KR20100027875A - Method for producing propylene polymer having a high melt-flowability - Google Patents
Method for producing propylene polymer having a high melt-flowability Download PDFInfo
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Abstract
Description
본 발명은, 높은 용융흐름성을 갖는 프로필렌 중합체의 제조방법에 관한 것으로서, 보다 상세하게는 프로필렌의 중합에 있어서 분자량 조절제인 수소의 반응성을 향상시킴으로써 높은 용융흐름성을 갖는 프로필렌 중합체를 용이하게 제조할 수 있는 방법에 관한 것이다.The present invention relates to a method for producing a propylene polymer having a high melt flow, and more particularly, to improve the reactivity of hydrogen as a molecular weight regulator in the polymerization of propylene to easily produce a propylene polymer having a high melt flow. It is about how it can be.
프로필렌의 기상중합, 슬러리중합 및 벌크중합에 사용되는 촉매계는 지글러계 촉매성분, 알킬알루미늄 및 외부전자공여체로 구성되는 것이 일반적이다. 이러한 일반적인 프로필렌 중합용 촉매계에 있어서, 외부전자공여체는, 고체촉매 표면 상에 존재하는 비입체규칙성의 활성점을 선택적으로 피독 또는 전환시키므로써, 생성되는 결과 중합체의 아이소탁틱 지수, 즉 입체규칙성을 향상시키는 역할을 하는 것으로 잘 알려져 있다. 요컨대, 사용되는 외부전자공여체의 분자구조에 따라, 제조되는 폴리프로필렌 중합체의 입체규칙성은 물론, 활성과 분자량분포 등이 달라지게 되며, 따라서, 이러한 물성들이 향상된 폴리프로필렌 중합체를 얻기 위하여, 특히 다양한 종류의 실란화합물을 외부전자공여체로서 사용하는 다양한 종래기술들이 알려져 있다.Catalyst systems used for gas phase polymerization, slurry polymerization and bulk polymerization of propylene are generally composed of Ziegler-based catalyst components, alkylaluminum and external electron donors. In this general catalyst system for propylene polymerization, the external electron donor selectively poisons or converts non-stereoregular active sites present on the surface of the solid catalyst, thereby resulting in an isotactic index, i.e., stereoregularity, of the resulting polymer. It is well known to play a role in improving. In short, depending on the molecular structure of the external electron donor used, the stereoregularity, activity, and molecular weight distribution of the produced polypropylene polymers are different. Therefore, in order to obtain an improved polypropylene polymer, these properties are particularly various. Various conventional techniques are known for using a silane compound as an external electron donor.
예를 들어, 일본공개특허 평3-33105호 및 평3-33106호에는, 실리카와 디알킬마그네슘을 반응시켜 얻은 담체로부터 합성된 고체촉매성분에 트리에틸알루미늄 및 외부전자공여체로서 디알킬디메톡시실란 화합물, 알킬트리메톡시실란 화합물을 단독으로 또는 혼합하여 사용하므로써 입체규칙성이 높은 폴리프로필렌을 중합하는 방법이 개시되어 있다. 그러나, 외부전자공여체로서 알킬트리메톡시실란 화합물을 사용하는 경우에는 촉매활성이 크게 저하되는 문제점이 있다.For example, Japanese Patent Laid-Open Nos. 3-33105 and 3-33106 disclose trialkylaluminum and a dialkyldimethoxysilane as an external electron donor to a solid catalyst component synthesized from a carrier obtained by reacting silica with dialkyl magnesium. A method of polymerizing polypropylene having high stereoregularity by using a compound or an alkyltrimethoxysilane compound alone or in combination is disclosed. However, when the alkyltrimethoxysilane compound is used as the external electron donor, there is a problem that the catalytic activity is greatly reduced.
한편, 미국특허 제4,952,649호에는, 2-에틸헥실알코올에 녹인 염화마그네슘 용액을 티타늄 테트라클로라이드 및 디알킬프탈레이트와 -20~130℃에서 반응시켜 재결정화된 고체촉매 입자를 형성시키고, 이를 조촉매인 트리에틸알루미늄 및 외부전자공여체인 각종의 디알킬디알콕시실란과 함께 사용하여 프로필렌을 벌크중합하므로써, 아이소탁틱 지수가 96~98%인 고입체규칙성의 폴리프로필렌을 제조하는 방법이 개시되어 있다. 또한, 미국특허 제6,384,160호에 따르면, 디에톡시마그네슘을 티타늄테트라클로라이드 및 내부전자공여체인 디이소부틸프탈레이트 또는 디에틸프탈레이트와 반응시켜 얻어지는 고체촉매 성분을 조촉매인 트리에틸알루미늄 및 외부전자공여체인 디알킬디메톡시실란과 함께 사용하므로써 아이소탁틱 지수가 92~98%인 폴리프로필렌을 제조하는 방법이 개시되어 있다.On the other hand, US Patent No. 4,952,649, a magnesium chloride solution dissolved in 2-ethylhexyl alcohol is reacted with titanium tetrachloride and dialkyl phthalate at -20 ~ 130 ℃ to form a recrystallized solid catalyst particles, which is a promoter A method for producing a high stereoregular polypropylene having an isotactic index of 96 to 98% by bulk polymerization of propylene in combination with triethylaluminum and various dialkyl dialkoxysilanes which are external electron donors is disclosed. Further, according to US Pat. No. 6,384,160, the solid catalyst component obtained by reacting diethoxy magnesium with titanium tetrachloride and the internal electron donor diisobutylphthalate or diethyl phthalate is cocatalyst triethylaluminum and the external electron donor di A method for producing polypropylene having an isotactic index of 92 to 98% by use with an alkyldimethoxysilane is disclosed.
그러나, 상기의 미국특허들에 의해 개시된 주촉매 성분과 외부전자공여체를 사용하는 경우에는, 분자량 조절제인 수소의 반응성이 충분하지 못하기 때문에 용융흐름지수가 50g/10분 이상인 폴리프로필렌을 제조하기에는 현실적으로 무리가 있 다. 즉, 실제 상용공정에 있어서 불충분한 수소 반응성을 보충하고자 중합반응기에 다량의 수소를 투입하게 되면, 장치설계압력의 한계로 인하여 폭발 등의 위험성이 있으므로, 실제 상용공정에서는 실질적으로 수소 투입량에 제약이 존재한다. 따라서, 실제 상용공정에서는, 상기의 미국특허들에 의해 개시된 주촉매 성분과 외부전자공여체를 사용하는 경우, 높은 용융흐름성을 갖는 폴리프로필렌을 제조하기 위해서 필요한 수준의 압력으로까지 수소를 투입할 수 없다는 문제점이 있다.However, in the case of using the main catalyst component and the external electron donor disclosed by the above-described US patents, since the reactivity of hydrogen as a molecular weight regulator is not sufficient, it is practical to prepare polypropylene having a melt flow index of 50 g / 10 minutes or more. There is a group. In other words, if a large amount of hydrogen is added to the polymerization reactor to compensate for insufficient hydrogen reactivity in the actual commercial process, there is a risk of explosion due to the limitation of the device design pressure. exist. Therefore, in a practical commercial process, when the main catalyst component and the external electron donor disclosed by the above-mentioned US patents are used, hydrogen can be introduced to the pressure necessary to produce polypropylene having high melt flowability. There is no problem.
한편, 일본특허공개공보 소57-63311호에 개시된, 외부전자공여체로서 페닐트리에톡시실란을 사용하는 올레핀 중합방법은, 중합후 외부전자공여체에서 이탈된 페닐기로 인한 유해성의 문제가 있고, 일본특허공개공보 평2-170803호에 개시된, 외부전자공여체로서 디알킬디메톡시실란을 사용하는 올레핀 중합방법은, 높은 용융지수를 갖는 중합체를 제조할 수 없다는 단점이 있다. 또한, 일본특허공개공보 평8-157520호에 개시된 올레핀 중합방법에서는 내부전자공여체로서 시클로알킬기로 치환된 알킬알콕시실란을 사용하는데, 이 경우 비교적 높은 수준의 용융흐름성을 가지는 중합체가 얻어질 수는 있으나, 촉매활성이 상대적으로 너무 낮다는 단점이 있다.On the other hand, the olefin polymerization method using phenyltriethoxysilane as an external electron donor disclosed in Japanese Patent Application Laid-Open No. 57-63311 has a problem of harmfulness due to phenyl groups released from the external electron donor after polymerization, and Japanese patent The olefin polymerization method using dialkyldimethoxysilane as an external electron donor, disclosed in Japanese Patent Application Laid-Open No. 2-170803, has a disadvantage in that a polymer having a high melt index cannot be prepared. In addition, in the olefin polymerization method disclosed in Japanese Patent Application Laid-Open No. 8-157520, an alkylalkoxysilane substituted with a cycloalkyl group is used as an internal electron donor. In this case, a polymer having a relatively high level of melt flow can be obtained. However, there is a disadvantage that the catalytic activity is relatively too low.
본 발명의 목적은, 지글러 촉매계를 사용한 프로필렌의 중합에 있어서, 아이소탁틱 지수가 97% 이상으로 상업적으로 사용하기에 충분히 높을 뿐만 아니라, 분자량 조절제인 수소의 반응성이 비약적으로 향상되어 동일한 양의 수소를 반응기에 투입하여도 훨씬 높은 용융흐름지수를 나타내는 프로필렌 중합체를 용이하게 제조할 수 있는 방법을 제공하는 것이다.An object of the present invention is not only high isotactic index of 97% or more, but also sufficiently high for commercial use in the polymerization of propylene using a Ziegler catalyst system. It is to provide a method for easily preparing a propylene polymer having a much higher melt flow index even when introduced into the reactor.
본 발명에 따르면, 주촉매 성분으로서 마그네슘, 티타늄, 할로겐 및 내부전자공여체를 포함하여 이루어지는 지글러계 촉매; 조촉매 성분으로서 알킬알루미늄 화합물; 및 외부전자공여체로서 1종의 디알콕시 실란계 화합물 및 서로 다른 2종의 트리알콕시 실란계 화합물을 포함하여 이루어지는 프로필렌 중합용 촉매계를 사용하여 프로필렌 중합체를 제조하는 방법이 제공된다.According to the present invention, a Ziegler-based catalyst comprising magnesium, titanium, halogen and an internal electron donor as main catalyst components; Alkyl aluminum compounds as cocatalyst components; And a catalyst system for propylene polymerization comprising one dialkoxy silane compound and two different trialkoxy silane compounds as an external electron donor is provided.
이상 설명한 바와 같이, 본 발명에 따르면, 아이소탁틱지수가 99% 이상으로 충분히 높으면서 고입체규칙성이고, 용융흐름성이 매우 우수한 프로필렌 중합체를 얻을 수 있다.As described above, according to the present invention, a propylene polymer having a high stereoregularity and excellent melt flow property while having an isotactic index sufficiently high of 99% or more can be obtained.
본 발명에 따른 프로필렌 중합체 제조 방법에서 사용되는 상기 프로필렌 중합용 촉매계에 있어서, 상기 주촉매 성분은 통상의 지글러계 고체 촉매로서, 바람 직하게는 마그네슘, 티타늄, 할로겐 및 내부전자공여체를 포함하여 이루어지며, 그 조성비에 있어서는 특별한 제한이 없으나, 촉매 활성의 측면을 고려해 볼 때, 마그네슘 5∼40중량%, 티타늄 0.5∼10중량%, 할로겐 50∼85중량% 및 내부전자공여체 2.5∼30중량%를 포함하여 이루어지는 것이 바람직하다.In the catalyst system for propylene polymerization used in the propylene polymer production method according to the present invention, the main catalyst component is a conventional Ziegler-based solid catalyst, and preferably comprises magnesium, titanium, halogen and internal electron donor. However, the composition ratio is not particularly limited, but considering the catalytic activity, 5 to 40 wt% magnesium, 0.5 to 10 wt% titanium, 50 to 85 wt% halogen, and 2.5 to 30 wt% internal electron donor are included. It is preferable to make it.
상기 주촉매 성분에 포함되는 마그네슘의 공급원에는 특별한 제한이 없다. 따라서 염화마그네슘, 디알콕시마그네슘, 알콕시마그네슘클로라이드 등과 같이, 올레핀 중합용 지글러계 촉매의 제조에 사용되는 마그네슘 화합물이라면 모두 제한없이 상기 주촉매 성분의 제조에 사용가능하며, 이 중에서도 디알콕시마그네슘을 사용하는 것이 가장 바람직하다. 상기 디알콕시마그네슘은 금속 마그네슘과 알코올을 반응시켜 제조될 수 있고, 구형의 입자 형상을 갖는 담체로서 작용하며, 이 구형의 입자 형상은 프로필렌의 중합시에도 그대로 유지된다.There is no particular limitation on the source of magnesium included in the main catalyst component. Therefore, any magnesium compound used in the preparation of the Ziegler-based catalyst for olefin polymerization, such as magnesium chloride, dialkoxymagnesium, alkoxymagnesium chloride, etc., can be used for the preparation of the main catalyst component without limitation, and among these, dialkoxy magnesium is used. Most preferred. The dialkoxymagnesium may be prepared by reacting metal magnesium with an alcohol, and serves as a carrier having a spherical particle shape, and the spherical particle shape is maintained even during the polymerization of propylene.
또한, 상기 주촉매 성분에 포함되는 티타늄의 공급원에도 특별한 제한은 없으며, 따라서 올레핀 중합용 지글러계 촉매의 제조에 사용되는 티타늄 화합물이라면 모두 제한없이 상기 주촉매 성분의 제조에 사용가능하며, 특히 티타늄테트라클로라이드를 사용하는 것이 바람직하다.In addition, there is no particular limitation on the source of titanium included in the main catalyst component, and therefore, any titanium compound used in the production of the Ziegler-based catalyst for olefin polymerization can be used for the production of the main catalyst component, and particularly, titanium tetra Preference is given to using chlorides.
또한, 상기 주촉매 성분에 포함되는 내부전자공여체에도 특별한 제한은 없으며, 따라서, 알코올류, 에테르류, 케톤류, 카르복시산류 등과 같이, 올레핀 중합용 지글러계 촉매의 제조에 내부전자공여체로서 사용가능한 화합물이라면 제한 없이 상기 주촉매 성분의 제조에 사용 가능하지만, 그 중에서도 카르복시산에스테르 화합물을 사용하는 것이 바람직하고, 좀더 구체적으로는 벤젠-1,2-디카르복시산에스 테르 화합물 또는 숙신산에스테르 화합물로부터 선택된 하나 또는 그 이상을 혼합하여 내부전자공여체로서 사용하는 것이 더욱 바람직하다. 상기 벤젠-1,2-디카르복시산에스테르 화합물의 구체적인 예로는, 디메틸프탈레이트, 디에틸프탈레이트, 디노말프로필프탈레이트, 디이소프로필프탈레이트, 디노말부틸프탈레이트, 디이소부틸프탈레이트, 디노말펜틸프탈레이트, 디(2-메틸부틸)프탈레이트, 디(3-메틸부틸)프탈레이트, 디네오펜틸프탈레이트, 디노말헥실프탈레이트, 디(2-메틸펜틸)프탈레이트, 디(3-메틸펜틸)프탈레이트, 디이소헥실프탈레이트, 디네오헥실프탈레이트, 디(2,3-디메틸부틸)프탈레이트, 디노말헵틸프탈레이트, 디(2-메틸헥실)프탈레이트, 디(2-에틸펜틸)프탈레이트, 디이소헵틸프탈레이트, 디네오헵틸프탈레이트, 디노말옥틸프탈레이트, 디(2-메틸헵틸)프탈레이트, 디이소옥틸프탈레이트, 디(3-에틸헥실)프탈레이트, 디네오옥틸프탈레이트, 디노말노닐프탈레이트, 디이소노닐프탈레이트, 디노말데실프탈레이트, 디이소데실프탈레이트 등을 들 수 있다.In addition, there are no particular limitations on the internal electron donor included in the main catalyst component, and therefore, as long as the compound can be used as the internal electron donor in the production of Ziegler-based catalysts for olefin polymerization, such as alcohols, ethers, ketones, carboxylic acids, etc. Although it can be used for preparation of the said main catalyst component without a restriction | limiting, it is preferable to use a carboxylic acid ester compound among these, More specifically, one or more selected from the benzene-1, 2- dicarboxylic acid ester compound or the succinic acid ester compound It is more preferable to use the mixture as an internal electron donor. Specific examples of the benzene-1,2-dicarboxylic acid ester compound include dimethyl phthalate, diethyl phthalate, dinormal propyl phthalate, diisopropyl phthalate, dinormal butyl phthalate, diisobutyl phthalate, dinomal pentyl phthalate, and di ( 2-methylbutyl) phthalate, di (3-methylbutyl) phthalate, dinopentylphthalate, dinormalhexylphthalate, di (2-methylpentyl) phthalate, di (3-methylpentyl) phthalate, diisohexylphthalate, di Neohexyl phthalate, di (2,3-dimethylbutyl) phthalate, dinomalheptyl phthalate, di (2-methylhexyl) phthalate, di (2-ethylpentyl) phthalate, diisoheptyl phthalate, dioheptyl phthalate, dinomal Octylphthalate, di (2-methylheptyl) phthalate, diisooctylphthalate, di (3-ethylhexyl) phthalate, dineoctylphthalate, dinomalnonyl phthalate, diisononyl Phthalate, dinormalyl phthalate, diisodecyl phthalate, etc. are mentioned.
상기 주촉매 성분의 제조방법에는 특별한 제한이 없으며, 따라서, 올레핀 중합용 지글러계 촉매를 제조하는 통상의 방법에 따라 제조될 수 있다. 즉, 예컨대 상기 주촉매 성분은, 불활성 기체 분위기하에서 수분을 충분히 제거시킨 교반기가 장착된 반응기내에서, 옥탄, 노난, 데칸, 또는 톨루엔, 크실렌 등과 같은 지방족 탄화수소 또는 방향족 탄화수소 용매 중에 상기 마그네슘 공급원 화합물과 티타늄 공급원 화합물을 현탁시키고, 여기에 내부전자공여체를 투입한 후, 90~130℃의 온도에서 반응시킨 다음, 필요에 따라 추가의 티타늄 화합물과 더 접촉시키고, 유기용매로 세척하므로써 제조될 수 있으며, 또한, 필요에 따라, 상기와 같은 과정을 2 회 이상 반복하여 수행함으로써 제조될 수도 있다.There is no particular limitation on the method of preparing the main catalyst component, and therefore, the main catalyst component may be prepared according to a conventional method of preparing a Ziegler-based catalyst for olefin polymerization. That is, for example, the main catalyst component may be mixed with the magnesium source compound in an aliphatic hydrocarbon or aromatic hydrocarbon solvent such as octane, nonane, decan, or toluene, xylene, or the like in a reactor equipped with a stirrer to remove moisture sufficiently in an inert gas atmosphere. It can be prepared by suspending a titanium source compound, adding an internal electron donor thereto, reacting at a temperature of 90 to 130 ° C., then further contacting with an additional titanium compound if necessary, and washing with an organic solvent. In addition, if necessary, it may be prepared by repeating the above two or more times.
본 발명에 따른 프로필렌 중합체 제조 방법에서 사용되는 상기 프로필렌 중합용 촉매계에 있어서, 상기 조촉매 성분으로는 프로필렌 중합에 사용되는 알킬알루미늄 화합물이 사용되고, 일반식 AlR1 3(여기에서, R1은 탄소수 1~4의 알킬기이다)로 표시되는 알킬알루미늄 화합물이 바람직하게 사용될 수 있으며, 그 구체적인 예로는, 트리메틸알루미늄, 트리에틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 트리이소부틸알루미늄 등을 들 수 있다.In the catalyst system for propylene polymerization used in the propylene polymer production method according to the present invention, as the cocatalyst component, an alkylaluminum compound used for propylene polymerization is used, and in general, AlR 1 3 (wherein R 1 is carbon number 1 Alkyl aluminum compound represented by the alkyl group of ˜4) may be preferably used, and specific examples thereof include trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum and the like.
본 발명에 따른 프로필렌 중합체 제조 방법에서 사용되는 상기 프로필렌 중합용 촉매계에 있어서는, 중합시 분자량 조절제로서 투입되는 수소의 반응성을 향상시키는 효과를 얻기 위하여, 상기 외부전자공여체는 디알콕시 실란계 및 트리알콕시 실란계 화합물로부터 선택된 3종의 실란계 화합물들로 이루어진 것이 바람직하다. 상기 외부전자공여체로서 사용되는 디알콕시 실란계 화합물로서는 일반식 R1R2Si(OR3)2 (여기에서, R1, R2는 탄소수 1~12의 알킬, 알릴, 또는 시클로알킬기를 나타내고, R3은 탄소수 1~3의 알킬기를 나타낸다)로 표시되는 디알콕시실란을 사용하는 것이 바람직하며, 그 중에서도 R1, R2가 탄소수 3~7의 알킬 또는 시클로알킬기이고, R3이 메틸기인 메톡시실란을 사용하는 것이 더욱 바람직하다. 또한 상기 외부전자공여체로서 사용되는 트리알콕시 실란계 화합물로서는 일반식 R4Si(OR5)3(여기 에서, R4는 탄소수 1~12의 포화 또는 불포화 알킬, 알케닐, 시클로알킬기, 알킬아민기, 알콕시기, 실릴기 또는 알콕시실릴기를 나타내고, R5은 탄소수 1~4의 알킬기를 나타낸다)로 표시되는 알킬트리알콕시실란, 알케닐트리알콕시실란, 또는 알킬아미노트리알콕시실란을 사용하는 것이 바람직하며, 그 중에서도 R2가 탄소수 3~7의 알킬, 알케닐, 시클로알킬 또는 알킬아미노기이고, R3이 에틸기인 알킬트리에톡시실란을 사용하는 것이 더욱 바람직하다.In the catalyst system for propylene polymerization used in the propylene polymer production method according to the present invention, in order to obtain the effect of improving the reactivity of hydrogen introduced as a molecular weight regulator during polymerization, the external electron donor is a dialkoxy silane system and a trialkoxy silane. It is preferable that it consists of 3 types of silane compounds selected from the system compounds. As a dialkoxy silane type compound used as said external electron donor, General formula R <1> R <2> Si (OR <3> ) 2 (Here, R <1> , R <2> represents a C1-C12 alkyl, allyl, or cycloalkyl group, R 3 represents an alkyl group having 1 to 3 carbon atoms), preferably a dialkoxysilane represented by R 1 , R 2 , an alkyl or cycloalkyl group having 3 to 7 carbon atoms, and R 3 is a methyl group. More preferably, oxysilane is used. In addition, as the trialkoxy silane-based compound used as the external electron donor, a general formula R 4 Si (OR 5 ) 3 (wherein R 4 is a C1-C12 saturated or unsaturated alkyl, alkenyl, cycloalkyl group, alkylamine group) , An alkoxy group, a silyl group, or an alkoxysilyl group, R 5 represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyltrialkoxysilane, an alkenyltrialkoxysilane, or an alkylaminotrialkoxysilane. Especially, it is more preferable to use the alkyl triethoxysilane whose R <2> is a C3-C7 alkyl, alkenyl, cycloalkyl, or alkylamino group, and R <3> is an ethyl group.
상기 외부전자공여체로서 사용되는 화합물들의 구체적인 예로는, n-C3H7Si(OCH3)3, (n-C3H7)2Si(OCH3)2, i-C3H7Si(OCH3)3, (i-C3H7)2Si(OCH3)2, n-C4H9Si(OCH3)3, (n-C4H9)2Si(OCH3)2, i-C4H9Si(OCH3)3, (i-C4H9)2Si(OCH3)2, t-C4H9Si(OCH3)3, (t-C4H9)2Si(OCH3)2, n-C5H11Si(OCH3)3, (1-프로페닐)Si(OC2H5)3, (n-C5H11)2Si(OCH3)2, (시클로펜틸)Si(OCH3)3, (시클로펜틸)2Si(OCH3)2, (시클로펜틸)(CH3)Si(OCH3)2, (시클로펜틸)(C2H5)Si(OCH3)2, (시클로펜틸)(C3H5)Si(OCH3)2, (시클로헥실)Si(OCH3)3, (시클로헥실)2Si(OCH3)2, (시클로헥실)(CH3)Si(OCH3)2, (시클로헥실)(C2H5)Si(OCH3)2, (시클로헥실)(C3H5)Si(OCH3)2, (시클로헵틸)Si(OCH3)3, (시클로시클로헵틸)2Si(OCH3)2, (시클로시클로헵틸)(CH3)Si(OCH3)2, (1-프로페닐)Si(OCH3)3, (시클로시클로헵틸)(C2H5)Si(OCH3)2, (시클로시클로헵틸)(C3H5)Si(OCH3)2, PhSi(OCH3)3, Ph2Si(OCH3)2(Ph는 페닐기), (N(CH3)2)Si(OCH3)3, (N(C2H5)2)Si(OCH3)3, (N(n-C3H7)2)Si(OCH3)3, (N(i-C3H7)2)Si(OCH3)3, (N(n-C4H9)2)Si(OCH3)3, (N(i-C4H9)2)Si(OCH3)3, (N(t-C4H9)2)Si(OCH3)3, n-C3H5Si(OC2H5)3, (n-C3H7)2Si(OC2H5)2, i-C3H7Si(OC2H5)3, (i-C3H7)2Si(OC2H5)2, n-C4H9Si(OC2H5)3, (n-C4H9)2Si(OC2H5)2, i-C4H9Si(OC2H5)3, (i-C4H9)2Si(OC2H5)2, (1-프로페닐)Si(OC2H5)3, (t-C4H9Si(OC2H5)3, (t-C4H9)2Si(OC2H5)2, n-C5H11Si(OC2H5)3, (n-C5H11)2Si(OC2H5)2, (N(CH3)2)Si(OC2H5)3, (N(C2H5)2)Si(OC2H5)3, (N(n-C3H7)2)Si(OC2H5)3, (N(i-C3H7)2)Si(OC2H5)3, (N(n-C4H9)2)Si(OC2H5)3, (N(i-C4H9)2)Si(OC2H5)3, (N(t-C4H9)2)Si(OC2H5)3, (시클로펜틸)Si(OC2H5)3, (시클로펜틸)2Si(OC2H5)2, (시클로펜틸)(CH3)Si(OC2H5)2, (시클로펜틸)(C2H5)Si(OC2H5)2, (시클로펜틸)(C3H5)Si(OC2H5)2, (시클로헥실)Si(OC2H5)3, (시클로헥실)2Si(OC2H5)2, (시클로헥실)(CH3)Si(OC2H5)2, (시클로헥실)(C2H5)Si(OC2H5)2, (시클로헥실)(C3H5)Si(OC2H5)2, (시클로헵틸)Si(OC2H5)3, (시클로헵틸)2Si(OC2H5)2, (시클로헵틸)(CH3)Si(OC2H5)2, (시클로헵틸)(C2H5)Si(OC2H5)2, (시클로헵틸)(C3H5)Si(OC2H5)2, (페닐)Si(OC2H5)3, (페닐)2Si(OC2H5)2, (CH3)3SiCH2Si(OCH3)3, (CH3)3SiCH2Si(OC2H5)3, (CH3)3SiCH2Si(OC3H7)3, (CH3)3Si(CH2)2Si(OCH3)3, (CH3)3Si(CH2)2Si(OC2H5)3, (CH3)3Si(CH2)2Si(OC3H7)3, (CH3)3Si(CH2)3Si(OCH3)3, (CH3)3Si(CH2)3Si(OC2H5)3, (CH3)3Si(CH2)3Si(OC3H7)3, (CH3)3Si(CH2)4Si(OCH3)3, (CH3)3Si(CH2)4Si(OC2H5)3, (CH3)3Si(CH2)4Si(OC3H7)3, [(CH3)3SiCH2]2Si(OCH3)2, [(CH3)3SiCH2]2Si(OC2H5)2, [(CH3)3Si(CH2)2]2Si(OCH3)2, [(CH3)3Si(CH2)2]2Si(OC2H5)2, [(CH3)3Si(CH2)2]2Si(OCH3)2, [(CH3)3Si(CH2)2]2Si (OC2H5)2, [(CH3)3Si(CH2)3]2Si(OCH3)2, [(CH3)3Si(CH2)3]2Si(OC2H5)2, [(CH3)3Si(CH2)4]2Si(OCH3)2, [(CH3)3Si(CH2)4]2Si(OC2H5)2, (C2H5)3SiCH2Si(OCH3)3, (C2H5)3SiCH2Si(OC2H5)3, (C2H5)3SiCH2Si(OC3H7)3, (C2H5)3Si(CH2)2Si(OCH3)3, (C2H5)3Si(CH2)2Si(OC2H5)3, (C2H5)3Si(CH2)2Si(OC3H7)3, (C2H5)3Si(CH2)3Si(OCH3)3, (C2H5)3Si(CH2)3Si(OC2H5)3, (C2H5)3Si(CH2)3Si(OC3H7)3, (C2H5)3Si(CH2)4Si(OCH3)3, (C2H5)3Si(CH2)4Si(OC2H5)3, (C2H5)3Si(CH2)4Si(OC3H7)3, (C2H5)3Si(CH2)4Si(OC2H5)3, [(C2H5)3SiCH2]2Si(OCH3)2, [(C2H5)3SiCH2]2Si(OC2H5)2, [(C2H5)3Si(CH2)2]2Si(OCH3)2, [(C2H5)3Si(CH2)2]2Si(OC2H5)2, [(C2H5)3Si(CH2)2]2Si(OCH3)2, [(C2H5)3Si(CH2)2]2Si(OC2H5)2, [(C2H5)3Si(CH2)3]2Si(OCH3)2, [(C2H5)3Si(CH2)3]2Si(OC2H5)2, [(C2H5)3Si(CH2)4]2Si(OCH3)2, [(C2H5)3Si(CH2)4]2Si(OC2H5)2, (iso-C3H7)(CH3)2SiCH2Si(OCH3)3, (iso-C3H7)(CH3)2SiCH2Si(OC2H5)3, (iso-C3H7)(CH3)2SiCH2Si(OC3H7)3, (iso- C3H7)(CH3)2Si(CH2)2Si(OCH3)3, (iso-C3H7)(CH3)2Si(CH2)2Si(OC2H5)3, (iso-C3H7)(CH3)2Si(CH2)2Si(OC3H7)3, (iso-C3H7)(CH3)2Si(CH2)3Si(OCH3)3, (iso-C3H7)(CH3)2Si(CH2)3Si(OC2H5)3, (iso-C3H7)(CH3)2Si(CH2)3Si(OC3H7)3, (iso-C3H7)(CH3)2Si(CH2)4Si(OCH3)3, (iso-C3H7)(CH3)2Si(CH2)4Si(OC2H5)3, (iso-C3H7)(CH3)2Si(CH2)4Si(OC3H7)3, [(iso-C3H7)(CH3)2SiCH2]2Si(OCH3)2, [(iso-C3H7)(CH3)2SiCH2]2Si(OC2H5)2, [(iso-C3H7)(CH3)2Si(CH2)2]2Si(OCH3)2, [(iso-C3H7)(CH3)2Si(CH2)2]2Si(OC2H5)2, [(iso-C3H7)(CH3)2Si(CH2)2]2Si(OCH3)2, [(iso-C3H7)(CH3)2Si(CH2)2]2Si(OC2H5)2, [(iso-C3H7)(CH3)2Si(CH2)3]2Si(OCH3)2, [(iso-C3H7)(CH3)2Si(CH2)3]2Si(OC2H5)2, [(iso-C3H7)(CH3)2Si(CH2)4]2Si(OCH3)2, [(iso-C3H7)(CH3)2Si(CH2)4]2Si(OC2H5)2, (tert-C4H9)(CH3)2SiCH2Si(OCH3)3, (tert-C4H9)(CH3)2SiCH2Si(OC2H5)3, (tert-C4H9)(CH3)2SiCH2Si(OC3H7)3, (tert-C4H9)(CH3)2Si(CH2)2Si(OCH3)3, (tert-C4H9)(CH3)2Si(CH2)2Si(OC2H5)3, (tert-C4H9)(CH3)2Si(CH2)2Si(OC3H7)3, (tert-C4H9)(CH3)2Si(CH2)3Si(OCH3)3, (tert-C4H9)(CH3)2Si(CH2)3Si(OC2H5)3, (tert-C4H9)(CH3)2Si(CH2)3Si(OC3H7)3, (tert-C4H9)(CH3)2Si(CH2)4Si(OCH3)3, (tert-C4H9)(CH3)2Si(CH2)4Si(OC2H5)3, (tert- C4H9)(CH3)2Si(CH2)4Si(OC3H7)3, [(tert-C4H9)(CH3)2SiCH2]2Si(OCH3)2, [(tert-C4H9)(CH3)2SiCH2]2Si(OC2H5)2, [(tert-C4H9)(CH3)2Si (CH2)2]2Si(OCH3)2, [(tert-C4H9)(CH3)2Si(CH2)2]2Si(OC2H5)2, [(tert-C4H9)(CH3)2Si(CH2)2]2Si(OCH3)2, [(tert-C4H9)(CH3)2Si(CH2)2]2Si(OC2H5)2, [(tert-C4H9)(CH3)2Si(CH2)3]2Si(OCH3)2, [(tert-C4H9)(CH3)2Si(CH2)3]2Si(OC2H5)2, [(tert-C4H9)(CH3)2Si(CH2)4]2Si(OCH3)2, [(tert-C4H9)(CH3)2Si(CH2)4]2Si(OC2H5)2 (CH3)3SiOSi(OCH3)3, (CH3)3SiOSi(OC2H5)3, (CH3)3SiOSi(OC3H7)3, [(CH3)3SiO]2Si(OCH3)2, [(CH3)3SiO]2Si(OC2H5)2, (C2H5)3SiOSi(OCH3)3, (C2H5)3SiOSi(OC2H5)3, (C2H5)3SiOSi(OC3H7)3, [(C2H5)3SiO]2Si(OCH3)2, [(C2H5)3SiO]2Si(OC2H5)2, (iso-C3H7)(CH3)2SiOSi(OCH3)3, (iso-C3H7)(CH3)2SiOSi(OC2H5)3, (iso-C3H7)(CH3)2SiOSi(OC3H7)3, [(iso-C3H7)(CH3)2SiO]2Si(OCH3)2, [(iso-C3H7)(CH3)2SiO]2Si(OC2H5)2, (tert-C4H9)(CH3)2SiOSi(OCH3)3, (tert-C4H9)(CH3)2SiOSi(OC2H5)3, (tert-C4H9)(CH3)2SiOSi(OC3H7)3, [(tert-C4H9)(CH3)2SiO]2Si(OCH3)2, [(tert-C4H9)2SiO]2Si(OC2H5)2 등이 있다.Specific examples of the compound used as the external electron donor include nC 3 H 7 Si (OCH 3 ) 3 , (nC 3 H 7 ) 2 Si (OCH 3 ) 2 , iC 3 H 7 Si (OCH 3 ) 3 , ( iC 3 H 7 ) 2 Si (OCH 3 ) 2 , nC 4 H 9 Si (OCH 3 ) 3 , (nC 4 H 9 ) 2 Si (OCH 3 ) 2 , iC 4 H 9 Si (OCH 3 ) 3 , ( iC 4 H 9 ) 2 Si (OCH 3 ) 2 , tC 4 H 9 Si (OCH 3 ) 3 , (tC 4 H 9 ) 2 Si (OCH 3 ) 2 , nC 5 H 11 Si (OCH 3 ) 3 , ( 1-propenyl) Si (OC 2 H 5 ) 3, (nC 5 H 11 ) 2 Si (OCH 3 ) 2 , (cyclopentyl) Si (OCH 3 ) 3 , (cyclopentyl) 2 Si (OCH 3 ) 2 , (Cyclopentyl) (CH 3 ) Si (OCH 3 ) 2 , (cyclopentyl) (C 2 H 5 ) Si (OCH 3 ) 2 , (cyclopentyl) (C 3 H 5 ) Si (OCH 3 ) 2 , (Cyclohexyl) Si (OCH 3 ) 3 , (cyclohexyl) 2 Si (OCH 3 ) 2 , (cyclohexyl) (CH 3 ) Si (OCH 3 ) 2 , (cyclohexyl) (C 2 H 5 ) Si ( OCH 3 ) 2 , (cyclohexyl) (C 3 H 5 ) Si (OCH 3 ) 2 , (cycloheptyl) Si (OCH 3 ) 3 , (cyclocycloheptyl) 2 Si (OCH 3 ) 2 , (cyclocycloheptyl ) (CH 3) Si (OCH 3) 2, (1- propenyl) Si (OCH 3) 3, ( cyclohexyl cycloheptyl ) (C 2 H 5) Si (OCH 3) 2, ( cyclohexyl cycloheptyl) (C 3 H 5) Si (OCH 3) 2, PhSi (OCH 3) 3, Ph 2 Si (OCH 3) 2 (Ph is a Phenyl group), (N (CH 3 ) 2 ) Si (OCH 3 ) 3, (N (C 2 H 5 ) 2 ) Si (OCH 3 ) 3, (N (nC 3 H 7 ) 2 ) Si (OCH 3 ) 3, (N (iC 3 H 7 ) 2 ) Si (OCH 3 ) 3, (N (nC 4 H 9 ) 2 ) Si (OCH 3 ) 3, (N (iC 4 H 9 ) 2 ) Si (OCH 3 ) 3, (N (tC 4 H 9 ) 2 ) Si (OCH 3 ) 3 , nC 3 H 5 Si (OC 2 H 5 ) 3 , (nC 3 H 7 ) 2 Si (OC 2 H 5 ) 2 , iC 3 H 7 Si (OC 2 H 5 ) 3 , (iC 3 H 7 ) 2 Si (OC 2 H 5 ) 2 , nC 4 H 9 Si (OC 2 H 5 ) 3 , (nC 4 H 9 ) 2 Si (OC 2 H 5 ) 2 , iC 4 H 9 Si (OC 2 H 5 ) 3 , (iC 4 H 9 ) 2 Si (OC 2 H 5 ) 2 , (1-propenyl) Si (OC 2 H 5 ) 3, (tC 4 H 9 Si (OC 2 H 5 ) 3 , (tC 4 H 9 ) 2 Si (OC 2 H 5 ) 2 , nC 5 H 11 Si (OC 2 H 5 ) 3 , (nC 5 H 11 ) 2 Si (OC 2 H 5 ) 2 , (N (CH 3 ) 2 ) Si (OC 2 H 5 ) 3, (N (C 2 H 5 ) 2 ) Si (OC 2 H 5 ) 3, (N (nC 3 H 7 ) 2 ) Si (OC 2 H 5 ) 3, (N (iC 3 H 7 ) 2 ) Si (OC 2 H 5 ) 3, (N (nC 4 H 9 ) 2 ) Si (OC 2 H 5 ) 3, (N (iC 4 H 9 ) 2 ) Si (OC 2 H 5 ) 3, (N (tC 4 H 9 ) 2 ) Si ( OC 2 H 5 ) 3, (cyclopentyl) Si (OC 2 H 5 ) 3 , (cyclopentyl) 2 Si (OC 2 H 5 ) 2 , (cyclopentyl) (CH 3 ) Si (OC 2 H 5 ) 2 , (Cyclopentyl) (C 2 H 5 ) Si (OC 2 H 5 ) 2 , (cyclopentyl) (C 3 H 5 ) Si (OC 2 H 5 ) 2 , (cyclohexyl) Si (OC 2 H 5 ) 3 , (cyclohexyl) 2 Si (OC 2 H 5 ) 2 , (cyclohexyl) (CH 3 ) Si (OC 2 H 5 ) 2 , (cyclohexyl) (C 2 H 5 ) Si (OC 2 H 5 ) 2 , (cyclohexyl) (C 3 H 5 ) Si (OC 2 H 5 ) 2 , (cycloheptyl) Si (OC 2 H 5 ) 3 , (cycloheptyl) 2 Si (OC 2 H 5 ) 2 , (cyclo Heptyl) (CH 3 ) Si (OC 2 H 5 ) 2 , (cycloheptyl) (C 2 H 5 ) Si (OC 2 H 5 ) 2 , (cycloheptyl) (C 3 H 5 ) Si (OC 2 H 5 ) 2 , (phenyl) Si (OC 2 H 5 ) 3 , (phenyl) 2 Si (OC 2 H 5 ) 2, (CH 3 ) 3 SiCH 2 Si (OCH 3 ) 3 , (CH 3 ) 3 SiCH 2 Si (OC 2 H 5 ) 3 , (CH 3 ) 3 SiCH 2 Si (OC 3 H 7 ) 3 , (CH 3 ) 3 Si (CH 2 ) 2 Si (OCH 3 ) 3 , (CH 3 ) 3 Si (CH 2 ) 2 Si (OC 2 H 5 ) 3 , (CH 3 ) 3 Si (CH 2 ) 2 Si (OC 3 H 7 ) 3 , (CH 3 ) 3 Si (CH 2 ) 3 Si (OCH 3 ) 3 , (CH 3 ) 3 Si (CH 2 ) 3 Si (OC 2 H 5 ) 3 , (CH 3 ) 3 Si (CH 2 ) 3 Si (OC 3 H 7 ) 3 , (CH 3 ) 3 Si (CH 2 ) 4 Si (OCH 3 ) 3 , (CH 3 ) 3 Si (CH 2 ) 4 Si (OC 2 H 5 ) 3 , (CH 3 ) 3 Si (CH 2 ) 4 Si (OC 3 H 7 ) 3 , [(CH 3 ) 3 SiCH 2 ] 2 Si (OCH 3 ) 2 , [(CH 3 ) 3 SiCH 2 ] 2 Si (OC 2 H 5 ) 2 , [(CH 3 ) 3 Si (CH 2 ) 2 ] 2 Si (OCH 3 ) 2 , [(CH 3 ) 3 Si (CH 2 ) 2 ] 2 Si (OC 2 H 5 ) 2 , [(CH 3 ) 3 Si (CH 2 ) 2 ] 2 Si (OCH 3 ) 2 , [(CH 3 ) 3 Si (CH 2 ) 2 ] 2 Si (OC 2 H 5 ) 2 , [(CH 3 ) 3 Si (CH 2 ) 3 ] 2 Si (OCH 3 ) 2 , [(CH 3 ) 3 Si (CH 2 ) 3 ] 2 Si (OC 2 H 5 ) 2 , [(CH 3 ) 3 Si (CH 2 ) 4 ] 2 Si (OCH 3 ) 2 , [(CH 3 ) 3 Si (CH 2 ) 4 ] 2 Si (OC 2 H 5 ) 2 , (C 2 H 5 ) 3 SiCH 2 Si (OCH 3 ) 3 , (C 2 H 5 ) 3 SiCH 2 Si ( OC 2 H 5 ) 3 , (C 2 H 5 ) 3 SiCH 2 Si (OC 3 H 7 ) 3 , (C 2 H 5 ) 3 Si (CH 2 ) 2 Si (OCH 3 ) 3 , (C 2 H 5 ) 3 Si (CH 2 ) 2 Si (OC 2 H 5 ) 3 , (C 2 H 5 ) 3 Si (CH 2 ) 2 Si (OC 3 H 7 ) 3 , (C 2 H 5 ) 3 Si (CH 2 ) 3 Si (OCH 3 ) 3 , (C 2 H 5 ) 3 Si (CH 2 ) 3 Si (OC 2 H 5 ) 3 , (C 2 H 5 ) 3 Si (CH 2 ) 3 Si (O C 3 H 7 ) 3 , (C 2 H 5 ) 3 Si (CH 2 ) 4 Si (OCH 3 ) 3 , (C 2 H 5 ) 3 Si (CH 2 ) 4 Si (OC 2 H 5 ) 3 , ( C 2 H 5 ) 3 Si (CH 2 ) 4 Si (OC 3 H 7 ) 3 , (C 2 H 5 ) 3 Si (CH 2 ) 4 Si (OC 2 H 5 ) 3 , [(C 2 H 5 ) 3 SiCH 2 ] 2 Si (OCH 3 ) 2 , [(C 2 H 5 ) 3 SiCH 2 ] 2 Si (OC 2 H 5 ) 2 , [(C 2 H 5 ) 3 Si (CH 2 ) 2 ] 2 Si (OCH 3 ) 2 , [(C 2 H 5 ) 3 Si (CH 2 ) 2 ] 2 Si (OC 2 H 5 ) 2 , [(C 2 H 5 ) 3 Si (CH 2 ) 2 ] 2 Si (OCH 3 ) 2 , [(C 2 H 5 ) 3 Si (CH 2 ) 2 ] 2 Si (OC 2 H 5 ) 2 , [(C 2 H 5 ) 3 Si (CH 2 ) 3 ] 2 Si (OCH 3 ) 2 , [(C 2 H 5 ) 3 Si (CH 2 ) 3 ] 2 Si (OC 2 H 5 ) 2 , [(C 2 H 5 ) 3 Si (CH 2 ) 4 ] 2 Si (OCH 3 ) 2 , [(C 2 H 5 ) 3 Si (CH 2 ) 4 ] 2 Si (OC 2 H 5 ) 2 , (iso-C 3 H 7 ) (CH 3 ) 2 SiCH 2 Si (OCH 3 ) 3 , (iso- C 3 H 7 ) (CH 3 ) 2 SiCH 2 Si (OC 2 H 5 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 SiCH 2 Si (OC 3 H 7 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 2 Si (OCH 3 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 2 Si (OC 2 H 5 ) 3 , ( iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 2 Si (OC 3 H 7 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 3 Si (OCH 3 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 3 Si (OC 2 H 5 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 3 Si (OC 3 H 7 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 4 Si (OCH 3 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 4 Si (OC 2 H 5 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 4 Si (OC 3 H 7 ) 3 , [(iso-C 3 H 7 ) (CH 3 ) 2 SiCH 2 ] 2 Si (OCH 3 ) 2 , [(iso-C 3 H 7 ) (CH 3 ) 2 SiCH 2 ] 2 Si (OC 2 H 5 ) 2 , [(iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 2 ] 2 Si (OCH 3 ) 2 , [(iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 2 ] 2 Si (OC 2 H 5 ) 2 , [(iso- C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 2 ] 2 Si (OCH 3 ) 2 , [(iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 2 ] 2 Si (OC 2 H 5 ) 2 , [(iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 3 ] 2 Si (OCH 3 ) 2 , [(iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 3 ] 2 Si (OC 2 H 5 ) 2 , [(iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 4 ] 2 Si (OCH 3 ) 2 , [(iso-C 3 H 7 ) (CH 3 ) 2 Si (CH 2 ) 4 ] 2 Si (OC 2 H 5 ) 2 , (tert-C 4 H 9 ) (CH 3 ) 2 SiCH 2 Si (OCH 3 ) 3 , (tert -C 4 H 9 ) (CH 3 ) 2 SiCH 2 Si (OC 2 H 5 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 SiCH 2 Si (OC 3 H 7 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 Si ( CH 2 ) 2 Si (OCH 3 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 2 Si (OC 2 H 5 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 2 Si (OC 3 H 7 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 3 Si (OCH 3 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 3 Si (OC 2 H 5 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 3 Si (OC 3 H 7 ) 3 , ( tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 4 Si (OCH 3 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 4 Si (OC 2 H 5 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 4 Si (OC 3 H 7 ) 3 , [(tert-C 4 H 9 ) (CH 3 ) 2 SiCH 2 ] 2 Si (OCH 3 ) 2 , [(tert-C 4 H 9 ) (CH 3 ) 2 SiCH 2 ] 2 Si (OC 2 H 5 ) 2 , [(tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 2 ] 2 Si (OCH 3 ) 2 , [(tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 2 ] 2 Si (OC 2 H 5 ) 2 , [(tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 2 ] 2 Si (OCH 3 ) 2 , [(tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 2 ] 2 Si (OC 2 H 5 ) 2 , [(tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 3 ] 2 Si (OCH 3 ) 2 , [(tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 3 ] 2 Si (OC 2 H 5 ) 2 , [(tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 4 ] 2 Si (OCH 3 ) 2 , [(tert-C 4 H 9 ) (CH 3 ) 2 Si (CH 2 ) 4 ] 2 Si (OC 2 H 5 ) 2 (CH 3 ) 3 SiOSi (OCH 3 ) 3 , (CH 3 ) 3 SiOSi (OC 2 H 5 ) 3 , (CH 3 ) 3 SiOSi (OC 3 H 7 ) 3 , [(CH 3 ) 3 SiO] 2 Si (OCH 3 ) 2 , [(CH 3 ) 3 SiO] 2 Si (OC 2 H 5 ) 2 , (C 2 H 5 ) 3 SiOSi (OCH 3 ) 3 , (C 2 H 5 ) 3 SiOSi (OC 2 H 5 ) 3 , (C 2 H 5 ) 3 SiOSi (OC 3 H 7 ) 3 , [(C 2 H 5 ) 3 SiO] 2 Si (OCH 3 ) 2 , [(C 2 H 5 ) 3 SiO] 2 Si (OC 2 H 5 ) 2 , (iso-C 3 H 7 ) (CH 3 ) 2 SiOSi (OCH 3 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 SiOSi (OC 2 H 5 ) 3 , (iso-C 3 H 7 ) (CH 3 ) 2 SiOSi (OC 3 H 7 ) 3 , [(iso-C 3 H 7 ) (CH 3 ) 2 SiO] 2 Si (OCH 3 ) 2 , [(iso-C 3 H 7 ) (CH 3 ) 2 SiO] 2 Si (OC 2 H 5 ) 2 , (tert-C 4 H 9 ) (CH 3 ) 2 SiOSi (OCH 3 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 SiOSi (OC 2 H 5 ) 3 , (tert-C 4 H 9 ) (CH 3 ) 2 SiOSi (OC 3 H 7 ) 3 , [(tert-C 4 H 9 ) (CH 3 ) 2 SiO] 2 Si (OCH 3 ) 2 , [(tert-C 4 H 9 ) 2 SiO] 2 Si (OC 2 H 5 ) 2, and the like. .
본 발명의 프로필렌 중합체 제조 방법에서 사용되는 상기 프로필렌 중합용 촉매계에 있어서, 상기 주촉매 성분에 대한 상기 조촉매 성분의 비율은, 중합방법 에 따라서 다소 차이는 있으나, 주촉매 성분 중의 티타늄 원자에 대한 조촉매 성분 중의 알루미늄 원자의 몰비가 1~1000의 범위인 것이 바람직하며, 10~300의 범위인 것이 보다 바람직하다. 만약 주촉매 성분 중의 티타늄 원자에 대한 조촉매 성분 중의 알루미늄 원자의 몰비가 상기 1~1000의 범위를 벗어나게 되면, 중합활성이 크게 저하되는 문제가 있다.In the catalyst system for propylene polymerization used in the propylene polymer production method of the present invention, the ratio of the cocatalyst component to the main catalyst component is somewhat different depending on the polymerization method, but the crude to the titanium atom in the main catalyst component It is preferable that it is the range of 1-1000, and, as for the molar ratio of the aluminum atom in a catalyst component, it is more preferable that it is the range of 10-300. If the molar ratio of aluminum atoms in the promoter component to titanium atoms in the main catalyst component is outside the range of 1 to 1000, there is a problem that the polymerization activity is greatly reduced.
본 발명의 프로필렌 중합체 제조 방법에서 사용되는 상기 프로필렌 중합용 촉매계에 있어서, 상기 주촉매 성분에 대한 상기 외부전자공여체의 비율은, 중합방법에 따라서 다소 차이는 있으나, 주촉매 성분 중의 티타늄 원자에 대한 외부전자공여체 중의 실리콘 원자의 총 몰비가 0.1~500의 범위인 것이 바람직하며, 1~100의 범위인 것이 보다 바람직하다. 만일, 상기 주촉매 성분 중의 티타늄 원자에 대한 외부전자공여체 중의 실리콘 원자의 몰비가 0.1 미만이면, 생성되는 프로필렌 중합체의 입체규칙성이 현저히 낮아지며, 500을 초과하면 촉매의 중합활성이 현저히 떨어지는 문제점이 있다. 상기 외부전자공여체에 있어서 1종의 디알콕시 실란계 화합물:2종의 트리알콕시 실란계 화합물의 합계량의 몰비는 1:0.5~2의 비율인 것이 본 발명의 효과를 얻기 위한 바람직한 범위이고, 서로 다른 2종의 트리알콕시실란계 화합물간의 몰비는 크게 제한되지 않으나, 1:1~1:3의 몰비인 것이 바람직하다.In the catalyst system for propylene polymerization used in the propylene polymer production method of the present invention, the ratio of the external electron donor to the main catalyst component is slightly different depending on the polymerization method, but is external to the titanium atom in the main catalyst component. The total molar ratio of silicon atoms in the electron donor is preferably in the range of 0.1 to 500, more preferably in the range of 1 to 100. If the molar ratio of silicon atoms in the external electron donor to the titanium atoms in the main catalyst component is less than 0.1, the stereoregularity of the resulting propylene polymer is significantly lowered, and if it exceeds 500, the polymerization activity of the catalyst is significantly lowered. . The molar ratio of the total amount of one dialkoxy silane compound: two trialkoxy silane compounds in the external electron donor is in a ratio of 1: 0.5 to 2, which is a preferred range for obtaining the effect of the present invention. The molar ratio between the two trialkoxysilane-based compounds is not particularly limited, but is preferably a molar ratio of 1: 1 to 1: 3.
본 발명의 프로필렌 중합체 제조 방법에 있어서, 중합반응의 온도는 20~120℃인 것이 바람직한데, 중합반응의 온도가 20℃ 미만이면 반응이 충분하게 진행되지 못하고, 120℃를 초과하면 활성의 저하가 심하고 중합체 물성에도 좋지 않은 영향을 주게 된다.In the propylene polymer production method of the present invention, it is preferable that the temperature of the polymerization reaction is 20 to 120 ° C., but if the temperature of the polymerization reaction is less than 20 ° C., the reaction does not proceed sufficiently, and if the temperature exceeds 120 ° C., the activity decreases. Severe and adversely affect polymer properties.
본 발명의 프로필렌 중합체 제조 방법은, 프로필렌 단독중합체 뿐만 아니라 프로필렌과 탄소수 2~6(3은 제외)의 알파-올레핀과의 공중합체의 제조에도 유효하게 적용될 수 있다.The propylene polymer production method of the present invention can be effectively applied not only to the propylene homopolymer but also to the production of a copolymer of propylene with an alpha-olefin having 2 to 6 carbon atoms (excluding 3).
이하 실시예에 의해 본 발명을 상세히 설명하나, 이들 실시예는 예시적인 목적일 뿐, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of examples, but these examples are for illustrative purposes only, and the present invention is not limited thereto.
실시예Example 1 One
[주촉매 성분의 제조] [Preparation of main catalyst component]
질소로 충분히 치환된 1리터 크기의 교반기가 설치된 유리반응기에 톨루엔 200ml와 디에톡시마그네슘(25g, 0.219몰)을 투입하고, 250rpm으로 교반시키면서 온도를 10℃로 유지하였다. 여기에 티타늄테트라클로라이드 75ml를 30분에 걸쳐 투입한 다음, 반응기의 온도를 110℃까지 분당 0.5℃의 속도로 승온시켰다. 승온 과정 중에 온도가 25℃에 도달했을 때, 디이소부틸프탈레이트(DIBP) 7.5ml(0.028몰)를 투입하였다. 결과물을 110℃에서 1시간 동안 반응시킨 다음, 교반을 멈추어 고체 생성물이 침전되기를 기다린 후, 상등액을 제거하고 새로운 톨루엔 250ml를 첨가하여 15분간 교반시켜 세척한 후, 동일한 방법으로 1회 더 세척하였다.200 ml of toluene and diethoxy magnesium (25 g, 0.219 mol) were added to a glass reactor equipped with a 1 liter stirrer sufficiently substituted with nitrogen, and the temperature was maintained at 10 ° C. while stirring at 250 rpm. 75 ml of titanium tetrachloride was added thereto over 30 minutes, and then the temperature of the reactor was raised to 110 ° C. at a rate of 0.5 ° C. per minute. When the temperature reached 25 ° C. during the temperature increase process, 7.5 ml (0.028 mol) of diisobutyl phthalate (DIBP) was added thereto. The resultant was reacted at 110 ° C. for 1 hour, and then the stirring was stopped to wait for a solid product to precipitate, and then the supernatant was removed, washed by adding 15 ml of toluene, stirred for 15 minutes, and washed once more in the same manner.
상기와 같이 하여 얻어진 고체 생성물에 톨루엔 200ml를 다시 첨가하고, 온도를 80℃로 유지한 상태에서 250rpm으로 교반시키면서 티타늄테트라클로라이드 75ml와 디이소부틸프탈레이트 5.0ml를 차례로 다시 투입한 후, 반응기의 온도를 110℃까지 30분에 걸쳐 승온시켰다. 110℃에서 1시간 동안 유지한 다음, 교반을 멈추고 상등액을 제거한 후, 새로운 톨루엔 250ml를 첨가하여 상기와 동일한 방법으 로 1회 세척하였다.200 ml of toluene was added again to the solid product obtained as described above, 75 ml of titanium tetrachloride and 5.0 ml of diisobutyl phthalate were sequentially added again while stirring at 250 rpm while maintaining the temperature at 80 ° C., and then the temperature of the reactor was increased. It heated up to 110 degreeC over 30 minutes. After maintaining at 110 ° C. for 1 hour, the stirring was stopped and the supernatant was removed, followed by washing once by adding 250 ml of fresh toluene.
상기와 같이 하여 얻어진 고체 생성물에 100℃의 톨루엔 250ml를 추가로 첨가하고, 동일한 방법으로 1회 더 세척한 후, 40℃에서 매회당 250ml의 노말헥산으로 6회 더 세척하여 연노랑색의 고체인 주촉매 성분을 얻었다. 흐르는 질소에서 8시간 건조시켜 얻어진 고체 주촉매 성분 중의 티타늄 함량은 2.6중량%였다.250 ml of toluene at 100 ° C. was further added to the solid product obtained as described above, and washed once more in the same manner, and then washed six more times with 250 ml of normal hexane each time at 40 ° C. to give a pale yellow solid. The catalyst component was obtained. The titanium content in the solid main catalyst component obtained by drying for 8 hours in flowing nitrogen was 2.6% by weight.
[프로필렌 중합][Propylene polymerization]
2리터 크기의 고압용 스테인레스제 반응기 내에 상기에서 얻어진 촉매 5mg이 채워진 작은 유리관을 장착한 후, 반응기를 질소로 충분히 치환시키고, 조촉매 성분으로서 트리에틸알루미늄 7.0밀리몰을, 외부전자공여체로서 디이소프로필디메톡시실란:이소부틸트리에톡시실란:비닐트리에톡시시란=4:2:1의 혼합물 0.7밀리몰과 함께 반응기 내에 투입하였다. 이어서 수소 1000ml와 액체상태의 프로필렌 1.2ℓ를 차례로 반응기 내에 투입한 후, 교반기를 작동시킴으로써 교반기의 회전과 동시에 내부에 장착되어 있던 유리관이 깨어져 중합이 시작되도록 하고, 이때부터 온도를 70℃까지 올리고, 70℃에서 1시간 동안 중합하였다. 중합이 끝난 후에는 미반응의 프로필렌을 완전히 탈기시킴으로써 프로필렌 단독중합체를 얻었다.After mounting a small glass tube filled with 5 mg of the catalyst obtained above in a 2-liter high-pressure stainless steel reactor, the reactor was sufficiently substituted with nitrogen, and 7.0 mmol of triethylaluminum as an external electron donor was used as an external electron donor. 0.7 mmol of a mixture of dimethoxysilane: isobutyltriethoxysilane: vinyltriethoxysilane = 4: 2: 1 was charged into the reactor. Subsequently, 1000 ml of hydrogen and 1.2 liters of propylene in a liquid state were sequentially introduced into the reactor, and then the stirrer was operated to simultaneously break the glass tube mounted inside the reactor and start the polymerization. The polymerization was carried out at 70 ° C. for 1 hour. After the polymerization was completed, propylene homopolymer was obtained by completely degassing unreacted propylene.
얻어진 프로필렌 단독중합체의 무게로부터 시간당 중합활성을 계산하고, 그 아이소탁틱지수(I.I) 및 용융흐름지수(MFR)를 측정하여 하기 표 1에 나타내었다.The polymerization activity per hour was calculated from the weight of the obtained propylene homopolymer, and the isotactic index (I.I) and the melt flow index (MFR) were measured and shown in Table 1 below.
상기에서, 중합활성, 아이소탁틱지수 및 용융흐름지수는 다음과 같은 방법으로 결정하였다.In the above, the polymerization activity, the isotactic index and the melt flow index were determined by the following method.
① 시간당 중합활성(kg/g-촉매):① hourly polymerization activity (kg / g-catalyst):
시간당 중합체의 생성량(kg) / 촉매의 양(g)Amount of polymer produced per hour (kg) / amount of catalyst (g)
② 아이소탁틱지수(I.I)(%):② isotactic index (I.I) (%):
100(g) - 중합체 100g 중에서, 혼합크실렌중에서 결정화되어 석출된 불용성분의 중량(g)100 g-weight of insoluble component crystallized and precipitated in mixed xylene in 100 g of polymer
③ 용융흐름지수(MFR)(g/10분):③ Melt Flow Index (MFR) (g / 10min):
ASTM1238에 의해, 230℃, 2.16kg 하중에서 측정.By ASTM1238, measured at 230 ° C., 2.16 kg load.
실시예Example 2~5 2 ~ 5
상기의 [프로필렌 중합] 단계에 있어서 수소 투입량을 2000ml, 3000ml, 5000ml, 7000ml로 하고, 외부전자공여체로서 디이소프로필디메톡시실란:이소부틸트리에톡시실란:비닐트리에톡시실란=4:2:1의 혼합물을 0.7밀리몰로 한 것 이외에는, 실시예 1과 동일한 촉매계를 사용하여 동일한 방법으로 프로필렌 중합체를 제조하였다.In the above [propylene polymerization] step, the hydrogen input amount is set to 2000 ml, 3000 ml, 5000 ml, and 7000 ml, and diisopropyldimethoxysilane: isobutyltriethoxysilane: vinyltriethoxysilane = 4: 2: 1 as an external electron donor. A propylene polymer was produced in the same manner using the same catalyst system as in Example 1, except that the mixture was changed to 0.7 mmol.
얻어진 프로필렌 중합체에 대하여, 실시예 1과 동일한 방법으로 중합활성, 아이소탁틱지수 및 용융흐름지수를 결정하였으며, 그 결과를 하기 표 1에 나타내었다.For the obtained propylene polymer, polymerization activity, isotactic index and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1 below.
실시예Example 6~8 6 ~ 8
상기 [프로필렌 중합] 단계에 있어서 수소 투입량을 각각 3000ml로 하고 외부전자공여체의 양을 각각 0.9밀리몰, 1.1밀리몰, 1.3밀리몰로 한 것 이외에는, 실시예 1과 동일한 촉매계를 사용하여 동일한 방법으로 프로필렌 중합체를 제조하였다.In the [propylene polymerization] step, the propylene polymer was prepared in the same manner using the same catalyst system as in Example 1, except that the amount of hydrogen introduced was 3000 ml and the amount of the external electron donor was 0.9 mmol, 1.1 mmol, and 1.3 mmol, respectively. Prepared.
얻어진 프로필렌 중합체에 대하여, 실시예 1과 동일한 방법으로 중합활성, 아이소탁틱지수 및 용융흐름지수를 결정하였으며, 그 결과를 하기 표 1에 나타었다.For the obtained propylene polymer, polymerization activity, isotactic index and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1 below.
실시예Example 9~10 9-10
상기 [프로필렌 중합] 단계에 있어서 수소 투입량을 각각 1000ml, 1000ml, 3000ml로 하고 외부전자공여체로서 디이소프로필디메톡시실란:이소부틸트리에톡시실란:비닐트리에톡시시란=4:1:2, 디이소프로필디메톡시실란:이소부틸트리에톡시실란:비닐트리에톡시시란=3.3:3:1.7, 디이소프로필디메톡시실란:디에틸아미노트리에톡시실란:비닐트리에톡시실란=4:2:1의 몰비로 혼합한 혼합물을 각각 0.7밀리몰로 사용한 것 이외에는 실시예 1과 동일한 촉매계를 사용하여 동일한 방법으로 프로필렌 중합체를 제조하였다.In the above [propylene polymerization] step, the hydrogen injection amount was set to 1000 ml, 1000 ml, and 3000 ml, respectively, and as the external electron donor, diisopropyldimethoxysilane: isobutyltriethoxysilane: vinyltriethoxysilane = 4: 1: 2, di Isopropyldimethoxysilane: isobutyltriethoxysilane: vinyltriethoxysilane = 3.3: 3: 1.7, diisopropyldimethoxysilane: diethylaminotriethoxysilane: vinyltriethoxysilane = 4: 2: A propylene polymer was prepared in the same manner using the same catalyst system as in Example 1, except that 0.7 mmol of the mixture mixed at a molar ratio of 1 was used.
얻어진 프로필렌 중합체에 대하여, 실시예 1과 동일한 방법으로 중합활성, 아이소탁틱지수 및 용융흐름지수를 결정하였으며, 그 결과를 하기 표 1에 나타내었다.For the obtained propylene polymer, polymerization activity, isotactic index and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1 below.
비교예 1~4Comparative Examples 1 to 4
상기 [프로필렌 중합] 단계에 있어서, 외부전자공여체로서 디시클로펜틸디메톡시실란:비닐트리에톡시실란=1:1의 혼합물 0.7밀리몰을 사용하고, 수소 투입량을 각각 1000ml, 2000ml, 3000ml 및 5000ml로 한 것 이외에는, 실시예 1과 동일한 촉매계를 사용하여 동일한 방법으로 프로필렌 중합체를 제조하였다.In the above [propylene polymerization] step, a mixture of dicyclopentyldimethoxysilane: vinyltriethoxysilane = 1: 1 is used as an external electron donor: 0.7 mmol, and the hydrogen input amounts are set to 1000 ml, 2000 ml, 3000 ml and 5000 ml, respectively. Except for the above, the propylene polymer was prepared in the same manner using the same catalyst system as in Example 1.
얻어진 프로필렌 중합체에 대하여, 실시예 1과 동일한 방법으로 중합활성, 아이소탁틱지수 및 용융흐름지수를 결정하였으며, 그 결과를 하기 표 1에 나타내었다.For the obtained propylene polymer, polymerization activity, isotactic index and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1 below.
비교예 5~6Comparative Examples 5-6
상기 [프로필렌 중합] 단계에 있어서, 외부전자공여체로서 디이소프로필디메톡시실란:디시클로펜틸디메톡시실란:비닐트리에톡시실란=1:3:2의 혼합물 0.7밀리몰을 사용하고, 수소 투입량을 각각 1000ml, 3000ml로 한 것 이외에는, 실시예 1과 동일한 촉매계를 사용하여 동일한 방법으로 프로필렌 중합체를 제조하였다.In the above [propylene polymerization] step, a mixture of 0.7 millimoles of diisopropyldimethoxysilane: dicyclopentyldimethoxysilane: vinyltriethoxysilane = 1: 3: 2 is used as an external electron donor, and the hydrogen input amount is respectively A propylene polymer was produced in the same manner using the same catalyst system as in Example 1, except that 1000 ml and 3000 ml were used.
얻어진 프로필렌 중합체에 대하여, 실시예 1과 동일한 방법으로 중합활성, 아이소탁틱지수 및 용융흐름지수를 결정하였으며, 그 결과를 하기 표 1에 나타내었다.For the obtained propylene polymer, polymerization activity, isotactic index and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1 below.
[표 1]TABLE 1
주) week)
DIPDMS : 디이소프로필디메톡시실란(Diisopropyldimethoxysilane)DIPDMS: Diisopropyldimethoxysilane
IBTES : 이소부틸트리에톡시실란(Isobutyltriethoxysilane)IBTES: Isobutyltriethoxysilane
VTES : 비닐트리에톡시실란(Vinyltriethoxysilane)VTES: Vinyltriethoxysilane
DCPDMS: 디시클로펜틸디메톡시실란(Dicyclopentyldimethoxysilane)DCPDMS: Dicyclopentyldimethoxysilane
DEATES: 디에틸아미노트리에톡시실란(Diethylaminotriethoxysilane)DEATES: Diethylaminotriethoxysilane
한편, 상기 표 1에 나타난 실시예 1~4 및 비교예 1~4의 결과를 바탕으로, 외부전자공여체의 종류와 조합에 따른 수소반응성을 비교하고자, 수소 투입량과 용융흐름지수와의 관계를 나타낸 그래프를 도 1에 도시하였다. 도 1의 그래프에 있어서, 그래프의 기울기는 수소반응성을 나타내는 척도이다. 도 1에 따르면, 외부전자공여체로서 디이소프로필디메톡시실란:이소부틸트리에톡시실란:비닐트리에톡시실란을 4:2:1의 비율로 혼합하여 사용한 실시예 1~4의 그래프 기울기가 디시클로펜틸디메톡시실란:비닐트리에톡시실란을 1:1의 비율로 혼합하여 사용한 비교예 1~4의 경우보다 월등히 큼을 알 수 있는 바, 이는 본 발명에 따를 경우 분자량조절제인 수소의 반응성이 비약적으로 향상되어, 동일한 양의 수소를 반응기에 투입하여도 훨씬 높은 용융흐름지수의 프로필렌 중합체를 제조할 수 있다는 것을 의미한다.On the other hand, based on the results of Examples 1 to 4 and Comparative Examples 1 to 4 shown in Table 1, to compare the hydrogen reactivity according to the type and combination of the external electron donor, showing the relationship between the hydrogen input amount and the melt flow index The graph is shown in FIG. In the graph of FIG. 1, the slope of the graph is a measure of hydrogen reactivity. According to FIG. 1, the graph slopes of Examples 1 to 4 using diisopropyldimethoxysilane: isobutyltriethoxysilane: vinyltriethoxysilane in a ratio of 4: 2: 1 as an external electron donor are dicyclo It can be seen that the pentyldimethoxysilane: vinyltriethoxysilane in a ratio of 1: 1 is much larger than that of Comparative Examples 1 to 4, and according to the present invention, the reactivity of hydrogen as a molecular weight regulator is dramatically increased. This means that even the same amount of hydrogen can be added to the reactor to produce propylene polymers of much higher melt flow index.
상기 표 1 및 도 1에 나타난 결과로부터, 프로필렌 중합용 지글러계 주촉매 성분과 알킬알루미늄 조촉매 성분 및 외부전자공여체로 이루어지는 촉매계를 사용한 프로필렌의 중합방법에 있어서, 외부전자공여체로서 사용되는 실란 화합물을, 2개의 알콕시기를 갖고 있는 화합물 1종과 3개의 알콕시기를 갖고 있는 화합물 2종을 적절한 비율로 혼합하여 사용하는 실시예 1~10의 경우, 기존에 상업적으로 사용되고 있는 외부전자공여체 2종을 혼합하여 사용하는 비교예 1~4 및 2개의 알콕시기를 갖는 실란 화합물 2종과 3개의 알콕시기를 갖는 실란 화합물 1종을 혼합하여 사용하는 비교예 5~6에 비해, 분자량 조절제인 수소의 반응성이 비약적으로 향상되어 소량의 수소를 사용하여도 융융흐름지수가 훨씬 높은 프로필렌 중합체를 용이하게 얻을 수 있었음을 알 수 있다.From the results shown in Table 1 and Figure 1, in the polymerization method of propylene using a catalyst system consisting of a Ziegler-based main catalyst component for propylene polymerization, an alkylaluminum cocatalyst component and an external electron donor, a silane compound used as an external electron donor In Examples 1 to 10, in which one compound having two alkoxy groups and two compounds having three alkoxy groups are mixed at an appropriate ratio, the external electron donor 종 two species which are conventionally used are mixed. The reactivity of hydrogen which is a molecular weight modifier is remarkably improved compared with Comparative Examples 1-4 to be used and Comparative Examples 5-6 which use two kinds of silane compounds which have two alkoxy groups, and one silane compound which has three alkoxy groups mixed. Even with a small amount of hydrogen, the propylene polymer with a much higher melt flow index could be easily obtained. Able to know.
도 1은, 본 발명의 실시예 1~5 및 비교예 1~4의 결과를 바탕으로, 외부전자 공여체의 종류에 따른 수소반응성을 비교하고자, 수소 투입량과 용융흐름지수와의 관계를 나타낸 그래프이다.1 is a graph showing the relationship between the hydrogen input amount and the melt flow index to compare the hydrogen reactivity according to the type of external electron donor based on the results of Examples 1 to 5 and Comparative Examples 1 to 4 of the present invention. .
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