KR101339474B1 - A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same - Google Patents

A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same Download PDF

Info

Publication number
KR101339474B1
KR101339474B1 KR1020110123752A KR20110123752A KR101339474B1 KR 101339474 B1 KR101339474 B1 KR 101339474B1 KR 1020110123752 A KR1020110123752 A KR 1020110123752A KR 20110123752 A KR20110123752 A KR 20110123752A KR 101339474 B1 KR101339474 B1 KR 101339474B1
Authority
KR
South Korea
Prior art keywords
catalyst
group
indenyl
polymerization
metallocene
Prior art date
Application number
KR1020110123752A
Other languages
Korean (ko)
Other versions
KR20130057814A (en
Inventor
양춘병
박준려
Original Assignee
삼성토탈 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 삼성토탈 주식회사 filed Critical 삼성토탈 주식회사
Priority to KR1020110123752A priority Critical patent/KR101339474B1/en
Priority to PCT/KR2012/003884 priority patent/WO2013077512A1/en
Publication of KR20130057814A publication Critical patent/KR20130057814A/en
Application granted granted Critical
Publication of KR101339474B1 publication Critical patent/KR101339474B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Abstract

본 발명은 올레핀 중합 및 공중합용 촉매 및 이를 사용하는 올레핀 중합 또는 공중합 방법에 관한 것으로서, 좀더 상세하게는 알콕시실란 화합물과 반응시킨 알루미녹산 및 메탈로센 화합물을 사용하여 촉매 성분을 제조함으로써 촉매활성이 우수한 고분자량의 폴리올레핀 중합 및 공중합용 촉매를 제공하고, 이를 사용하는 올레핀 중합 또는 공중합 방법에 관한 것이다.The present invention relates to a catalyst for olefin polymerization and copolymerization and an olefin polymerization or copolymerization method using the same. More particularly, the catalytic activity is improved by preparing a catalyst component using an aluminoxane and a metallocene compound reacted with an alkoxysilane compound. The present invention provides a catalyst for polyolefin polymerization and copolymerization of high molecular weight, and a method for olefin polymerization or copolymerization using the same.

Description

올레핀 중합 및 공중합용 촉매 및 이를 사용하는 올레핀 중합 또는 공중합 방법{A CATALYST FOR OLEFIN POLYMERIZATION AND CO-POLYMERIZATION AND A METHOD FOR OLEFIN POLYMERIZATION AND CO-POLYMERIZATION WITH USING THE SAME}A catalyst for olefin polymerization and copolymerization and an olefin polymerization or copolymerization method using the same

본 발명은 올레핀 중합 및 공중합용 촉매 및 이를 사용하는 올레핀 중합 또는 공중합 방법에 관한 것으로서, 좀더 상세하게는 알콕시실란 화합물과 반응시킨 알루미녹산 및 메탈로센 화합물을 사용하여 촉매 성분을 제조함으로써 촉매활성이 탁월히 우수한 고분자량의 폴리올레핀 중합 및 공중합용 촉매를 제공하고, 이를 사용하는 올레핀 중합 또는 공중합 방법에 관한 것이다.The present invention relates to a catalyst for olefin polymerization and copolymerization and an olefin polymerization or copolymerization method using the same. More particularly, the catalytic activity is improved by preparing a catalyst component using an aluminoxane and a metallocene compound reacted with an alkoxysilane compound. It provides an excellent catalyst for polyolefin polymerization and copolymerization of high molecular weight, and relates to an olefin polymerization or copolymerization method using the same.

메탈로센은 일반적으로 실험식 LnMQp로 표시될 수 있는데, 여기서 M은 IIIB족, IVB족, VB족 또는 VIB족의 금속이고; Q는 1~20개의 탄소 원자를 갖는 하이드로카르빌기 또는 할로겐이며; p는 M의 원자가-2이고, L은 금속 M과 결합한 리간드이다. 이 메탈로센 화합물을 조촉매인 메틸알루미녹산(MAO)과 병용하여 올레핀 중합체 또는 공중합체를 제조한다. 메틸알루미녹산류(이하 호환적으로 "MAO"라 칭함)는 선형 및/또는 시클릭 메틸알루미녹산 올리고머를 포함하며, 상기 메틸알루미녹산은, 선형 메틸알루미녹산 올리고머인 경우 화학식 R-(Al(R)-O)n-AlR2로 표시되고, 시클릭 메틸알루미녹산 올리고머인 경우에는 화학식 (-Al(R)-O-)m으로 표시되며, 여기서 R은 C1~C8알킬기, 바람직하게는 메틸이고, n은 1~40, 바람직하게는 10~20이고, m은 3~40, 바람직하게는 3~20이다. 메틸알루미녹산은 통상 트리메틸알루미늄을 물과 반응시키거나, 수화된 무기 염류, 예컨대 CuSO4ㆍH2O 또는 Al2(SO4)3ㆍH2O와 반응시킴으로써 제조된다. 또한 메틸알루미녹산은 중합 반응기에 트리메틸알루미늄과 물 또는 함수 무기 염류를 첨가함으로써 중합 반응기내 동일계상에서 생성시킬 수도 있다. 메틸알루미녹산은 분자량 분포가 매우 넓은 올리고머들의 혼합물이며, 통상 평균 분자량은 약 900~1200이다.　메틸알루미녹산은 대개 톨루엔 중에서 용액으로 유지된다. Metallocenes can generally be represented by the empirical formula L n MQ p , where M is a metal of Group IIIB, IVB, VB or VIB; Q is a hydrocarbyl group or halogen having 1 to 20 carbon atoms; p is valence-2 of M, and L is a ligand bound to the metal M. The metallocene compound is used in combination with methylaluminoxane (MAO) as a promoter to produce an olefin polymer or copolymer. Methylaluminoxanes (hereinafter interchangeably referred to as " MAO ") include linear and / or cyclic methylaluminoxane oligomers, wherein the methylaluminoxanes are of the formula R- (Al (R ) -O) n -AlR 2 , and in the case of cyclic methylaluminoxane oligomers, is represented by the formula (-Al (R) -O-) m , where R is a C1-C8 alkyl group, preferably methyl and n are 1-40, Preferably it is 10-20, m is 3-40, Preferably it is 3-20. Methylaluminoxane is usually prepared by reacting trimethylaluminum with water or with hydrated inorganic salts such as CuSO 4 .H 2 O or Al 2 (SO 4 ) 3 .H 2 O. Methylaluminoxane can also be produced in situ in the polymerization reactor by adding trimethylaluminum and water or hydrous inorganic salts to the polymerization reactor. Methylaluminoxane is a mixture of oligomers with a very wide molecular weight distribution, usually having an average molecular weight of about 900-1200. Methylaluminoxane is usually maintained in solution in toluene.

상기 메탈로센 촉매는 유동층 반응기 또는 슬러리 반응기에서 사용되기 위해서는 적절한 지지체 위에 담지되어야 하며, 또한 메탈로센이 담지된 개개의 촉매 입자는 충분한 활성을 나타내어야 촉매 지지체 잔사로 인한 문제를 일으키지 않는다. 현재 개발되어 사용되고 있는 대표적인 메탈로센 담지 촉매의 제조 방법중 하나는　메탈로센 촉매를 메틸알루미녹산과 함께 실리카에 담지시키는 방법이다(미국특허 제4,808,561호, 미국특허 제4,897,455호, 미국 특허 제5,240,894호　　참조).　The metallocene catalyst must be supported on an appropriate support in order to be used in a fluidized bed reactor or slurry reactor, and the individual catalyst particles loaded with metallocene must exhibit sufficient activity so as not to cause problems due to catalyst support residues. One of the representative methods for preparing a metallocene supported catalyst currently being developed and used is a method of supporting a metallocene catalyst on silica together with methylaluminoxane (US Pat. No. 4,808,561, US Pat. No. 4,897,455, US Pat. No. 5,240,894). See reference).

이 방법은 실리카의 히드록시기와 메틸알루미녹산을 반응하게 하여 실리카 표면에 메틸알루미녹산을 담지시키고, 메탈로센 촉매를 담지된 메틸알루미녹산에 담지되게 하는 방법이다. 메탈로센 촉매 성분은 메틸알루미녹산과 동시에 담지되거나, 메틸알루미녹산이 담지된 후에 추가적인 반응을 통하여 담지되기도 한다. 담지된 촉매의 활성은 담지된 메탈로센 성분의 양에 비례하며, 또한 메탈로센 촉매 성분의 담지를 도와주는 메틸알루미녹산의 담지량에도 비례한다. 메틸알루미녹산은 메탈로센 촉매의 담지를 도와줄 뿐만 아니라 메탈로센 촉매 성분을 촉매 독으로부터 보호하는 역할을 수행하게 된다. 따라서 메틸알루미녹산의 담지량은 촉매의 활성에 직접적으로 영향을 미치게 된다.This method is a method in which the hydroxyl group of silica reacts with methylaluminoxane to support methylaluminoxane on the surface of silica, and to be supported on methylaluminoxane supported with a metallocene catalyst. The metallocene catalyst component may be supported simultaneously with the methylaluminoxane or through additional reaction after the methylaluminoxane is supported. The activity of the supported catalyst is proportional to the amount of the metallocene component supported, and also to the amount of methylaluminoxane which assists the support of the metallocene catalyst component. Methylaluminoxane not only supports the metallocene catalyst but also serves to protect the metallocene catalyst component from the catalyst poison. Therefore, the supported amount of methylaluminoxane directly affects the activity of the catalyst.

담지된 메탈로센 촉매의 활성은 촉매의 경제성에 직접적으로 영향을 미치는 주요한 요인이다. 그러나 대개의 경우 상기와 같은 방법으로 담지시킬 경우에 메탈로센 촉매는 비담지 촉매에 비해서는 촉매활성이 많이 줄어든다.　따라서 담지 메탈로센 촉매는 촉매의 종류에 따라서 촉매의 경제성을 만족시키기 어려운 촉매도 많이 있다. The activity of the supported metallocene catalyst is a major factor directly affecting the economics of the catalyst. However, in most cases, when supported by the above method, the metallocene catalyst is much less catalytic activity than the unsupported catalyst. Therefore, the supported metallocene catalyst has many catalysts which are difficult to satisfy the economics of the catalyst depending on the type of catalyst.

이러한 담지 메탈로센 촉매의 촉매활성을 증가시키기 위하여　많은 연구가 진행되어 왔다. 예를 들어, 유기실리콘화합물을 실리카와 반응시켜 기능성 실리카 담체를 제조하고, 여기에 MAO와 메탈로센 화합물을 반응시켜 촉매를 제조하는 방법 (미국특허 제 4874734호, 미국특허 제 5206199호, Makromol. Chem., 1993, 194, 3499, J. Mol. Cat.A:Chem., 2000, 154, 103, J. Mol. Cat.A:Chem., 2003, 197, 233 ), 실리콘 테트라클로라이드(SiCl4)와 실리카를 반응시켜 기능성 실리카 담체를 제조하고, 여기에 MAO와 메탈로센 화합물을 반응시켜 촉매를 제조하는 방법 (Makromol. Rapid Commun., 2002, 23, 672) 등이 알려져 있다. 이러한 방법들에 의하여 개선된 메탈로센 담지 촉매를 제조하려면,　실리카를 처리시 비교적 다량의 실리콘화합물을 사용하고, 실리카와 반응후에 세척을 통해 미반응의 실리콘 화합물을 제거해야 하는 등의 복잡한 과정을 거쳐야 하는 단점이 있다. Many studies have been conducted to increase the catalytic activity of such supported metallocene catalysts. For example, a method of preparing a functional silica carrier by reacting an organosilicon compound with silica, and then reacting MAO with a metallocene compound to prepare a catalyst (US Pat. No. 4,874,734, US Pat. No. 5,206,199, Makromol. Chem., 1993, 194, 3499, J. Mol. Cat. A: Chem., 2000, 154, 103, J. Mol. Cat. A: Chem., 2003, 197, 233), silicon tetrachloride (SiCl 4) A functional silica carrier is prepared by reacting with silica, and a method of preparing a catalyst by reacting MAO with a metallocene compound is known (Makromol. Rapid Commun., 2002, 23, 672). In order to prepare an improved metallocene supported catalyst by these methods, a complicated process such as using a relatively large amount of silicon compound when treating silica and removing unreacted silicon compound by washing after reaction with silica is performed. There are drawbacks to go through.

유기주석화합물을 실리카와 반응시켜 기능성 실리카 담체를 제조하고, 여기에 MAO와 메탈로센 화합물을 반응시켜 촉매를 제조하는 방법(미국특허 제 6908876호, 유럽특허 제 1613667 A2, WO 2004094480 A2, Makromol. Reaction 　Eng., 2008, 2, 339, J. Appl. Polym. Sci. 2007, 106, 3149)에 의하여 개선된 메탈로센 담지 촉매를 제조하면,　사용한 유기주석화합물의 루이스 산성도에 따라서 촉매의 활성이 개선되는 경우가 많이 있으나, 그 산성도의 영향에 따라서 사슬성장 반응의 속도보다 사슬정지 반응의 속도가 증가하여 생성된 분자량이 감소하는 경향이 나타나는 단점이 있다. A method of preparing a functional silica carrier by reacting an organotin compound with silica, and reacting MAO with a metallocene compound to prepare a catalyst (US Pat. No. 6,908,876, EP 1613667 A2, WO 2004094480 A2, Makromol. Reaction Eng., 2008, 2, 339, J. Appl.Polym. Sci. 2007, 106, 3149), prepared metallocene-supported catalysts, the activity of the catalyst was dependent on the Lewis acidity of the organotin compound used. There are many cases of improvement, but there is a disadvantage in that the rate of the chain stop reaction increases rather than the rate of the chain growth reaction according to the effect of the acidity tends to decrease the molecular weight produced.

한편으로는,　메탈로센 촉매를 루이스 베이스인 유기화합물을 MAO와 중합 반응시에 첨가함으로써 촉매성능을 개선하는 연구가 진행되어 왔다. 예를 들어, 테트라히드로퓨란(Tetrahydrofuran), 에틸벤조에이트(Ethyl benzoate), 아세토니트릴(Acetonitrile)을 중합반응시에 MAO와 투입하는 방법(J. Polym. Sci., Part A: Polym. Chem. 1991, 29, 1595), 　tBuMe2SiH, Et3SiH, 폴리(히드로메틸실록산)과 같은 하이드로실란(Hydrosilane)을 중합반응시에 MAO와 투입하는 방법(미국특허 제 6939930호, 미국특허 제 6642326호) 등이 발표되었다. 이 방법들은 촉매의 분자량을 증가시키는 부분에서는 효과적인 것으로 보고되었지만, 촉매의 활성을 감소시켜 촉매의 경제성을 약화시키는 단점이 있다. 　　On the other hand, studies have been conducted to improve the catalytic performance by adding a metallocene catalyst to the base of the Lewis compound-based organic compound during the polymerization reaction with MAO. For example, tetrahydrofuran, ethyl benzoate, and acetonitrile are added with MAO during the polymerization reaction (J. Polym. Sci., Part A: Polym. Chem. 1991). , 29, 1595), a method of adding a hydrosilane such as tBuMe 2 SiH, Et 3 SiH, poly (hydromethylsiloxane) with MAO during the polymerization reaction (US Patent No. 6939930, US Patent No. 6642326) And so on. These methods have been reported to be effective in increasing the molecular weight of the catalyst, but have the disadvantage of reducing the activity of the catalyst by reducing the activity of the catalyst.

따라서 담지 메탈로센 촉매를 적절히 개선하여 촉매의 활성을 증가시키는　개선된 촉매 및 촉매 제조 방법이 요구되고 있다고 할 수 있다.Therefore, it can be said that there is a need for an improved catalyst and a method for preparing the catalyst that appropriately improve the supported metallocene catalyst to increase the activity of the catalyst.

본 발명은 상기와 같은 문제를 해결하기 위한 것으로, 본 발명의 목적은 알콕시실란 화합물과 반응시킨 알루미녹산 및 메탈로센 화합물을 사용하여 촉매 성분을 제조함으로써 촉매활성이 우수한 올레핀 중합 및 공중합용 촉매를 제공하는 것이다.The present invention is to solve the above problems, an object of the present invention is to prepare a catalyst component using aluminoxane and metallocene compound reacted with an alkoxysilane compound to produce a catalyst for olefin polymerization and copolymerization excellent in catalytic activity To provide.

본 발명의 또 다른 목적은 본 발명의 촉매를 이용하므로써 촉매활성이 탁월히 우수한 고분자량의 올레핀 중합체 및 공중합체를 제조할 수 있는 올레핀 중합 또는 공중합 방법에 관한 것이다.Still another object of the present invention relates to an olefin polymerization or copolymerization method capable of producing a high molecular weight olefin polymer and copolymer having excellent catalytic activity by using the catalyst of the present invention.

본 발명에서 제공하고자 하는 촉매활성이 우수하고, 고분자량의 올레핀 (공)중합체의 제조를 가능하게 하는 올레핀 중합　및 공중합용 촉매는 다음의 단계들을 포함하는 제조방법에 의해 제조되는 것을　특징으로 한다:The catalyst for olefin polymerization and copolymerization which is excellent in the catalytic activity to be provided in the present invention and enables the production of high molecular weight olefin (co) polymers is characterized by being prepared by a production method comprising the following steps:

(1) 담체에, 알콕시실란 화합물과 반응시킨 알루미녹산 및 메탈로센 화합물을 담지시키는 단계, (1) supporting an aluminoxane and a metallocene compound reacted with an alkoxysilane compound on a carrier,

(2) 상기 (1)단계에서 얻어진 담지 촉매를 유기용매로 세척하는 단계,(2) washing the supported catalyst obtained in step (1) with an organic solvent,

(3)　상기 (2)단계의 세척된 촉매를 건조시킨 후 촉매 분말로서 회수하는 단계. (3) 단계 drying the washed catalyst of step (2) and recovering it as a catalyst powder.

본 발명에 따른 폴리올레핀 촉매의 제조방법에 있어서, 상기 (1)단계의 담지 과정은 알콕시실란 화합물과 반응시킨 알루미녹산의 용액에 메탈로센 화합물을 용해시켜 얻어진 용액을 담체 슬러리에 첨가하고, 교반시키므로써 수행될 수 있다(담지 (a)과정). 또는 상기 (1)단계의 담지 반응은 담체 슬러리에 알콕시실란 화합물과 반응시킨 알루미녹산 용액을 첨가하고, 교반시켜 담체에 알콕시실란 화합물과 알루미녹산을 담지시켜 얻어진 알루미녹산 담지 담체 슬러리에 메탈로센 화합물을 첨가하여 교반시키므로써 수행될 수도 있다(담지 (b)과정).In the method for preparing a polyolefin catalyst according to the present invention, the supporting step of step (1) is a solution obtained by dissolving a metallocene compound in a solution of aluminoxane reacted with an alkoxysilane compound is added to a carrier slurry and stirred. This can be done by (support process (a)). Alternatively, in the supporting reaction of step (1), the aluminoxane solution reacted with the alkoxysilane compound is added to the carrier slurry, followed by stirring to support the alkoxysilane compound and the aluminoxane on the carrier, thereby obtaining the metallocene compound in the aluminoxane-supported carrier slurry. It may be carried out by adding and stirring (support (b) process).

상기 (1)단계에서 사용되는 메탈로센 화합물은, 그 종류에 특별히 제한은 없으나, 바람직한 예로서 디시클로펜타디에닐 메탈로센 또는 다리결합 메탈로센 또는 모노시클로펜타디에닐 메탈로센을 들 수 있다.The metallocene compound used in the step (1) is not particularly limited in its kind, but examples thereof include dicyclopentadienyl metallocene or bridged metallocene or monocyclopentadienyl metallocene. Can be.

먼저, 디시클로펜타디에닐 메탈로센은 다음의 일반식(1)로 나타낼 수 있다.First, dicyclopentadienyl metallocene can be represented by following General formula (1).

(CpRn)(CpR'm)MLq　‥‥‥ (1)(CpR n ) (CpR ' m ) ML q ‥‥‥ (1)

여기에서 Cp는 시클로펜타디에닐, 인데닐, 또는 플루오레닐이고,Wherein Cp is cyclopentadienyl, indenyl, or fluorenyl,

R과 R'는 각각 독립적으로 수소, 알킬, 알킬에테르(alkylether), 알릴에테르(allylether), 포스핀(phosphine) 또는 아민(amine)을 나타내고,R and R 'each independently represent hydrogen, alkyl, alkylether, allylther, phosphine or amine,

L은 알킬, 알릴, 아릴알킬, 아마이드(amide), 알콕시 또는 할로겐(halogen)을 나타내고,L represents alkyl, allyl, arylalkyl, amide, alkoxy or halogen,

M은 주기율표의 4족 또는 5족의 전이금속(Transition metal)을 나타내고,M represents a transition metal of Group 4 or 5 of the periodic table,

n은 0 ≤ n < 5, 　m은 0 ≤ m < 5, q는 1 ≤ q ≤ 4를 만족하는　정수이다.n is 0 ≦ n <5, m is 0 ≦ m <5, and q is 1 ≦ q ≦ 4.

다리결합 메탈로센은 다음의 일반식(2)로 나타낼 수 있다.The bridged metallocene can be represented by the following general formula (2).

Q(CpRn)(CpR'm)MLq　‥‥‥ (2)Q (CpR n ) (CpR ' m ) ML q ‥‥‥ (2)

여기서 Cp, R, R', M, L은 상기 일반식(1)과 동일한 의미를 가지며, Q는 C고리 사이의 다리결합으로서, 디알킬(Dialkyl), 알킬아릴(Alkylaryl), 디아릴실리콘(Diaryl silicon), 또는 탄소수 1~20개의 탄화수소기를 나타내며, 　n은 0 ≤ n < 4, 　m은 0 ≤ m <4, q는 1 ≤ q ≤ 4를 만족하는　정수이다.Where Cp, R, R ', M, L has the same meaning as in the general formula (1), Q is a bridge bond between the C ring, Dialkyl, Alkylaryl, Diarylsilicon ( Diaryl silicon), or a hydrocarbon group of 1 to 20 carbon atoms, where n is 0 ≦ n <4, m is 0 ≦ m <4, and q is 1 ≦ q ≦ 4.

모노시클로펜타디에닐 메탈로센은 다음의 일반식(3)으로 표시할 수 있다.Monocyclopentadienyl metallocene can be represented by following General formula (3).

Figure 112011093339519-pat00001
　　　‥‥‥ (3)
Figure 112011093339519-pat00001
‥‥‥ (3)

여기에서 (C5H5 -y- xRx)는 시클로펜타디에닐에 붙어있는 치환기의 수를 나타내는 것으로, x는 0, 1, 2, 3 또는 4이며, y는 0 또는 1이다. R은 수소, 탄소수 1~20개의 탄화수소기, 실릴기, 게르밀기, 시아노기, 할로겐 또는 이들의 복합기로 이루어진 1 내지 20개의 비수소 원자를 갖는 치환기를 나타내고, Y'는 -O-, -S-, -NR*-, 또는 -PR*-를 나타내고(R*는 수소, 탄소수 1 내지 12개의 탄화수소기), 탄소수 1 내지 8개의 히드로카르빌옥시기, 실릴기, 탄소수 1 내지 8개의 할로겐화 알킬기, 탄소수 6 내지 20개의 할로겐화 아릴기 또는 이들의 복합기를 나타내고, Z는 SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2 또는 GeR*2를 나타내며, R*는 상기에서 정의한 바와 같고, L은 각각 독립적으로 할라이드, 탄소수 1 내지 20개의 탄화수소기, 탄소수 1 내지 18개의 히드로카르빌옥시기, 탄소수 1 내지 19개의 히드로카르빌아미노기, 탄소수 1 내지 18개의 히드로카르빌아미드기, 탄소수 1 내지 18개의 히드로카르빌포스피드기, 탄소수 1 내지 18개의 히드로카르빌설피드기, 및 이들의 복합기로 이루어진 군에서 선택되는 1 내지 20개의 비수소 치환기를 갖는 치환기를 나타내거나, 또는 2개의 치환기 L이 함께 탄소수 1 내지 30개의 중성 공액 디엔 또는 2가의 기를 나타내고, M은 주기율표의 4족 또는 5족의 전이금속(Transition metal)을 나타낸다.(C 5 H 5 -y- x R x ) represents the number of substituents attached to the cyclopentadienyl, x is 0, 1, 2, 3 or 4, and y is 0 or 1. R represents a substituent having 1 to 20 non-hydrogen atoms consisting of hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group, a germanyl group, a cyano group, a halogen or a combination thereof, and Y 'represents -O-, -S -, -NR *-or -PR *-(R * is hydrogen, a C1-12 hydrocarbon group), a C1-C8 hydrocarbyloxy group, a silyl group, a C1-C8 halogenated alkyl group, A halogenated aryl group having 6 to 20 carbon atoms or a complex group thereof, Z is SiR * 2 , CR * 2 , SiR * 2 SiR * 2 , CR * 2 CR * 2 , CR * = CR *, CR * 2 SiR * 2 or GeR * 2 , R * is as defined above, and L each independently represents a halide, a C1-20 hydrocarbon group, a C1-C18 hydrocarbyloxy group, and a C1-C19 hydrocarbyl Amino group, C1-C18 hydrocarbylamide group, C1-C18 hydrocarbyl Or a substituent having 1 to 20 non-hydrogen substituents selected from the group consisting of phosphide groups, hydrocarbyl sulfide groups having 1 to 18 carbon atoms, and complexes thereof, or two substituents L having 1 to 30 carbon atoms together. Neutral conjugated dienes or divalent groups, and M represents a transition metal of Group 4 or 5 of the periodic table.

상기 일반식(1)로 표시되는 디시클로펜타디에닐 메탈로센의 종류에는, 비스(시클로펜타디에닐)지르코늄디메틸, 비스(메틸시클로펜타디에닐)지르코늄디메틸, 비스(n-부틸시클로펜타디에닐)지르코늄디메틸, 비스(인데닐)지르코늄디메틸, 비스(1,3-디메틸시클로펜타디에닐)지르코늄디메틸, (펜타메틸시클로펜타디에닐)(시클로펜타디에닐)지르코늄디메틸, 비스(펜타메틸시클로펜타디에닐)지르코늄디메틸, 비스(플루오레닐)지르코늄디메틸, 비스(2-메틸인데닐)지르코늄디메틸, 비스(2-페닐인데닐)지르코늄디메틸, 시클로펜타디에닐(2-페닐인데닐)지르코늄디메틸 등과 같은 비스시클로펜타디에닐 메탈로센을 들 수 있고,Examples of the dicyclopentadienyl metallocene represented by General Formula (1) include bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, and bis (n-butylcyclopentadiene). Nil) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl, (pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclo Pentadienyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, bis (2-methylindenyl) zirconium dimethyl, bis (2-phenylindenyl) zirconium dimethyl, cyclopentadienyl (2-phenylindenyl) zirconium Biscyclopentadienyl metallocenes such as dimethyl, and the like.

상기 일반식(2)로 표시되는 다리결합 메탈로센으로는, 디메틸실릴비스(1-인데닐)지르코늄디메틸, 디메틸실릴(9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 디메틸실릴비스(1-시클로펜타디에닐)지르코늄디메틸, 디메틸실릴(9-플루오레닐)(1-인데닐)지르코늄디메틸, 디메틸실릴비스(1-인데닐)하프늄디메틸, 디메틸실릴(9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 디메틸실릴비스(1-시클로펜타디에닐)하프늄디메틸, 디메틸실릴(9-플루오레닐)(1-인데닐)하프늄디메틸, 에틸렌비스(1-시클로펜타디에닐)지르코늄디메틸, 에틸렌비스(1-인데닐)지르코늄디메틸, 에틸렌비스(4,5,6,7-테트라히드로-1-인데닐)지르코늄디메틸, 에틸렌비스(4-메틸-1-인데닐)지르코늄디메틸, 에틸렌비스(5-메틸-1-인데닐)지르코늄디메틸, 에틸렌비스(6-메틸-1-인데닐)지르코늄디메틸, 에틸렌비스(7-메틸-1-인데닐)지르코늄디메틸, 에틸렌비스(4-페닐-1-인데닐)지르코늄디메틸, 에틸렌비스(5-메톡시-1-인데닐)지르코늄디메틸, 에틸렌비스(2,3-디메틸-1-인데닐)지르코늄디메틸, 에틸렌비스(4,7-디메틸-1-인데닐)지르코늄디메틸, 에틸렌비스(4,7-디메톡시-1-인데닐)지르코늄디메틸, 에틸렌비스(트리메틸시클로펜타디에닐)지르코늄디메틸, 에틸렌비스(5-디메틸아미노-1-인데닐)지르코늄디메틸, 에틸렌비스(6-디프로필아미노-1-인데닐)지르코늄디메틸, 에틸렌비스(4,7-비스(디메틸아미노)-1-인데닐)지르코늄디메틸, 에틸렌비스(5-디페닐포스피노-1-인데닐)지르코늄디메틸, 에틸렌(1-디메틸아미노-9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 에틸렌(4-부틸티오-9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 에틸렌(9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 에틸렌비스(9-플루오레닐)지르코늄디메틸, 에틸렌비스(1-시클로펜타디에닐)하프늄디메틸, 에틸렌비스(1-인데닐)하프늄디메틸, 에틸렌비스(4,5,6,7-테트라히드로-1-인데닐)하프늄디메틸, 에틸렌비스(4-메틸-1-인데닐)하프늄디메틸, 에틸렌비스(5-메틸-1-인데닐)하프늄디메틸, 에틸렌비스(6-메틸-1-인데닐)하프늄디메틸, 에틸렌비스(7-메틸-1-인데닐)하프늄디메틸, 에틸렌비스(4-페닐-1-인데닐)하프늄디메틸, 에틸렌비스(5-메톡시-1-인데닐)하프늄디메틸, 에틸렌비스(2,3-디메틸-1-인데닐)하프늄디메틸, 에틸렌비스(4,7-디메틸-1-인데닐)하프늄디메틸, 에틸렌비스(4,7-디메톡시-1-인데닐)하프늄디메틸, 에틸렌비스(트리메틸시클로펜타디에닐)하프늄디메틸, 에틸렌비스(5-디메틸아미노-1-인데닐)하프늄디메틸, 에틸렌비스(6-디프로필아미노-1-인데닐)하프늄디메틸, 에틸렌비스(4,7-비스(디메틸아미노)-1-인데닐)하프늄디메틸, 에틸렌비스(5-디페닐포스피노-1-인데닐)하프늄디메틸, 에틸렌(1-디메틸아미노-9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 에틸렌(4-부틸티오-9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 에틸렌(9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 에틸렌비스(9-플루오레닐)하프늄디메틸, 2,2-프로필비스(1-시클로펜타디에닐)지르코늄디메틸, 2,2-프로필비스(1-인데닐)지르코늄디메틸, 2,2-프로필비스(4,5,6,7-테트라히드로-1-인데닐)지르코늄디메틸, 2,2-프로필비스(4-메틸-1-인데닐)지르코늄디메틸, 2,2-프로필비스(5-메틸-1-인데닐)지르코늄디메틸, 2,2-프로필비스(6-메틸-1-인데닐)지르코늄디메틸, 2,2-프로필비스(7-메틸-1-인데닐)지르코늄디메틸, 2,2-프로필비스(4-페닐-1-인데닐)지르코늄디메틸, 2,2-프로필비스(5-메톡시-1-인데닐)지르코늄디메틸, 2,2-프로필비스(2,3-디메틸-1-인데닐)지르코늄디메틸, 2,2-프로필비스(4,7-디메틸-1-인데닐)지르코늄디메틸, 2,2-프로필비스(4,7-디메톡시-1-인데닐)지르코늄디메틸, 2,2-프로필비스(트리메틸시클로펜타디에닐)지르코늄디메틸, 2,2-프로필비스(5-디메틸아미노-1-인데닐)지르코늄디메틸, 2,2-프로필비스(6-디프로필아미노-1-인데닐)지르코늄디메틸, 2,2-프로필비스(4,7-비스(디메틸아미노)-1-인데닐)지르코늄디메틸, 2,2-프로필비스(5-디페닐포스피노-1-인데닐)지르코늄디메틸, 2,2-프로필(1-디메틸아미노-9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 2,2-프로필(4-부틸티오-9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 2,2-프로필(9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 2,2-프로필비스(9-플루오레닐)지르코늄디메틸, 2,2-프로필비스(1-시클로펜타디에닐)하프늄디메틸, 2,2-프로필비스(1-인데닐)하프늄디메틸, 2,2-프로필비스(4,5,6,7-테트라히드로-1-인데닐)하프늄디메틸, 2,2-프로필비스(4-메틸-1-인데닐)하프늄디메틸, 2,2-프로필비스(5-메틸-1-인데닐)하프늄디메틸, 2,2-프로필비스(6-메틸-1-인데닐)하프늄디메틸, 2,2-프로필비스(7-메틸-1-인데닐)하프늄디메틸, 2,2-프로필비스(4-페닐-1-인데닐)하프늄디메틸, 2,2-프로필비스(5-메톡시-1-인데닐)하프늄디메틸, 2,2-프로필비스(2,3-디메틸-1-인데닐)하프늄디메틸, 2,2-프로필비스(4,7-디메틸-1-인데닐)하프늄디메틸, 2,2-프로필비스(4,7-디메톡시-1-인데닐)하프늄디메틸, 2,2-프로필비스(트리메틸시클로펜타디에닐)하프늄디메틸, 2,2-프로필비스(5-디메틸아미노-1-인데닐)하프늄디메틸, 2,2-프로필비스(6-디프로필아미노-1-인데닐)하프늄디메틸, 2,2-프로필비스(4,7-비스(디메틸아미노)-1-인데닐)하프늄디메틸, 2,2-프로필비스(5-디페닐포스피노-1-인데닐)하프늄디메틸, 2,2-프로필(1-디메틸아미노-9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 2,2-프로필(4-부틸티오-9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 2,2-프로필(9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 2,2-프로필비스(9-플루오레닐)하프늄디메틸, 디페닐메틸비스(1-시클로펜타디에닐)지르코늄디메틸, 디페닐메틸비스(1-인데닐)지르코늄디메틸, 디페닐메틸비스(4,5,6,7-테트라히드로-1-인데닐)지르코늄디메틸, 디페닐메틸비스(4-메틸-1-인데닐)지르코늄디메틸, 디페닐메틸비스(5-메틸-1-인데닐)지르코늄디메틸, 디페닐메틸비스(6-메틸-1-인데닐)지르코늄디메틸, 디페닐메틸비스(7-메틸-1-인데닐)지르코늄디메틸, 디페닐메틸비스(4-페닐-1-인데닐)지르코늄디메틸, 디페닐메틸비스(5-메톡시-1-인데닐)지르코늄디메틸, 디페닐메틸비스(2,3-디메틸-1-인데닐)지르코늄디메틸, 디페닐메틸비스(4,7-디메틸-1-인데닐)지르코늄디메틸, 디페닐메틸비스(4,7-디메톡시-1-인데닐)지르코늄디메틸, 디페닐메틸비스(트리메틸시클로펜타디에닐)지르코늄디메틸, 디페닐메틸비스(5-디메틸아미노-1-인데닐)지르코늄디메틸, 디페닐메틸비스(6-디프로필아미노-1-인데닐)지르코늄디메틸, 디페닐메틸비스(4,7-비스(디메틸아미노)-1-인데닐)지르코늄디메틸, 디페닐메틸비스(5-디페닐포스피노-1-인데닐)지르코늄디메틸, 디페닐메틸(1-디메틸아미노-9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 디페닐메틸(4-부틸티오-9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 디페닐메틸(9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 디페닐메틸비스(9-플루오레닐)지르코늄디메틸, 디페닐메틸비스(1-시클로펜타디에닐)하프늄디메틸, 디페닐메틸비스(1-인데닐)하프늄디메틸, 디페닐메틸비스(4,5,6,7-테트라히드로-1-인데닐)하프늄디메틸, 디페닐메틸비스(4-메틸-1-인데닐)하프늄디메틸, 디페닐메틸비스(5-메틸-1-인데닐)하프늄디메틸, 디페닐메틸비스(6-메틸-1-인데닐)하프늄디메틸, 디페닐메틸비스(7-메틸-1-인데닐)하프늄디메틸, 디페닐메틸비스(4-페닐-1-인데닐)하프늄디메틸, 디페닐메틸비스(5-메톡시-1-인데닐)하프늄디메틸, 디페닐메틸비스(2,3-디메틸-1-인데닐)하프늄디메틸, 디페닐메틸비스(4,7-디메틸-1-인데닐)하프늄디메틸, 디페닐메틸비스(4,7-디메톡시-1-인데닐)하프늄디메틸, 디페닐메틸비스(트리메틸시클로펜타디에닐)하프늄디메틸, 디페닐메틸비스(5-디메틸아미노-1-인데닐)하프늄디메틸, 디페닐메틸비스(6-디프로필아미노-1-인데닐)하프늄디메틸, 디페닐메틸비스(4,7-비스(디메틸아미노)-1-인데닐)하프늄디메틸, 디페닐메틸비스(5-디페닐포스피노-1-인데닐)하프늄디메틸, 디페닐메틸(1-디메틸아미노-9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 디페닐메틸(4-부틸티오-9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 디페닐메틸(9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 디페닐메틸비스(9-플루오레닐)하프늄디메틸, 디페닐실릴비스(1-시클로펜타디에닐)지르코늄디메틸, 디페닐실릴비스(1-인데닐)지르코늄디메틸, 디페닐실릴비스(4,5,6,7-테트라히드로-1-인데닐)지르코늄디메틸, 디페닐실릴비스(4-메틸-1-인데닐)지르코늄디메틸, 디페닐실릴비스(5-메틸-1-인데닐)지르코늄디메틸, 디페닐실릴비스(6-메틸-1-인데닐)지르코늄디메틸, 디페닐실릴비스(7-메틸-1-인데닐)지르코늄디메틸, 디페닐실릴비스(4-페닐-1-인데닐)지르코늄디메틸, 디페닐실릴비스(5-메톡시-1-인데닐)지르코늄디메틸, 디페닐실릴비스(2,3-디메틸-1-인데닐)지르코늄디메틸, 디페닐실릴비스(4,7-디메틸-1-인데닐)지르코늄디메틸, 디페닐실릴비스(4,7-디메톡시-1-인데닐)지르코늄디메틸, 디페닐실릴비스(트리메틸시클로펜타디에닐)지르코늄디메틸, 디페닐실릴비스(5-디메틸아미노-1-인데닐)지르코늄디메틸, 디페닐실릴비스(6-디프로필아미노-1-인데닐)지르코늄디메틸, 디페닐실릴비스(4,7-비스(디메틸아미노)-1-인데닐)지르코늄디메틸, 디페닐실릴비스(5-디페닐포스피노-1-인데닐)지르코늄디메틸, 디페닐실릴(1-디메틸아미노-9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 디페닐실릴(4-부틸티오-9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 디페닐실릴(9-플루오레닐)(1-시클로펜타디에닐)지르코늄디메틸, 디페닐실릴비스(9-플루오레닐)지르코늄디메틸, 디페닐실릴비스(1-시클로펜타디에닐)하프늄디메틸, 디페닐실릴비스(1-인데닐)하프늄디메틸, 디페닐실릴비스(4,5,6,7-테트라히드로-1-인데닐)하프늄디메틸, 디페닐실릴비스(4-메틸-1-인데닐)하프늄디메틸, 디페닐실릴비스(5-메틸-1-인데닐)하프늄디메틸, 디페닐실릴비스(6-메틸-1-인데닐)하프늄디메틸, 디페닐실릴비스(7-메틸-1-인데닐)하프늄디메틸, 디페닐실릴비스(4-페닐-1-인데닐)하프늄디메틸, 디페닐실릴비스(5-메톡시-1-인데닐)하프늄디메틸, 디페닐실릴비스(2,3-디메틸-1-인데닐)하프늄디메틸, 디페닐실릴비스(4,7-디메틸-1-인데닐)하프늄디메틸, 디페닐실릴비스(4,7-디메톡시-1-인데닐)하프늄디메틸, 디페닐실릴비스(트리메틸시클로펜타디에닐)하프늄디메틸, 디페닐실릴비스(5-디메틸아미노-1-인데닐)하프늄디메틸, 디페닐실릴비스(6-디프로필아미노-1-인데닐)하프늄디메틸, 디페닐실릴비스(4,7-비스(디메틸아미노)-1-인데닐)하프늄디메틸, 디페닐실릴비스(5-디페닐포스피노-1-인데닐)하프늄디메틸, 디페닐실릴(1-디메틸아미노-9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 디페닐실릴(4-부틸티오-9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 디페닐실릴(9-플루오레닐)(1-시클로펜타디에닐)하프늄디메틸, 디페닐실릴비스(9-플루오레닐)하프늄디메틸을 들 수 있고,As a bridge | crosslinking metallocene represented by the said General formula (2), dimethyl silyl bis (1-indenyl) zirconium dimethyl, dimethyl silyl (9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, dimethyl Silylbis (1-cyclopentadienyl) zirconiumdimethyl, dimethylsilyl (9-fluorenyl) (1-indenyl) zirconiumdimethyl, dimethylsilylbis (1-indenyl) hafniumdimethyl, dimethylsilyl (9-fluore Nil) (1-cyclopentadienyl) hafnium dimethyl, dimethylsilylbis (1-cyclopentadienyl) hafnium dimethyl, dimethylsilyl (9-fluorenyl) (1-indenyl) hafnium dimethyl, ethylene bis (1- Cyclopentadienyl) zirconium dimethyl, ethylenebis (1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4-methyl-1- Indenyl) zirconium dimethyl, ethylene bis (5-methyl-1-indenyl) zirconium dimethyl, ethylene bis (6-methyl-1-indenyl) zirconium dimethyl , Ethylenebis (7-methyl-1-indenyl) zirconium dimethyl, ethylenebis (4-phenyl-1-indenyl) zirconium dimethyl, ethylenebis (5-methoxy-1-indenyl) zirconium dimethyl, ethylenebis ( 2,3-dimethyl-1-indenyl) zirconium dimethyl, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dimethyl, ethylenebis (4,7-dimethoxy-1-indenyl) zirconium dimethyl, ethylene Bis (trimethylcyclopentadienyl) zirconium dimethyl, ethylene bis (5-dimethylamino-1-indenyl) zirconium dimethyl, ethylene bis (6-dipropylamino-1-indenyl) zirconium dimethyl, ethylene bis (4,7 -Bis (dimethylamino) -1-indenyl) zirconium dimethyl, ethylenebis (5-diphenylphosphino-1-indenyl) zirconium dimethyl, ethylene (1-dimethylamino-9-fluorenyl) (1-cyclo Pentadienyl) zirconium dimethyl, ethylene (4-butylthio-9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, ethylene (9-fluorenyl) (1-cyclo Tadienyl) zirconiumdimethyl, ethylenebis (9-fluorenyl) zirconiumdimethyl, ethylenebis (1-cyclopentadienyl) hafniumdimethyl, ethylenebis (1-indenyl) hafniumdimethyl, ethylenebis (4,5, 6,7-tetrahydro-1-indenyl) hafnium dimethyl, ethylenebis (4-methyl-1-indenyl) hafniumdimethyl, ethylenebis (5-methyl-1-indenyl) hafniumdimethyl, ethylenebis (6- Methyl-1-indenyl) hafniumdimethyl, ethylenebis (7-methyl-1-indenyl) hafniumdimethyl, ethylenebis (4-phenyl-1-indenyl) hafniumdimethyl, ethylenebis (5-methoxy-1- Indenyl) hafniumdimethyl, ethylenebis (2,3-dimethyl-1-indenyl) hafniumdimethyl, ethylenebis (4,7-dimethyl-1-indenyl) hafniumdimethyl, ethylenebis (4,7-dimethoxy- 1-indenyl) hafniumdimethyl, ethylenebis (trimethylcyclopentadienyl) hafniumdimethyl, ethylenebis (5-dimethylamino-1-indenyl) hafniumdimethyl, ethylenebis (6-dipropylamino-1- Denyl) hafnium dimethyl, ethylene bis (4,7-bis (dimethylamino) -1-indenyl) hafnium dimethyl, ethylene bis (5-diphenylphosphino-1-indenyl) hafnium dimethyl, ethylene (1-dimethylamino -9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, ethylene (4-butylthio-9- fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, ethylene (9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, ethylenebis (9-fluorenyl) hafnium dimethyl, 2,2-propylbis (1-cyclopentadienyl) zirconium dimethyl, 2,2-propylbis (1- Nil) zirconium dimethyl, 2,2-propylbis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, 2,2-propylbis (4-methyl-1-indenyl) zirconium dimethyl, 2,2-propylbis (5-methyl-1-indenyl) zirconium dimethyl, 2,2-propylbis (6-methyl-1-indenyl) zirconium dimethyl, 2,2-propylbis (7-methyl-1 Indenyl) zirconium dimethyl, 2,2-propylbis (4-phenyl-1-indenyl ) Zirconium dimethyl, 2,2-propylbis (5-methoxy-1-indenyl) zirconium dimethyl, 2,2-propylbis (2,3-dimethyl-1-indenyl) zirconium dimethyl, 2,2-propyl Bis (4,7-dimethyl-1-indenyl) zirconium dimethyl, 2,2-propylbis (4,7-dimethoxy-1-indenyl) zirconium dimethyl, 2,2-propylbis (trimethylcyclopentadienyl ) Zirconium dimethyl, 2,2-propylbis (5-dimethylamino-1-indenyl) zirconium dimethyl, 2,2-propylbis (6-dipropylamino-1-indenyl) zirconium dimethyl, 2,2-propyl Bis (4,7-bis (dimethylamino) -1-indenyl) zirconium dimethyl, 2,2-propylbis (5-diphenylphosphino-1-indenyl) zirconium dimethyl, 2,2-propyl (1- Dimethylamino-9-fluorenyl) (1-cyclopentadienyl) zirconiumdimethyl, 2,2-propyl (4-butylthio-9-fluorenyl) (1-cyclopentadienyl) zirconiumdimethyl, 2, 2-propyl (9-fluorenyl) (1-cyclopentadienyl) zirconiumdimethyl, 2,2-propyl S (9-fluorenyl) zirconium dimethyl, 2,2-propylbis (1-cyclopentadienyl) hafniumdimethyl, 2,2-propylbis (1-indenyl) hafniumdimethyl, 2,2-propylbis ( 4,5,6,7-tetrahydro-1-indenyl) hafniumdimethyl, 2,2-propylbis (4-methyl-1-indenyl) hafniumdimethyl, 2,2-propylbis (5-methyl-1 -Indenyl) hafniumdimethyl, 2,2-propylbis (6-methyl-1-indenyl) hafniumdimethyl, 2,2-propylbis (7-methyl-1-indenyl) hafniumdimethyl, 2,2-propyl Bis (4-phenyl-1-indenyl) hafniumdimethyl, 2,2-propylbis (5-methoxy-1-indenyl) hafniumdimethyl, 2,2-propylbis (2,3-dimethyl-1- Nil) hafnium dimethyl, 2,2-propylbis (4,7-dimethyl-1-indenyl) hafnium dimethyl, 2,2-propylbis (4,7-dimethoxy-1-indenyl) hafnium dimethyl, 2, 2-propylbis (trimethylcyclopentadienyl) hafniumdimethyl, 2,2-propylbis (5-dimethylamino-1-indenyl) hafniumdimethyl, 2,2-propylbis (6-dipropyl Mino-1-indenyl) hafniumdimethyl, 2,2-propylbis (4,7-bis (dimethylamino) -1-indenyl) hafniumdimethyl, 2,2-propylbis (5-diphenylphosphino-1 Indenyl) hafniumdimethyl, 2,2-propyl (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl) hafniumdimethyl, 2,2-propyl (4-butylthio-9-fluore Nil) (1-cyclopentadienyl) hafnium dimethyl, 2,2-propyl (9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, 2,2-propylbis (9-fluorenyl) hafnium Dimethyl, diphenylmethylbis (1-cyclopentadienyl) zirconiumdimethyl, diphenylmethylbis (1-indenyl) zirconiumdimethyl, diphenylmethylbis (4,5,6,7-tetrahydro-1-indenyl Zirconium dimethyl, diphenylmethylbis (4-methyl-1-indenyl) zirconium dimethyl, diphenylmethylbis (5-methyl-1-indenyl) zirconium dimethyl, diphenylmethylbis (6-methyl-1- Nil) zirconium dimethyl, diphenylmethylbis (7-methyl-1-indenyl) zirconium Dimethyl, diphenylmethylbis (4-phenyl-1-indenyl) zirconium dimethyl, diphenylmethylbis (5-methoxy-1-indenyl) zirconium dimethyl, diphenylmethylbis (2,3-dimethyl-1- Indenyl) zirconium dimethyl, diphenylmethylbis (4,7-dimethyl-1-indenyl) zirconium dimethyl, diphenylmethylbis (4,7-dimethoxy-1-indenyl) zirconium dimethyl, diphenylmethylbis ( Trimethylcyclopentadienyl) zirconium dimethyl, diphenylmethylbis (5-dimethylamino-1-indenyl) zirconium dimethyl, diphenylmethylbis (6-dipropylamino-1-indenyl) zirconium dimethyl, diphenylmethylbis (4,7-bis (dimethylamino) -1-indenyl) zirconium dimethyl, diphenylmethylbis (5-diphenylphosphino-1-indenyl) zirconium dimethyl, diphenylmethyl (1-dimethylamino-9- Fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, diphenylmethyl (4-butylthio-9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, diphenylmethyl (9-ple Orenyl) (1-cyclopentadienyl) zirconium dimethyl, diphenylmethylbis (9-fluorenyl) zirconium dimethyl, diphenylmethylbis (1-cyclopentadienyl) hafnium dimethyl, diphenylmethylbis (1- Indenyl) hafniumdimethyl, diphenylmethylbis (4,5,6,7-tetrahydro-1-indenyl) hafniumdimethyl, diphenylmethylbis (4-methyl-1-indenyl) hafniumdimethyl, diphenylmethyl Bis (5-methyl-1-indenyl) hafniumdimethyl, diphenylmethylbis (6-methyl-1-indenyl) hafniumdimethyl, diphenylmethylbis (7-methyl-1-indenyl) hafniumdimethyl, diphenyl Methylbis (4-phenyl-1-indenyl) hafnium dimethyl, diphenylmethylbis (5-methoxy-1-indenyl) hafnium dimethyl, diphenylmethylbis (2,3-dimethyl-1-indenyl) hafnium Dimethyl, diphenylmethylbis (4,7-dimethyl-1-indenyl) hafniumdimethyl, diphenylmethylbis (4,7-dimethoxy-1-indenyl) hafniumdimethyl, diphenylmethylbis (trimethylcyclopentadier Nil) hafnium dimethyl, di Phenylmethylbis (5-dimethylamino-1-indenyl) hafniumdimethyl, diphenylmethylbis (6-dipropylamino-1-indenyl) hafniumdimethyl, diphenylmethylbis (4,7-bis (dimethylamino) -1-indenyl) hafnium dimethyl, diphenylmethylbis (5-diphenylphosphino-1-indenyl) hafnium dimethyl, diphenylmethyl (1-dimethylamino-9-fluorenyl) (1-cyclopentadier Hafnium dimethyl, diphenylmethyl (4-butylthio-9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, diphenylmethyl (9-fluorenyl) (1-cyclopentadienyl) hafnium Dimethyl, diphenylmethylbis (9-fluorenyl) hafniumdimethyl, diphenylsilylbis (1-cyclopentadienyl) zirconiumdimethyl, diphenylsilylbis (1-indenyl) zirconiumdimethyl, diphenylsilylbis (4 , 5,6,7-tetrahydro-1-indenyl) zirconiumdimethyl, diphenylsilylbis (4-methyl-1-indenyl) zirconiumdimethyl, diphenylsilylbis (5-methyl-1-indenyl) zirconium Dimethyl, Diphenylsilylbis (6-methyl-1-indenyl) zirconium dimethyl, diphenylsilylbis (7-methyl-1-indenyl) zirconium dimethyl, diphenylsilylbis (4-phenyl-1-indenyl) zirconium dimethyl , Diphenylsilylbis (5-methoxy-1-indenyl) zirconium dimethyl, diphenylsilylbis (2,3-dimethyl-1-indenyl) zirconium dimethyl, diphenylsilylbis (4,7-dimethyl-1 Indenyl) zirconium dimethyl, diphenylsilyl bis (4,7-dimethoxy-1-indenyl) zirconium dimethyl, diphenyl silyl bis (trimethylcyclopentadienyl) zirconium dimethyl, diphenyl silyl bis (5-dimethylamino -1-indenyl) zirconium dimethyl, diphenylsilylbis (6-dipropylamino-1-indenyl) zirconium dimethyl, diphenylsilyl bis (4,7-bis (dimethylamino) -1-indenyl) zirconium dimethyl Diphenylsilylbis (5-diphenylphosphino-1-indenyl) zirconium dimethyl, diphenylsilyl (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, Phenylsilyl (4-butylthio-9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, diphenylsilyl (9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, diphenylsilylbis (9-fluorenyl) zirconium dimethyl, diphenylsilylbis (1-cyclopentadienyl) hafnium dimethyl, diphenylsilylbis (1-indenyl) hafnium dimethyl, diphenylsilylbis (4,5,6,7 -Tetrahydro-1-indenyl) hafniumdimethyl, diphenylsilylbis (4-methyl-1-indenyl) hafniumdimethyl, diphenylsilylbis (5-methyl-1-indenyl) hafniumdimethyl, diphenylsilylbis (6-methyl-1-indenyl) hafnium dimethyl, diphenylsilylbis (7-methyl-1-indenyl) hafniumdimethyl, diphenylsilylbis (4-phenyl-1-indenyl) hafniumdimethyl, diphenylsilyl Bis (5-methoxy-1-indenyl) hafniumdimethyl, diphenylsilylbis (2,3-dimethyl-1-indenyl) hafniumdimethyl, diphenylsilylbis (4,7-dimethyl-1-indenyl) Hafnium dimethyl, diphenylsilylbis (4,7-dime Methoxy-1-indenyl) hafniumdimethyl, diphenylsilylbis (trimethylcyclopentadienyl) hafniumdimethyl, diphenylsilylbis (5-dimethylamino-1-indenyl) hafniumdimethyl, diphenylsilylbis (6-di Propylamino-1-indenyl) hafniumdimethyl, diphenylsilylbis (4,7-bis (dimethylamino) -1-indenyl) hafniumdimethyl, diphenylsilylbis (5-diphenylphosphino-1-indenyl Hafnium dimethyl, diphenylsilyl (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, diphenylsilyl (4-butylthio-9-fluorenyl) (1-cyclopenta Dienyl) hafnium dimethyl, diphenylsilyl (9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, diphenylsilylbis (9-fluorenyl) hafnium dimethyl,

상기 일반식(3)으로 표시되는 모노시클로펜타디에닐 메탈로센의 예로는, [(N-t-부틸아미드)(테트라메틸-η5-시클로펜타디에닐)-1,2-에탄디일]티타늄디메틸, [(N-t-부틸아미드)(테트라메틸-η5-시클로펜타디에닐)-디메틸실란]티타늄디메틸, [(N-메틸아미드)(테트라메틸-η5-시클로펜타디에닐)-1,2-에탄디일]티타늄디메틸, [(N-메틸아미드)(테트라메틸-η5-시클로펜타디에닐)-디메틸실란]티타늄디메틸, [(N-페닐아미드)(테트라메틸-η5-시클로펜타디에닐)-디메틸실란]티타늄디메틸, [(N-벤질아미드)(테트라메틸-η5-시클로펜타디에닐)-디메틸실란]티타늄디메틸, (N-메틸아미드)(η5-시클로펜타디에닐)-1,2-에탄디일]티타늄디메틸, [(N-메틸아미드)(η5-시클로펜타디에닐)-디메틸실란]티타늄디메틸, [(N-t-부틸아미드)(η5-인데닐)-디메틸실란]티타늄디메틸, [(N-벤질아미드)(η5-인데닐)-디메틸실란]티타늄디메틸, 디메틸실릴테트라메틸 시클로펜타디에닐-tert-부틸아미도 지르코늄디메틸, 디메틸실릴테트라메틸 시클로펜타디에닐-tert-부틸아미도 하프늄디메틸, 디메틸실릴 tert-부틸 시클로펜타디에닐-tert-부틸아미도 지르코늄디메틸, 디메틸실릴 tert-부틸 시클로펜타디에닐-tert-부틸아미도 하프늄디메틸, 디메틸실릴 트리메틸실릴 시클로펜타디에닐-tert-부틸아미도 지르코늄디메틸, 디메틸실릴테트라메틸 시클로펜타디에닐-페닐아미도 지르코늄디메틸, 디메틸실릴테트라메틸 시클로펜타디에닐-페닐아미도 하프늄디메틸, 메틸페닐실릴 테트라메틸 시클로펜타디에닐-페닐아미도 지르코늄디메틸, 메틸페닐실릴 테트라메틸 시클로펜타디에닐-페닐아미도 하프늄디메틸, 메틸페닐실릴 tert-부틸 시클로펜타디에닐-tert-부틸아미도 지르코늄디메틸, 메틸페닐실릴 tert-부틸 시클로펜타디에닐-tert-부틸아미도 하프늄디메틸, 디메틸실릴테트라메틸 시클로펜타디에닐-p-n-페닐아미도 지르코늄디메틸, 디메틸실릴테트라메틸 시클로펜타디에닐-p-n-페닐아미도 하프늄디메틸, 디브로모비스트리페닐포스핀니켈, 디클로로비스트리페닐포스핀니켈, 디브로모디아세토니트릴니켈, 디브로모디벤조니트릴니켈, 디브로모(1,2-비스디페닐포스피노에탄)니켈, 디브로모(1,3-비스디페닐포스피노에탄)니켈, 디브로모(1,1'-디페닐비스포스피노페로센)니켈, 디메틸비스디페닐포스핀니켈, 디메틸(1,2-비스디페닐포스피노에탄)니켈, 메틸(1,2-비스디페닐포스피노에탄)니켈 테트라플루오로보레이트, (2-디페닐포스피노-1-페닐에틸렌옥시)페닐피리딘니켈, 디클로로비스트리페닐포스핀팔라듐, 디클로로디아세토니트릴팔라듐, 디클로로(1,2-비스디페닐포스피노에탄)팔라듐, 비스트리페닐포스핀팔라듐 비스테트라플루오로보레이트, 비스(2,2'-비피리딘)메틸 철 테트라플루오로보레이트 에테레이트 등과, 또한 상기에서 열거된 각 티타늄, 지르코늄, 및 하프늄 화합물의 "디메틸" 부분을 -디클로로, -디브로모, -디요오드, -디에틸, -디부틸, -디벤질, -디페닐, -비스-2-(N,N-디메틸아미노)벤질, -2-부텐-1,4-디일, -s-트랜스-η4-1,4-디페닐-1,3-부타디엔, 　-s-트랜스-η4-3-메틸-1,3-펜타디엔, -s-트랜스-η4-1,4-디벤질-1,3-부타디엔, -s-트랜스-η4-2,4-헥사디엔, -s-트랜스-η4-1,3-펜타디엔, -s-트랜스-η4-1,4-디톨릴-1,3-부타디엔, -s-트랜스-η4-1,4-비스(트리메틸실릴)-1,3-부타디엔, -s-시스-η4-1,4-디페닐-1,3-부타디엔, -s-시스-η4-3-메틸-1,3-펜타디엔, -s-시스-η4-1,4-디벤질-1,3-부타디엔, -s-시스-η4-2,4-헥사디엔, -s-시스-η4-1,3-펜타디엔, -s-시스-η4-1,4-디톨릴-1,3-부타디엔, -s-시스-η4-1,4-비스(트리메틸실릴)-1,3-부타디엔 등의 화합물로 대체한 화합물을 예로 들 수 있다.Examples of the monocyclopentadienyl metallocene represented by the general formula (3) include [(Nt-butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(Nt-butylamide) (tetramethyl-η5-cyclopentadienyl) -dimethylsilane] titaniumdimethyl, [(N-methylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl ] Titaniumdimethyl, [(N-methylamide) (tetramethyl-η5-cyclopentadienyl) -dimethylsilane] Titaniumdimethyl, [(N-phenylamide) (tetramethyl-η5-cyclopentadienyl) -dimethylsilane ] Titaniumdimethyl, [(N-benzylamide) (tetramethyl-η5-cyclopentadienyl) -dimethylsilane] titaniumdimethyl, (N-methylamide) (η5-cyclopentadienyl) -1,2-ethanediyl ] Titanium dimethyl, [(N-methylamide) (η5-cyclopentadienyl) -dimethylsilane] titanium dimethyl, [(Nt-butylamide) (η5-indenyl) -dimethylsilane] titanium dimethyl, [(N- Benzylamide) (η5- Dimethyl) -dimethylsilane] titaniumdimethyl, dimethylsilyltetramethyl cyclopentadienyl-tert-butylamido zirconium dimethyl, dimethylsilyltetramethyl cyclopentadienyl-tert-butylamido hafnium dimethyl, dimethylsilyl tert-butyl cyclopenta Dienyl-tert-butylamido zirconium dimethyl, dimethylsilyl tert-butyl cyclopentadienyl-tert-butylamido hafnium dimethyl, dimethylsilyl trimethylsilyl cyclopentadienyl-tert-butylamido zirconium dimethyl, dimethylsilyltetramethyl Cyclopentadienyl-phenylamido zirconium dimethyl, dimethylsilyltetramethyl cyclopentadienyl-phenylamido hafnium dimethyl, methylphenylsilyl tetramethyl cyclopentadienyl-phenylamido zirconium dimethyl, methylphenylsilyl tetramethyl cyclopentadienyl- Phenylamido hafnium dimethyl, methylphenylsilyl tert-butyl cyclopentadienyl-tert-butylamido zir Dimethyldimethyl, methylphenylsilyl tert-butyl cyclopentadienyl-tert-butylamido hafnium dimethyl, dimethylsilyltetramethyl cyclopentadienyl-pn-phenylamido zirconium dimethyl, dimethylsilyltetramethyl cyclopentadienyl-pn-phenyl Amido hafnium dimethyl, dibromobistriphenylphosphine nickel, dichlorobistriphenylphosphine nickel, dibromodiacetonitrile nickel, dibromodibenzonitrile nickel, dibromo (1,2-bisdiphenylphosphinoethane ) Nickel, dibromo (1,3-bisdiphenylphosphinoethane) nickel, dibromo (1,1'-diphenylbisphosphinoferrocene) nickel, dimethylbisdiphenylphosphinenickel, dimethyl (1, 2-bisdiphenylphosphinoethane) nickel, methyl (1,2-bisdiphenylphosphinoethane) nickel tetrafluoroborate, (2-diphenylphosphino-1-phenylethyleneoxy) phenylpyridinenickel, dichlorobis Triphenylphosphinepalladium, dichlorodiacetonitrile Palladium, dichloro (1,2-bisdiphenylphosphinoethane) palladium, bistriphenylphosphinepalladium bistetrafluoroborate, bis (2,2'-bipyridine) methyl iron tetrafluoroborate etherate and the like, and also The "dimethyl" portion of each of the titanium, zirconium, and hafnium compounds listed above is selected from -dichloro, -dibromo, -diiodine, -diethyl, -dibutyl, -dibenzyl, -diphenyl, -bis-2 -(N, N-dimethylamino) benzyl, -2-butene-1,4-diyl, -s-trans-η4-1,4-diphenyl-1,3-butadiene, VII-s-trans-η4-3 -Methyl-1,3-pentadiene, -s-trans-η4-1,4-dibenzyl-1,3-butadiene, -s-trans-η4-2,4-hexadiene, -s-trans-η4 -1,3-pentadiene, -s-trans-η4-1,4-ditolyl-1,3-butadiene, -s-trans-η4-1,4-bis (trimethylsilyl) -1,3-butadiene , -s-cis-η4-1,4-diphenyl-1,3-butadiene, -s-cis-η4-3-methyl-1,3-pentadiene, -s-cis-η4-1,4- Dibenzyl-1,3-butadiene, -s-cis-η4-2,4-hexadi N, -s-cis-η4-1,3-pentadiene, -s-cis-η4-1,4-ditolyl-1,3-butadiene, -s-cis-η4-1,4-bis (trimethyl The compound substituted by compounds, such as a silyl) -1, 3- butadiene, is mentioned.

본 발명의 촉매계는 상기와 같은 메탈로센 촉매 성분을 사용하지만, 전술한 바와 같은 메탈로센 촉매 성분을 1종 이상 포함할 수 있다. 또한, 추가의 촉매, 필요할 경우, 예컨대 본 발명에 의한 메탈로센 촉매 성분 이외에 기타 공지의 촉매 성분을 더 포함할 수 있다.The catalyst system of the present invention uses the metallocene catalyst component as described above, but may include one or more metallocene catalyst components as described above. It may also further comprise other known catalyst components in addition to the additional catalyst, if desired, for example the metallocene catalyst component according to the invention.

본 발명에 사용되는 메탈로센 화합물은 이미 잘 알려진 문헌의 방법에 의하여 제조되거나, mCAT GmBH(www.mcat.de 참조) 또는 Strem(www.strem.com 참조) 또는 Boulder Scientific(www.bouldersci.com 참조)사에서 상업적으로 판매되고 있는 것을 사용할 수 있다.Metallocene compounds used in the present invention may be prepared by methods of well-known literature, or may be mCAT GmBH (see www.mcat.de) or Strem (see www.strem.com) or Boulder Scientific (www.bouldersci.com). Commercially available from the company can be used.

상기 (1)단계에서 사용되는 알콕시실란 화합물은 R-O-Si- 결합을 갖는 실리콘 화합물로서, 다음의 일반식(4)로 나타낼 수 있다. 　The alkoxysilane compound used in step (1) is a silicone compound having an R—O—Si— bond, and may be represented by the following general formula (4).

(R'O)4-n(R)nSi　‥‥‥ (4) ( R'O) 4-n (R) n Si ... 4

여기에서 R'와 R은 탄소수 1~20개의 탄화수소(Hydrocarbon)기를 나타내며, 같거나 서로 다를 수 있으며, n은 0, 1, 2 또는 3이다.Here, R 'and R represent a hydrocarbon group having 1 to 20 carbon atoms, may be the same or different, and n is 0, 1, 2 or 3.

상기의 일반식을 만족하는　R-O-Si- 결합을 가진 실리콘 화합물의 종류에는, 테트라메톡시실란, 메틸트리메톡시실란, 디메틸디메톡시실란, 트리메틸메톡시실란, 에틸트리메톡시실란, 디에틸디메톡시실란, 트리에틸메톡시실란, 이소프로필트리메톡시실란, 디이소프로필디메톡시실란, 트리이소프로필메톡시실란, 부틸트리메톡시실란, 디부틸디메톡시실란, 트리부틸메톡시실란, 페닐트리메톡시실란, 디페닐디메톡시실란, 트리페닐메톡시실란, 시클로헥실메틸디메톡시실란 , 디시클로헥실디메톡시실란테트라에톡시실란, 메틸트리에톡시실란, 디메틸디에톡시실란, 메틸트리에톡시실란, 에틸트리에톡시실란, 디에틸디에톡시실란, 에틸트리에톡시실란, 이소프로필트리에톡시실란, 디이소프로필디에톡시실란, 트리이소프로필에톡시실란, 부틸트리에톡시실란, 디부틸디에톡시실란, 트리부틸에톡시실란, 페닐트리에톡시실란, 페닐디에톡시실란, 트리페닐에톡시실란, 비릴트리에톡시실란, 테트라부톡시실란, 메틸트리부톡시실란, 디메틸디부톡시실란, 메틸트리부톡시실란, 에틸트리부톡시실란, 디에틸디부톡시실란, 에틸트리부톡시실란, 이소프로필트리부톡시실란, 디이소프로필디부톡시실란, 트리이소프로필부톡시실란, 부틸트리부톡시실란, 디부틸디부톡시실란, 트리부틸부톡시실란, 페닐트리부톡시실란, 디페닐디부톡시실란, 트리페닐부톡시실란 등이 있다.Examples of the silicone compound having an RO-Si- bond satisfying the above general formula include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, ethyltrimethoxysilane, and diethyldimethol. Methoxysilane, triethylmethoxysilane, isopropyltrimethoxysilane, diisopropyldimethoxysilane, triisopropylmethoxysilane, butyltrimethoxysilane, dibutyldimethoxysilane, tributylmethoxysilane, phenyltri Methoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilanetetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane , Ethyl triethoxy silane, diethyl diethoxy silane, ethyl triethoxy silane, isopropyl triethoxy silane, diisopropyl diethoxy silane, triisopropyl ethoxy silane, butyl triethoxy Silane, dibutyl diethoxysilane, tributylethoxysilane, phenyltriethoxysilane, phenyl diethoxysilane, triphenylethoxysilane, biryltriethoxysilane, tetrabutoxysilane, methyltributoxysilane, dimethyldibu Methoxysilane, methyltributoxysilane, ethyltributoxysilane, diethyldibutoxysilane, ethyltributoxysilane, isopropyltributoxysilane, diisopropyldibutoxysilane, triisopropylbutoxysilane, butyl tree Butoxysilane, dibutyldibutoxysilane, tributylbutoxysilane, phenyltributoxysilane, diphenyldibutoxysilane, triphenylbutoxysilane and the like.

본 발명에서 사용되는 알콕시실란 화합물의 양은 담지 고체 촉매에 포함되는 메탈로센 화합물 몰당 0.05몰~10몰인 것이 바람직하다. 알콕시실란 화합물의 양이 0.05몰 미만인 경우에는 충분한 활성증가의 효과를 얻기가 어려워 바람직하지 않고, 10몰 이상인 경우에는 중합활성이 크게 저하되고, 분자량이 크게 저하되어 바람직하지 않다. It is preferable that the quantity of the alkoxysilane compound used by this invention is 0.05 mol-10 mol per mol of metallocene compounds contained in a supported solid catalyst. When the amount of the alkoxysilane compound is less than 0.05 mole, it is difficult to obtain a sufficient effect of increasing the activity, which is undesirable.

상기 (1)단계에서 사용되는 알루미녹산은 직쇄 및 시클릭 알루미녹산 올리고머로부터 1종 이상 선택되며, 상기 알루미녹산이 직쇄 알루미녹산 올리고머인 경우, 화학식 R-(Al(R)-O)n-AlR2로 표시되고, 시클릭 알루미녹산 올리고머인 경우에는, 화학식 (-Al(R)-O-)m으로 표시되며, 여기에서 R은 C1~C8 알킬기, 바람직하게는 메틸이고, n은 1~40, 바람직하게는 10~20이고, m은 3~40, 바람직하게는 3~20이다. 상기 알루미녹산은 분자량 분포가 매우 넓은 올리고머들의 혼합물이며, 통상 평균 분자량은 약 800~1200이며, 주로 톨루엔 중에서 용액으로 유지되고, 그 구체예로서, Albemarle사에서 제조되는 10% 또는 30% 메틸알루미녹산 등이 있다.The aluminoxane used in step (1) is selected from one or more types of linear and cyclic aluminoxane oligomers, and when the aluminoxane is a linear aluminoxane oligomer, the formula R- (Al (R) -O) n -AlR In the case of a cyclic aluminoxane oligomer, it is represented by the formula (-Al (R) -O-) m , wherein R is a C1-C8 alkyl group, preferably methyl, and n is 1-40. Preferably, it is 10-20, m is 3-40, Preferably it is 3-20. The aluminoxane is a mixture of oligomers having a very high molecular weight distribution and usually has an average molecular weight of about 800 to 1200. The aluminoxane is usually kept in a solution in toluene, and examples thereof include 10% or 30% methyl aluminoxane .

상기 (1)단계가 상기 담지과정 (a)에 의해 수행되는 경우, 메탈로센 화합물을 알콕시실란과 반응시킨 알루미녹산의 용액에 용해시켜 얻어진 용액에 있어서 알루미녹산의 농도는 5~30중량%이고, 메탈로센 촉매성분의 농도는 금속 원소(M)로서 계산하여 0.001~1.0중량%인 것이 바람직한데, 각 성분의 농도가 상기 범위를 벗어나는 경우에는 촉매활성이 너무 낮거나 너무 높아서　바람직하지 않다.When the step (1) is carried out by the supporting step (a), the concentration of aluminoxane in the solution obtained by dissolving a metallocene compound in a solution of aluminoxane reacted with an alkoxysilane is 5-30% by weight. The concentration of the metallocene catalyst component is preferably 0.001 to 1.0% by weight, calculated as the metal element (M). However, when the concentration of each component is out of the above range, the catalytic activity is too low or too high.

상기 용액은 용매로서 방향족 탄화수소, 지방족 탄화수소 또는 지방족 고리 탄화수소를 포함할 수 있다.The solution may comprise aromatic hydrocarbons, aliphatic hydrocarbons or aliphatic ring hydrocarbons as solvent.

본 발명에 따른 폴리올레핀 촉매　및 촉매의 제조방법에 있어서, 상기 (1) 단계에서 사용되는 담체는, 고체 미립상의 다공성, 바람직하게는 무기물질, 예를 들면 실리콘 및/또는 알루미늄 옥사이드이고, 가장 바람직하게는 구형입자, 예를 들면 분무건조방법에 의해 얻어지는 입자의 형태로 존재하고, OH기 또는 활성 수소 원자를 함유하는 다른 작용기를 가진 실리카가 가장 바람직하다.In the method for producing a polyolefin catalyst and a catalyst according to the present invention, the carrier used in the step (1) is a solid particulate porous, preferably an inorganic material such as silicon and / or aluminum oxide, most preferably Is present in the form of spherical particles, for example particles obtained by a spray drying method, most preferably silica having an OH group or another functional group containing an active hydrogen atom.

상기 담체는 평균 입도가 10~250㎛, 바람직하게는 평균 입도가 10~150㎛이고, 평균 직경이 50~500Å인 미세기공을 가지고, 미세기공　부피는 0.1~10㎖/g이고, 바람직하게는 0.5~5㎖/g이고, 상기 담체의 표면적은 5~1000㎡/g, 바람직하게는 50~600㎡/g이다.The carrier has an average particle size of 10 to 250 μm, preferably an average particle size of 10 to 150 μm, an average diameter of 50 to 500 μm, and a fine pore volume of 0.1 to 10 ml / g, preferably It is 0.5-5 ml / g, and the surface area of the said carrier is 5-1000 m <2> / g, Preferably it is 50-600 m <2> / g.

상기 담체로서 실리카가 사용되는 경우, 적어도 일부의 활성 히드록시[OH]기를 가져야 하는데, 히드록시기 농도는 상기 실리카 1g당 0.5~2.5mmole인 것이 바람직하고, 0.7~1.6mmole/g인 것이 더욱 바람직한데, 상기 히드록시기 농도가 0.5mmole 미만인 경우에는 알루미녹산의 담지량이 감소하여 활성이 저하되어 바람직하지 않고, 2.5mmol을 초과하는 경우에는 히드록시기에 의하여 촉매성분이 비활성화되어 바람직하지 않다.When silica is used as the carrier, it should have at least a part of active hydroxy [OH] group, the hydroxyl group concentration is preferably 0.5 to 2.5mmole per 1g of silica, more preferably 0.7 to 1.6mmole / g, When the hydroxy group concentration is less than 0.5 mmol, the amount of aluminoxane supported decreases and the activity decreases. When the hydroxyl group concentration exceeds 2.5 mmol, the catalyst component is inactivated by the hydroxy group, which is not preferable.

상기 실리카의 히드록시기는 IR 분광 분석에 의해 검출할 수 있고, 실리카상의 히드록시기 농도의 정량은 실리카 샘플을 메틸마그네슘브로마이드와 접촉시켜, 메탄 발포량을 측정(압력 측정에 의함)함으로써 이루어진다.The hydroxyl group of the silica can be detected by IR spectroscopy, and the hydroxy group concentration on the silica is determined by contacting the silica sample with methylmagnesium bromide and measuring the amount of methane foamed (by pressure measurement).

본 발명에 적합한 [OH]농도 및 물리적 특성을 가진 실리카로는, 표면적 300㎡/g, 기공 부피 1.6㎖/g인, W.R. 그레이스 앤드 컴파니의 Davison 케미칼 디비젼에서 구입가능한 상품명 XPO-2402, XPO-2410, XPO-2411 및 XPO-2412 등을 사용할 수 있고, 또한 상품명 Davision　948, 952 및 955　등의 탈수 전 실리카를 구매하여 가열과정을 거쳐 원하는 [OH]농도로 조절하여 사용할 수도 있다.Silicas having [OH] concentration and physical properties suitable for the present invention include W.R. The brand names XPO-2402, XPO-2410, XPO-2411 and XPO-2412 available from Grace and Company's Davison Chemical Division may be used, and silicas such as Davision® 948, 952 and 955 may be purchased and heated. It can also be used by adjusting to the desired [OH] concentration through the process.

상기 (1)단계에서 담지 과정은, 바람직하게는 알루미녹산이 담체에 담지된 후, 메탈로센이 담지되는데, 상기 (1)단계에서 담체로서 실리카가 사용되는 경우 실리카의 히드록시기는 산소가 없는 무수 조건하에서, 알루미녹산과 반응하여 알루미녹산을 담지시켜 메탈로센이 담지될 위치(site)를 제공함과 동시에 외부 촉매독에 매우 민감하게 반응하여 활성을 잃어버리기 쉬운 메탈로센을 보호하는 역할을 한다. 따라서, 알루미녹산의 담지량이 높을수록 메탈로센의 담지량은 높아지고, 외부 촉매독에 피독되지 않는 확률이 높아져 활성이 높아질 수 있다.In the step (1), the supporting process, preferably, after the aluminoxane is supported on the carrier, the metallocene is supported. When silica is used as the carrier in step (1), the hydroxyl group of the silica is anhydrous without oxygen Under the conditions, it reacts with aluminoxane to support the aluminoxane, providing a site for the metallocene to be supported, and at the same time, it is very sensitive to external catalyst poisons to protect metallocene that is easily lost. . Therefore, the higher the supported amount of aluminoxane, the higher the supported amount of metallocene, and the higher the probability of not being poisoned by an external catalyst poison, thereby increasing activity.

상기 (1)단계에서 사용되는 담체 슬러리는 탄화수소 용매 또는 탄화수소 용매 혼합물에 담체를 현탁시켜 제조된다.The carrier slurry used in step (1) is prepared by suspending the carrier in a hydrocarbon solvent or a hydrocarbon solvent mixture.

상기 (1)단계의 담지과정의 온도는 40~160℃인 것이 바람직하고, 80~120℃인 것이 더욱 바람직한데, 상기 온도범위를 벗어나면 활성이 저하되고, 반응기내에서 고분자 뭉침현상이 발생하여 바람직하지 않고, 담지 시간은 30분~4시간인 것이 바람직하고, 1~2시간이 더욱 바람직한데, 상기 시간 범위를 벗어나면 경제성이 떨어지거나 반응이 충분하지 않아서 촉매로서 기능이 충분하지 못하여 바람직하지 않다.The temperature of the supporting process of step (1) is preferably 40 ~ 160 ℃, more preferably 80 ~ 120 ℃, outside the temperature range activity is lowered, polymer aggregation occurs in the reactor It is not preferable, and the supporting time is preferably 30 minutes to 4 hours, and more preferably 1 to 2 hours. If it is out of the above time range, the economical efficiency is low or the reaction is not sufficient, so the function as a catalyst is not sufficient, which is not preferable. not.

상기 (1)단계의 담지 과정이 완료된 담지 촉매 용액에는 미반응 알루미녹산과 미담지 메탈로센 촉매가 미량 존재하고, 이들은 건조과정 전에 제거될 필요가 있는데, 미반응 알루미녹산이 제거되지 않을 경우, 담지 촉매들은 서로 달라붙게 되어 촉매를 건조된 형태로 중합 반응기로 주입시 주입불량문제를 일으키게 되며, 덩어리진 촉매의 주입은 반응기 내에서 국부적인 과반응이 진행되어 시트(sheet) 및 덩어리 형성의 문제를 일으키게 된다. 또한 미담지 메탈로센은 중합 반응시 담지체로부터 쉽게 분리되어 매우 미세한 입자의 중합체를 형성하여 반응기 파울링의 문제를 일으키게 된다. In the supported catalyst solution of step (1), the unsupported aluminoxane and the unsupported metallocene catalyst are present in trace amounts, and they need to be removed before the drying process, but if the unreacted aluminoxane is not removed, The supported catalysts stick to each other and cause a poor injection problem when the catalyst is injected into the polymerization reactor in a dried form, and the injection of the agglomerated catalyst causes a local overreaction in the reactor, resulting in sheet and agglomeration problems. Will cause. In addition, the unsupported metallocene is easily separated from the carrier during the polymerization reaction to form a polymer of very fine particles, causing problems of reactor fouling.

이러한 미담지 물질의 제거를 목적으로, 상기 (2)단계에서는 담지 촉매를 세척하는데, 방향족 탄화수소 용매 및 지방족 탄화수소 용매 등의 유기용매로 2차에 걸쳐 세척하는 것이 바람직하다. 1차 세척 단계에서 미담지 메탈로센과 알루미녹산을 제거하게 되는데, 이 단계에서 담지된 메탈로센의 탈착이 일어나게 되면 담지 촉매의 활성을 떨어뜨리는 요소로 작용하게 되므로, 본 발명에서는 이를 방지하기 위하여 저온의 1차 세척 단계를 수행하여 담지된 메탈로센과 알루미녹산 성분의 고착을 심화시킴으로써, 이후 진행되는 2차 세척과정에서 담지된 메탈로센 성분의 탈착을 방지하게 해준다. 상기 1차 세척 온도는 -10~60℃인 것이 바람직하다.For the purpose of removing these unsupported substances, in the step (2), the supported catalyst is washed, and it is preferable to wash twice with an organic solvent such as an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent. In the first washing step, unsupported metallocene and aluminoxane are removed. When desorption of the supported metallocene occurs in this step, it acts as an element that lowers the activity of the supported catalyst. By performing a low temperature primary washing step to deepen the adhesion of the supported metallocene and aluminoxane component, it is possible to prevent the desorption of the supported metallocene component in the subsequent secondary washing process. The first washing temperature is preferably -10 ~ 60 ℃.

상기 (3)단계에서의 건조는 통상의 건조과정을 이용하여 수행될 수 있다. Drying in the step (3) can be carried out using a conventional drying process.

상기와 같은 본 발명의 방법에 따라 제조된 메탈로센 담지 촉매내의 Al 함량은 10중량% 이상이다.Al content in the metallocene supported catalyst prepared according to the method of the present invention as described above is 10% by weight or more.

본 발명에 따른 제조방법에 의해 제조된 폴리올레핀 중합용 촉매를 이용한 폴리올레핀 중합방법은, 주촉매로서 상기한 바와 같이 제조된 메탈로센 담지 촉매의 존재 하에서, 수소, 올레핀, 필요에 따라 공단량체를 포함하여 이루어지는 기상중합용　조성물을 반응시켜 올레핀 중합체 또는 공중합체를 제조한다.The polyolefin polymerization method using the catalyst for polyolefin polymerization prepared by the production method according to the present invention includes hydrogen, olefin, and comonomer as necessary in the presence of a metallocene supported catalyst prepared as described above as a main catalyst. An olefin polymer or copolymer is prepared by reacting the gas phase polymerization composition.

상기 올레핀의 일예로는 에틸렌을 들 수 있고, 이 경우 상기 공단량체로는 프로필렌, 1-부텐, 1-헥센, 4-메틸-1-펜텐 등과 같은 에틸렌 이외의 알파-올레핀이 바람직하며, 상기 공단량체와 상기 에틸렌의 함량비는 공단량체/에틸렌이 몰비로 0.005~0.02인 것이 바람직하고, 0.008~0.015인 것이 더욱 바람직하다. 이 경우, 공단량체/에틸렌 몰비가 0.005 미만이거나 0.02를 초과하는 경우에는, 목적하는 수준의 공중합체를 얻을 수 없어 바람직하지 않다. Examples of the olefin include ethylene, and in this case, the comonomer is preferably an alpha-olefin other than ethylene such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and the like. As for the content ratio of a monomer and the said ethylene, it is preferable that it is 0.005-0.02 in molar ratio of comonomer / ethylene, and it is more preferable that it is 0.008-0.015. In this case, when the comonomer / ethylene molar ratio is less than 0.005 or more than 0.02, a desired level of copolymer cannot be obtained, which is not preferable.

이러한 올레핀 (공)중합체 제조방법에 있어서, 메탈로센 촉매는 1종 이상의 활성화제와 배합되어 올레핀 중합 촉매 시스템을 형성한다. 이 때 사용되는 바람직한 활성화제에는 알킬알루미늄 화합물(예컨대, 디에틸알루미늄 클로라이드), 알루미녹산, 변형 알루미녹산, 중성 또는 이온성 이온화 활성화제, 비배위 음이온, 비배위 13족 금속 또는 메탈로이드 음이온, 보란, 붕산염 등이 있다. In such a method of preparing an olefin (co) polymer, the metallocene catalyst is combined with one or more activators to form an olefin polymerization catalyst system. Preferred activators used in this case include alkylaluminum compounds (e.g. diethylaluminum chloride), aluminoxanes, modified aluminoxanes, neutral or ionic ionizing activators, noncoordinating anions, noncoordinating group 13 metal or metalloid anions, boranes And borate salts.

상기 알킬알루미늄 화합물로는, 일반식 AlRnX(3-n)(여기에서, R은 탄소수 1~16의 알킬기이고, X는 할로겐 원소이며, 1≤n≤3이다)으로 표시되는 알킬알루미늄 화합물을 사용할 수 있다. 상기 알킬알루미늄 화합물의 구체적인 예로는, 바람직하게는, 트리에틸알루미늄, 트리메틸알루미늄, 트리노말프로필알루미늄, 트리노말부틸알루미늄, 트리이소부틸알루미늄, 트리노말헥실알루미늄, 트리노말옥틸알루미늄, 트리2-메틸펜틸알루미늄 등이 사용되며, 특히 바람직하게는, 트리이소부틸알루미늄, 트리에틸알루미늄, 트리노말헥실알루미늄 또는 트리노말옥틸알루미늄이 사용된다. With the alkyl aluminum compound has the general formula AlR n X (3-n) alkyl aluminum compounds represented by (wherein, R is an alkyl group of carbon number 1 ~ 16, X is a halogen element, and 1≤n≤3) Can be used. Specific examples of the alkyl aluminum compound are preferably triethyl aluminum, trimethyl aluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, tri2-methylpentyl Aluminum etc. are used, Especially preferably, triisobutyl aluminum, triethyl aluminum, trinormal hexyl aluminum, or trinormal octyl aluminum is used.

상기 알킬알루미늄 화합물은, 원하는 고분자 특성에 따라서 다음과 같은 몰비로 기상 중합시에 사용하는 것이 바람직하다.It is preferable to use the said alkylaluminum compound at the time of gas phase superposition | polymerization in the following molar ratio according to desired polymer property.

1 ≤ 알킬알루미늄 화합물/주촉매 중의 전이금속 ≤ 10001 ≤ transition metal in the alkylaluminum compound / main catalyst ≤ 1000

보다 바람직하게는More preferably,

10 ≤ 알킬알루미늄 화합물/주촉매 중의 전이금속 ≤ 30010 ≤ transition metal in the alkylaluminum compound / main catalyst ≤ 300

상기 알킬알루미늄 화합물/주촉매 중의 전이금속의 몰비가 1　미만이면 충분한 중합활성을 얻을 수 없고, 1000을 초과하면 오히려 중합활성이 낮아지는 역효과가 나타난다. If the molar ratio of the transition metal in the alkylaluminum compound / main catalyst is less than 1 kPa, sufficient polymerization activity cannot be obtained, whereas if it exceeds 1000, the adverse effect of lowering the polymerization activity appears.

상기와 같은 올레핀 (공)중합체 제조방법에 있어서, 중합반응은 탄화수소용매의 부재하에서　60~120℃에서 수행되는 것이 바람직하고, 65~100℃인 것이 더욱 바람직하며, 70~80℃인 것이 가장 바람직하며, 2~40기압에서 수행되는 것이 바람직하고, 10~30기압에서 수행되는 것이 더욱 바람직하다. In the above olefin (co) polymer production method, the polymerization reaction is preferably carried out at # 60 ~ 120 ℃ in the absence of a hydrocarbon solvent, more preferably 65 ~ 100 ℃, most preferably 70 ~ 80 ℃. And, it is preferably performed at 2 to 40 atm, more preferably at 10 to 30 atm.

반응기에서의 상기 중합온도가 60℃ 미만인 경우에는, 충분한 중합효율을 얻을 수 없어 바람직하지 않고, 120℃를 초과하는 경우에는, 중합체 덩어리가 생성되기 쉽다는 문제점이 있어 바람직하지 않다. 또한,　반응기에서의 상기 운전압력이 2기압 미만인 경우에는, 에틸렌 분압이 낮아 충분한 중합 효율을 얻을 수 없어 바람직하지 않고, 40기압을 초과하는 경우에는 반응의 제어가 어려워지고, 반응기에 무리를 가하게 되어 바람직하지 않다. When the polymerization temperature in the reactor is less than 60 ° C, sufficient polymerization efficiency cannot be obtained, which is not preferable. When the polymerization temperature is higher than 120 ° C, there is a problem that a polymer mass is easily generated, which is not preferable. In addition, when the operating pressure in the reactor is less than 2 atmospheres, the partial pressure of ethylene is not low enough to obtain sufficient polymerization efficiency, which is undesirable. When the pressure exceeds 40 atmospheres, the control of the reaction becomes difficult, and the reactor is exerted. Not desirable

본 발명의 주촉매로서 상기에서　제조된 메탈로센 담지 촉매　성분은 중합 반응에 성분으로 사용되기 전에 에틸렌 또는 α-올레핀으로 전중합하여 사용할 수 있다. 전중합은 헥산과 같은 탄화수소 용매 존재하에서 충분히 낮은 온도와 에틸렌 또는 α-올레핀 압력 조건에서 상기의 촉매 성분과 트리이소부틸알루미늄과 같은 유기알루미늄 화합물의 존재하에서　행할 수 있다. 전중합은 촉매 입자를 폴리머로 둘러싸서 촉매 형상을 유지시켜 중합후에 폴리머의 형상을 좋게 하는데 도움을 준다. 전중합 후의 폴리머/촉매의 무게비는 대개 0.1:1 내지 200:1이다. 바람직한 유기금속 화합물로는 트리에틸알루미늄, 트리이소부틸알루미늄과 같은 탄소수 1개 내지 6개의 알킬기를 가진 트리알킬알루미늄과 이들의 혼합물이 유익하다. 경우에 따라서는 에틸알루미늄디클로라이드, 디에틸알루미늄클로라이드, 에틸알루미늄세스퀴클로라이드, 디이소부틸알루미늄히드리드와 같은 한개 이상의 할로겐 또는 히드리드기를 갖는 유기알루미늄 화합물이 사용될 수 있다.As the main catalyst of the present invention, the metallocene supported catalyst component prepared above may be prepolymerized with ethylene or α-olefin before being used as a component in a polymerization reaction. Prepolymerization can be carried out in the presence of an organoaluminum compound, such as triisobutylaluminum, with the above catalyst component at sufficiently low temperatures and ethylene or α-olefin pressure conditions in the presence of a hydrocarbon solvent such as hexane. Prepolymerization helps to improve the shape of the polymer after polymerization by surrounding the catalyst particles with a polymer to maintain the catalyst shape. The weight ratio of polymer / catalyst after prepolymerization is usually from 0.1: 1 to 200: 1. Preferred organometallic compounds are trialkylaluminums having 1 to 6 carbon atoms, such as triethylaluminum and triisobutylaluminum, and mixtures thereof. In some cases, an organoaluminum compound having one or more halogen or hydride groups such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride may be used.

본 발명의 촉매는 알콕시실란 화합물과 반응시킨 알루미녹산 및 메탈로센 화합물을 사용하여 촉매 성분을 제조함으로써, 이를 이용하여 중합체를 제조할 경우, 촉매활성이 우수하며, 저용융지수를 가지는 고분자량의 중합체를 제조할 수 있다.The catalyst of the present invention is prepared by using the aluminoxane and metallocene compound reacted with the alkoxysilane compound to prepare a catalyst component. When the polymer is produced using the catalyst, the catalyst has excellent catalytic activity and has a low melt index. Polymers can be prepared.

또한, 본 발명의 중합방법에서 얻어진 생성물은 고체의 고분자량의　폴리올레핀　단독중합체　또는 공중합체이며, 중합체의 수율도 충분히 높아서 촉매 잔사의 제거가 필요하지 않고, 우수한 겉보기 밀도와 유동성을 갖고 있다.In addition, the product obtained by the polymerization method of the present invention is a solid high molecular weight polyolefin homopolymer or copolymer, and the yield of the polymer is also high enough that the removal of the catalyst residue is not necessary, and has an excellent apparent density and fluidity.

이하 실시예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나, 이들 실시예들은 예시적인 목적일 뿐 본 발명이 이들 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are for illustrative purposes only, and the present invention is not limited to these embodiments.

실시예 1Example 1

[메탈로센 담지 촉매의 제조][Preparation of supported metallocene catalyst]

메틸알루미녹산 용액(10중량%) 50ml를 메스실린더에서 정량한 후　여기에 알콕시실란인 테트라에톡시실란(테트라에톡시실란/메탈로센=0.6몰/몰)을 주입한 후 상온에서 30분 이상 교반하여 반응시켰다. 상품명 XPO-2402(평균입도　~50마이크론, 표면적 300㎡/g, 미세기공 부피 1.6ml/g, OH농도 1mmol/g)의 탈수 실리카를 무수조건하에서 5g 정량하고, 톨루엔 20ml를 사용하여 슬러리 상태로 교반시켰다. 이를 교반기와 냉각 응축기가 구비된 1L 반응기에 주입하였다. 　250ml 쉬렌크(schlenk)에 미리 정량된 메탈로센　화합물 Et(IND)2ZrCl2(메탈로센/실리카=180μmol/g실리카)과 상기에서 테트라에톡시실란과 반응시킨 메틸알루미녹산 용액을 상온에서 혼합하고, 20분간 교반하여 메탈로센 화합물을　용해시킴과 동시에 반응시켰다. 상기 반응기의 온도를 상온으로　유지한 상태에서 상기 메틸알루미녹산-메탈로센 용액을 첨가하였다. 이후 교반과 동시에 반응 온도를 90℃로 승온시켰다. 이 온도에서 담지 반응을 120분 동안 진행시켰다. 반응 종료 후, 반응물을 쉬렌크 용기로 이송 후, 상부 용액을 따라냈다(decantation). 반응물을 교반한 후, 상온에 도달하면 10분간 정치 후 상부 용액을 따라내고, -5℃에서 톨루엔 100ml를 사용하여 반응물을 1차 세척하였다. 반응물을 교반한 후, 상온에 도달하면 정치 후 상부 용액을 따라내고, 상온의 톨루엔 100ml로 2차 세척하였다. 그 후, 얻어진 촉매계는 정제 헥산으로 세척한 후, 온화한 진공　하에서 건조시켰다.　50 ml of methylaluminoxane solution (10% by weight) was quantified in a measuring cylinder, and tetraethoxysilane (tetraethoxysilane / metallocene = 0.6 mol / mol), which is an alkoxysilane, was injected thereinto at least 30 minutes at room temperature. The reaction was stirred. Dehydrated silica of XPO-2402 (average particle size ~ 50 microns, surface area 300m2 / g, micropore volume 1.6ml / g, OH concentration 1mmol / g) was weighed 5g under anhydrous conditions, and used as a slurry using 20ml of toluene. Stirred. It was injected into a 1 L reactor equipped with a stirrer and a cooling condenser. A pre-quantified metallocene compound Et (IND) 2 ZrCl 2 (metallocene / silica = 180 μmol / g silica) in 250 ml Schlenk and the methylaluminoxane solution reacted with tetraethoxysilane in the above at room temperature The mixture was stirred for 20 minutes to dissolve and react with the metallocene compound. The methylaluminoxane-metallocene solution was added while maintaining the temperature of the reactor at room temperature. Then, the reaction temperature was raised to 90 ° C with stirring. At this temperature, the support reaction was allowed to proceed for 120 minutes. After the reaction was completed, the reaction was transferred to a Schlenk vessel, followed by decantation. After the reaction mixture was stirred at room temperature, the reaction mixture was allowed to stand for 10 minutes and then the upper solution was taken out. The reaction mixture was firstly washed with 100 ml of toluene at -5 ° C. After the reaction was stirred, the reaction solution was allowed to stand, and after standing up, the upper solution was decanted and washed twice with 100 ml of toluene at room temperature. The resulting catalyst system was then washed with purified hexane and then dried under mild vacuum.

[중합][polymerization]

하기의 표 1에 나타낸 조건으로, 상기에서 제조된　메탈로센 담지 촉매를 이용하여 다음의 방법으로 중합을 실시하였다. Under the conditions shown in Table 1 below, polymerization was carried out by the following method using the metallocene supported catalyst prepared above.

교반기 및 가열/냉각장치가 구비된 2L의 스테인레스스틸 반응기에 1000ml의 정제된 헥산과 1-헥센　50mL을 주입하였다. 반응기는 사용 전에 순수한 질소에 의해 충분히 세척되었다. 다음으로, 촉매독 제거제로서 트리이소부틸알루미늄(TiBA)의 1M 헥산 희석액 1.5cc를 반응기에 주입하고,　교반하며 60℃로 승온 후, 교반을 중지하였다.　주촉매로서 상기 단계에서 제조된 메탈로센 담지 촉매 15~25mg을 글러브 박스에서 정량하여 5ml 실린지에 옮긴 후, 활성화제로 트리이소부틸알루미늄(TiBA)의 1M 헥산 희석액 1.0cc를　취했다. 활성화된 촉매 슬러리는 반응기로 옮겨져 60℃의 반응기에 주입하였다. 이어서, 반응기 온도를 80℃까지 상승시키며, 반응기의 전체압력이 200psig가 되도록 에틸렌을 공급한 다음, 1000rpm으로 교반함으로써 반응을 시작하였다. 반응이 진행되는 동안 반응기의 전체 압력이　200psig로 일정하게 유지될 수 있도록 에틸렌을 충분히 공급하면서, 20분 동안 중합반응을 수행하였다. 20분의　중합반응 후, 에틸렌 주입을 중단하여 반응을 종결시키고, 결과 중합체를 얻었다. 얻어진 결과 중합체를 여과기로 분리하고, 충분히 건조하여 중합체를　얻었다. 중합결과는 표 1에 나타내었다.Into a 2L stainless steel reactor equipped with a stirrer and a heating / cooling device, 1000 ml of purified hexane and 50 mL of 1-hexene 주입 were injected. The reactor was thoroughly washed with pure nitrogen before use. Next, 1.5 cc of 1 M hexane dilution solution of triisobutylaluminum (TiBA) was injected into the reactor as a catalyst poison remover, and the mixture was stirred and heated to 60 ° C, and then stirring was stopped. 15-25 mg of the metallocene supported catalyst prepared in the above step as a main catalyst was quantified in a glove box, transferred to a 5 ml syringe, and 1.0 cc of 1 M hexane dilution of triisobutylaluminum (TiBA) was taken as an activator. The activated catalyst slurry was transferred to the reactor and injected into the reactor at 60 ° C. Subsequently, the reactor temperature was raised to 80 ° C., ethylene was fed so that the total pressure of the reactor was 200 psig, and the reaction was started by stirring at 1000 rpm. The polymerization was carried out for 20 minutes while supplying enough ethylene so that the total pressure of the reactor was kept constant at 200 psig during the reaction. After 20 minutes of kneading polymerization, ethylene injection was stopped to terminate the reaction to obtain a resultant polymer. The resultant polymer was separated by a filter and sufficiently dried to obtain a polymer. The polymerization results are shown in Table 1.

[중합체 분석][Polymer analysis]

중합에서 얻은 중합체는 다음의 분석을 실시하였다.The polymer obtained in the polymerization was subjected to the following analysis.

1) 밀도(Density, g/mL) : ASTM1505를 기준으로 분석을 실시하였다.1) Density (g / mL): The analysis was performed based on ASTM1505.

2) 분자량(Mw, g/mol) : 분자량은 젤 퍼미에이션 　크로마토그라피(GPC)를 이용하여 160℃에서 측정하여 중량평균 분자량(Mw)을 구하였다.2) Molecular weight (Mw, g / mol): The molecular weight was measured at 160 ° C using gel permeation chromatography (GPC) to obtain a weight average molecular weight (Mw).

비교예 1Comparative Example 1

실시예　1에서, 알콕시실란인 테트라에톡시실란을 사용하지 않고, 실시예 1과 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example # 1, a catalyst was prepared under the same conditions as in Example 1 without using tetraethoxysilane, which is an alkoxysilane, and polymerization was carried out. The results are shown in Table 1.

비교예 2Comparative Example 2

[메탈로센 담지 촉매의 제조][Preparation of supported metallocene catalyst]

상품명 XPO-2402(평균입도　~50마이크론, 표면적 300㎡/g, 미세기공 부피 1.6ml/g, OH농도 1mmol/g)의 탈수 실리카를 무수조건하에서 5g 정량하고, 톨루엔 20ml를 사용하여 슬러리 상태로 교반시켰다. 이를 교반기와 냉각 응축기가 구비된 1L 반응기에 주입하였다. 여기에 알콕시실란인 테트라에톡시실란(테트라에톡시실란/실리카=10.0밀리몰/g실리카)을 상온에서 주입한후 온도를 90℃까지 올려서　5시간 동안 반응시켰다. 반응후 반응물의 온도를 상온으로 내리고,　20분간 정치 후 상부 용액을 따라내고, 톨루엔 100ml를 사용하여 반응물을 1차 세척하였다. 반응물을 교반한 후, 정치 후 상부 용액을 따라내고, 상온의 톨루엔 100ml로 2차 세척하였다.　상기와 같은 조작으로 추가로 3회 세척을 실시하였다. 그 후, 얻어진 실리카는　정제 헥산으로 세척한 후, 온화한 진공　하에서 건조시켜 분말로 얻었다.　　Dehydrated silica of XPO-2402 (average particle size: 50 microns, surface area 300 m2 / g, micropore volume 1.6 ml / g, OH concentration 1 mmol / g) was quantified 5 g under anhydrous conditions, and in a slurry state using 20 ml of toluene. Stirred. It was injected into a 1 L reactor equipped with a stirrer and a cooling condenser. Tetraethoxysilane (tetraethoxysilane / silica = 10.0 mmol / g silica), which is an alkoxysilane, was injected therein at room temperature, and then the temperature was raised to 90 ° C. for 5 hours. After the reaction, the temperature of the reaction was lowered to room temperature. After standing for 20 minutes, the upper solution was decanted and the reaction was first washed with 100 ml of toluene. After the reaction was stirred, the top solution was decanted after standing and washed twice with 100 ml of toluene at room temperature. Washing was further performed three times in the same manner as described above. Thereafter, the obtained silica was washed with table hexane, dried under mild vacuum, and obtained as a powder.

250ml 쉬렌크(schlenk)에 미리 정량된 메탈로센　화합물 Et(IND)2ZrCl2(메탈로센/실리카=180μmol/g실리카)와 메틸알루미녹산 용액(10중량%) 50ml를 메스실린더에서 정량한 후　메탈로센 화합물과 상온에서 혼합하고, 20분간 교반하여 메탈로센 화합물을　용해시킴과 동시에 반응시켰다.Pre-quantified metallocene compound Et (IND) 2 ZrCl 2 (metallocene / silica = 180 μmol / g silica) and 50 ml of methylaluminoxane solution (10% by weight) in 250 ml Schlenk were quantified in a measuring cylinder. After mixing with the metallocene compound at room temperature, the mixture was stirred for 20 minutes to dissolve and react with the metallocene compound.

반응기의 온도를 상온으로　유지한 상태에서 상기에서 제조한 실리카 5g을 정량하여 톨루엔 20ml를 사용하여 슬러리 상태로 교반시켰다.　상기 메틸알루미녹산-메탈로센 용액을 첨가하고,　교반과 동시에 반응 온도를　90℃로 승온시켰다. 이 온도에서 담지 반응을 120분 동안 진행시켰다. 반응 종료 후, 반응물을 쉬렌크 용기로 이송 후, 상부 용액을 따라냈다(decantation). 반응물을 교반한 후, 상온에 도달하면 10분간 정치 후 상부 용액을 따라내고, -5℃에서 톨루엔 100ml를 사용하여 반응물을 1차 세척하였다. 반응물을 교반한 후, 상온에 도달하면 정치 후 상부 용액을 따라내고, 상온의 톨루엔 100ml로 2차 세척하였다. 그 후, 얻어진 촉매계는 정제 헥산으로 세척한 후, 온화한 진공　하에서 건조시켰다.While keeping the temperature of the reactor at room temperature, 5 g of the silica prepared above was quantified and stirred in a slurry state using 20 ml of toluene. The methylaluminoxane-metallocene solution was added thereto, and the reaction temperature was raised to 90 ° C at the same time as kneading. At this temperature, the supporting reaction proceeded for 120 minutes. After the reaction was completed, the reaction was transferred to a Schlenk vessel, followed by decantation. After the reaction was stirred, the mixture was allowed to stand for 10 minutes, followed by decantation of the upper solution, and the reaction was first washed with 100 ml of toluene at -5 ° C. After the reaction was stirred, the reaction solution was allowed to stand, and after standing up, the upper solution was decanted and washed twice with 100 ml of toluene at room temperature. Thereafter, the obtained catalyst system was washed with purified hexane and then dried under mild vacuum.

[중합][polymerization]

상기에서 제조된 촉매로 실시예 1과 동일한 조건으로 중합을 실시하였다. 그 결과는 표 1에 나타내었다.The polymerization was carried out under the same conditions as in Example 1 with the catalyst prepared above. The results are shown in Table 1.

비교예 3Comparative Example 3

비교예 2에서 알콕시실란인 테트라에톡시실란을 사용하지 않고 촉매를 제조하였고, 제조된 촉매로 실시예 1과 동일한 조건으로 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Comparative Example 2, a catalyst was prepared without using tetraethoxysilane, which is an alkoxysilane, and polymerization was carried out under the same conditions as in Example 1 with the prepared catalyst. The results are shown in Table 1.

실시예 2Example 2

실시예　1에서, 알콕시실란인 테트라에톡시실란 대신에 디이소프로필디메톡시실란(디이소프로필디메톡시실란/메탈로센=0.9몰/몰)을 사용하여 실시예 1과 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example 1, a catalyst was prepared under the same conditions as in Example 1 using diisopropyldimethoxysilane (diisopropyldimethoxysilane / metallocene = 0.9 mol / mol) instead of tetraethoxysilane, which is an alkoxysilane. And polymerization was carried out. The results are shown in Table 1.

실시예 3Example 3

실시예　1에서, 알콕시실란인 테트라에톡시실란 대신에 이소부틸트리에톡시실란(이소부틸트리에톡시실란/메탈로센=0.3몰/몰)을 사용하여 실시예 1과 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example 1, a catalyst was prepared under the same conditions as in Example 1 using isobutyltriethoxysilane (isobutyltriethoxysilane / metallocene = 0.3 mol / mol) instead of tetraethoxysilane, which is an alkoxysilane. The polymerization was carried out. The results are shown in Table 1.

실시예 4Example 4

실시예　1에서, 알콕시실란인 테트라에톡시실란 대신에 시클로헥실메틸디메톡시실란(시클로헥실메틸디메톡시실란/메탈로센=0.3몰/몰)을 사용하여 실시예 1과 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example 1, a catalyst was prepared under the same conditions as in Example 1 using cyclohexylmethyldimethoxysilane (cyclohexylmethyldimethoxysilane / metallocene = 0.3 mol / mol) instead of tetraethoxysilane, which is an alkoxysilane. And polymerization was carried out. The results are shown in Table 1.

실시예 5Example 5

실시예　1에서, 알콕시실란인 테트라에톡시실란 대신에 디페닐디메톡시실란(디페닐디메톡시실란/메탈로센=0.3몰/몰)을 사용하여 실시예 1과 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example 1, a catalyst was prepared under the same conditions as in Example 1 using diphenyldimethoxysilane (diphenyldimethoxysilane / metallocene = 0.3 mol / mol) instead of tetraethoxysilane, which is an alkoxysilane. The polymerization was carried out. The results are shown in Table 1.

실시예 6Example 6

실시예　1에서, 알콕시실란인 테트라에톡시실란 대신에 메틸트리메톡시실란(메틸트리메톡시실란/메탈로센=0.9몰/몰)을 사용하여 실시예 1과 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example 1, a catalyst was prepared under the same conditions as in Example 1 using methyltrimethoxysilane (methyltrimethoxysilane / metallocene = 0.9 mol / mol) instead of tetraethoxysilane, which is an alkoxysilane, The polymerization was carried out. The results are shown in Table 1.

실시예 7Example 7

실시예　1에서, 알콕시실란인 테트라에톡시실란 대신에 페닐트리에톡시실란(페닐트리에톡시실란/메탈로센=0.3몰/몰)을 사용하여 실시예 1과 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example 1, a catalyst was prepared under the same conditions as in Example 1 using phenyltriethoxysilane (phenyltriethoxysilane / metallocene = 0.3 mol / mol) instead of tetraethoxysilane, which is an alkoxysilane. The polymerization was carried out. The results are shown in Table 1.

실시예 8Example 8

실시예　4에서　메탈로센 촉매 성분 Et(IND)2ZrCl2를 (IND)2ZrCl2로 교체하여 사용한 것 이외에는　실시예 4와 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.A catalyst was prepared under the same conditions as in Example 4 except that the metallocene catalyst component Et (IND) 2 ZrCl 2 was replaced with (IND) 2 ZrCl 2 in Example 4, and polymerization was performed. The results are shown in Table 1.

실시예 9Example 9

실시예　4에서　메탈로센 촉매 성분 Et(IND)2ZrCl2를 (nBuCp)2ZrCl2로 교체하여 사용한 것 이외에는　실시예 4와 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.A catalyst was prepared under the same conditions as in Example 4 except that the metallocene catalyst component Et (IND) 2 ZrCl 2 was replaced with (nBuCp) 2 ZrCl 2 in Example 4, and polymerization was carried out. The results are shown in Table 1.

실시예 10Example 10

실시예　4에서　메탈로센 촉매 성분 Et(IND)2ZrCl2를 (1,3-Et,MeCp)2ZrCl2로 교체하여 사용한 것 이외에는　실시예 4와 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.Example 4 In the metallocene catalyst component Et (IND) 2 to ZrCl 2 (1,3-Et, MeCp ) was used to replace it with a 2 ZrCl 2 except that the catalyst was prepared under the same conditions as in Example 4, the polymerization It was. The results are shown in Table 1.

실시예 11Example 11

실시예　2에서　메탈로센 촉매 성분 Et(IND)2ZrCl2를 (IND)2ZrCl2로 교체하여 사용한 것 이외에는　실시예 2와 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.A catalyst was prepared under the same conditions as in Example 2 except that the metallocene catalyst component Et (IND) 2 ZrCl 2 was replaced with (IND) 2 ZrCl 2 in Example 2, and polymerization was performed. The results are shown in Table 1.

실시예 12Example 12

실시예　2에서　메탈로센 촉매 성분 Et(IND)2ZrCl2를 (nBuCp)2ZrCl2로 교체하여 사용한 것 이외에는　실시예 2와 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.The catalyst was prepared under the same conditions as in Example 2 except that the metallocene catalyst component Et (IND) 2 ZrCl 2 was replaced with (nBuCp) 2 ZrCl 2 in Example 2, and polymerization was performed. The results are shown in Table 1.

실시예 13Example 13

실시예　2에서　메탈로센 촉매 성분 Et(IND)2ZrCl2를 (1,3-Et,MeCp)2ZrCl2로 교체하여 사용한 것 이외에는　실시예 2와 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.Example 2 In the metallocene catalyst component Et (IND) 2 ZrCl 2 a (1,3-Et, MeCp) was used to replace it with a 2 ZrCl 2 except that the catalyst was prepared under the same conditions as in Example 2, the polymerization It was. The results are shown in Table 1.

비교예 4Comparative Example 4

실시예　8에서　시클로헥실메틸디메톡시실란을 사용하지 않고, 실시예 8과 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example # 8, a catalyst was prepared under the same conditions as in Example 8 without using a cyclohexylmethyldimethoxysilane, and polymerization was carried out. The results are shown in Table 1.

비교예 5Comparative Example 5

실시예　9에서　시클로헥실메틸디메톡시실란을 사용하지 않고, 실시예 9와 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example 9, a catalyst was prepared under the same conditions as Example 9 without using cyclohexylmethyldimethoxysilane, and polymerization was carried out. The results are shown in Table 1.

비교예 6Comparative Example 6

실시예　10에서　시클로헥실메틸디메톡시실란을 사용하지 않고, 실시예 10과 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Example # 10, a catalyst was prepared under the same conditions as in Example 10 without using a cyclohexylmethyldimethoxysilane, and polymerization was carried out. The results are shown in Table 1.

비교예 7Comparative Example 7

비교예　2에서　테트라에톡시실란 대신에 디이소프로필디메톡시실란(디이소프로필디메톡시실란/실리카=10.0밀리몰/g실리카)을 사용하여 비교예 2와　동일한 조건으로 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Comparative Example # 2, a catalyst was prepared under the same conditions as in Comparative Example 2 using diisopropyldimethoxysilane (diisopropyldimethoxysilane / silica = 10.0 mmol / g silica) instead of tetratetoxysilane. The polymerization was carried out. The results are shown in Table 1.

비교예 8Comparative Example 8

비교예　2에서　테트라에톡시실란 대신에 이소부틸트리에톡시실란(이소부틸트리에톡시실란/실리카=10.0밀리몰/g실리카)을 사용하여 비교예 2와　동일한 조건으로 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Comparative Example 2, a catalyst was prepared under the same conditions as in Comparative Example 2 using isobutyltriethoxysilane (isobutyltriethoxysilane / silica = 10.0 mmol / g silica) instead of tetrateoxysilane, and polymerization was performed. Was carried out. The results are shown in Table 1.

비교예 9Comparative Example 9

비교예　2에서　테트라에톡시실란 대신에 시클로헥실메틸디메톡시실란(시클로헥실메틸디메톡시실란/실리카=10.0밀리몰/g실리카)을 사용하여 비교예 2와　동일한 조건으로 동일한 조건으로 촉매를 제조하였고, 중합을 실시하였다. 그 결과는 표 1에 나타내었다.In Comparative Example 2, a catalyst was prepared under the same conditions as in Comparative Example 2 using cyclohexylmethyldimethoxysilane (cyclohexylmethyldimethoxysilane / silica = 10.0 mmol / g silica) instead of tetratetoxysilane. The polymerization was carried out. The results are shown in Table 1.

Figure 112011093339519-pat00002
Figure 112011093339519-pat00002

표 1에서 알 수 있듯이, 실시예 1~7의 알콕시실란 화합물과 반응시킨 알루미녹산을 사용하여 제조한 촉매는 알콕시실란 화합물을 사용하지 않은 비교예 1과 3의 촉매와 비교하여 중량 평균 분자량(Mw)이 줄어 들지 않으면서 촉매활성이 우수함을 알 수 있다. 추가적으로 밀도 (Density)측면에서도 실시예 1~4의 담지 촉매가 비교예 1의 촉매와 유사하게 유지됨을 알 수 있다. 실시예 8~10에서 메탈로센 촉매 성분을 변경하여 알콕시실란 화합물과 반응시킨 알루미녹산을 사용한 경우에도, 알콕시실란 화합물을 사용하지 않은 비교예 4~6과 비교하여 중량 평균 분자량(Mw)이 줄어들지 않으면서 촉매활성이 우수함을 알 수 있다. 비교예 2 및 비교예 7~9에서 알콕시실란 화합물을 실리카에 반응시킨 후 제조한 촉매의 경우에는 촉매활성이 저하됨을 알 수 있었다.As can be seen from Table 1, the catalyst prepared using the aluminoxane reacted with the alkoxysilane compound of Examples 1 to 7 was compared with the catalyst of Comparative Examples 1 and 3 without using the alkoxysilane compound, and the weight average molecular weight (Mw It can be seen that the catalytic activity is excellent without decreasing). In addition, it can be seen that the supported catalysts of Examples 1 to 4 remain similar to those of Comparative Example 1 in terms of density. Even when the aluminoxane reacted with the alkoxysilane compound by changing the metallocene catalyst component in Examples 8 to 10 was used, the weight average molecular weight (Mw) was not reduced compared to Comparative Examples 4 to 6 without using the alkoxysilane compound. It can be seen that the catalytic activity is excellent without. In Comparative Example 2 and Comparative Examples 7 to 9, it was found that in the case of the catalyst prepared after the alkoxysilane compound was reacted with silica, the catalytic activity was lowered.

　　

Claims (6)

다음의 단계들을 포함하는 방법에 따라 제조되는 올레핀 중합　또는 공중합용　촉매 :
(1) 담체에, 알콕시실란 화합물과 반응시킨 알루미녹산, 및 메탈로센 화합물을 담지시키는 단계, 여기에서 상기 알콕시실란 화합물의 사용량은 담지 고체 촉매에 포함되는 메탈로센 화합물 몰당 0.05몰~10몰이고, 상기 메탈로센 화합물은　다음의　일반식 (1)　내지 (3)으로 표시되는 화합물들로부터 선택되며, 상기 알콕시실란 화합물은 다음의 일반식 (4)로 표시되는 화합물들로부터 선택된다:
(CpRn)(CpR'm)MLq　‥‥‥ (1)
여기에서 Cp는 시클로펜타디에닐, 인데닐, 또는 플루오레닐이고,
R과 R'는 각각 독립적으로 수소, 알킬, 알킬에테르, 알릴에테르, 포스핀 또는 아민을 나타내고,
L은 알킬, 알릴, 아릴알킬, 아마이드, 알콕시 또는 할로겐을 나타내고,
M은 주기율표의 4족 또는 5족의 전이금속을 나타내고,
n은 0 ≤ n < 5, 　m은 0 ≤ m < 5, q는 1 ≤ q ≤ 4를 만족하는　정수이다;
Q(CpRn)(CpR'm)MLq　‥‥‥ (2)
여기서 Cp, R, R', M, L은 상기 일반식 (1)과 동일한 의미를 가지며, Q는 C고리 사이의 다리결합으로서, 디알킬, 알킬아릴, 디아릴실리콘, 또는 탄소수 1~20개의 탄화수소기를 나타내며, n은 0 ≤ n < 4, 　m은 0 ≤ m <4, q는 1 ≤ q ≤ 4를 만족하는　정수이다;
Figure 112013070324228-pat00004
　　　‥‥‥ (3)

여기에서 x는 0, 1, 2, 3 또는 4이며, y는 0 또는 1이고, R은 수소, 탄소수 1~20개의 탄화수소기, 실릴기, 게르밀기, 시아노기, 할로겐 또는 이들의 복합기로 이루어진 1 내지 20개의 비수소 원자를 갖는 치환기를 나타내고, Y'는 -O-, -S-, -NR*-, 또는 -PR*-를 나타내고(R*는 수소, 탄소수 1 내지 12개의 탄화수소기, 탄소수 1 내지 8개의 히드로카르빌옥시기, 실릴기, 탄소수 1 내지 8개의 할로겐화 알킬기, 탄소수 6 내지 20개의 할로겐화 아릴기 또는 이들의 복합기), Z는 SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2 또는 GeR*2를 나타내며, R*는 상기에서 정의한 바와 같고, L은 각각 독립적으로 할라이드, 탄소수 1 내지 20개의 탄화수소기, 탄소수 1 내지 18개의 히드로카르빌옥시기, 탄소수 1 내지 19개의 히드로카르빌아미노기, 탄소수 1 내지 18개의 히드로카르빌아미드기, 탄소수 1 내지 18개의 히드로카르빌포스피드기, 탄소수 1 내지 18개의 히드로카르빌설피드기, 및 이들의 복합기로 이루어진 군에서 선택되는 1 내지 20개의 비수소 치환기를 갖는 치환기를 나타내거나, 또는 2개의 치환기 L이 함께 탄소수 1 내지 30개의 중성 공액 디엔 또는 2가의 기를 나타내고, M은 주기율표의 4족 또는 5족의 전이금속을 나타낸다;
(R'O)4-n(R)nSi　‥‥‥ (4)
여기에서 R'와 R은 탄소수 1~20개의 탄화수소기를 나타내며, 같거나 서로 다를 수 있으며, n은 0, 1, 2 또는 3이다;
(2) 상기 (1)단계에서 얻어진 담지 촉매를 유기용매로 세척하는 단계,
(3) 상기 (2)단계의 세척된 촉매를 건조시킨 후 촉매 분말로서 회수하는 단계. Catalyst for olefin polymerization or copolymerization prepared according to the method comprising the following steps:
(1) supporting an aluminoxane reacted with an alkoxysilane compound and a metallocene compound on a carrier, wherein the amount of the alkoxysilane compound used is 0.05 mol to 10 mol per mol of the metallocene compound included in the supported solid catalyst. Wherein the metallocene compound is selected from compounds represented by the following general formulas (1) to (3), and the alkoxysilane compound is selected from compounds represented by the following general formula (4):
(CpR n ) (CpR ' m ) ML q ‥‥‥ (1)
Wherein Cp is cyclopentadienyl, indenyl, or fluorenyl,
R and R 'each independently represent hydrogen, alkyl, alkylether, allylether, phosphine or amine,
L represents alkyl, allyl, arylalkyl, amide, alkoxy or halogen,
M represents a transition metal of group 4 or 5 of the periodic table,
n is an integer satisfying 0 ≦ n <5, m is 0 ≦ m <5, and q is 1 ≦ q ≦ 4;
Q (CpR n ) (CpR ' m ) ML q ‥‥‥ (2)
Where Cp, R, R ', M, L has the same meaning as in the general formula (1), Q is a bridge bond between the C ring, dialkyl, alkylaryl, diarylsilicone, or 1 to 20 carbon atoms A hydrocarbon group, n is 0 ≦ n <4, m is 0 ≦ m <4, q is an integer satisfying 1 ≦ q ≦ 4;
Figure 112013070324228-pat00004
‥‥‥ (3)

Wherein x is 0, 1, 2, 3 or 4, y is 0 or 1, and R is hydrogen, a hydrocarbon group of 1 to 20 carbon atoms, a silyl group, a germanyl group, a cyano group, a halogen or a complex group thereof A substituent having 1 to 20 non-hydrogen atoms, Y 'represents -O-, -S-, -NR *-, or -PR *-(R * represents hydrogen, a hydrocarbon group of 1 to 12 carbon atoms, Hydrocarbyloxy group having 1 to 8 carbon atoms, silyl group, halogenated alkyl group having 1 to 8 carbon atoms, halogenated aryl group having 6 to 20 carbon atoms or a combination thereof), Z is SiR * 2 , CR * 2 , SiR * 2 SiR * 2 , CR * 2 represents CR * 2 , CR * = CR *, CR * 2 SiR * 2 or GeR * 2 , R * is as defined above and L is each independently a halide, C 1-20 hydrocarbon Group, C1-C18 hydrocarbyloxy group, C1-C19 hydrocarbylamino group, C1-C18 hydrocarbylami Or a substituent having 1 to 20 non-hydrogen substituents selected from the group consisting of a group, a C1-C18 hydrocarbyl phosphide group, a C1-C18 hydrocarbyl sulfide group, and a complex group thereof, or Two substituents L together represent a neutral conjugated diene or a divalent group having 1 to 30 carbon atoms, and M represents a transition metal of group 4 or 5 of the periodic table;
(R'O) 4-n (R) n Si ... 4
Wherein R ′ and R represent a hydrocarbon group of 1 to 20 carbon atoms, may be the same or different, and n is 0, 1, 2 or 3;
(2) washing the supported catalyst obtained in step (1) with an organic solvent,
(3) drying the washed catalyst of step (2) and recovering it as catalyst powder. 제 1항에 있어서, 상기 (1) 단계의 담지 과정은, 알콕시실란 화합물과 반응시킨 알루미녹산의 용액에 메탈로센 화합물을 용해시켜 얻어진 용액을 담체 슬러리에 첨가하고, 교반시키므로써 수행되는 것을 특징으로 하는 올레핀 중합　또는 공중합용　촉매.The method of claim 1, wherein the supporting step (1) is performed by adding a solution obtained by dissolving a metallocene compound in a solution of aluminoxane reacted with an alkoxysilane compound to a carrier slurry and stirring. Olefin polymerization or copolymerization catalyst. 제 1항에 있어서, 상기 (1) 단계의 담지 과정은, 담체 슬러리에 알콕시실란 화합물과 반응시킨 알루미녹산 용액을 첨가하고, 교반시켜 담체에 알콕시실란 화합물과 반응시킨 알루미녹산을 담지시켜 얻어진 알루미녹산 담지 담체 슬러리에 메탈로센 화합물을 첨가하여 교반시키므로써 수행되는 것을 특징으로 하는 올레핀 중합　또는 공중합용　촉매.The aluminoxane according to claim 1, wherein the supporting step of step (1) is performed by adding the aluminoxane solution reacted with the alkoxysilane compound to the carrier slurry and stirring the aluminoxane reacted with the alkoxysilane compound on the carrier. A catalyst for olefin polymerization or copolymerization, which is performed by adding and stirring a metallocene compound to a supported carrier slurry. 제 1항에 있어서, 상기 담체는 평균 입도가 10　~　250㎛이고, 평균직경이 50~500Å인 미세기공을 가지고, 미세기공　부피는 0.1~10㎖/g이고, 표면적은 5~1000㎡/g인 실리카인 것을 특징으로 하는 올레핀 중합　또는 공중합용 촉매.　According to claim 1, wherein the carrier has a micropore having an average particle size of 10 ~ 250㎛, an average diameter of 50 ~ 500 Å, a micropore volume of 0.1 ~ 10ml / g, the surface area is 5 ~ 1000㎡ / g A catalyst for olefin polymerization or copolymerization, which is phosphorus silica. 제 1항에 있어서, 상기 알루미녹산은　직쇄 알루미녹산 올리고머 및 시클릭 알루미녹산 올리고머로부터 선택되는 것을 특징으로 하는 올레핀 중합　또는 공중합용 촉매.The catalyst for olefin polymerization or copolymerization according to claim 1, wherein the aluminoxane is selected from a straight chain aluminoxane oligomer and a cyclic aluminoxane oligomer. 제 1항 내지 제 5항 중 어느 한 항에 따른 촉매를 사용하여　올레핀을 중합 또는 올레핀과 공단량체를 공중합하는 것을 포함하는 올레핀 중합 또는 공중합 방법.





An olefin polymerization or copolymerization process comprising polymerizing an olefin or copolymerizing an olefin with a comonomer using the catalyst according to any one of claims 1 to 5.





KR1020110123752A 2011-11-24 2011-11-24 A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same KR101339474B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020110123752A KR101339474B1 (en) 2011-11-24 2011-11-24 A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same
PCT/KR2012/003884 WO2013077512A1 (en) 2011-11-24 2012-05-17 Catalyst for olefin polymerization and copolymerization, and olefin polymerization or copolymerization method using same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020110123752A KR101339474B1 (en) 2011-11-24 2011-11-24 A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same

Publications (2)

Publication Number Publication Date
KR20130057814A KR20130057814A (en) 2013-06-03
KR101339474B1 true KR101339474B1 (en) 2013-12-10

Family

ID=48469928

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020110123752A KR101339474B1 (en) 2011-11-24 2011-11-24 A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same

Country Status (2)

Country Link
KR (1) KR101339474B1 (en)
WO (1) WO2013077512A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100262245B1 (en) 1993-11-05 2000-07-15 스르무넨 페카 Supported olefin polymerization catalyst, its preparation and use
KR20110101386A (en) * 2010-03-08 2011-09-16 주식회사 엘지화학 Hybrid supported metallocene catalyst, method for preparing the same, and method for preparing polyolefin using the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1005957A5 (en) * 1992-06-05 1994-04-05 Solvay Preparation method of catalyst system, process (co) polymerization of olefins and (co) polymer at least one olefine.
US5587439A (en) * 1995-05-12 1996-12-24 Quantum Chemical Corporation Polymer supported catalyst for olefin polymerization
CN1279694A (en) * 1997-10-22 2001-01-10 智索公司 Supported metalloeene catalyst, process for preparing the same, and process for producing oclefin polymers
KR100288272B1 (en) * 1998-10-13 2001-05-02 유현식 Novel metallocene catalyst for olefin polymerization and preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100262245B1 (en) 1993-11-05 2000-07-15 스르무넨 페카 Supported olefin polymerization catalyst, its preparation and use
KR20110101386A (en) * 2010-03-08 2011-09-16 주식회사 엘지화학 Hybrid supported metallocene catalyst, method for preparing the same, and method for preparing polyolefin using the same

Also Published As

Publication number Publication date
KR20130057814A (en) 2013-06-03
WO2013077512A1 (en) 2013-05-30

Similar Documents

Publication Publication Date Title
KR101339550B1 (en) A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same
FI111080B (en) Supported catalysts for the polymerization of olefins
EP0712416B1 (en) Components and catalysts for the polymerization of olefins
EP0927201B1 (en) Catalyst system for (co)polymerization of olefins and process for the preparation of olefin (co)polymers using the catalyst system
JP6247751B2 (en) Method for producing hybrid supported metallocene catalyst
EP1097175A1 (en) Aluminum-based lewis acid cocatalysts for olefin polymerization
KR101795748B1 (en) Method for preparing polyolefin
KR20170055149A (en) Ethylene copolymer having excellent processing properties
KR101689456B1 (en) Ethylene-Olefin Copolymer and preparation thereof
JP2004521165A (en) Catalyst systems and their use in polymerization processes
KR101495423B1 (en) A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same
KR101058282B1 (en) Method for preparing metallocene supported catalyst for polyolefin polymerization and polyolefin polymerization method using metallocene supported catalyst prepared thereby
KR101474114B1 (en) Linear low density polyethylene resin with excellent processability
JP2005526175A (en) Solid granular heterogeneous spray-dried catalyst composition
KR20170114056A (en) metallocene supported catalyst for polymerization of olefin, its preparation method and production method of a polyolefin using the same
KR101339474B1 (en) A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same
KR100992715B1 (en) Preparation method of a catalyst for polyolefin copolymerization and method for polymerizing polyolefin using a catalyst produced by the same
JP2009120748A (en) Ethylene based polymer and manufacturing method
US6884749B2 (en) Supported catalysts which reduce sheeting in olefin polymerization, process for the preparation and the use thereof
JP2000327702A (en) Control of molecular weight and molecular weight distribution in polymer produced by using single-site catalyst
KR101718239B1 (en) A catalyst for olefin polymerization and co-polymerization, a method for preparing the same and an olefin polymerization and co-polymerization using the same
KR101849475B1 (en) Ethylene-Olefin Copolymer
KR102001965B1 (en) Polyolefin catalyst and preparing method of polyolefin using same
KR101844152B1 (en) Process for ethylene/alpha olefin/diene terpolymer using new transition metal compound
KR102010630B1 (en) Catalyst for olefin polymerization and olefin polymerization method thereof

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20160927

Year of fee payment: 4

FPAY Annual fee payment

Payment date: 20170920

Year of fee payment: 5

FPAY Annual fee payment

Payment date: 20180905

Year of fee payment: 6

FPAY Annual fee payment

Payment date: 20190923

Year of fee payment: 7