KR20180036390A - Catalyst composition for polymerization of olefin, preparation method of the same, and preparation method of polyolefin using the same - Google Patents

Abstract

The present invention relates to a catalyst composition for polyolefin polymerization comprising a specific internal electron donor which is eco-friendly, a method for manufacturing a catalyst composition for polyolefin polymerization, and a method for manufacturing a polyolefin using the same. More particularly, the present invention relates to a catalyst composition which does not contain a phthalate derivative which is harmful to humans and environment, and which is eco-friendly, excellent in polymerization activity, and capable of manufacturing a polyolefin having excellent stereoregularity.

Description

TECHNICAL FIELD The present invention relates to a catalyst composition for polyolefin polymerization, a process for producing the same, and a process for producing a polyolefin using the catalyst composition,

The present invention relates to a catalyst composition for polyolefin polymerization, a process for producing the same, and a process for producing a polyolefin using the same. More specifically, it relates to a catalyst composition for polyolefin polymerization capable of enhancing the polymerization activity of a catalyst by using a specific environmentally-friendly internal electron donor without using a phthalate derivative harmful to humans and the environment and improving the physical properties of the polyolefin finally prepared A process for producing the same, and a process for producing a polyolefin using the same.

In the process of preparing polyolefins by polymerization or copolymerization of olefin monomers, various catalyst compounds have been used in order to obtain higher reaction efficiency and polymers having desired physical properties. Various catalysts such as a Ziegler-Natta catalyst, a Cr-based catalyst, and a metallocene catalyst are used as the catalysts used in the polyolefin polymerization, depending on the type of the central metal. These catalysts are selectively used depending on the respective production processes and application products because of their different catalytic activities, molecular weight distribution characteristics, stereoregularity and reaction characteristics with respect to the comonomers produced using the catalysts.

The catalyst for polyolefin polymerization generally referred to as a Ziegler-Natta catalyst refers to a solid catalyst comprising a combination of a main catalyst which is a main component of a transition metal compound, a promoter which is an organic metal compound, and an electron donor, And a lot of related technologies have been proposed.

The Ziegler-Natta catalyst directly affects the properties and properties of the polyolefin produced according to its constituent components, structure and preparation method. Therefore, in order to change the properties of the produced polyolefin, it is necessary to change the constituents of the catalyst, the structure of the carrier and the production method of the catalyst during the production of the catalyst. The activity of the different catalysts and the molecular weight and stereoregularity of the polymerized polymer should be studied simultaneously.

As described above, in the polyolefin polymerization, in order to improve the physical properties of the resulting polymer by lowering the cost by increasing the catalyst activity and improving the catalyst performance such as stereoregularity, a method of using a phthalate compound as an internal electron donor or agglomerate This is widely known. However, the phthalate compound is a type of 'endocrine disrupter' that interferes with or disrupts the action of hormones by entering into the body of an animal or a human. As a small amount, It has been found out that it can have a bad influence on human and ecosystem like induction, and it is prohibited to use at present. Accordingly, many studies have been made to synthesize a compound for replacing the phthalate compound with an internal electron donor. However, phthalate compounds such as phthalic anhydride or phthalic chloride have been mainly used as coagulant.

Accordingly, there is a demand for the development of a Ziegler-Natta catalyst for polyolefin polymerization, which contains an environmentally-friendly coagulant and an internal electron donor, exhibits a high polymerization activity, and has excellent stereoregularity in the resulting polymer.

An object of the present invention is to provide a catalyst composition for polyolefin polymerization which exhibits high catalytic activity, can improve the physical properties of a polymer to be produced, and contains an environmentally friendly internal electron donor.

The present invention also provides a process for producing the catalyst composition.

The present invention also provides a process for producing a polyolefin using the catalyst composition.

The present invention relates to an internal electron donor comprising a compound represented by the formula (1) and a compound represented by the formula (2); And a transition metal compound,

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₃ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An arylalkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, S, N, O, A heteroalkyl group having 2 to 20 carbon atoms substituted with at least one heteroatom selected from the group consisting of Si, P and B or a heteroalkyl group having 1 to 20 carbon atoms selected from the group consisting of S, N, O, Si, P, A heteroaryl group having 5 to 20 carbon atoms substituted with at least one hetero atom,

(2)

In Formula 2,

R ₄ to R ₅ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms,

R ₆ to R ₇ each independently represent hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An arylalkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, S, N, O, A heteroalkyl group having 2 to 20 carbon atoms substituted with at least one heteroatom selected from the group consisting of Si, P and B or a heteroalkyl group having 1 to 20 carbon atoms selected from the group consisting of S, N, O, Si, P, Or a heteroaryl group (aryl) having 5 to 20 carbon atoms substituted with at least one heteroatom.

The present invention also provides a process for preparing a catalyst composition for polyolefin polymerization comprising the step of reacting an internal electron donor comprising a transition metal compound, a compound represented by the formula (1) and a compound represented by the formula (2).

The present invention also provides a process for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition for synthesizing polyolefin.

Hereinafter, a catalyst composition for polyolefin polymerization according to a specific embodiment of the present invention, a method for producing the catalyst composition, and a method for producing a polyolefin using the catalyst composition will be described in detail.

According to one embodiment of the invention, the catalyst composition for polyolefin polymerization can be provided.

The present inventors have recognized the harmfulness and danger of the phthalate compound which has been used as an internal electron donor of the catalyst composition for polyolefin polymerization to be used in the conventional polyolefin polymerization, It has been confirmed that when a ketoester-based compound and a diether-based compound are used as a catalyst composition together with a transition metal compound as an internal electron donor, the polyolefin having an increased catalytic activity and excellent stereoregularity can be produced Thereby completing the invention.

The polyolefin polymerization means both a polymerization process using one kind of olefin monomer and a copolymerization process using two or more kinds of monomers.

According to one embodiment of the invention, there is provided a catalyst composition for polyolefin polymerization comprising an internal electron donor and a transition metal compound comprising a compound represented by the following formula (1) and a compound represented by the following formula (2).

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₃ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An arylalkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, S, N, O, A heteroalkyl group having 2 to 20 carbon atoms substituted with at least one heteroatom selected from the group consisting of Si, P and B or a heteroalkyl group having 1 to 20 carbon atoms selected from the group consisting of S, N, O, Si, P, A heteroaryl group having 5 to 20 carbon atoms substituted with at least one hetero atom,

 (2)

In Formula 2,

R ₄ to R ₅ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms,

R ₆ to R ₇ each independently represent hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An arylalkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, S, N, O, A heteroalkyl group having 2 to 20 carbon atoms substituted with at least one heteroatom selected from the group consisting of Si, P and B or a heteroalkyl group having 1 to 20 carbon atoms selected from the group consisting of S, N, O, Si, P, Or a heteroaryl group (aryl) having 5 to 20 carbon atoms substituted with at least one heteroatom.

As used herein, a cycloalkyl group means a monovalent functional group derived from a cycloalkane, and an aryl group means a monovalent or divalent functional group derived from an aromatic hydrocarbon arene. Further, the alkylsilyl group means a silyl group substituted with an alkyl group, the arylalkyl group means an alkyl group substituted with an aryl group, and the alkylaryl group means an aryl group substituted with an alkyl group.

In the catalyst composition for polyolefin polymerization according to this embodiment, the internal electron donor is used together with the transition metal compound to increase the activity of the catalyst in the polyolefin polymerization reaction and improve the stereoregularity and hydrogen reactivity of the produced polyolefin can do. Specifically, the compound of Chemical Formula 1 is a ketoester-based compound, and has a chemical structure in which a ketone group and an ester group are introduced centering on a divalent substituent of R ₂ . The compound of formula (2) is a diether compound having a chemical structure in which an ester group is introduced at the end of an isopropyl group substituted with R ₆ and R ₇ , respectively.

More specifically, in the ketoester-based compound of Formula 1, the ketone structure may function as a donor that is a Lewis base by the introduction of a carboxyl group. That is, the structure of the compound of Formula 1 is similar to the phthalate-based compound, so that it can exhibit the characteristics and effects of the phthalate-based donor, and is environmentally friendly because it is not harmful to the environment and human body. The ether structure of the diether compound of Formula 2 is characterized by excellent stereoregularity and a high melt index. Accordingly, the internal electron donor including the compound of Formula 2 together with Formula 1 enhances the activity of the catalyst more effectively in the polyolefin polymerization reaction, and can produce a polyolefin having excellent stereoregularity.

In formula (1), R ₁ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and R ₂ and R ₃ are each independently preferably an aryl group having 6 to 20 carbon atoms aryl. In the above formula (2), R ₆ and R ₇ are each independently preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and R ₂ and R ₃ are preferably a group having 6 to 20 carbon atoms, Lt; / RTI > may be an aryl group having 1 to 20 carbon atoms.

The substituents R ₁ to R ₇ in the general formulas (1) and (2) are a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An aryl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an alkylamine having 1 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms and an ether group having 2 to 20 carbon atoms ), Which may be further substituted with one or more selected from the group consisting of

Examples of the compound represented by the formula (1) include methyl 2-benzoyl benzoate, ethyl 2-benzoyl benzoate, propyl 2-benzoyl benzoate, isopropyl 2-benzoyl benzoate, butyl 2-benzoyl Benzoyl benzoate, isobutyl 2-benzoyl benzoate, pentyl 2-benzoyl benzoate, isopentyl 2-benzoyl benzoate, hexyl 2-benzoyl benzoate, ethyl 2- (4'- (2 ', 4'-dimethylbenzoyl) benzoate, ethyl 2- (2', 4'-trimethylbenzoyl) benzoate, ethyl 2- -Isobutyl) benzoate, methyl 3-benzoyl propionate, ethyl 3-benzoyl propionate, butyl 3-benzoyl propionate, isobutyl 3-benzoyl propionate, pentyl 3-benzoyl propionate, 3-benzoyl propionate, methyl 3-benzoyl butylate, ethyl 3-benzoate Butyl 3-benzoylbutylate, isobutyl 3-benzoylbutylate, isopentyl 3-benzoylbutylate, methyl-4-benzoylbutylate, isopropyl 3-benzoylbutylate, 4-phenyl-2-butenoate, isobutyl-4-oxo-4-phenyl-2-butenoate, (1-oxopropyl) benzoate, isobutyl 2- (1-oxopropyl) benzoate, isopentyl 2- (1-oxopropyl) benzoate , Ethyl 2- (2-methyl-1-oxopropyl) benzoate, isobutyl 2- (2-methyl-1-oxopropyl) benzoate, isopentyl 2- And one or more of them may be mixed to be used as an internal electron donor. Of these, methyl 2-benzoyl benzoate and ethyl 2- (4'-methylbenzoyl) benzoate are preferable in terms of imparting excellent stereoregularity.

Examples of the compound represented by the formula (2) in the internal electron donor include 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, Diisobutyl-1,3-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2,2-diisopentyl-1,3-dimethoxypropane, 2,2- 1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) Butyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-ethoxypropane, 2-ethyl- Ethyl-2-isopropenyl-1,3-dimethoxypropane, 2-ethyl-2-isopentyl-1,3-dimethoxypropane, Ethyl-2-benzyl-1,3-dimethoxypropane, 2-ethyl-2-cyclopentyl-1,3-dimethoxypropane, 2- Hexyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl Dimethoxypropane, 2-methyl-2-butyl-1,3-dimethoxypropane, 2-methyl- Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2- 1,3-dimethoxypropane, 2-methyl-2-isopentyl-1,3-dimethoxypropane, 2- Isopropyl-2-isopropyl-2-isopropyl-2-phenyl-1,3-dimethoxypropane, 2-isopropyl- Isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2- Isobutyl-1, 3-dimethoxypropane, 2-isobutyl-2-phenyl-1,3-dimethoxypropane, 2-benzyl-1,3-dimethoxypropane, 2- 2-cyclohexyl-1,3-dimethoxypropane, 2-isopentyl-2-butyl-1,3-dimethoxypropane Isopentyl-2-phenyl-1,3-dimethoxypropane, 2-isopentyl-2-benzyl-1,3-dimethoxypropane, 2- And 2-isopentyl-2-cyclohexyl-1,3-dimethoxypropane. Of these, one or more of them may be mixed and used as an internal electron donor. Among them, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxy Propane and the like are preferable.

Further, in addition to the compounds of the formulas (1) and (2), various internal electron donor compounds known in the art such as a succinate compound, a silane compound, or a fluorene compound may be further included as the internal electron donor.

The compounds of the formulas (1) and (2) are preferably reacted as an internal electron donor in an amount of 0.001 to 0.017 mol based on 1 mol of the transition metal compound, more preferably 0.003 to 0.01 mol. If the content of the internal electron donor is less than 0.001 mole based on 1 mole of the transition metal compound, the content of the internal electron donor is too small and the stereoregularity may be lowered. When the internal electron donor content is more than 0.017 mole, It is not preferable.

The content ratio of the compound of the formula (1) and the compound of the formula (2) in the internal electron donor is 0.1 to 10 (based on 1 mole of the ketoester compound of the formula (1) Mol, more preferably 0.2 to 5 mol. When the amount of the diether compound of Formula 2 is less than 0.1 mole based on 1 mole of the ketoester compound of Formula 1, the stereoregularity of the resultant polyolefin may be lowered, , High hydrogen reactivity may be exhibited, which is not preferable.

Further, in the catalyst composition for polyolefin polymerization of the present invention, specific examples of the transition metal compound may be used in the production of the catalyst component without limitation as long as it is a transition metal compound known to be used as a Ziegler-Natta catalyst for polyolefin synthesis. In particular, preferred examples of the transition metal compound include compounds represented by the following general formula (3).

(3)

MX _n (OR ⁸ ) _{4 -n}

In Formula 3, M is selected from the group consisting of transition metal elements of Group IVB, VB and VIB of the periodic table, X is halogen, R ⁸ is an alkyl group having 1 to 10 carbon atoms, and n is 0 to 4.

Examples of the M include Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W and Sg. Among them, a transition metal compound containing at least one of them can be used . As the transition metal compound of the above formula (3), it is preferable to use zirconium (IV) chloride, chromium (III) chloride, titanium tetrachloride or the like.

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

The specific compounds of the internal electron donors do not contain the phthalate derivatives used mainly in the conventional Ziegler-type solid catalyst for producing polyolefins, so that they are environmentally friendly and have catalytic activity equal to or higher than that of the conventional catalyst compositions using phthalate compounds And the stereoregularity of the polyolefin to be produced can be remarkably improved.

On the other hand, the catalyst composition for polyolefin polymerization of the present invention may further comprise a support. In the catalyst composition for polyolefin polymerization, the transition metal compound and the internal electron donor may be in a state of being fixed or supported on such a support. The order in which the transition metal compound and the internal electron donor are supported on the support is not limited. However, the support and the transition metal compound may be first reacted to form an active site, and then an internal electron donor may be added It is more preferable to increase the catalytic activity.

There is no particular limitation on the above carrier, and it is possible to use any carrier known to be commonly used in the production of a general Ziegler-Natta catalyst. Preferably, the support is silica, alumina, zeolite, a magnesium compound, a mixture thereof, or a mixed carrier thereof, more preferably a magnesium compound. The hybrid carrier means a state in which two or more of silica, alumina, zeolite, and magnesium compounds react or bind.

Specific examples of the magnesium compound include dihalogenated magnesium, dialkoxymagnesium, alkylmagnesium halide, alkoxymagnesium halide, and aryloxymagnesium halide, and when magnesium dihalide or dialkoxymagnesium is used as the carrier, The stereoregularity of the polyolefin to be synthesized can be further improved.

In addition, the catalyst composition for polyolefin polymerization may further comprise a cocatalyst. The cocatalyst can reduce the transition metal compound to form an active site, thereby enhancing the catalytic activity. The cocatalyst is not particularly limited, and any organometallic compound known to be used in the production of a catalyst for general polyolefin synthesis can be used without limitation. Among them, it is preferable to use an alkylaluminum compound represented by the following formula (4).

[Chemical Formula 4]

R ⁹ _n AlX _{3 -n}

In Formula 4, R ⁹ is an alkyl group having 1 to 8 carbon atoms, X is halogen, and n is 0 to 3.

Specific examples of the cocatalyst include trimethylaluminum, triethylaluminum, triisobutylaluminum, tributylaluminum, diethylaluminum dichloride, ethylaluminum dichloride, ethylaluminum cesium skew chloride, tripropylaluminum, tributylaluminum, tripentylaluminum , Trihexyl aluminum, trioctyl aluminum and the like. Of these, at least one of them can be selected and used.

In addition, the catalyst composition for polyolefin polymerization may further include an external electron donor. In the catalyst composition for polyolefin polymerization, the transition metal compound is reduced to remove a portion of the internal electron donor, and the external electron donor binds to the vacancy to allow the polymerization reaction to proceed. Therefore, the role of the external electron donor in the catalyst composition for polyolefin polymerization is similar to that of the internal electron donor described above. That is, it can increase the activity of the catalyst more effectively in the polyolefin polymerization reaction and increase stereoregularity in the olefin polymerization.

The external electron donor may be an external electron donor ordinarily used in polyolefin synthesis without particular limitation, and it is particularly preferable to use a silane-based compound represented by the following formula (5).

[Chemical Formula 5]

R ¹⁰ _n Si (OR ¹¹ ) _{4 -n}

Wherein R ¹⁰ and R ¹¹ are each independently selected from the group consisting of hydrogen, a linear 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, an amino group having 1 to 10 carbon atoms An alkyl group, and an alkoxyalkyl group having 2 to 10 carbon atoms.

Specific examples of the external electron donor include cyclic hexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, vinyltriethoxysilane, triethylmethoxysilane, trimethylethoxysilane, dicyclo Ethyl trimethoxy silane, diphenyl diethoxy silane, phenyl propyl dimethoxy silane, pentyl trimethoxy silane, tertiary butyl trimethoxy silane, cyclic hexyl ethyl dimethoxy silane , Cyclic hexylmethyldimethoxysilane, cyclopentyltriethoxysilane, diisobutyldiethoxysilane, isobutyltriethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, cyclic heptylmethyldiethoxy Silane, dicycloheptyldiethoxysilane, and the like, and at least one of them may be selected and used.

The external electron donor is used together with the cocatalyst during polymerization and can optionally be used as required. The concentration of the external electron donor and the cocatalyst may each include 0.01 to 10 mol, preferably 0.1 to 10 mol, per mol of the transition metal compound.

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

When the average diameter of the catalyst composition for polyolefin polymerization is reduced to less than 5 占 퐉, the size of the catalyst for polyolefin polymerization can not be sufficiently secured and it is difficult to generate a smooth flow in the fluidized bed reactor (gas phase reactor) The particles are passed to the top of the reactor, which lowers the operation stability of the reactor and can reduce the catalyst mileage.

The catalyst composition for polyolefin polymerization may further contain excipients or additives conventionally employed in the art to which the present invention pertains, in addition to the internal electron donor, transition metal compound, carrier, co-catalyst, external electron donor, .

On the other hand, according to another embodiment of the present invention, a method for producing the catalyst composition for polyolefin polymerization as described above can be provided.

As described above, the present inventors have recognized the hazards and hazards of phthalate compounds, which have been used as internal electron donors in conventional catalyst compositions for polyolefin polymerization, and have studied to synthesize compounds that can replace them, Environmentally friendly compounds that can be used as internal electron donors in the synthesis catalysts were prepared. Then, the prepared inner electron donor is reacted with a transition metal compound to prepare a solid catalyst for polyolefin synthesis, and the olefin is polymerized using the solid catalyst, whereby the prepared catalyst exhibits increased activity, and the stereoregularity of the produced polymer It is confirmed that the physical properties can be improved and the invention is completed.

According to another embodiment of the present invention, there is provided a process for producing a catalyst composition for polyolefin polymerization, which comprises reacting an internal electron donor comprising a transition metal compound, a compound represented by the following formula 1 and a compound represented by the following formula 2 / RTI >

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₃ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An arylalkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, S, N, O, A heteroalkyl group having 2 to 20 carbon atoms substituted with at least one heteroatom selected from the group consisting of Si, P and B or a heteroalkyl group having 1 to 20 carbon atoms selected from the group consisting of S, N, O, Si, P, A heteroaryl group having 5 to 20 carbon atoms substituted with at least one hetero atom,

(2)

In Formula 2,

R ₄ to R ₅ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms,

R ₆ to R ₇ each independently represent hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An arylalkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, S, N, O, A heteroalkyl group having 2 to 20 carbon atoms substituted with at least one heteroatom selected from the group consisting of Si, P and B or a heteroalkyl group having 1 to 20 carbon atoms selected from the group consisting of S, N, O, Si, P, Or a heteroaryl group (aryl) having 5 to 20 carbon atoms substituted with at least one heteroatom.

The compounds of the formulas (1) and (2), transition metal compounds and the like which are the internal electron donors can be applied without limitation to those described in the catalyst composition for polyolefin polymerization of one embodiment of the invention described above.

Specifically, the aforementioned catalyst for polyolefin polymerization can be produced by reacting a transition metal compound and an internal electron donor compound at a predetermined temperature. When it is fixed to a carrier to be selectively used, the temperature may be gradually increased from -30 ° C to 50 ° C, and the reaction temperature at the step of reacting the transition metal compound with the internal electron donor may be 80 ° C or higher.

The method for preparing a catalyst for polyolefin polymerization may further comprise the step of supporting the reactant on a magnesium compound, silica, alumina, zeolite, a mixture thereof, or a hybrid sludge thereof.

For example, the transition metal compound and the two internal electron donors may be carried on the carrier at the same time. In the step of supporting the reactants on the support, the three components Can be sequentially carried on the carrier.

The step of supporting the reactant on the carrier includes a step of reacting the carrier and the transition metal compound, and a step of reacting the transition metal compound with the carrier on which the transition metal compound is supported, It is preferable to gradually add the solution over time. When the carrier and the transition metal compound are first reacted and the inner electron donor is reacted, a catalyst having an active site through the reaction of the carrier and the transition metal compound is produced, and then the inner electron donor is added to increase the activity The catalyst can be produced and the stereoregularity of the produced polyolefin can be improved, which is preferable. The step of reacting the carrier with the transition metal compound is preferably performed at -30 캜 to 50 캜, preferably -25 캜 to -10 캜. If the temperature is lower than -30 ° C, the reaction temperature is too low to complete the reaction. If the temperature is higher than 50 ° C, the particle shape of the catalyst may be destroyed and the process stability may be lowered.

The step of reacting the carrier bearing the transition metal compound with the internal electron donor is preferably performed at -20 ° C to 150 ° C, more preferably 60 ° C to 135 ° C. If the temperature is lower than -20 ° C, the reaction is difficult to complete. If the temperature is higher than 150 ° C, the polymerization activity and stereoregularity of the resultant catalyst may be lowered due to side reactions, which is not preferable.

The internal electron donor may be heated during the step of raising the temperature of the step of reacting the carrier carrying the transition metal compound with the internal electron donor from the reaction temperature of the step of reacting the carrier and the transition metal compound, can do. At this time, the input temperature, the number of times of application, and the time of injection are not limited.

The reaction molar ratio of the transition metal compound and the support may be 3: 1 to 30: 1, preferably 9: 1 to 20: 1. If the content of the transition metal compound is too small as compared with the content of the carrier, the catalytic performance may be lowered because there are few transition metal compounds showing catalytic activity. If the content of the transition metal compound is too high compared to the content of the carrier, An excessive amount of transition metal component may exist in the catalyst as compared with the retardation, which may not be economical.

The reaction molar ratio of the internal electron donor including the compound of Formula 1 and Formula 2 to the support may be 0.05: 1 to 1: 1, preferably 0.1: 1 to 0.2: 1. The internal electron donor enhances the activity of the catalyst in the polymerization reaction and improves the stereoregularity of the polyolefin to be synthesized. When the content of the internal electron donor is too small as compared with the content of the support, It may be difficult to control the property, and if the content of the internal electron donor is too large, the activity of the catalyst may be low.

The method for producing a solid catalyst for polyolefin synthesis according to one embodiment of the present invention may further comprise the step of introducing a cocatalyst containing the compound of Formula 4. The timing of introduction of the co-catalyst is not limited, but it is preferable to add the co-catalyst after the step of reacting the magnesium compound solution with the transition metal compound and the internal electron donor since the activity of the catalyst can be increased. The specific examples, content and the like of the cocatalyst containing the compound of the formula (4) can be applied without limitation to those described in the catalyst composition for polyolefin polymerization of the embodiment.

In addition, the method for preparing a solid catalyst for polyolefin synthesis may further include the step of injecting an external electron donor including the compound of formula (5). The time for introducing the external electron donor is not limited, but it is preferable to add the magnesium compound solution after the step of reacting the magnesium compound solution and the transition metal compound and the internal electron donor, as in the case of the co-catalyst, because the activity of the catalyst can be increased. The specific examples, content and the like of the external electron donor including the compound of the formula (5) can be applied without limitation to those described in the catalyst composition for polyolefin polymerization of the embodiment.

The method for producing a catalyst composition for polyolefin polymerization may further include steps that are conventionally employed in the art to which the present invention belongs, in addition to the steps described above.

According to another embodiment of the present invention, there is provided a process for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition for polyolefin polymerization as described above.

As described above, a polyolefin can be synthesized in the presence of a catalyst composition for polyolefin polymerization in the form of a solid catalyst comprising a transition metal compound and an internal electron donor. The polyolefin synthesized using such a solid catalyst or catalyst system can be synthesized, And a phthalate-based compound harmful to the environment as an internal electron donor, so that the phthalate compound does not remain in the polymer.

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-aotocene, norbornene, norbornene, ethylidenenorbornene, phenylobodene, vinylnorbornene, dicyclopentadiene, - pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, or mixtures thereof.

The polymerization reaction may be carried out in a gas phase, a liquid phase, or a solution phase. When the polymerization reaction is carried out in a liquid phase, a hydrocarbon solvent can be used, and the olefin itself can be used as a solvent. The polymerization temperature may be from 25 캜 to 200 캜, and preferably from 30 캜 to 150 캜. If the polymerization temperature is less than 25 ° C, the activity of the catalyst is not good, and if it exceeds 200 ° C, the stereoregularity becomes poor, which is not preferable.

The polymerization pressure can be from 1 to 100 bar, preferably from 2 to 50 bar or from 5 to 40 bar. Here, from the viewpoint of improving the polymerization performance and the process efficiency of the polyolefin production process, the polymerization process can be carried out in the pressure range as described above. Particularly, when the polymerization pressure exceeds 100 bar, it is not preferable from the industrial and economical point of view.

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

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

The method for producing the polyolefin may further include a step that is conventionally employed in the art to which the present invention belongs, in addition to the steps described above.

According to the present invention, there is provided a catalyst composition for polyolefin polymerization comprising an environmentally friendly internal electron donor, a method for producing a solid catalyst, and a process for producing a polyolefin using the same. The solid catalyst for polyolefin synthesis exhibits a high catalytic activity and can produce a polyolefin which is sufficient for commercial use and has significantly improved stereoregularity and the like.

Hereinafter, a method for producing homopolypropylene according to one preferred embodiment of the present invention and homopolypropylene produced therefrom will be described in more detail.

[Example]

Example 1

1. Preparation of solid catalyst

180 mL of titanium tetrachloride was placed in a nitrogen-circulating reactor, cooled to a low temperature of -20 DEG C or lower, 13 g of a magnesium carrier was added and stirred. After maintaining at the same temperature for about 1 hour, the temperature of the reactor was gradually raised to 100 ° C. After the temperature was raised to 100 DEG C, 1.3 g of methyl 2-benzoyl benzoate and 2 g of 2-isopropyl-2-isopentyl (2-isopropyl- -1,3-dimethoxypropane). After raising the temperature to 110 占 폚, the mixture was stirred at the same temperature for 1 hour, stirring was stopped, and the supernatant liquid was removed. The flask was washed twice with 180 mL of titanium tetrachloride at the same temperature and then washed five times with 200 mL of hexane each time at 70 DEG C to obtain a solid catalyst as a catalyst composition for polyolefin polymerization.

2. Polymerization of polypropylene

A 2 L high-pressure reactor heated to 120 占 폚 was evacuated with nitrogen for 1 hour to bring the state of the high-pressure reactor to a nitrogen atmosphere. The temperature of the reactor was lowered to 25 占 폚 in a nitrogen atmosphere, and the reactor was kept in a propylene atmosphere by ventilation with propylene. To the reactor maintained in the propylene gas atmosphere, 2 mmol (mmol) of triethylaluminum diluted in the decane solvent was added in a concentration of 1 mol, and the cyclohexylmethyldimethoxysilane external electron donor diluted in the decane solvent was added to the reactor having the Si / Ti molar ratio 30. ≪ / RTI > 5 mg of catalyst, 1000 mL of hydrogen and 500 g of propylene were charged, and the polymerization was carried out for 5 minutes by operating the agitator. After the polymerization, the reactor was heated to 70 ° C and polymerized at 70 ° C for 1 hour.

Example 2

A solid catalyst was prepared in the same manner as in Example 1, except that 0.65 g of methyl 2-benzoylbenzoate and 1.8 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were used as an internal electron donor And the polypropylene was polymerized in the same manner as in Example 1 by using this.

Example 3

A solid catalyst was prepared in the same manner as in Example 1 except that 1.97 g of methyl 2-benzoylbenzoate and 0.59 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were used as an internal electron donor And the polypropylene was polymerized in the same manner as in Example 1 by using this.

Comparative Example 1

A solid catalyst was prepared in the same manner as in Example 1 except that only 2.63 g of methyl 2-benzoylbenzoate was used as an internal electron donor, and polypropylene was polymerized in the same manner as in Example 1 using the same.

Comparative Example 2

A solid catalyst was prepared in the same manner as in Example 1 except that only 2.38 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was used as an internal electron donor, The polypropylene was polymerized in the same manner.

Comparative Example 3

A solid catalyst was prepared in the same manner as in Example 1, except that a known phthalate compound (Diisobutyl phthalate) as an internal electron donor was used in an amount of 2.54 g, and polypropylene was prepared in the same manner as in Example 1 .

Experimental Example

Catalyst properties and polymer physical properties of the solid catalysts of Examples 1 to 3 and Comparative Examples 1 to 3 and the polypropylene produced therefrom were measured by the following methods.

a) catalytic activity

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

b) Stereoregularity measurement

First, 200 mL xylene is prepared in the flask and filtered with 200 mm No.4 extraction paper. The aluminum pan was dried in an oven at 150 DEG C for 30 minutes, cooled in a desiccator, and the mass was measured. Next, 100 mL of the filtered o-xylene was picked with a pipette, transferred to an aluminum pan, and heated at 145 ° C to 150 ° C to evaporate all o-xylene. The aluminum pan was then vacuum dried for 1 hour at a temperature of 100 ± 5 ° C and a pressure of 1 hr, 13.3 kPa. The aluminum pan was then cooled in a desiccator and the above procedure was repeated twice to complete a blank test of o-xylene only within a weight error of 0.0002 g. Next, the polymer obtained in Examples and Comparative Examples was dried (70 ° C, 13.3 kPa, 60 minutes, vacuum drying), and 2 g ± 0.0001 g of a polymer sample cooled in a desiccator was placed in a 500 mL flask 200 mL o-xylene was added. The flask was connected to nitrogen and cooling water, and o-xylene was continuously refluxed by heating the flask for 1 hour. Thereafter, the flask was placed in the air for 5 minutes to cool it to 100 ° C or lower, and the flask was shaken and placed in a thermostatic chamber (25 ± 0.5 ° C) for 30 minutes to precipitate insolubles. The resulting precipitate was repeatedly filtered until it was clean with 200 mm No.4 extraction paper. After drying at 150 ° C for 30 minutes, the aluminum pan was cleaned in a desiccator and then filtered thoroughly with an aluminum pan. The aluminum pan was heated at 145 ° C to 150 ° C to evaporate o-xylene . The evaporated 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 to measure the weight within an error of 0.0002 g.

As shown in the following equation 1, the weight% (Xs) of the portion of the produced polymer dissolved in o-xylene was determined, and the weight ratio (= 100-Xs) of the polymer not extracted to o- Later, it was referred to as a stereoscopic diagram (XI).

[Equation 1]

The stereoregularity diagram (XI) = 100 - Xs

c) Method of measuring the melt index

The amount of the resin extruded at 230 DEG C and 2.16 kg for 10 minutes was measured by ASTM1238.

The catalyst activity, catalyst size, and stereoregularity of the prepared polymer of the solid catalysts of Examples 1 to 3 and Comparative Examples 1 to 3 are as shown in Table 1 below.

activation
(kg-PP / g-cat, hr) Stereoregularity
(wt%) Melt Index
(g / 10 min) Example 1 41 2.8 12 Example 2 48 2.1 15 Example 3 40 3.0 8.5 Comparative Example 1 38 3.6 7.5 Comparative Example 2 52 1.4 18 Comparative Example 3 35 2.6 8.7

In Examples 1 to 3, a solid catalyst for polyolefin polymerization was prepared using a keto ester-based and diether-based internal electron donor, and polyolefin was polymerized using the same. The activity, stereoregularity and melt index of the polymerized polyolefin are shown in Table 1 above.

As shown in Table 1, the solid catalysts of Examples 1 to 3 exhibited activity, stereoregularity and hydrogen reactivity equal to or higher than those of the solid catalysts of Comparative Examples 1 and 2 using an inner electron donor alone, It is confirmed that a polymer can be efficiently formed and a polyolefin having physical properties equal to or higher than those of Comparative Example 3 using a conventional phthalate compound can be produced.

In particular, the catalyst of the present invention exhibits a higher activity than the phthalate-based catalyst, excellent stereoregularity, and excellent melt index. Such an excellent melt index makes it possible to produce various polymer products, It is advantageous to lower production cost. Further, the present invention can produce a polyolefin having excellent stereoregularity and a good melt index with excellent catalytic activity equal to or higher than that of a phthalate type internal electron donor which is an environmentally harmful substance.

Claims (17)

A catalyst composition for polyolefin polymerization comprising an internal electron donor and a transition metal compound comprising a compound represented by the following formula (1) and a compound represented by the following formula (2)
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₃ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, C 2 -C 20 arylalkyl groups, C 7 -C 20 alkylaryl groups, S, N, O, Si, P, and B, which is substituted with at least one heteroatom selected from the group consisting of Or a heteroaryl group having 5 to 20 carbon atoms and substituted with at least one heteroatom selected from the group consisting of S, N, O, Si, P, and B,
(2)

In Formula 2,
R ₄ to R ₅ are each independently hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms,
R ₆ to R ₇ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, C 2 -C 20 arylalkyl groups, C 7 -C 20 alkylaryl groups, S, N, O, Si, P, and B, which is substituted with at least one heteroatom selected from the group consisting of Or a heteroaryl group having 5 to 20 carbon atoms and substituted with at least one heteroatom selected from the group consisting of S, N, O, Si, P, and B;
The method according to claim 1,
Benzoyl benzoate, isopropyl 2-benzoyl benzoate, butyl 2-benzoyl benzoate, isobutyl 2-benzoyl benzoate, ethyl 2-benzoyl benzoate, Benzoyl benzoate, ethyl 2- (4'-methylbenzoyl) benzoate, ethyl 2- (2 ', 4'-dimethylbenzoyl) benzoate, isopentyl 2-benzoyl benzoate, Benzoate, ethyl 2- (4'-isobutyl) benzoate, methyl 3 (4'-chlorobenzoyl) benzoate, ethyl 2- Benzoyl propionate, ethyl 3-benzoyl propionate, butyl 3-benzoyl propionate, isobutyl 3-benzoyl propionate, pentyl 3-benzoyl propionate, isopentyl 3-benzoyl propionate, methyl 3 Benzoylbutylate, ethyl 3-benzoylbutylate, propyl 3-benzoylbutylate, Butyl 3-benzoyl butyrate, isobutyl 3-benzoyl butyrate, isopentyl 3-benzoyl butyrate, methyl-4-oxo- 4-oxo-4-phenyl-2-butenoate, isobutyl-4-oxo- (1-oxopropyl) benzoate, isobutyl 2- (1-oxopropyl) benzoate, ethyl 2- (2-methyl- 1-oxopropyl) benzoate, isobutyl 2- (2-methyl-1-oxopropyl) benzoate, and isopentyl 2- By weight based on the total weight of the polyolefin.
The method according to claim 1,
The compound represented by the general formula (2) is preferably selected from the group consisting of 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2- 3-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2,2-diisopentyl-1,3-dimethoxypropane, 2,2- Propane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane , 2,2-diisobutyl-1,3-ethoxypropane, 2-ethyl-2-butyl-1,3-dimethoxypropane, 2- Ethyl-2-isopropenyl-1,3-dimethoxypropane, 2-ethyl-2-isopentyl-1,3-dimethoxypropane, 2-ethyl-2-cyclohexyl-1,3-dimethoxypropane, 2-ethyl-2- Methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-butyl- Methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-cyclopentyl-1,3-dimethoxypropane Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, Isopropyl-2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isobutyl-1 3-dimethoxypropane, 2-isopropyl-2-phenyl-1,3-dimethoxypropane, Isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isobutyl-2-butyl-1,3-dimethoxypropane, 2- Isobutyl-2-phenyl-1,3-dimethoxypropane, 2-isobutyl-2-benzyl-1,3-dimethoxypropane, 2-isobutyl Cyclopentyl-1,3-dimethoxypropane Isobutyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopentyl-2-butyl-1,3-dimethoxypropane, Isopentyl-2-benzyl-1,3-dimethoxypropane, 2-isopentyl-2-cyclopentyl-1,3-dimethoxypropane and 2-isopentyl-2-cyclohexyl- 1,3-dimethoxypropane. ≪ / RTI >
The method according to claim 1,
Wherein the internal electron donor comprises 0.1 to 10 moles of the compound of formula (2) based on 1 mole of the compound of formula (1).
The method according to claim 1,
Wherein the transition metal compound comprises a compound represented by the following general formula (3): < EMI ID =
(3)
MX _n (OR ⁸ ) _{4 -n}
In Formula 3,
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 ⁸ is an alkyl group having 1 to 10 carbon atoms, and n is 0 to 4.
The method according to claim 1,
Wherein the catalyst composition further comprises at least one carrier selected from the group consisting of a magnesium compound, silica, alumina, zeolite, and a hybrid carrier thereof.
The method according to claim 6,
Wherein the magnesium compound is at least one selected from the group consisting of dialkoxymagnesium, dihalogenated magnesium, alkylmagnesium halide, alkoxymagnesium halide, and aryloxymagnesium halide.
The method according to claim 1,
A catalyst composition for polyolefin polymerization, further comprising a cocatalyst comprising a compound of the following formula:
[Chemical Formula 4]
R ⁹ _n AlX _{3 -n}
In Formula 4,
R ⁹ is an alkyl group having 1 to 8 carbon atoms, X is halogen, and n is 0 to 3.
The method according to claim 1,
A catalyst composition for polyolefin polymerization further comprising an external electron donor comprising a compound of formula (5): < EMI ID =
[Chemical Formula 5]
R ¹⁰ _n Si (OR ¹¹ ) _{4 -n}
In Formula 5,
R ¹⁰ and R ¹¹ are each independently hydrogen, a linear 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, an aminoalkyl group having 1 to 10 carbon atoms, To 10 alkoxyalkyl groups.
A method for preparing a catalyst composition for polyolefin polymerization comprising reacting an internal electron donor comprising a transition metal compound, a compound represented by the following formula (1) and a compound represented by the following formula (2)
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₃ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, C 2 -C 20 arylalkyl groups, C 7 -C 20 alkylaryl groups, S, N, O, Si, P, and B, which is substituted with at least one heteroatom selected from the group consisting of Or a heteroaryl group having 5 to 20 carbon atoms and substituted with at least one heteroatom selected from the group consisting of S, N, O, Si, P, and B,
(2)

In Formula 2,
R ₄ to R ₅ are each independently hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms,
R ₆ to R ₇ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, C 2 -C 20 arylalkyl groups, C 7 -C 20 alkylaryl groups, S, N, O, Si, P, and B, which is substituted with at least one heteroatom selected from the group consisting of Or a heteroaryl group having 5 to 20 carbon atoms and substituted with at least one heteroatom selected from the group consisting of S, N, O, Si, P, and B;
11. The method of claim 10,
Further comprising the step of supporting the reactant on at least one carrier selected from the group consisting of a magnesium compound, silica, alumina, zeolite and a hybrid carrier thereof.
12. The method of claim 11,
The step of supporting the reactant on the carrier includes:
Reacting the carrier with the transition metal compound
And a step of reacting the carrier carrying the transition metal compound with the internal electron donor.
13. The method of claim 12,
Wherein the step of reacting the carrier with the transition metal compound is carried out at -30 to 50 캜.
13. The method of claim 12,
Wherein the step of reacting the carrier having the transition metal compound carried thereon with the internal electron donor is carried out at -20 to 150 캜.
A process for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition for polyolefin polymerization according to any one of claims 1 to 9.
16. The method of claim 15,
Wherein the step of polymerizing the olefin monomer is carried out at a temperature of 25 to 200 DEG C and a pressure of 1 to 100 bar.
16. The method of claim 15,
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-aotocene, norbornene, norbornene, ethylidenenorbornene, phenylobodene, vinylnorbornene, dicyclopentadiene, Wherein the polyolefin is at least one selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.