Polyolefin and preparation method thereof

Abstract

A polyolefin has 1) a density in the range of 0.93 to 0.97 g/cm 3 , 2) a BOCD (Broad Orthogonal Co-monomer Distribution) index defined by a given equation in the range of 1 to 5, and 3) a molecular weight distribution (weight average molecular weight/number average molecular weight) in the range of 4 to 10. A supported hybrid metallocene catalyst comprises a first metallocene compound represented by a first given formulae, a second metallocene compound represented by one of three given formulae, and a support.

1 . A polyolefin that has 1) a density in the range of 0.93 to 0.97 g/cm 3 , 2) a BOCD (Broad Orthogonal Co-monomer Distribution) index defined by the following Equation 1 in the range of 1 to 5, and 3) a molecular weight distribution (weight average molecular weight/number average molecular weight) in the range of 4 to 10:
   BOCD Index=(Content of  SCB  at the high molecular weight side−Content of  SCB  at the low molecular weight side)/(Content of  SCB  at the low molecular weight side)  [Equation 1]
   wherein the “Content of SCB at the high molecular weight side” means the content of the SCB(the number of branches/1000 carbon atoms) included in a polymer chain having a molecular weight of Mw of the polyolefin or more and 1.3×Mw or less, and the “Content of SCB at the low molecular weight side” means the content of the SCB(the number of branches/1000 carbon atoms) included in a polymer chain having a molecular weight of 0.7×Mw of the polyolefin or more and less than Mw.   
     
     
         2 . The polyolefin according to  claim 1 , wherein a melt flow index (190° C., 2.16 kg load condition) of the polyolefin is in the range of 0.05 to 2 g/10 min. 
     
     
         3 . The polyolefin according to  claim 1 , wherein a melt flow rate ratio (MFRR) of the polyolefin is in the range of 40 to 150. 
     
     
         4 . The polyolefin according to  claim 1 , wherein a die swell ratio of the polyolefin is in the range of 70 to 95%. 
     
     
         5 . The polyolefin according to  claim 1 , wherein a SCB (short chain branching) content per 1,000 carbon atoms of the polyolefin is in the range of 0 to 6. 
     
     
         6 . The polyolefin according to  claim 1 , wherein the polyolefin is a copolymer of an olefin monomer and an alpha olefin comonomer. 
     
     
         7 . The polyolefin according to  claim 6 , wherein the content of the alpha olefin comonomer is in the range of 0.1 to 45% by weight. 
     
     
         8 . The polyolefin according to  claim 6 , wherein the alpha olefin comonomer is one or more selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. 
     
     
         9 . The polyolefin according to  claim 1 , wherein the weight average molecular weight of the polyolefin is in the range of 80,000 to 300,000. 
     
     
         10 . The polyolefin according to  claim 1 , wherein the polyolefin is used for the blow molding purpose. 
     
     
         11 . A supported hybrid metallocene catalyst, comprising a first metallocene compound represented by the following Formula 1, a second metallocene compound represented by the following Formulae 2, 3 or 4, and a support:
   (L 1 ) p (L 2 )MQ 3-p   [Formula 1]
   wherein M is a Group 4 transition metal of the periodic table,   L 1  and L 2  are each independently a hydrogen radical, a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, a C 7˜30  arylalkyl radical, a metalloid radical of a Group 14 metal that is substituted with a C 1˜20  hydrocarbyl radical, or a ligand that forms a tetragonal to octagonal ring formed by connecting two adjacent carbon atoms using a hydrocarbyl radical,   Q is a halogen radical, a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, or a C 7˜30  arylalkyl radical, and two Qs may form a C 1˜20  hydrocarbon ring,   p is 1 or 0,   
       
         
           
           
               
               
           
         
         wherein M is a Group 4 transition metal of the periodic table; 
         R 3 , R 4  and R 5  are same or different from each other, and are each independently a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 3˜30  cycloalkyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, a C 7˜30  arylalkyl radical, or a C 8˜30  arylalkenyl radical; 
         Q and Q′ are same or different from each other, and are each independently a halogen radical, a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, or a C 7˜30  arylalkyl radical, and Q and Q′ may form a C 1˜20  hydrocarbon ring; 
         B is a C 1˜4  alkylene radical, dialkylsilicon, germanium, alkyl phosphine, or amine, and a bridge that bonds two cyclopentadienyl ligands or cyclopentadienyl ligand and JR 9   z-y  by using a covalent bond; 
         R 9  is a hydrogen radical, a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, or a C 7˜30  arylalkyl radical; 
         J is a Group 15 or 16 element of the periodic table; 
         z is the number of oxidation of the element of J; 
         y is the incorporation number of the element of J; 
         a, a′, n, and n′ are same or different from each other, and are each independently a positive integer of 0 or more; 
         m is an integer in the range of 0 to 3; 
         o is an integer in the range of 0 to 2; 
         r is an integer in the range of 0 to 2; 
         Y is a hetero atom of O, S, N or P; 
         A is hydrogen or a C 1˜10  alkyl radical; 
         R7s are the same as or different from each other, and are each independently selected from hydrogen and a methyl radical; and 
         Q5 and Q6 are the same as or different from each other, and are each independently selected from a methyl radical and a chloride radical. 
       
     
     
         12 . The supported hybrid metallocene catalyst according to  claim 11 , wherein the second metallocene compound represented by the Formula 4 is [(6-methyl-1,2,3,4-tetrahydroquinolin-8-yl)trimethylcyclopentadienyl- .η.η5 ,κ-N] TiCl 2 . 
     
     
         13 . The supported hybrid metallocene catalyst according to  claim 11 , wherein the first and the second metallocene compounds are supported in one support. 
     
     
         14 . A method of preparing a polyolefin of  claim 1  by using a supported hybrid metallocene catalyst in which at least two different metallocene compounds are supported in one support,
 wherein a first metallocene compound, which is one of the metallocene compounds, is a compound represented by the following Formula 1, and a second metallocene compound, which is another type of the metallocene compounds, is a compound represented by the following Formulae 2, 3 or 4:
   (L 1 ) p (L 2 )MQ 3-p   [Formula 1]
 
 
 wherein M is a Group 4 transition metal of the periodic table, 
 L 1  and L 2  are each independently a hydrogen radical, a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, a C 7˜30  arylalkyl radical, a metalloid radical of a Group 14 metal that is substituted with a C 1˜20  hydrocarbyl radical, or a ligand that forms a tetragonal to octagonal ring formed by connecting two adjacent carbon atoms using a hydrocarbyl radical, 
 Q is a halogen radical, a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, or a C 7˜30  arylalkyl radical, and two Qs may form a C 1˜20  hydrocarbon ring, 
 p is 1 or 0, 
 
       
         
           
           
               
               
           
         
         wherein M is a Group 4 transition metal of the periodic table; 
         R 3 , R 4  and R 5  are same or different from each other, and are each independently a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 3˜30  cycloalkyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, a C 7˜30  arylalkyl radical, or a C 8˜30  arylalkenyl radical; 
         Q and Q′ are same or different from each other, and are each independently a halogen radical, a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, or a C 7˜30  arylalkyl radical, and Q and Q′ may form a C 1˜20  hydrocarbon ring; 
         B is a C 1˜4  alkylene radical, dialkylsilicon, germanium, alkyl phosphine, or amine, and a bridge that bonds two cyclopentadienyl ligands or cyclopentadienyl ligand and JR 9   z-y  by using a covalent bond; 
         R 9  is a hydrogen radical, a C 1˜20  alkyl radical, a C 2˜20  alkenyl radical, a C 6˜30  aryl radical, a C 7˜30  alkylaryl radical, or a C 7˜30  arylalkyl radical; 
         J is a Group 15 or 16 element of the periodic table; 
         z is the number of oxidation of the element of J; 
         y is the incorporation number of the element of J; 
         a, a′, n, and n′ are same or different from each other, and are each independently a positive integer of 0 or more; 
         m is an integer in the range of 0 to 3; 
         o is an integer in the range of 0 to 2; 
         r is an integer in the range of 0 to 2; 
         Y is a hetero atom of O, S, N or P; 
         A is hydrogen or a C 1˜10  alkyl radical; 
         R7s are the same as or different from each other, and are each independently selected from hydrogen and a methyl radical; and 
         Q5 and Q6 are the same as or different from each other, and are each independently selected from a methyl radical and a chloride radical. 
       
     
     
         15 . The method of preparing a polyolefin according to  claim 14 , wherein the second metallocene compound represented by the Formula 4 is [(6-methyl-1,2,3,4-tetrahydroquinolin-8-yl)trimethylcyclopentadienyl- .η,η5 ,κ-N] TiCl 2 . 
     
     
         16 . The method of preparing a polyolefin according to  claim 14 , wherein the first metallocene compound is a catalyst used to obtain a polyolefin having a low molecular weight in the range of 1,000 to 100,000, the second metallocene compound is a catalyst used to obtain a polyolefin having a high molecular weight in the range of 10,000 to 1,000,000, and the molecular weight of the polyolefin obtained by the second metallocene compound is higher than the molecular weight of the polyolefin obtained by the first metallocene compound. 
     
     
         17 . The method of preparing a polyolefin according to  claim 14 , wherein the supported hybrid metallocene catalyst is manufactured by using a method which comprises:
 a) bringing a supported metallocene catalyst in which at least one metallocene compound is supported into contact with a cocatalyst to manufacture an activated supported metallocene catalyst; and   b) additionally supporting one or more metallocene compounds that are different from the metallocene compound in the activated supported metallocene catalyst.   
     
     
         18 . The method of preparing a polyolefin according to  claim 17 , wherein the cocatalyst comprises a Group 13 metal of the periodic table, and a molar ratio of the Group 13 metal/Group 4 metal of the supported hybrid metallocene catalyst is in the range of 1 to 10,000. 
     
     
         19 . The method of preparing a polyolefin according to  claim 17 , wherein the cocatalyst is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, tripentafluorophenyl boron, and tributylammoniumtetrapentafluorophenyl boron. 
     
     
         20 . The method of preparing a polyolefin according to  claim 14 , wherein the content of the Group 4 metal of the supported hybrid metallocene catalyst is in the range of 0.1 to 20% by weight. 
     
     
         21 . The method of preparing a polyolefin according to  claim 14 , wherein the supporting amount of the second metallocene compound in the supported hybrid metallocene catalyst is in the range of 0.5 to 2 moles based on 1 mole of the first metallocene compound. 
     
     
         22 . The method of preparing a polyolefin according to  claim 14 , wherein the supported hybrid metallocene catalyst further comprises the cocatalyst, and the supporting amount of the cocatalyst is in the range of 1 to 10,000 moles based on the metal included in the cocatalyst in respects to 1 mole of the metal included in the first and second metallocene compounds. 
     
     
         23 . The method of preparing a polyolefin according to  claim 14 , wherein the polyolefin is prepared in a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor. 
     
     
         24 . The method of preparing a polyolefin according to  claim 14 , wherein a polymerization temperature is in the range of 25 to 500° C., and a polymerization pressure is in the range of 1 to 100 Kgf/cm 2 . 
     
     
         25 . A blow molded material comprising the polyolefin of  claim 1 .