KR102467581B1 - Catalyst COMPOSITION for Polymerization of oleFin, METHOD OF PRODUCING THE SAME, AND METHOD OF PRODUCING POLYOLEFIN USING THE SAME METHOD - Google Patents

Abstract

The present invention relates to a catalyst composition for olefin polymerization, a method for preparing the same, and a method for preparing polyolefin using the same. More specifically, the present invention relates to a catalyst composition for olefin polymerization containing an environmentally friendly internal electron donor, which exhibits high catalytic activity and can improve the physical properties of a polymer produced, a method for preparing the same, and a method for producing polyolefin using the same .

Description

Catalyst composition for olefin polymerization, method for preparing the same, and method for producing polyolefin using the same

The present invention relates to a catalyst composition for olefin polymerization, a method for preparing the same, and a method for preparing polyolefin using the same. More specifically, the present invention relates to a catalyst composition for olefin polymerization containing an environmentally friendly internal electron donor, which exhibits high catalytic activity and can improve the physical properties of a polymer produced, a method for preparing the same, and a method for producing polyolefin using the same .

The Ziegler-Natta catalyst directly affects the properties and characteristics of the polyolefin produced according to its components, structure and manufacturing method. Therefore, in order to change the characteristics of the polyolefin produced, changes in the catalyst's constituents, the structure of the support, and the catalyst's manufacturing method must be accompanied during the preparation of the catalyst, depending on the manufacturing method of each catalyst or the difference in constituents. Research on the activity of the changed catalyst and the molecular weight and stereoregularity of the polymerized polymer should be carried out in parallel.

As described above, in olefin polymerization, a method using a phthalate-based compound as an internal electron donor or coagulant in order to reduce cost through increased catalytic activity and improve physical properties of polymers produced by improving catalytic performance such as stereoregularity This is widely known. However, phthalate-based compounds are a kind of 'endocrine disrupter' that enters the body of animals or humans and disrupts or disrupts the action of hormones, and even in small amounts, human reproductive function decline, growth disorders, deformities, and cancer It has been found that it can have adverse effects on humans and the ecosystem, such as triggering, and its use has now been banned.

Accordingly, many studies have been conducted to synthesize a compound to replace the phthalate-based compound as an internal electron donor, but phthalate-based compounds such as phthalic anhydride or phthalic chloride are still mainly used as coagulants.

Therefore, there is still a need to develop a Ziegler-Natta solid catalyst for synthesizing polyolefins, which includes an environmentally friendly coagulant and an internal electron donor, exhibits high polymerization activity, and allows the resulting polymer to have excellent stereoregularity.

JP 1993-001112 A US 2015-0299346 A EP 2803679

The present invention is to provide a catalyst composition for olefin polymerization that exhibits high catalytic activity, can improve the physical properties of a polymer produced, and includes an environmentally friendly internal electron donor.

And, the present invention is to provide a method for preparing the catalyst composition for olefin polymerization.

In addition, the present invention is to provide a method for producing polyolefin using the catalyst composition.

The present invention to solve the above problems

At least one carrier selected from the group consisting of a magnesium compound, silica, alumina, zeolite, and a hybrid carrier thereof; A compound represented by Formula 1 below; And it provides a catalyst composition for olefin polymerization comprising a transition metal compound:

[Formula 1]

In Formula 1,

R ₁ to R ₆ are each independently a hydrogen atom, C ₁ ~ C ₂₀ linear, branched, or cyclic alkyl, C ₂ ~ C ₂₀ alkenyl, C ₃ ~ C ₂₀ Cycloalkyl (cycloalkyl), S, N, O, Si, P, B and one or more heteroatoms substituted or unsubstituted with one or more heteroatoms selected from the group consisting of C ₆ ~ C ₂₀ Aryl of (aryl), C ₁ ~ C ₂₀ alkylsilyl, C ₇ ~C ₂₀ arylalkyl, C ₇ ~C ₂₀ alkylaryl, or hetero consisting of S, N, O, Si, P, B and halogen An alkyl containing a cycloalkyl of C ₃ ~C ₂₀ unsubstituted or substituted with one or more atoms selected from the atomic group,

R ₇ is a straight-chain or branched C ₁ -C ₆ alkylene, C ₂ -C ₆ alkenylene or C ₃ -C ₆ cycloalkylene.

In addition, the present invention includes the step of supporting a transition metal compound and the compound represented by Formula 1 on at least one support selected from the group consisting of a magnesium compound, silica, alumina, zeolite, and a hybrid support thereof, It provides a method for preparing a catalyst composition for olefin polymerization.

In addition, the present invention provides a method for producing a polyolefin, comprising polymerizing or copolymerizing an olefin-based monomer in the presence of the catalyst composition for olefin polymerization.

According to the present invention, a catalyst composition for olefin polymerization containing an environmentally friendly internal electron donor, a method for preparing the same, and a method for producing polyolefin using the same are provided. The catalyst composition for olefin polymerization exhibits high catalytic activity and is sufficient for commercial use, and polyolefin having improved stereoregularity can be prepared by using the catalyst composition.

The present inventors recognized the harmfulness and danger of phthalate compounds, which have been used as internal electron donors of catalyst compositions for olefin polymerization used in existing olefin polymerization, and conducted research on compounds that can replace them, and specific 2 - The present invention was completed by confirming that, when a 2-acetyloxy methyl benzoate-based compound was used in a catalyst composition, polyolefin with increased catalytic activity and excellent stereoregularity could be prepared.

The present invention provides a catalyst composition for olefin polymerization comprising a compound represented by Formula 1 below and a transition metal compound:

[Formula 1]

In Formula 1,

R ₁ to R ₆ are each independently a hydrogen atom, C ₁ ~ C ₂₀ linear, branched, or cyclic alkyl, C ₂ ~ C ₂₀ alkenyl, C ₃ ~ C ₂₀ Cycloalkyl (cycloalkyl), S, N, O, Si, P, B and one or more heteroatoms substituted or unsubstituted with one or more heteroatoms selected from the group consisting of C ₆ ~ C ₂₀ Aryl of (aryl), C ₁ ~ C ₂₀ alkylsilyl, C ₇ ~C ₂₀ arylalkyl, C ₇ ~C ₂₀ alkylaryl, or hetero consisting of S, N, O, Si, P, B and halogen An alkyl containing a cycloalkyl of C ₃ ~C ₂₀ unsubstituted or substituted with one or more atoms selected from the atomic group,

R ₇ is a straight-chain or branched C ₁ -C ₆ alkylene, C ₂ -C ₆ alkenylene or C ₃ -C ₆ cycloalkylene.

In the present specification, a cycloalkyl group refers to a monovalent functional group derived from a cycloalkane, and an aryl group refers to a monovalent or divalent functional group derived from arene, an aromatic hydrocarbon. In addition, the alkylsilyl group refers to a silyl group substituted with an alkyl group, the arylalkyl group refers to an alkyl group substituted with an aryl group, and the alkylaryl group refers to an aryl group substituted with an alkyl group.

The compound represented by Formula 1 is an internal electron donor, and is used together with a transition metal compound in a catalyst composition for olefin polymerization to increase the activity of the catalyst in the olefin polymerization reaction and to improve the stereoregularity and hydrogen reactivity of the polyolefin produced. It can do a helping job.

More specifically, in the 2-acetyloxy methyl benzoate-based compound of Chemical Formula 1, two carboxyl groups are introduced to act as Lewis base donors. That is, the structure of the compound represented by Chemical Formula 1 is similar to that of a phthalate-based compound, so that it can exhibit the characteristics and effects of a phthalate-based donor, but is environmentally friendly because it is not harmful to the environment and human body, and has excellent stereoregularity and high melt index. Accordingly, the internal electron donor including the compound of Chemical Formula 1 increases the activity of the catalyst more effectively in the olefin polymerization reaction, and enables the production of polyolefin having excellent stereoregularity.

Specific examples of the compound represented by Formula 1 include [2-(acetyloxy)methyl]methyl benzoate, [2-(acetyloxy)methyl]ethyl benzoate, and [2-(acetyloxy)methyl]propyl benzoate. Eight, [2-(acetyloxy)methyl]isobutyl benzoate, [2-(acetyloxy)methyl]isopentyl benzoate, [2-(acetyloxy)methyl]isopropyl benzoate, [2-(acetyloxy) )methyl]hexyl benzoate, [2-(acetyloxy)methyl]pentyl benzoate, [2-(benzoyloxy)methyl]methyl benzoate, [2-(benzoyloxy)methyl]ethyl benzoate, [2-( Benzoyloxy)methyl]isobutyl benzoate, [2-(benzoyloxy)methyl]isopentyl benzoate, [2-(benzoyloxy)methyl]isopropyl benzoate, [2-(benzoyloxy)methyl]hexyl benzoate , [2-[[1-oxopropyl]oxy]methyl]methyl benzoate, [2-[[1-oxopropyl]oxy]methyl]ethyl benzoate, [2-[[1-oxopropyl]oxy]methyl ]isobutyl benzoate, [2-[[1-oxopropyl]oxy]methyl]isopentyl benzoate, [2-[[1-oxopropyl]oxy]methyl]isopropyl benzoate, [2-[[1 -oxopropyl]oxy]methyl]hexyl benzoate, [2-[[2-methyl-1-oxobutyl]oxy]methyl]methyl benzoate, [2-[[2-methyl-1-oxobutyl]oxy] Methyl]ethyl benzoate, [2-[[2-methyl-1-oxobutyl]oxy]methyl]isopentyl benzoate, [2-[[2-methyl-1-oxobutyl]oxy]methyl]isobutyl benzoate ates, [2-[[2-methyl-1-oxobutyl]oxy]methyl]isopropyl benzoate, [2-[[2-methyl-1-oxobutyl]oxy]methyl]hexyl benzoate, etc. Among them, one type or a mixture of two or more types may be used as an internal electron donor.

Among these, [2-[[1-oxopropyl]oxy]methyl]isobutyl benzoate, [2-(benzoyloxy)methyl]isobutyl benzoate and the like are preferable from the viewpoint of imparting excellent stereoregularity.

In addition, as the internal electron donor, various conventionally known internal electron donor compounds such as succinate compounds, silane compounds, or fluorene-based compounds may be further included in addition to the compound of Formula 1.

The compound of Formula 1 is preferably reacted in an amount of 0.001 to 0.017 mol, more preferably 0.003 to 0.01 mol, based on 1 mol of the transition metal compound. If the content of the compound of Formula 1 is less than 0.001 mol based on 1 mol of the transition metal compound, the activity and stereoregularity may be lowered because the content of the internal electron donor is too small, and if it exceeds 0.017 mol, the activity of the catalyst is lowered, which is not preferable. not.

In addition, as a specific example of the transition metal compound in the catalyst composition for olefin polymerization of the present invention, any transition metal compound known to be used as a Ziegler-Natta catalyst for polyolefin synthesis may be used without particular limitation. Specific examples of the transition metal compound include a compound represented by Formula 2 below.

[Formula 2]

MX _n (OR ⁸ ) _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 a halogen;

R ⁸ is an alkyl group having 1 to 10 carbon atoms;

n is 0 to 4;

Preferred examples of the M include Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, and the like, and a transition metal compound containing one or more of these may be used. . And, as the transition metal compound of Formula 2, it is preferable to use zirconium tetrachloride [zirconium(IV) chloride], chromium chloride [chromium(III) chloride], or titanium tetrachloride.

The content of the transition metal compound may be 0.1 to 10% by weight, or 2.1 to 10% by weight based on the total weight of the catalyst. If the content of the transition metal compound is excessively reduced to less than 0.1% by weight, the activity of the catalyst for olefin polymerization may decrease.

The specific compounds of the internal electron donor are eco-friendly because they do not contain phthalate-based derivatives, which are mainly used in conventional Ziegler-Natta-based solid catalysts for polyolefin production, and have catalytic activity equal to or higher than that of conventional catalyst compositions using phthalate-based compounds. , and the stereoregularity of the polyolefin produced can be significantly improved.

Meanwhile, the catalyst composition for olefin polymerization of the present invention may further include a support. In the catalyst composition for olefin polymerization, the transition metal compound and the internal electron donor may be fixed or supported on the support. In addition, the order in which the transition metal compound and the internal electron donor are supported on the support is not particularly limited, but the support and the transition metal compound are first reacted to form an active site, and then the internal electron donor is added to It is more preferable to react to increase the catalytic activity.

There is no particular limitation on the support, and supports known to be commonly used in the preparation of general Ziegler-Natta catalysts can be used without limitation. Preferably, silica, alumina, zeolite, a magnesium compound, a mixture thereof, or a hybrid support may be used as the support, and more preferably, a magnesium compound may be used. The hybrid carrier means a state in which two or more of silica, alumina, zeolite, and magnesium compounds react or are combined.

Specific examples of the magnesium compound include magnesium halide, dialkoxy magnesium, alkylmagnesium halide, alkoxy magnesium halide, or aryloxy magnesium halide, and the use of magnesium halide increases the activity of the catalyst and is more preferable. In one embodiment, the magnesium compound is 1 selected from the group consisting of magnesium halide, dialkoxy magnesium, alkylmagnesium halide having 1 to 20 carbon atoms, alkoxymagnesium halide having 1 to 20 carbon atoms, and aryloxy magnesium halide having 6 to 20 carbon atoms. It may be a compound of more than one species.

In addition, the catalyst composition for olefin polymerization may further include a cocatalyst. The cocatalyst can reduce the transition metal compound to form an active site, thereby increasing catalytic activity. The cocatalyst is not particularly limited, and any organometallic compound known to be used in the preparation of catalysts for general polyolefin synthesis may be used without limitation. Among them, it is preferable to use an alkyl aluminum compound represented by the following formula (3).

[Formula 3]

R 9n AlX ³ _{- n}

In Formula 3,

R ⁹ is an alkyl group having 1 to 8 carbon atoms;

X is a halogen;

n is 0 to 3;

Specific examples of the cocatalyst include trimethylaluminum, triethylaluminum, triisobutylaluminum, tributylaluminum, diethylaluminum dichloride, ethylaluminum dichloride, ethylaluminum sesquichloride, tripropylaluminum, and tributyl. aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, etc. may be mentioned, and one or more types may be selected and used among them.

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 external electron donor binds to the vacancy so that the polymerization reaction can proceed. Therefore, the role of the external electron donor in the catalyst composition for olefin polymerization is similar to that of the aforementioned internal electron donor. That is, it is possible to increase the activity of the catalyst more effectively in the olefin polymerization reaction and to increase the stereoregularity during the olefin polymerization.

As the external electron donor, any external electron donor commonly used in polyolefin synthesis may be used without particular limitation, but it is particularly preferable to use a silane-based compound represented by Formula 4 below.

[Formula 4]

R ¹⁰ _n Si(OR ¹¹ ) _4-n

In Formula 4,

R ¹⁰ and R ¹¹ are each independently hydrogen, a straight-chain, branched or cyclic 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 aminoalkyl group having 1 to 10 carbon atoms. , And is selected from the group consisting of an alkoxyalkyl group having 2 to 10 carbon atoms,

n is 0 to 4;

Specific examples of the external electron donor include cyclic hexylmethyldimethoxysilane, dicyclic pentyldimethoxysilane, diisopropyldimethoxysilane, vinyltriethoxysilane, triethylmethoxysilane, trimethylethoxysilane, dicyclo Pentyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, diphenyldiethoxysilane, phenylpropyldimethoxysilane, phenyltrimethoxysilane, tert-butyltrimethoxysilane, cyclic hexylethyldimethoxysilane , cyclic hexylmethyldimethoxysilane, cyclic pentyltriethoxysilane, diisobutyldiethoxysilane, isobutyltriethoxysilane, normalpropyltrimethoxysilane, isopropyltrimethoxysilane, cyclic heptylmethyldiethoxy silane, dicycloheptyldiethoxysilane, etc., and one or more types may be selected and used among them.

The external electron donor is used together with a cocatalyst during polymerization, and may be selectively used as needed. Concentrations of the external electron donor and the cocatalyst may include 0.01 to 10 mol, preferably 0.1 to 10 mol, per 1 mol of the transition metal compound.

In addition, the catalyst composition for olefin polymerization may be a catalyst in a solid form, 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 is reduced to less than 5 μm, the size of the catalyst for olefin polymerization is not sufficiently secured, and it is difficult to generate a smooth flow in a fluidized bed reactor (gas phase reactor). Particles may migrate to the top of the reactor, degrading the operation stability of the reactor, and reducing catalyst mileage.

As the internal electron donor compound of Formula 1, a magnesium compound, a transition metal compound, and the like, those described in the solid catalyst composition for synthesizing polyolefin according to an embodiment of the present invention may be applied without limitation.

Specifically, the above-described catalyst for olefin polymerization may be prepared by reacting a transition metal compound and an internal electron donor compound at a predetermined temperature. In the case of fixing to a supporting material that is selectively used, the temperature may be gradually increased starting at a temperature of -50 to 50 °C, and the reaction temperature in the step of reacting the transition metal compound with the internal electron donor may be 80 °C or higher.

In one embodiment of the present invention, the method for preparing the catalyst composition for olefin polymerization includes a transition metal compound and an internal electron donor, a magnesium compound, silica, alumina, zeolite, and a hybrid carrier thereof. It includes the step of supporting on the support.

In one embodiment of the present invention, the internal electron donor includes a compound represented by Formula 1.

In the step of supporting the transition metal compound and the internal electron donor on the support, the order of supporting the transition metal compound and the internal electron donor on the support is not particularly limited. For example, the transition metal compound and the internal electron donor are simultaneously supported. It may be supported on a carrier, or the two components may be sequentially supported on a carrier.

In one embodiment, the step of supporting the transition metal compound and the internal electron donor on a carrier includes (A) supporting the transition metal compound on the carrier, and (B) supporting the transition metal compound on the carrier. and further supporting an internal electron donor on the support.

In the step of supporting the transition metal compound on the support and the step of additionally supporting the internal electron donor on the support on which the transition metal compound is supported, it is preferable to gradually introduce the transition metal compound over 10 minutes to 2 hours. desirable. In this way, when the transition metal compound is first supported on the support and then the internal electron donor is supported, a catalyst having an active point is created through the reaction between the support and the transition metal compound, and then the internal electron donor is added to increase the activity. It is preferable because it can make a catalyst and can also improve the stereoregularity of the polyolefin produced. The step of supporting the transition metal compound on the carrier is preferably performed at -30 to 50 °C, preferably -25 to -10 °C. If the temperature is less than -30 ° C, the reaction temperature is too low to complete the reaction, and if it exceeds 50 ° C, the particle shape of the catalyst may be destroyed and process stability may be lowered.

Further, the step of additionally supporting the internal electron donor on the support on which the transition metal compound is supported is preferably performed at -20 to 150°C. If the temperature is less than -20 ° C, it is difficult to complete the reaction, and if it exceeds 150 ° C, polymerization activity and stereoregularity of the resulting catalyst may be lowered due to side reactions, which is not preferable.

During the process of raising the temperature of the internal electron donor from the temperature in the step of supporting the transition metal compound on the carrier to the temperature in the step of additionally supporting the carrier on which the transition metal compound is supported on the internal electron donor, or by raising the temperature can be put in afterwards. At this time, the input temperature, the number of inputs, and the input time are not significantly limited.

The molar ratio between the transition metal compound and the support may be 3:1 to 30:1, preferably 9:1 to 20:1. The magnesium compound serves as a support, and when the content of the transition metal compound is too small compared to the content of the magnesium compound, the catalytic performance may be reduced due to the small number of transition metal compounds exhibiting catalytic activity. If the content of the transition metal compound is too large compared to the content, an excessively large amount of the transition metal component compared to the magnesium compound may be present in the catalyst, which may not be economical.

The molar ratio of the internal electron donor to the carrier may be 0.05:1 to 1:1, preferably 0.1:1 to 0.2:1. The internal electron donor serves to increase the activity of the catalyst in the polymerization reaction and improve the stereoregularity of the synthesized polyolefin, when the content of the internal electron donor is too small compared to the content of the support, the stereoregularity If the properties cannot be controlled and the content of the internal electron donor is too large, the activity of the catalyst may be low.

In addition, the method for preparing a solid catalyst for synthesizing polyolefin according to an embodiment may further include introducing a cocatalyst including the compound of Formula 3. The timing of adding the cocatalyst is not particularly limited, but it is preferable to add the cocatalyst after the step of reacting the magnesium compound solution with the transition metal compound and the internal electron donor because it can increase the activity of the catalyst. Specific examples and contents of the cocatalyst including the compound of Chemical Formula 3 may be applied without limitation as described in the solid catalyst composition for synthesizing polyolefin according to an embodiment of the present invention.

In addition, the method for preparing the solid catalyst for synthesizing polyolefin may further include introducing an external electron donor including the compound of Chemical Formula 4. The timing of introducing the external electron donor is not particularly limited, but, like the cocatalyst, it is preferable to add the magnesium compound solution after the step of reacting the transition metal compound and the internal electron donor because it can increase the activity of the catalyst. Specific examples and contents of the external electron donor including the compound of Formula 4 may be applied without limitation as described in the catalyst composition for olefin polymerization.

Meanwhile, according to another embodiment of the present invention, a method for producing polyolefin may be provided, including the step of polymerizing an olefin-based monomer in the presence of the solid catalyst composition for synthesizing polyolefin.

As described above, polyolefins can be synthesized by polymerizing or copolymerizing olefinic monomers in the presence of a solid catalyst containing a transition metal compound and an internal electron donor, and the polyolefins synthesized in this way are free from phthalates harmful to the human body and the environment in the manufacturing process. It is an eco-friendly polymer with improved physical properties without using a phthalate compound as an internal electron donor.

The olefinic monomer 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-aitocene, norbornene, norbornadiene, ethylidenenorbodene, phenylnorbodene, vinylnorbodene, dicyclopentadiene, 1,4-butadiene, 1,5 -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, or mixtures thereof.

Polymerization can be carried out in gas phase, liquid phase, or solution phase. When carrying out the polymerization reaction in a liquid phase, a hydrocarbon solvent can be used, and olefin itself can also be used as a solvent. Polymerization temperature may be 0 to 200 ℃, preferably in the range of 30 to 150 ℃. If the polymerization temperature is less than 0°C, the activity of the catalyst is not good, and if it exceeds 200°C, the stereoregularity is deteriorated, which is not preferable.

The polymerization pressure may be carried out at 1 to 100 atm, preferably at 2 to 40 atm. When the polymerization pressure exceeds 100 atm, it is undesirable from an industrial and economical point of view.

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

In addition, the polyolefin prepared using the solid catalyst composition of one embodiment may further include additives such as heat stabilizers, light stabilizers, flame retardants, carbon black, pigments, antioxidants, etc., which are commonly added. In addition, the prepared polyolefin may be mixed with linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), polypropylene, polybutene, EP (ethylene/propylene) rubber, and the like.

Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, this is presented as an example of the invention, and thereby the scope of the invention is not limited in any sense.

Example

[Example 1]

1. Preparation of solid catalyst

180 mL of titanium tetrachloride was put into a reactor in which nitrogen was circulated, and after cooling to a low temperature of -20 ° C or less, 13 g of a magnesium carrier (MgCl ₂ ) was added and stirred. After maintaining at the same temperature for about 1 hour, the temperature of the reactor was gradually raised. After the temperature was raised to 80°C, 1.9 g of [2-(benzoyloxy)methyl]isobutyl benzoate was added. After raising the temperature to 110 ° C., stirring at the same temperature for 1 hour, stopping the stirring and removing the supernatant. After washing twice using 180 mL of titanium tetrachloride at the same temperature and then washing 5 times using 200 mL of hexane each time at 70 ° C, a solid catalyst was obtained.

2. Polypropylene polymerization

A 2 L high-pressure reactor heated at 120° C. was purged with nitrogen for 1 hour to make the state of the high-pressure reactor a nitrogen atmosphere. The temperature of the reactor was lowered to 25° C. under a nitrogen atmosphere and propylene was purged to maintain the reactor in a propylene atmosphere. In a reactor maintained in a propylene atmosphere, 2 mmol of triethylaluminum diluted in decane solvent at a concentration of 1 molar was added, and cyclohexylmethyldimethoxysilane external electron donor diluted in decane solvent was added so that the Si / Ti molar ratio was 30. put in. 5 mg of the solid catalyst, 1000 ml of hydrogen, and 500 g of propylene were added, and pre-polymerization was performed for 5 minutes by operating a stirrer. After pre-polymerization, the temperature of the reactor was heated to 70 °C and polymerization was performed at 70 °C for 1 hour. The measurement results are shown in Table 1.

[Example 2]

A solid catalyst was prepared in the same manner as in Example 1, except that 2.9 g of [2-(benzoyloxy)methyl]isobutyl benzoate was used instead of 1.9 g of [2-(benzoyloxy)methyl]isobutyl benzoate, Polypropylene was polymerized using this.

[Example 3]

A solid catalyst was prepared in the same manner as in Example 1, except that 2.3 g of [2-(acetyloxy)methyl]isobutyl benzoate was used instead of 1.9 g of [2-(benzoyloxy)methyl]isobutyl benzoate, Polypropylene was polymerized using this.

[Example 4]

A solid catalyst was prepared in the same manner as in Example 1, except that 1.9 g of [2-(acetyloxy)methyl]methyl benzoate was used instead of 1.9 g of [2-(benzoyloxy)methyl]isobutyl benzoate. Polypropylene was polymerized using

[Comparative Example 1]

A solid catalyst was prepared in the same manner as in Example 1, except that 2.5 g of di-n-butyl phthalate was used instead of 1.9 g of [2-(benzoyloxy)methyl]isobutyl benzoate, and polypropylene polymerization was performed using the catalyst. conducted.

[Comparative Example 2]

A solid catalyst was prepared in the same manner as in Example 1, except that 2.5 g of diisobutyl phthalate was used instead of 1.9 g of [2-(benzoyloxy)methyl]isobutyl benzoate, and polypropylene polymerization was carried out using the catalyst. .

Experimental Example: Measurement of catalytic activity and stereoregularity

[Catalyst activity]

The weight (Kg) of the polymer prepared for 1 hour per weight (g) of the catalyst used was measured.

[Measurement of stereoregularity]

First, prepare 200 ml xylene in a flask and filter it with 200 mm No.4 extraction paper. The aluminum pan was dried in an oven at 150° C. for 30 minutes, cooled in a desiccator, and the mass was measured. Next, 100 ml of filtered o-xylene was collected with a pipette, transferred to an aluminum pan, and heated to 145 to 150° C. to evaporate all o-xylene. Thereafter, the aluminum pan was vacuum dried for 1 hour at a temperature of 100±5° C. and a pressure of 13.3 kPa for 1 hr. Thereafter, the aluminum pan was cooled in a desiccator and the above process was repeated twice, thereby completing the blank test of only o-xylene within a weight error of 0.0002 g. Next, after drying the polymers obtained in Examples and Comparative Examples (70° C., 13.3 kPa, 60 minutes, vacuum drying), 2 g ± 0.0001 g of the polymer sample cooled in a desiccator was placed in a 500 ml flask, and 200 ml o-xylene was added. Nitrogen and cooling water were connected to the flask, and o-xylene was continuously refluxed by heating the flask for 1 hour. Thereafter, the flask was placed in air for 5 minutes to cool down to 100° C. or less, and then the flask was shaken and placed in a thermostat (25±0.5° C.) for 30 minutes to precipitate insoluble matter. The resultant solution in which a precipitate formed was repeatedly filtered with 200 mm No. 4 extraction paper until it became clear. After drying at 150 ° C for 30 minutes, after cooling in a desiccator, 100 ml of the resultant solution was added to a pre-weighed aluminum pan, and o-xylene was evaporated by heating the aluminum pan to 145 to 150 ° C. . After evaporation, the aluminum pan was vacuum-dried for 1 hour at a temperature of 70 ± 5 ° C and a pressure of 13.3 kP, and the process of cooling in a desiccator was repeated twice, and the weight was measured within an error of 0.0002 g.

The weight % (Xs) of the portion dissolved in o-xylene among the resulting polymers is obtained, and the weight ratio (=100-Xs) of the polymer not extracted in o-xylene is obtained from this, and then the stereoregularity (XI ) was called.

* Stereoregularity (XI) = 100-Xs

[Measurement method of melting index]

According to ASTM1238, the amount of resin extruded at 230° C. and 2.16 kg for 10 minutes was measured.

catalytic activity
(kg-PP/g-cat,hr) Tacticity (wt%) melt index
(g/10min) Example 1 40 2.3 14 Example 2 38 2.0 12 Example 3 44 2.4 15 Example 4 40 2.4 17 Comparative Example 1 30 2.3 11 Comparative Example 2 32 2.0 12

In the above example, a solid catalyst for olefin polymerization was prepared using a 2-acetyloxy methyl benzoate-based compound as an internal electron donor, and polyolefin was polymerized using the 2-acetyloxy methyl benzoate-based compound.

As shown in Table 1, it can be confirmed that the solid catalysts of Examples can produce polyolefins having physical properties equal to or greater than those of Comparative Examples using conventional phthalate-based compounds.

Claims (15)

At least one carrier selected from the group consisting of a magnesium compound, silica, alumina, zeolite, and a hybrid carrier thereof; A compound represented by Formula 1 below; And a catalyst composition for olefin polymerization comprising a transition metal compound:
[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently a hydrogen atom, C ₁ ~ C ₂₀ straight-chain or branched alkyl, C ₂ ~ C ₂₀ alkenyl, C ₃ ~ C ₂₀ cycloalkyl ), C ₆ ~ C ₂₀ aryl, C ₁ ~ C ₂₀ alkylsilyl unsubstituted or substituted with one or more heteroatoms selected from the group consisting of S, N, O, Si, P, B and halogen (alkylsilyl), C ₇ ~C ₂₀ arylalkyl (arylalkyl), C ₇ ~C ₂₀ alkylaryl (alkylaryl), or 1 selected from the heteroatom group consisting of S, N, O, Si, P, B and halogen It is an alkyl including a cycloalkyl of C ₃ ~C ₂₀ substituted or unsubstituted with more than one atom,
R ₇ is a straight-chain C ₁ -C ₆ alkylene. The method of claim 1, wherein the compound represented by Formula 1 is [2- (acetyloxy) methyl] methyl benzoate, [2- (acetyloxy) methyl] ethyl benzoate, [2- (acetyloxy) methyl] propyl Benzoate, [2-(acetyloxy)methyl]isobutyl benzoate, [2-(acetyloxy)methyl]isopentyl benzoate, [2-(acetyloxy)methyl]isopropyl benzoate, [2-(acetyl Roxy)methyl]hexyl benzoate, [2-(acetyloxy)methyl]pentyl benzoate, [2-(benzoyloxy)methyl]methyl benzoate, [2-(benzoyloxy)methyl]ethyl benzoate, [2- (benzoyloxy)methyl]isobutyl benzoate, [2-(benzoyloxy)methyl]isopentyl benzoate, [2-(benzoyloxy)methyl]isopropyl benzoate, [2-(benzoyloxy)methyl]hexyl benzoate Eight, [2-[[1-oxopropyl]oxy]methyl]methyl benzoate, [2-[[1-oxopropyl]oxy]methyl]ethyl benzoate, [2-[[1-oxopropyl]oxy] Methyl]isobutyl benzoate, [2-[[1-oxopropyl]oxy]methyl]isopentyl benzoate, [2-[[1-oxopropyl]oxy]methyl]isopropyl benzoate, [2-[[ 1-oxopropyl]oxy]methyl]hexyl benzoate, [2-[[2-methyl-1-oxobutyl]oxy]methyl]methyl benzoate, [2-[[2-methyl-1-oxobutyl]oxy ]methyl]ethyl benzoate, [2-[[2-methyl-1-oxobutyl]oxy]methyl]isopentyl benzoate, [2-[[2-methyl-1-oxobutyl]oxy]methyl]isobutyl The group consisting of benzoates, [2-[[2-methyl-1-oxobutyl]oxy]methyl]isopropyl benzoate and [2-[[2-methyl-1-oxobutyl]oxy]methyl]hexyl benzoate A catalyst composition for olefin polymerization comprising at least one compound selected from. The catalyst composition for olefin polymerization according to claim 1, wherein the transition metal compound comprises a compound represented by Formula 2 below:
[Formula 2]
MX _n (OR ⁸ ) _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 a halogen;
R ⁸ is an alkyl group having 1 to 10 carbon atoms;
n is 0 to 4; The method of claim 1, wherein the magnesium compound is selected from the group consisting of magnesium halide, dialkoxy magnesium, alkylmagnesium 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. At least one compound, a catalyst composition for olefin polymerization. The catalyst composition for olefin polymerization according to claim 1, further comprising a compound represented by Formula 3 below:
[Formula 3]
R 9n AlX ³ _{- n}
In Formula 3,
R ⁹ is an alkyl group having 1 to 8 carbon atoms;
X is a halogen;
n is 0 to 3; The catalyst composition for olefin polymerization according to claim 1, further comprising a compound represented by Formula 4 below:
[Formula 4]
R ¹⁰ _n Si(OR ¹¹ ) _4-n
In Formula 4,
R ¹⁰ and R ¹¹ are each independently hydrogen, a straight-chain, branched or cyclic 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 aminoalkyl group having 1 to 10 carbon atoms. , And is selected from the group consisting of an alkoxyalkyl group having 2 to 10 carbon atoms,
n is 0 to 4; A transition metal compound and a compound represented by Formula 1 below,
A method for producing a catalyst composition for olefin polymerization according to claim 1, comprising the step of supporting on at least one support selected from the group consisting of a magnesium compound, silica, alumina, zeolite, and a hybrid support thereof:
[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently a hydrogen atom, C ₁ ~ C ₂₀ straight-chain or branched alkyl, C ₂ ~ C ₂₀ alkenyl, C ₃ ~ C ₂₀ cycloalkyl ), C ₆ ~ C ₂₀ aryl, C ₁ ~ C ₂₀ alkylsilyl unsubstituted or substituted with one or more heteroatoms selected from the group consisting of S, N, O, Si, P, B and halogen (alkylsilyl), C ₇ ~C ₂₀ arylalkyl (arylalkyl), C ₇ ~C ₂₀ alkylaryl (alkylaryl), or 1 selected from the heteroatom group consisting of S, N, O, Si, P, B and halogen It is an alkyl including a cycloalkyl of C ₃ ~C ₂₀ substituted or unsubstituted with more than one atom,
R ₇ is a straight-chain C ₁ -C ₆ alkylene. The method of claim 7, wherein the step of supporting the transition metal compound and the compound represented by Formula 1 on the carrier,
(A) supporting the transition metal compound on the support, and
(B) a method for preparing a catalyst composition for olefin polymerization comprising the step of additionally supporting a compound represented by Formula 1 on the support on which the transition metal compound is supported. The method for preparing a catalyst composition for olefin polymerization according to claim 7, wherein the transition metal compound comprises a compound represented by Formula 2 below:
[Formula 2]
MX _n (OR ₈ ) _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 a halogen;
R ₈ is an alkyl group having 1 to 10 carbon atoms;
n is 0 to 4; The method for preparing a catalyst composition for olefin polymerization according to claim 8, wherein step (A) is performed at -30 to 50 °C. The method of claim 8, wherein step (B) is performed at -20 to 150 °C. The method of claim 7, wherein the molar ratio of the transition metal compound to the support is 3:1 to 30:1. The method of claim 7, wherein the molar ratio of the compound of Formula 1 and the support is 0.05:1 to 1:1. A method for producing polyolefin, comprising the step of polymerizing an olefin-based monomer in the presence of the catalyst composition for olefin polymerization according to any one of claims 1 to 6. 15. 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-undecene Sene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, norbornadiene, ethylidenenovoden, phenylnovodenum, vinylnovodenum, dicyclopentadiene, 1,4 -Process for producing polyolefin containing at least one selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene .