KR101495781B1 - Catalyst composition for polymerization of polyolefin, preparation method of the same, and preparation method of polyolefin - Google Patents

Abstract

The present invention relates to an environmentally friendly catalyst composition for polyolefin synthesis, which can provide polyolefins having high catalytic activity and excellent stereoregularity and which does not contain substances harmful to humans and the environment, a process for producing a catalyst composition for synthesizing polyolefins, And a manufacturing method thereof.

Description

Technical Field The present invention relates to a catalyst composition for polyolefin synthesis, a method for producing a catalyst composition for polyolefin synthesis, and a method for producing a polyolefin,

The present invention relates to a catalyst composition for synthesizing polyolefins, a process for producing a catalyst composition for synthesizing polyolefins, and a process for producing polyolefins. More particularly, the present invention relates to an environmentally friendly catalyst composition for polyolefin synthesis, which can provide a polyolefin having a high catalytic activity and excellent stereoregularity and does not contain substances harmful to human bodies and the environment, a method for producing a catalyst composition for polyolefin synthesis, ≪ RTI ID = 0.0 > polyolefin < / RTI &

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 or a metallocene catalyst are used as catalysts for the synthesis of polyolefins, depending on the type of the core 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 synthesizing polyolefins 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 organometallic 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.

In the polyolefin polymerization, a method of using phthalate as an electron donor is widely known in order to lower the cost by increasing the catalytic activity and to improve the physical properties of the resulting polymer by improving catalytic performance such as stereoregularity. For example, Korean Patent Registration No. 0270011 discloses a Ziegler-Natta catalyst system comprising a titanium-containing solid component, an aluminum compound and an electron donor, wherein the electron donor is a phthalic acid ester containing alkoxy having 1 to 10 carbon atoms Can be used.

However, previously used phthalate compounds are a kind 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, such as disorder, malformation, and cancer induction.

Accordingly, there is a need to develop a catalyst system containing an electron donor capable of securing an improved polymerization efficiency, catalytic activity and high stereoregularity by replacing a phthalate-based compound.

Korean Patent No. 0270011

An object of the present invention is to provide a catalyst composition for environmentally friendly polyolefin synthesis which can provide a polyolefin having a high catalytic activity and excellent stereoregularity and which does not contain substances harmful to humans and the environment.

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

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

The present invention relates to a transition metal compound; And an internal electron donor comprising a compound of formula (1): < EMI ID = 1.1 >

[Chemical Formula 1]

In the general formula (1), n is an integer of 1 to 10, R ¹ and R ² may be the same or different and each represents hydrogen, a straight or branched alkyl group having 1 to 10 carbon atoms, a straight chain or branching group having 2 to 10 carbon atoms A cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 4 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and R ³ and R ⁴ are the same or different from each other Each independently represent hydrogen, a straight or branched alkyl group of 1 to 10 carbon atoms, a straight or branched alkenyl group of 2 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, a cycloalkylalkyl group of 4 to 11 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms, an oxoalkyl group having 3 to 10 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, or an alkoxyalkyl group having 1 to 10 carbon atoms substituted with an alkoxy group having 1 to 5 carbon atoms It is a small alkyl group.

The present invention also relates to a transition metal compound; And reacting an internal electron donor comprising the compound of formula (1). The present invention also provides a process for preparing a catalyst composition for polyolefin synthesis.

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 a polyolefin.

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

In the present specification, the polyolefin synthesis includes both a polymerization process using one olefin monomer and a copolymerization process using two or more monomers.

According to one embodiment of the invention, a transition metal compound; And an internal electron donor comprising the compound of Formula 1, may be provided.

The present inventors have recognized the hazards and hazards of phthalate compounds which have previously been used as electron donors and have been studying compounds that can replace them. When the compound of formula (1) is used as an internal electron donor, It is possible to provide a polyolefin having excellent stereoregularity and a catalyst composition for environmentally friendly polyolefin synthesis that does not contain substances harmful to humans and the environment.

The - [CR ³ R ⁴ ] n - moiety in the above formula (1) makes it possible to more effectively bond with a moiety that becomes a catalytically active point in the transition metal compound. In particular, R ³ and R ⁴ are stereoregular Of the population. R ¹ and R ² located at both ends of the compound of Formula 1 may have a certain influence on the electronic arrangement of neighboring oxygen, thereby improving the activity of the catalyst composition and the stereoregularity of the polyolefin to be produced It seems to play a role.

In the general formula (1), n is an integer of 1 to 10, preferably an integer of 1 to 5.

The cycloalkylalkyl group refers to an alkyl group substituted with a cycloalkyl group, the alkoxyalkyl group refers to an alkyl group substituted with an alkoxy group, and the arylalkyl group refers to an alkyl group substituted with an aryl group.

The oxoalkyl group means a functional group having an acyl group (-CO-) in the main chain, and may be, for example, a 2-oxoalkyl group.

The oxoalkyl group having 1 to 5 carbon atoms substituted with an alkoxy group having 1 to 5 carbon atoms means a functional group in which an alkoxy group having 1 to 5 carbon atoms is substituted with a carbon atom of an acyl group of an oxoalkyl group, Oxoalkyl group.

Specific examples of the internal electron donor including the compound of Formula 1 include N, N'-dimethoxy 2,2-dimethylmalonamide, N, N'-dimethoxy 2,2-diethylmalonamide, N, N Dimethoxy 2,2-dipentylmalonamide, N, N'-dimethoxy 2,2-dibutylmalonamide, N, N'-dimethoxy 2,2- Dimethoxy 2,2-dihexylmalonamide, N, N'-dimethoxy 2,2-dimethylpropylmalonamide, N, N'-dimethoxy 2,2-diisopropylmalonamide, N, N, N'-dimethoxy 2,2-bisbenzylmalonamide, N, N'-dimethoxy 2,2-bisoxopropylmalonamide, N, N, N'-dimethoxy 2,2-bisethyl ethyl ether malonamide, N, N'-dimethoxy 2,2-bistemethyl propionate malonamide, dimethoxy 2,2- N, N'-dimethoxy 2,2-bisethyl propionate Malonate flax Diethoxy 2,2-dimethylmalonamide, N, N'-diethoxy 2,2-diethylmalonamide, N, N'-diethoxy 2,2- N, N'-diethoxy 2,2-diphenylmalonamide, N, N'-diethoxy 2,2-diphenylmalonamide, N, Diethoxy 2,2-diisopropylmalonamide, N, N'-diethoxy 2,2-dimethylpropylmalonamide, N, N'-diethoxy 2,2-diisopropylmalonamide, N, N'- Diethoxy 2,2-bisbenzylmalonamide, N, N'-diethoxy 2,2-bisoxopropylmalonamide, N, N'-diethoxy 2,2- Diethoxy 2,2-bisethyl methyl ether malonamide, N, N'-diethoxy 2,2-bisethyl ethyl ether malonamide, N, N'-diethoxy 2,2-bis methyl propionate N, N'-diethoxy 2,2-bisethyl propionate malonamide, N, N'-diethoxy 2 , 2-dicyclopentylmalonamide, N, N'-dibenzyloxy 2,2-dimethylmalonamide, N, N'-dibenzyloxy 2,2-diethylmalonamide, N, N, N'-dibenzyloxy 2,2-diphenylmalonamide, 2,2-diphenylmalonamide, 2,2-diphenylmalonamide, 2,2- Diisopropylmalonamide, N, N'-dibenzyloxy 2,2-dimethylpropylmalonamide, N, N'-dibenzyloxy 2,2-diisopropylmalonamide, N, Dibenzyloxy 2,2-bisbenzylmalonamide, N, N'-dibenzyloxy 2,2-bisoxopropylmalonamide, N, N'-dibenzyloxy 2,2-bisbenzylmalonamide, N , N'-dibenzyloxy 2,2-bisethylmethyl ether malonamide, N, N'-dibenzyloxy 2,2-bisethyl ethyl ether malonamide, N, N'-dibenzyloxy 2,2-bis Methyl propionate malonamide, N, N'-dibenzyloxy 2,2-bisethyl propionate malonamide, N, N'-dibenzyloxy 2,2-dicyclopentylmalonamide, N, N'-dimethoxy 2,2-dimethyl succinic amide, N, N'-dimethoxy 2,2- , N'-dimethoxy 2,2-dipropyl succinic amide, N, N'-dimethoxy 2,2-dibutyl succinic amide, N, N'-dimethoxy 2,2- Dimethoxy 2,2-diisopropyl amic acid amide, N, N'-dimethoxy 2,2-dimethylpropyl succinate amide, N, N'-dimethoxy 2,2- N, N'-dimethoxy 2,2-dibenzyl succinic amide, N, N'-dimethoxy 2,2-bisoxopropyl amide amide, dimethoxy 2,2-dimethylcyclohexyl succinimide, -Dimethoxy 2,2-bisethyl methyl ether succinate amide, N, N'-dimethoxy 2,2-bisethyl ethyl ether succinate amide, N, N'-dimethoxy 2,2-bismethyl propionate succinate amide, , N, N'-dimethoxy 2,2-bisethyl propionate pumpkin May be mentioned amide, N, N'--dimethoxy-2,2-cyclopentane-succinic acid amide.

On the other hand, the catalyst composition for polyolefin synthesis may further comprise not only the compound of Formula 1 but also a compound known to be used as an internal electron donor, for example, a diaster compound, a benzoate compound, a succinate compound, or a silane compound .

A specific example of the preparation method of the compound of formula (1) is shown in the following general formula (1). However, the following general formula (1) shows only a method for producing a part of the compounds included in the formula (1), and the compound of the formula (1) can be obtained through various production methods, and specific examples thereof are limited to the following general formula no.

[Formula 1]

상기 일반식1에서, 디메틸포름아마이드 용매 하에서 염기인 소듐하이드라이드를 사용하여 N,N'-디메톡시말론아마이드를 R²-Br 또는 R²-I와 반응시켜 2번 화합물을 합성할 수 있다. 상기 2번 화합물을 1N 수산화나트륨 수용액을 메탄올 용매하에서 가수분해시켜 메틸에스테르를 카복실산으로 치환시킨 화합물 3을 합성할 수 있다. 상기 3번 화합물을 염화티오닐을 사용하여 엑시드클로라이드로 치환시킨 화합물 4을 합성할 수 있다. 그리고, 염화메틸렌과 테트라히드로푸란을 섞은 용매에 피리딘 염기와 H₂N-OR¹을 사용하여 클로라이드를 N-옥사이드로 치환시킨 최종 화합물 1을 합성할 수 있다.

In the above general formula 1, the compound No. 2 can be synthesized by reacting N, N'-dimethoxymalonamide with R ² -Br or R ² -I using sodium hydride as a base in a dimethylformamide solvent. Compound No. 2 can be synthesized by hydrolyzing 1N aqueous sodium hydroxide solution in a methanol solvent to replace the methyl ester with a carboxylic acid. Compound 3 in which the above-mentioned compound 3 is substituted with an acid chloride using thionyl chloride can be synthesized. Final compound 1 in which chloride is substituted with N-oxide can be synthesized by using pyridine base and H ₂ N-OR ¹ in a solvent in which methylene chloride and tetrahydrofuran are mixed.

The catalyst composition for polyolefin synthesis may contain 5 to 100 parts by weight of the internal electron donor per 100 parts by weight of the transition metal compound. If the content of the internal electron donor in the catalyst composition for synthesizing polyolefin is too small, it may not be easy to control the stereoregularity or stereospecificity of the polyolefin resin to be produced. If the content of the internal electron donor is too large, The activity may be rather lowered.

Specific examples of the transition metal compound may be any transition metal compound known to be used in polyolefin synthesis without any particular limitation. For example, the transition metal compound may include a compound of the following formula (2).

(2)

MX _n (OR ⁴ ) _4-n

Wherein M is a transition metal of the group IVB, VB, or VIB, X is a halogen, R ³ is an alkyl group having 1 to 10 carbon atoms, and n is 0 to 4 as an oxidation number of the metal. Preferred examples of M include Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W and Sg. Specific examples of the transition metal compound represented by the above formula (2) include zirconium (IV) chloride, chromium (III) chloride or titanium tetrachloride.

The catalyst composition for synthesizing polyolefins may further include a carrier, wherein the transition metal compound and the internal electron donor may be fixed or supported on the carrier. The order of the transition metal compound and the internal electron donor to be supported on the support is not limited. However, it is preferable that the support and the transition metal compound are reacted first to form an active site, To enhance the catalytic activity.

Although the specific kind of the carrier is not particularly limited, a carrier known to be usable for the transition metal catalyst for polyolefin synthesis can be used. For example, the catalyst composition for polyolefin synthesis may contain silica, alumina, zeolite, a magnesium compound, a mixture thereof, or a mixture of two or more thereof as a support. The hybrid substance means a state in which the examples of the above-mentioned carrier are reacted or combined.

Preferable examples of the carrier include a magnesium compound. Specific examples of such a magnesium compound include dihalogenated magnesium, dialkoxymagnesium, alkylmagnesium halide, alkoxymagnesium halide, or aryloxymagnesium halide, and more preferably, magnesium dihalide or dialkoxymagnesium is used as the carrier, And the stereoregularity of the polyolefin to be synthesized can be further improved.

The dialkoxymagnesium is a spherical particle obtained by reacting metal magnesium with an anhydrous alcohol in the presence of a reaction initiator such as magnesium chloride and having a smooth surface, and the spherical particle shape is maintained in the polymerization of the olefin, Can be increased. The dialkoxymagnesium may have an average particle diameter of 10 to 1000 mu m, preferably 30 to 500 mu m. When the average particle diameter is less than 10 탆, the fine particles of the prepared catalyst are undesirably increased, and when the average particle diameter exceeds 1000 탆, the apparent density tends to be small.

The catalyst composition for polyolefin synthesis may contain 10 to 1000 parts by weight, preferably 100 to 800 parts by weight, of the transition metal compound with respect to 100 parts by weight of the carrier. If the content of the transition metal compound is too small as compared with the above carrier, the amount of the transition metal to be fixed may be reduced and the catalytic activity may be lowered. If the content of the transition metal compound is too large as compared with the above carrier, The activity of the catalyst composition may be lowered.

The catalyst composition for polyolefin synthesis may further include a cocatalyst or an external electron donor.

The cocatalyst can reduce the transition metal compound to form an active site, thereby enhancing the catalytic activity. As the cocatalyst, an organometallic compound known to be usable as a catalyst for polyolefin synthesis can be used without any limitation, and preferably a compound of the following formula (3) can be used.

(3)

R ⁶ _n AlX _{3 -n}

In Formula 3, R ⁶ is an alkyl group having 1 to 8 carbon atoms, X is halogen, and n is 0 to 3.

Specific examples of the formula (3) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tributylaluminum, diethylaluminum dichloride, ethylaluminum dichloride, ethylaluminum cesium sucrochloride, tripropylaluminum, tributylaluminum, tri Pentyl aluminum, trihexyl aluminum, trioctyl aluminum, or a mixture of two or more thereof.

When the catalyst composition for synthesizing polyolefin includes an external electron donor, a part of the internal electron donor may be removed while the transition metal compound is reduced, and an external electron donor may be bonded to the vacant space to allow the polymerization reaction to proceed. That is, the external electron donor enhances the activity of the catalyst more effectively in the polyolefin polymerization reaction and can increase the stereoregularity in the olefin polymerization.

As the external electron donor, a compound known to be usable for the catalyst for synthesizing polyolefin may be used without any limitation, and preferably a compound of the following formula (4) can be used.

[Chemical Formula 4]

R ⁷ _n Si (OR ⁸ ) _4-n

Wherein R ⁷ and R ⁸ 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 aminoalkyl group having 1 to 10 carbon atoms, And an alkoxyalkyl group having 2 to 10 carbon atoms.

Specific examples of the compound of Formula 4 include cyclic hexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, vinyltriethoxysilane, triethylmethoxysilane, trimethylethoxysilane, dicyclopentyldimethoxysilane, But are not limited to, cyclopentyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, diphenyldiethoxysilane, phenylpropyldimethoxysilane, penyltrimethoxysilane, tertiarybutyltrimethoxysilane, cyclic hexylethyldimethoxy Silane, cyclic hexylmethyldimethoxysilane, cyclopentyltriethoxysilane, diisobutyldiethoxysilane, isobutyltriethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, cyclic heptylmethyl di Ethoxy silane, dicycloheptyl diethoxy silane, or a mixture of two or more thereof.

The catalyst composition for polyolefin synthesis may include 10 to 200 parts by weight of the co-catalyst per 100 parts by weight of the transition metal compound.

Also, the catalyst composition for synthesizing polyolefin may include 10 to 100 parts by weight of the external electron donor per 100 parts by weight of the transition metal compound.

If the content of the co-catalyst and the external electron donor is too small, it may be difficult for the co-catalyst and the external electron donor to exert the appropriate action and effect. If the content of the co-catalyst and the external electron donor is too large, It may be uneven or the activity may be lowered.

The catalyst composition for polyolefin synthesis may be a solid, and may be in the form of a solid organic solvent or a solution in a water-soluble solvent.

On the other hand, according to another embodiment of the invention, a transition metal compound; And a step of reacting an internal electron donor comprising a compound represented by the following formula (1): < EMI ID = 1.0 >

[Chemical Formula 1]

In the formula 1, n is an integer of 1 to 10, R ¹ and R ² may be the same or different and each represents a straight or branched alkyl group having 1 to 10 carbon atoms, a straight or branched chain alkyl group having 2 to 10 carbon atoms An alkenyl group, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

R ³ and R ⁴ may be the same or different and each is a straight or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an oxoalkyl group having 3 to 10 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms To 10 oxoalkyl groups.

More specific details regarding the above-described formula (1) and specific details regarding the above-mentioned functional groups are as described above.

The details of the transition metal compound are as described above.

The catalyst composition for polyolefin synthesis can be prepared by reacting the transition metal compound and the internal electron donor comprising the compound of Formula 1. As described above, the catalyst composition for synthesizing polyolefins does not contain a substance harmful to humans and the environment, and can provide a polyolefin having high catalytic activity and excellent stereoregularity.

The method for producing a catalyst composition for polyolefin synthesis is characterized in that the transition metal compound and the internal electron donor are fixed to a carrier containing at least one compound selected from the group consisting of silica, alumina, zeolite, a magnesium compound, Step < / RTI >

In the step of fixing the transition metal compound and the internal electron donor to the support, the order of fixing the transition metal compound and the internal electron donor to the support is not limited. For example, both the transition metal compound and the internal electron donor may be supported on the support And the two components may be sequentially carried on the carrier.

Specifically, the step of immobilizing the transition metal compound and the internal electron donor on the carrier includes: reacting the carrier and the transition metal compound; And reacting the carrier having the transition metal compound carried thereon with the internal electron donor.

The step of reacting the carrier with the transition metal compound may be carried out by slowly introducing the transition metal compound into the carrier over a period of 30 minutes to 5 hours. When the carrier and the transition metal compound are reacted first and then the internal electron donor is reacted, a catalyst having an active site through the reaction of the carrier and the transition metal compound is formed, and then an internal electron donor is introduced, This increased catalyst can be produced, and the stereoregularity of the resulting polyolefin can be improved.

The step of reacting the carrier and the transition metal compound may be performed at -50 to 50 ° C, preferably -30 to 20 ° C. When the reaction temperature is lower than -50 ° C or higher than 50 ° C, the particle shape of the catalyst as the final product is not easy, so that the process stability in commercial production may be lowered.

The step of reacting the carrier bearing the transition metal compound with the internal electron donor may be performed at -20 to 150 ° 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 of the resultant catalyst or the stereoregularity of the polymer may be lowered due to side reactions, which is not preferable.

The step of reacting the carrier carrying the transition metal compound with the internal electron donor may be performed after the step of reacting the carrier and the transition metal compound, and a step of raising the temperature of the reactant may be performed between the both reaction steps Can proceed. Specifically, the step of reacting the carrier and the transition metal compound may be gradually started 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 is It may be more than 80 ℃.

On the other hand, the step of reacting the carrier and the transition metal compound may include a step of reacting the carrier with the transition metal compound in the presence of at least one nonpolar organic compound selected from the group consisting of aliphatic hydrocarbons having 6 to 20 carbon atoms, alicyclic hydrocarbons having 3 to 20 carbon atoms, and aromatic hydrocarbons having 6 to 20 carbon atoms And mixing the carrier with the solvent or alcohol to form a carrier precursor solution.

The carrier precursor solution means a solution capable of forming the carrier, or a solution capable of reacting with the transition metal compound or the internal electron donor to form a carrier on which the components are immobilized.

Although the alcohol that can be used in the step of forming the carrier precursor solution is not particularly limited, for example, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, neopentane Aliphatic or alicyclic alcohols such as cyclohexanol, cyclohexanol, cyclohexanol, cyclohexanol, cyclohexanol, cyclohexanol, cyclohexanol, n-hexanol, ; Aryl cyclic alcohols such as cyclohexanol and methylcyclohexanol; Or aromatic alcohols such as benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol and? -Methylbenzyl alcohol; Can be used.

The details of the carrier are as described above.

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 application time are not limited.

In the step of reacting the internal electron donor comprising the transition metal compound and the compound of the following formula 1, 5 to 100 parts by weight of the internal electron donor may be reacted with 100 parts by weight of the transition metal compound. If the amount of the internal electron donor is too small, the reaction does not sufficiently take place, and the action and effect of the internal electron donor may not be exhibited. If the amount of the internal electron donor is too large, the catalytic activity may be lowered.

In the step of reacting the carrier and the transition metal compound, 10 to 1000 parts by weight of the transition metal compound may be reacted with 100 parts by weight of the carrier. If the amount of the transition metal compound is too small as compared with the above-mentioned carrier, the amount of the transition metal compound to be supported is small and the catalytic activity may be insufficient. When the amount of the transition metal compound is too large as compared with the above carrier, An excessive amount of transition metal component is present in the catalyst, which is not economical and the catalytic activity may be lowered.

The method for preparing a catalyst composition for polyolefin synthesis may further include the step of reacting the transition metal compound and the internal electron donor with a cocatalyst or an external electron donor.

In the method for producing a catalyst composition for polyolefin synthesis, 10 to 200 parts by weight of the co-catalyst may be reacted with 100 parts by weight of the transition metal compound, and the external electron donor may be added to 100 to 100 parts by weight of the transition metal compound. By weight can be reacted.

As the cocatalyst, an organometallic compound known to be usable as a catalyst for polyolefin synthesis can be used without any limitation, and the compound of the above formula (3) can be preferably used.

As the external electron donor, a compound known to be usable for the catalyst for synthesizing polyolefin may be used without limitation, and the compound of the above formula (4) may be preferably used.

According to the present invention, there is provided an environmentally friendly catalyst composition for polyolefin synthesis, which can provide a polyolefin having a high catalytic activity and excellent stereoregularity and which does not contain substances harmful to human and environment, a method for producing the same, A process for producing a polyolefin using a catalyst composition can be provided.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example : Of the inner electron donor  synthesis, Polyolefin  Preparation of synthetic catalyst composition, synthesis of polyolefin]

< Example  1>

One. Of the inner electron donor  synthesis

N, N'-dimethoxy 2,2-methylmalonamide is prepared by the following procedure.

a) N, N'-Dimethoxy 2,2-methylmalonate is prepared by the following procedure. Dimethylmalonate (4.32 mL, 37.8 mmol) was added to a 100 mL round-bottomed flask charged with 60% sodium hydride (6.04 g, 151 mmol) in tetrahydrofuran and dimethylformamide (1: 1) ^o Under C, slowly drop. After stirring at 10 ^° C for 10 minutes, iodomethane (9.4 mL, 151 mmol) is slowly added dropwise at room temperature for 30 minutes. After stirring for about 30 minutes at room temperature, the reaction liquid is heated to 50 ° C to conduct the reaction. The mixture is stirred overnight. After lowering the temperature to room temperature, water is slowly added to terminate the reaction and extracted with ethyl acetate (3 x 60 ml). The combined organic layers are washed once with 1N aqueous hydrochloric acid solution and dried over magnesium sulfate. After filtration, the filtrate is concentrated to obtain a mixture. This mixture was purified by column chromatography (ethyl acetate: n -hexane = 1:30) to give the product N, N'-dimethoxy 2,2-methylmalonate (4.8 g, 79%).

b) N, N'-dimethoxy 2,2-methylmalonic acid is prepared as follows. To a solution of N, N -dimethoxy 2,2-methylmalonate (4.8 g, 29.9 mmol) in methanol (10 mL) is added dropwise 1N sodium hydroxide (5 mL) to a 100 mL round bottom flask. After stirring for about 10 minutes, the reaction is refluxed at 70 ^° C and stirred for 5 hours. After lowering the temperature to room temperature, the methanol solvent is removed by using a reduced pressure apparatus, followed by extraction with ethyl acetate and water. At this time, the pH of the water layer is adjusted to 2 to 3. Extract with ethyl acetate (5 x 60 mL). After drying with magnesium sulfate and filtration, the filtrate was concentrated to give N, N'-dimethoxy 2,2-methyl maloic acid (2.8 g, 72%).

c) N, N'-Dimethoxy 2,2-methyl maloyl chloride is prepared by the following procedure. Add thionyl chloride (8 mL) to N, N'-dimethoxy 2,2-methyl maloic acid (2.8 g, 21.5 mmol) in a 100 mL round bottom flask. The reaction solution was stirred at 60 ^° C for 5 hours, and then the solvent was removed using a rotary evaporator. Proceed to the next step without further purification.

d) N, N'-dimethoxy 2,2-methylmalonamide is prepared by the following procedure. To a solution of methoxyamine hydrochloride (3.95 g, 47.3 mmol) in methylene chloride in a 100 mL round bottom flask was added N, N'-dimethoxy 2,2-methyl maloyl chloride (3.6 g, 21.5 mmol) a (8.9 mL, 64.5 mmol) was added under 0 ^o C. The mixture was stirred at 0 ^° C for 20 minutes and then at room temperature for 12 hours. After removing all of the solvent with a rotary evaporator, add ether solvent to form a precipitate, and then remove the precipitate through a filter. After filtration, the filtrate was concentrated and purified by column chromatography (methanol: chloro chloride = 1: 2) to give the final compound N, N'-dimethoxy 2,2-methylmalonamide (2.2 g, 56%).

2. Polyolefin  Preparation of catalyst composition for synthesis

A 2 L size glass reactor equipped with a stirrer, an oil circulation heater and a cooling reflux was sufficiently ventilated with nitrogen, and 20 g of diethoxy magnesium carrier was added to 200 ml of titanium tetrachloride while maintaining the temperature at a low temperature of 0 ° C or lower. Respectively. After the addition was completed, the temperature was maintained for 1 hour, and then the temperature of the reactor was gradually raised to 100 ° C.

After the addition of 2.8 g of N, N'-dimethoxy 2,2-methylmalonamide at 100 ° C. and reaction for 1 hour, the stirring was stopped and the supernatant liquid was removed. And washed twice with 300 ml of titanium tetrachloride at the same temperature. And washed five times with 200 ml of n-hexane at 70 ° C to obtain a pale yellow solid catalyst. The catalyst obtained by vacuum drying was found to have a titanium content of 2.9%.

3. Polypropylene polymerization

First, a 2 L high-pressure reactor heated at 120 ° C was ventilated with nitrogen for 1 hour to make the state of the high-pressure reactor to a nitrogen atmosphere. The temperature of the reactor was lowered to 25 캜 in a nitrogen atmosphere, and the reactor was ventilated with propylene to maintain the reactor in a propylene atmosphere. In a reactor maintained in a propylene gas atmosphere, 2 mmol of triethylaluminum diluted in a decane solvent at a molar concentration of 1 mol was added, and a cyclohexylmethyldimethoxysilane external electron donor diluted in a decane solvent was added to a Si / Ti molar ratio of 30 Respectively. 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 stirrer. After the polymerization, the reactor was heated to 70 ° C and polymerized at 70 ° C for 1 hour. The measurement results are shown in Table 1.

< Example  2>

One. Of the inner electron donor  synthesis

N, N'-dimethoxy 2,2-methylpropanemalonamide is prepared by the following procedure.

a) N, N'-Dimethoxy 2,2-methylpropane malonate is prepared by the following procedure. Dimethylmalonate (4.32 mL, 37.8 mmol) was added to a 100 mL round-bottom flask charged with 60% sodium hydride (6.04 g, 151 mmol) in tetrahydrofuran and dimethyl formamide (1: 1) ^o Under C, slowly drop. After stirring at 10 ^° C for 10 min, 1-bromo-2-methylpropane (16.4 mL, 151 mmol) is slowly added dropwise at room temperature for 30 min. After stirring for about 30 minutes at room temperature, the reaction liquid is heated to 50 ° C to conduct the reaction. The mixture is stirred overnight. After lowering the temperature to room temperature, water is slowly added to terminate the reaction and extracted with ethyl acetate (3 x 60 ml). The combined organic layers are washed once with 1N aqueous hydrochloric acid solution and dried over magnesium sulfate. After filtration, the filtrate is concentrated to obtain a mixture. This mixture was purified by column chromatography (ethyl acetate: n -hexane = 1: 30) to give the product N, N'-dimethoxy 2,2-methylpropane malonate (6.9 g, 75%).

b) N, N'-dimethoxy 2,2-methylpropanemalonic acid is prepared as follows. To the solution obtained by dissolving N, N'-dimethoxy 2,2-methylmalonate (6.9 g, 28.3 mmol) in methanol (10 mL) into a 100 mL round bottom flask, 1 N sodium hydroxide (5 mL) was added dropwise. After stirring for about 10 minutes, the reaction is refluxed at 70 ^° C and stirred for 5 hours. After lowering the temperature to room temperature, the methanol solvent is removed by using a reduced pressure apparatus, followed by extraction with ethyl acetate and water. At this time, the pH of the water layer is adjusted to 2 to 3. Extract with ethyl acetate (5 x 60 mL). After drying over magnesium sulfate and filtration, the filtrate was concentrated to give N, N'-dimethoxy 2,2-methyl maloic acid (4.3 g, 71%).

c) N, N'-Dimethoxy 2,2-methylpropane maloyl chloride is prepared by the following procedure. Into a 100 mL round-bottomed flask, add thionyl chloride (10 mL) to N, N'-dimethoxy 2,2-methyl maloic acid (4.3 g, 20.1 mmol). The reaction solution was stirred at 60 ^° C for 5 hours, and then the solvent was removed using a rotary evaporator. Proceed to the next step without further purification.

d) N, N'-dimethoxy 2,2-methylpropanemalonamide is prepared by the following procedure. To a solution of methoxyamine hydrochloride (3.7 g, 44.2 mmol) in methylene chloride in a 100 mL round bottom flask was added N, N'-dimethoxy 2,2-methylpropane maloyl chloride (5.0 g, 20.1 mmol) Add ethylamine (8.4 mL, 60.3 mmol) at 0 ^° C. The mixture was stirred at 0 ^° C for 20 minutes and then at room temperature for 12 hours. After removing all of the solvent with a rotary evaporator, add ether solvent to form a precipitate, and then remove the precipitate through a filter. After filtration, the filtrate was concentrated and purified by column chromatography (methanol: chloro chloride = 1: 2) to give the final compound N, N'-dimethoxy 2,2-methylpropane malonamide (5.4 g, 45% .

2. Preparation of solid catalyst and polypropylene polymerization

In the preparation of the solid catalyst of Example 1, a catalyst was synthesized by using 4.0 g of N, N'-dimethoxy 2,2-methylpropane malonamide instead of 2.8 g of N, N'-dimethoxy 2,2-methylmalonamide , Where the titanium content was 2.7%. The same procedure as in the polymerization of polypropylene in Example 1 was carried out, and the results are shown in Table 1.

< Example  3>

In the preparation of the solid catalyst of Example 1, a catalyst was synthesized by using 5.4 g of N, N'-dimethoxy 2,2-methylpropane malonamide instead of 2.8 g of N, N'-dimethoxy 2,2-methylmalonamide , Where the titanium content was 2.8%. The same procedure as in the polymerization of polypropylene in Example 1 was carried out, and the results are shown in Table 1.

< Comparative Example >

A catalyst was synthesized using 4.1 g of diisobutylphthalate instead of 2.8 g of N, N'-dimethoxy 2,2-methylmalonamide in the preparation of the solid catalyst of Example 1, wherein the titanium content was 2.8%. The same procedure as in the polymerization of polypropylene in Example 1 was carried out, and the results are shown in Table 1.

[ Experimental Example : The activity of the catalyst composition and the Polyolefin  Measurement of stereoregularity]

1. Measurement of catalytic activity

In the above Examples and Comparative Examples, the catalyst activity was measured by measuring the weight (Kg) of the polymer produced for 1 hour per weight (g) of the catalyst used. [Measuring equipment: midiclave (manufacturer Buchiglasuster)]

2. Stereoregularity measurement

The polypropylene obtained in the above Examples and Comparative Examples was dissolved in xylene, cooled, and then filtered. Then, the weight of the solid obtained by evaporating the filtrate was measured, and the stereoregularity was measured.

The measured results are shown in Table 1 below.

Yes Activity (kg-PP / g-cat, hr) Stereoregularity (XIS) Example 1 26 94.8 Example 2 27 95.3 Example 3 26 95.4 Comparative Example 1 29 97.5

As shown in Table 1, the catalyst compositions of Examples 1 to 3 can secure superior catalytic activity and stereoregularity equal to or higher than that of Comparative Example 1 without using a phthalate-based compound harmful to humans and the environment The point was confirmed.

Claims (19)

Transition metal compounds; And
A catalyst composition for polyolefin synthesis, comprising an internal electron donor comprising a compound of formula
[Chemical Formula 1]

In Formula 1,
n is an integer of 1 to 10,
R ¹ and R ² may be the same or different from each other and each represent hydrogen, a straight or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A cycloalkyl group having 4 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
R ³ and R ⁴ may be the same or different from each other and each represent hydrogen, a straight or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A cycloalkyl group having 4 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an oxoalkyl group having 3 to 10 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms An oxoalkyl group having 1 to 10 carbon atoms.
The method according to claim 1,
Wherein the transition metal compound comprises a compound represented by the following formula (2): &lt; EMI ID =
(2)
MX _n (OR ⁵ ) _4-n
In Formula 2, M is selected from the group consisting of transition metal elements of groups IVB, VB, and VIB,
X is halogen,
R ⁵ represents an alkyl group having 1 to 10 carbon atoms,
n is from 0 to 4;
The method according to claim 1,
And 5 to 100 parts by weight of the internal electron donor based on 100 parts by weight of the transition metal compound.
The method according to claim 1,
Further comprising a carrier containing at least one compound selected from the group consisting of silica, alumina, zeolite, a magnesium compound, and a mixture thereof.
5. The method of claim 4,
Wherein the magnesium compound comprises at least one member selected from the group consisting of magnesium dihalide, dialkoxymagnesium, alkylmagnesium halide, alkoxymagnesium halide, and aryloxymagnesium halide.
5. The method of claim 4,
And 10 to 1000 parts by weight of the transition metal compound with respect to 100 parts by weight of the carrier.
The method according to claim 1,
Further comprising a cocatalyst or an external electron donor.
8. The method of claim 7,
10 to 200 parts by weight of the co-catalyst or 10 to 100 parts by weight of an external electron donor based on 100 parts by weight of the transition metal compound.
8. The method of claim 7,
Wherein the cocatalyst comprises a compound represented by the following general formula (3): &lt; EMI ID =
(3)
R ⁶ _n AlX _{3 -n}
In Formula 3, R ⁶ is an alkyl group having 1 to 8 carbon atoms, X is halogen, and n is 0 to 3.
8. The method of claim 7,
Wherein said external electron donor comprises a compound of formula (4): &lt; EMI ID =
[Chemical Formula 4]
R ⁷ _n Si (OR ⁸ ) _4-n
In Formula 4,
R ⁷ and R ⁸ are each hydrogen, a straight 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, Lt; / RTI &gt; alkoxyalkyl group.
Transition metal compounds; And reacting an internal electron donor comprising a compound of formula (1): &lt; EMI ID =
[Chemical Formula 1]

In Formula 1,
n is an integer of 1 to 10,
R ¹ and R ² may be the same or different and are each a straight or branched alkyl group of 1 to 10 carbon atoms, a straight or branched alkenyl group of 2 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, An aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
R ³ and R ⁴ may be the same or different and each is a straight or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an oxoalkyl group having 3 to 10 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms To 10 oxoalkyl groups.
12. The method of claim 11,
Further comprising the step of fixing the transition metal compound and the internal electron donor to a carrier containing at least one compound selected from the group consisting of silica, alumina, zeolite, a magnesium compound, and a mixture thereof, &Lt; / RTI &gt;
13. The method of claim 12,
The step of immobilizing the transition metal compound and the internal electron donor on the carrier includes:
Reacting the carrier with the transition metal compound; And
And reacting the carrier having the transition metal compound carried thereon with the internal electron donor.
14. The method of claim 13,
The step of reacting the carrier with the transition metal compound may include:
At least one nonpolar solvent or alcohol selected from the group consisting of aliphatic hydrocarbons having 6 to 20 carbon atoms, alicyclic hydrocarbons having 3 to 20 carbon atoms and aromatic hydrocarbons having 6 to 20 carbon atoms is mixed with the carrier to form a carrier precursor solution Wherein the catalyst composition is a polyolefin.
14. The method of claim 13,
Wherein the step of reacting the carrier and the transition metal compound is carried out at -50 to 50 캜.
14. The method of claim 13,
Wherein the step of reacting the carrier bearing the transition metal compound with the internal electron donor is carried out at -20 to 150 ° C.
12. The method of claim 11,
Further comprising reacting the transition metal compound and the internal electron donor with a cocatalyst or an external electron donor.
A process for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition for polyolefin synthesis according to claim 1.
19. The method of claim 18,
The olefin-based monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-tetradecene, 1-hexadecene, 1-aidocene, norbornene, norbornian, ethylidene norbornene, phenyl novodene, vinyl novodene, dicyclopentadiene, - at least one compound selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.