like, which are usually added. In addition, the prepared olefin may be mixed with linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), polypropylene, polybutene, and EP (ethylene/propylene) rubber.

The polymerization reaction may be conducted in a gas phase, a liquid phase, or a solution phase. When carrying out the polymerization reaction in a liquid phase, a hydrocarbon solvent can be used, and an olefin itself can also be used as a solvent.

The polymerization pressure may be performed at 1 to 100 bar, and it is preferable to proceed at 2 to 50 bar or 5 to 40 bar condition. Here, in terms of improving the polymerization performance and process efficiency of the polyolefin manufacturing process, the polymerization process may be performed in the pressure range as described above. Particularly, when the polymerization pressure exceeds 100 bar, it is not preferable from the industrial and economic point of view.

The polymerization reaction can be carried out in any of batch, semi-continuous, and continuous methods.

In addition, the method for producing the olefin may further include a step commonly employed in the technical field to which the present invention pertains, in addition to the steps described above.

The olefin polymer according to the present invention thus prepared has an apparent density of 0.40 g/ml or more, a particle size distribution (D90-D10)/D50 of 0.68 g/ml or less, and a sphericity of 0.80 or more.

Hereinafter, the present invention will be described in detail with reference to specific examples. The examples presented are only intended to specifically illustrate the present invention and do not limit the claims of the present invention.

<Production Example 1: Preparation of dialkoxymagnesium solid carrier>

After sufficiently ventilating a 0.5L-sized glass reactor equipped with an oil heater and a cooling refluxer with nitrogen, 120ml of ethyl alcohol was added, and 0.15g of iodine (I ₂ ) was added dropwise to completely dissolve it. After maintaining the inner temperature of the reactor at 75°C, 1.5 g of 105 μm magnesium powder was added to the reactor, and 15 ml of ethyl alcohol was added to wash the magnesium powder on the wall, followed by stirring at a speed of 240 rpm to proceed the reaction for 10 minutes. . Magnesium and alcohol were added dropwise and the reaction for 10 minutes was repeated four additional times, followed by additional reaction for 5 hours to confirm that no hydrogen was generated, and then the reactor temperature was cooled to 25°C to terminate the reaction. After the reaction, 120 ml of ethyl alcohol was added twice to stop stirring, and the carrier was washed by sedimentation to remove the supernatant.

<Preparation Example 2: Post-treatment of diethoxymagnesium solid carrier>

120 ml of ethyl alcohol was added dropwise to 30 g of the dialkoxymagnesium solid carrier prepared in Preparation Example 1, and the mixture was stirred at a speed of 240 rpm. Subsequently, methyl alcohol corresponding to 10 wt% of the weight of the carrier was added dropwise, stirred at a speed of 240 rpm for 1 hour at 60° C., and precipitated and the supernatant was removed. Thereafter, after washing with 120 ml of ethyl alcohol twice, the solvent was completely removed through nitrogen purge at 70° C. after washing twice with 120 ml of normal hexane in the same manner. The carrier from which the solvent was removed was transferred to a glovebox filled with nitrogen and the apparent density was measured. Part of the carrier samples were taken and subjected to particle size analysis, and are shown in Table 1 below, and a particle size distribution graph of the post-treated carrier is shown in FIG. In addition, SEM images of the post-treated carrier are shown in Figs. 2(a) and 2(b), respectively. According to Figures 1 and 2, the Ziegler-Natta olefin polymerization catalyst carrier according to the present invention is removed by post-treating the surface of dialkoxymagnesium with a polar solvent to improve the morphology of the carrier surface, which has a large sphericity and completely dissolves and removes fine particles. It can be seen that the particle size distribution is uniform.

<Production Example 3: Preparation of solid catalyst for polypropylene polymerization>

In a high-purity nitrogen atmosphere, 10 g of diethoxy magnesium and 80 ml of toluene, which had undergone the post-treatment according to Preparation Example 2, were added in a double jacketed glass reactor equipped with a stirrer, and 20 ml of titanium tetrachloride and 30 ml of toluene were added while maintaining at 15°C. After stirring for 1 hour and raising the temperature of the reactor to 110°C, 3 g of diisobutylphthalate (DIBP) was added. After the reaction at 110° C. for 1 hour, the stirring was stopped, the supernatant was removed, 80 ml of toluene and 20 ml of titanium tetrachloride were added, followed by an additional 1 hour reaction. Stirring was stopped and precipitated at 100° C. to remove the supernatant. After washing the solid component three times with toluene and three times with normal hexane, the solvent was completely removed through nitrogen purge at a temperature of 70° C. to obtain a solid catalyst.

Example 1: Bulk propylene polymerization using a solid catalyst

In order to evaluate the performance of the Ziegler-Natta catalyst for olefin polymerization prepared in Preparation Example 3, polymerization of propylene was carried out using a polymerization reactor having a size of 2 L. The inside of the reactor was reduced to a vacuum of 3 torr or less, and the process of filling high-purity nitrogen was repeated 5 times. After filling the reactor with 500 g of propylene and 750 cc of hydrogen at room temperature, 3 mmol of triethylaluminum, 0.18 mmol of dicyclopentyldimethoxysilane, and 0.0044 mmol of the catalyst prepared according to Preparation Example 3 were added, and the reactor temperature was 70 It was raised to ℃ and reacted for 1 hour. Propylene was removed from the polymer and a final polymerization product was obtained.

The activity of the catalyst was determined in units of g-polymer/g-catalyst from the weight of the final polymerization product. The stereoregularity (I.I.:Isotacticity Index) of polypropylene was determined by the weight ratio of the extracted polymer and the dissolved polymer while lowering the temperature after dissolving in boiling xylene. Measurement of the bulk density and particle size analysis of the polymerized powder were performed. The polymerization activity of the catalyst, stereoregularity of the polymerization product, bulk density, and particle size characteristics are shown in Table 2 below.

Example 2: Bulk polymerization of propylene using a solid catalyst

In Preparation Example 2, a solid carrier was prepared in the same manner as in Preparation Example 2, except that 5wt% of the weight of the carrier was added in the post-treatment process of the diethoxymagnesium solid carrier, and the results were shown in the following table. It is shown in 1. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

Example 3: Bulk polymerization of propylene using a solid catalyst

In Preparation Example 2, a solid carrier was prepared in the same manner as in Preparation Example 2, except that 20wt% of the weight of the carrier was added in the post-treatment process of the diethoxymagnesium solid carrier, and the results were shown in the following table. It is shown in 1. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

Example 4: Bulk polymerization of propylene using a solid catalyst

In Preparation Example 2, a solid carrier was prepared in the same manner as in Preparation Example 2, except that 40wt% of the weight of the carrier was added in the post-treatment process of the diethoxymagnesium solid carrier, and the results were shown in the following table. It is shown in 1. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

Example 5: Bulk propylene polymerization using solid catalyst

In Preparation Example 2, a solid carrier was prepared in the same manner as in Preparation Example 2, except that the post-treatment temperature was lowered to 0°C in the post-treatment process of the diethoxymagnesium solid carrier, and the post-treatment was performed, and the results are shown in Table 1 below. Indicated. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

Example 6: Bulk polymerization of propylene using a solid catalyst

In Preparation Example 2, in the post-treatment process of the diethoxymagnesium solid carrier, a solid carrier was prepared in the same manner as in Preparation Example 2, except that the post-treatment temperature was raised to 78°C, which is the boiling point of ethyl alcohol, and the post-treatment was performed. It is shown in Table 1 below. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

Example 7: Bulk propylene polymerization using solid catalyst

In Preparation Example 2, in the post-treatment process of the diethoxymagnesium solid carrier, a solid carrier was prepared and post-treated in the same manner as in Preparation Example 2, except that acetonitrile having a dielectric constant of 37.5 was added to 10 wt% of the weight of the carrier instead of methyl alcohol. And the results are shown in Table 1 below. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

Example 8: Bulk polymerization of propylene using a solid catalyst

In Preparation Example 2, in the post-treatment process of the diethoxymagnesium solid carrier, a solid carrier was prepared in the same manner as in Preparation Example 2, except that dimethyl sulfoxide having a dielectric constant of 46.7 was added instead of methyl alcohol. Treatment proceeded and the results are shown in Table 1 below. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

Example 9: Bulk propylene polymerization using solid catalyst

In Preparation Example 2, in the post-treatment process of the diethoxymagnesium solid carrier, a solid carrier was prepared in the same manner as in Preparation Example 2, except that hexamethylphosphoamide having a dielectric constant of 30 was added instead of methyl alcohol. And the post-treatment was carried out, and the results are shown in Table 1 below. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

<Comparative Preparation Example 1: Preparation of solid catalyst for polypropylene polymerization>

A solid carrier was prepared in the same manner as in Preparation Example 3, except that the post-treatment process of the diethoxymagnesium solid carrier according to Preparation Example 2 was omitted, and the results are shown in Table 1 below, and a particle size distribution graph of the post-treated carrier It is shown in Figure 3. In addition, the SAM images of the post-treated carrier are shown in FIGS. 4(a) and 4(b), respectively.

Comparative Example 1: Bulk polymerization of propylene using a solid catalyst

Using the solid catalyst for polymerization of polypropylene prepared in Comparative Preparation Example 1, the evaluation of bulk polymerization of propylene using the solid catalyst was performed in the same manner as in Example 1, and is shown in Table 1.

Comparative Example 2: Bulk polymerization of propylene using a solid catalyst

In Preparation Example 2, a solid carrier was prepared in the same manner as in Preparation Example 2, except that 50 wt% of the weight of the carrier was added in the post-treatment process of the diethoxymagnesium solid carrier, and the results were shown in the following table. It is shown in 1. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

Comparative Example 3: Bulk polymerization of propylene using a solid catalyst

In Preparation Example 2, in the post-treatment process of the diethoxymagnesium solid carrier, a solid carrier was prepared and post-treated in the same manner as in Preparation Example 2, except that 10 wt% of the weight of the carrier was added to ethyl alcohol having a dielectric constant of 24.5 instead of methyl alcohol. And the results are shown in Table 1 below. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

Comparative Example 4: Bulk polymerization of propylene using a solid catalyst

In Preparation Example 2, in the post-treatment process of the diethoxymagnesium solid carrier, a solid carrier was prepared in the same manner as in Preparation Example 2, except that pure water having a dielectric constant of 80.1 was added to 10 wt% of the weight of the carrier instead of methyl alcohol. Proceeding and the results are shown in Table 1 below. Using the solid carrier prepared as described above, the bulk polymerization of propylene was evaluated in the same manner as in Example 1 using the solid catalyst prepared in the same manner as in Preparation Example 3, and is shown in Table 2.

a) Dimethyl sulfoxide, b) Hexamethylphosphoramide

^{1) In a} container having a volume of 20 ml, a carrier sample was poured onto the top of the funnel at a constant rate, and the weight of the sample filled on the container surface was calculated to measure the apparent density.

^{2) Using a} Microtrac S3500 instrument, a carrier sample prepared under ethyl alcohol medium was added and measured five times to calculate the average.

^{3) The} particle size distribution was calculated from the values of D90, D50, and D10 measured using a Microtrac S3500 instrument.

⁴⁾ Circularity was measured using a Microtrac S3500 device.

* Circularity = Volume average (Mv)/Surface area average (Ma)

⁵⁾ The apparent density of PP Powder was measured through ASTM D1895 A_Type.

According to Tables 1 and 2, the carrier of the olefin polymerization catalyst according to the present invention has improved surface morphology, so that the particle size distribution is uniform and the bulk density is high. The catalyst for olefin polymerization prepared using such a support not only exhibits high activity, but also has excellent process stability in the polymerization process because it can produce olefins with no fine powder and high apparent density. In addition, when the bulk density is increased by 0.01, the olefin productivity per unit time can be increased by about 3%.

Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and the structure of the present invention can be variously changed and modified without departing from the spirit or scope of the present invention. The fact will be apparent to a person skilled in the art. Therefore, the scope of protection of the present invention should be determined by the appended claims and the scope equivalent thereto.

Claims (16)

(a) preparing a dialkoxymagnesium solid support; (b) modifying the surface of the dialkoxymagnesium solid support by post-treating the surface of the dialkoxymagnesium solid support with a polar solvent; And (c) adding titanium tetrachloride to prepare an olefin polymerization catalyst, wherein the polar solvent is composed of methyl alcohol, acetonitrile, dimethyl sulfoxide, and hexamethylphosphoamide. It is at least one selected from the group, and the step of modifying the surface of the carrier includes adding the polar solvent dropwise in an amount of 5 to 40 wt% based on the weight of the carrier of dialkoxymagnesium, and reacting at a temperature range of 0°C to 78°C Method for producing a catalyst composition for olefin polymerization.
The method of claim 1, wherein the polar solvent has a dielectric constant in the range of 30 to 46.7.
delete delete delete delete The method of claim 1, wherein the preparing the dialkoxymagnesium solid carrier comprises dissolving an iodine initiator in alcohol and then adding magnesium metal powder dropwise.
The method of claim 1, wherein the modifying the surface of the carrier comprises: dissolving a dialkoxymagnesium carrier in a polar solvent to prepare a reactant in which a solid carrier is dispersed; Adding a polar solvent to the reactant dropwise, stirring, and precipitated, and removing the supernatant; A method for producing a catalyst composition for olefin polymerization comprising the step of washing the reactant from which the supernatant has been removed with an organic solvent.
The method of claim 8, wherein the organic solvent comprises a polar solvent and a non-polar solvent having a dielectric constant of 24.7 or less.
The catalyst for olefin polymerization according to claim 1, wherein the dialkoxymagnesium carrier has an apparent density of 0.29 g/ml or more, a particle size distribution (D90-D10)/D50 of 0.69 g/ml or less, and a sphericity (Mv/Ma) of 0.82 or more. Method of making the composition.
The method of claim 1, wherein the dialkoxymagnesium carrier is represented by the following formula (1).
[Formula 1]
Mg(OR ¹ ) ₂
In the above formula, R ¹ is selected from primary, secondary and tertiary alkyl groups including C1-20 linear and branched aliphatic structures.
The method of claim 7, wherein the iodine initiator adds 0.001 to 0.100 mole fraction of magnesium metal.
A catalyst composition for olefin polymerization prepared by the method for preparing a catalyst composition for olefin polymerization according to any one of claims 1, 2, and 7 to 12.
A method for producing an olefin polymer comprising the step of polymerizing an olefin-based monomer in the presence of the catalyst composition for olefin polymerization according to claim 13.
The method of claim 14, wherein the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undee Sen, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4 -A method for producing at least one olefin polymer selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
The method of claim 14, wherein the olefin polymer has an apparent density of 0.40 g/ml or more, a particle size distribution (D90-D10)/D50 of 0.68 g/ml or less, and a sphericity of 0.80 or more.

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