Supported polymerization catalyst using a catalyst precursor having functional group and surface modified carrier and olefin polymerization using the same

A process for polymerizing an olefin using a catalyst system comprising

• a) a supported metallocene catalyst wherein a metallocene compound is supported on a carrier by contact reacting
• i) one or more kinds of metallocene catalyst compound ingredient wherein at least one hydrogen radical existing on R1, R2 or B of metallocene compound represented by the following Chemical Formula 1 or 2 is substituted with a radical selected from a group consisting of a radical represented by the following Chemical Formula 3, a radical represented by the following Chemical Formula 4 and a radical represented by the following Chemical Formula 5;
• and
• ii) a carrier, in the presence of an organic solvent
• to break a carbon-oxygen bond, carbon-sulfur bond or silicon-oxygen bond existing on a radical represented by the following Chemical Formula 3, 4 or 5 of the i) metallocene catalyst ingredient
• thereby forming a novel chemical bond between the i) metallocene catalyst and ii) a carrier;
• and
• b) a cocatalyst seleceted from a group consisting of a compound represented by the following Chemical Formula 6, a compound represented by the following Chemical Formula 7 and a compound represented by the following Chemical Formula 8,
• characterized in that the a) ii) carrier is a silica prepared by silane-treating a silica dehydrated at 500° C. or more to selectively remove hydroxy groups out of hydroxy groups and siloxane groups existing on a silica surface:
• (C5R1m)pBs(C5R1m)MQ3-p [Chemical Formula 1] 15
• M is Group 4 transition metal,
• (C5R1m) and (C5R1n) are independently a cyclopentadienyl or substituted cyclopentadienyl ligand wherein each R1, which may be identical or different, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl radical or hydrocarbyl-substituted Group 14 metalloid, or a substituted cyclopentadienyl ligand wherein two neighboring carbon atoms in C5 are connected each other through a hydrocarbyl radical to form one or more 4-16 angular rings;
• B, which is a bridge connecting two cyclopentadienyl ligand or one cyclopentadienyl ligand and JR2z-y through covalent bonds, is carbon chain alkylene, carbon chain arylene, carbon chain alkenylene, dialkylsilicone, dialkylgermanium, alkyl phosphine or alkylamine;
• R2 is hydrogen radical, C1-40 alkyl radical, alkenyl radical, aryl radical, alkylaryl radical, or arylalkyl radical;
• J is a VA Group atom or VIA Group atom;
• Q, which may be identical or different, is halogen radical, C1-20 alkyl radical, alkenyl radical, aryl radical, alkylaryl radical, arylakyl radical or C1-20 alkylidene radical;
• L is a Lewis base;
• s is 0 or 1, and p is 0, 1 or 2,
• provided that s is 0 when p is 0, m is 4 when s is 1, m is 5 when s is 0;
• z is an atomic valence of J, which is 3 for VA Group atoms and 2 for VIA Group atoms;
• and
• x is 0 or 1,
• provided that when x is 0, n is 5, y is 1, and w is more than 0, and
• when x is 1, n is 4, y is 2, and w is 0.)
• 16
• Z is an oxygen or sulfur atom;
• R, which may be identical or different, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical;
• R′, which may be identical or different, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylakneyl radical, and two R′ may be connected with each other to form a ring;
• Y is C1-40 alkoxy, aryloxy, alkylthio, arylthio, phenyl or substituted phenyl, and it may be connected with R′ to form a ring;
• provided that when Z is a sulfur atom, Y must be alkoxy or aryloxy, and when Y is alkylthio, arylthio, phenyl or substituted phenyl, Z must be an oxygen atom;
• and
• A is a carbon or silicon atom.)
• 17
• Z is an oxygen or sulfur atom, and at least one is an oxygen atom;
• R″ is hydrogen radical, C1-40 alkyl, cycloalkyl, arylalkenyl, alkylaryl, arylalkyl, or arylalkenyl radical, and it may be connected with R′″ to form a ring;
• R′″, which may be identical or different, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical, and two R′″ may be connected with each other to form a ring;
• and
• A is a carbon or silicon atom.)
• 18
• R″″, which may be identical or different, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical;
• R′″″, which may be identical or different, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical, and two neighboring R′″″ may be connected with each other to form a ring;
• provided that when at least one R″″ is hydrogen radical, all R′″″ is not a hydrogen radical, and when at least one R′″″ is hydrogen radical, all R″″ is not hydrogen radical;
• and
• A is carbon or silicon atom.)
• 19
• R3, which may be identical or different, is halogen radical, C1-40 hydrocarbyl radical or halogen substituted C1-40 hydrocarbyl radical;
• and
• d is an integer of 2 or more.)
• Al(R4)3 [Chemical Formula 7]
• (In the Chemical Formula 7,
• R4, which may be identical or different, is halogen radical, C1-40 hydrocarbyl radical or halogen substituted C1-40 hydrocarbyl radical)
• [L]+[NE4]− [Chemical Formula 8]
• (In the Chemical Formula 8,
• [L]+ is a cation consisting of inorganic organic group;
• N is a Group 13 atom on periodic table;
• and
• E, which may be identical or different, is C6-40 arylradical substituted with one or more of halogen radical, C1-40 hydrocarbyl, alkoxy, phenyl radical, or C1-40 hydrocarbyl radical comprising nitrogen, phosphorus, sulfur and oxygen atoms)