Metallocene compositions

Abstract

This invention relates to metallocene compositions and their use in the preparation of catalyst systems for olefin polymerization, particularly propylene polymerization. The metallocene compositions may be represented by the formula: wherein M 1 is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, preferably zirconium, hafnium or titanium, most preferably zirconium; R 1 and R 2 are identical or different, and are one of a hydrogen atom, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 2 -C 40 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, an OH group or a halogen atom, or a conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30 atoms not counting hydrogen; preferably R 1 and R 2 are identical and are a C 1 -C 3 alkyl or alkoxy group, a C 6 -C 8 aryl or aryloxy group, a C 2 -C 4 alkenyl group, a C 7 -C 10 arylalkyl group, a C 7 -C 12 alkylaryl group, or a halogen atom, preferably chlorine; R 3 are identical or different and are each a hydrogen atom, a halogen atom, a C 1 -C 10 alkyl group which may be halogenated, a C 6 -C 10 aryl group which may be halogenated, a C 2 -C 10 alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, a —NR′ 2 , —SR′ 1 , —OR′, —OSiR′ 3 or —PR′ 2 radical, wherein R′ is one of a halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group; preferably R 3 is not a hydrogen atom; preferably each R 3 is identical and is a fluorine, chlorine or bromine, atom, a C 1 -C 4 alkyl group which may be halogenated, a C 6 -C 8 aryl group which may be halogenated, a —NR′ 2 , —SR′, —OR′, —OSiR′ 3 or —PR′ 2 radical, wherein R′ is one of a chlorine atom, a C 1 -C 4 alkyl group, or a C 6 -C 8 aryl group; more preferably, R 3 are identical and are each a C 3 alkyl group, most preferably isopropyl groups; alternatively, R 3 is a C 1 or C 2 alkyl group; R 4 to R 7 are identical or different and are hydrogen, as defined for R 3 or two or more adjacent radicals R 5 to R 7 together with the atoms connecting them form one or more rings, preferably a 4-8 membered ring , more preferably a 6-membered ring; —B(R 14 )—, —Al(R 14 )—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO2-, —N(R 14 )—, —CO—, —P(R 14 )—, or —P(O)(R 14 )—, or an amidoborane radical; wherein: R 14 , R 15 and R 16 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl or silaalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 14 and R 15 , together with the atoms binding them, form a cyclic ring; preferably, R 14 , R 15 and R 16 are identical and are a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a CF 3 group, a C 6 -C 8 aryl group, a C 6 -C 10 fluoroaryl group, more preferably a pentafluorophenyl group, a C 1 -C 4 alkoxy group, in particular a methoxy group, a C 2 -C 4 alkenyl group, a C 7 -C 10 arylalkyl group, a C 8 -C 12 arylalkenyl group, or a C 7 -C 12 alkylaryl group; or, R 13 is represented by the formula: wherein R 17 to R 24 are as defined for R 1 and R 2 , or two or more adjacent radicals R 17 to R 24 , including R 20 and R 21 , together with the atoms connecting them form one or more rings; preferably, R 17 to R 24 are hydrogen. M 2 is one or more carbons, silicon, germanium or tin, preferably silicon; R 8 , R 10 and R 12 are identical or different and have the meanings stated for R 4 to R 7 ; R 9 and R 11 are identical or different and are a Group IVA radical having from 1 to 20 carbon atoms or are each primary, secondary or tertiary butyl groups, aryl groups, isopropyl groups, fluoroalkyl groups, trialkyl silyl groups, or other groups of similar size, preferably a tertiary butyl group.

We claim:  
     
         1 . A polymerization process comprising contacting under suitable polymerization conditions one or more monomers and the reaction product of one or more activators and one ore more compounds represented by the formula:  
       
         
           
           
               
               
           
         
         wherein: M 1  is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;  
         R 1  and R 2  are identical or different, and are one of a hydrogen atom, a C 1 -C 10  alkyl group, a C 1 -C 10  alkoxy group, a C 6 -C 10  aryl group, a C 6 -C 10  aryloxy group, a C 2 -C 10  alkenyl group, a C 2 -C 40  alkenyl group, a C 7 -C 40  arylalkyl group, a C 7 -C 40  alkylaryl group, a C 8 -C 40  arylalkenyl group, an OH group or a halogen atom, or a conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30 atoms not counting hydrogen;  
         R 3  are identical or different and are each a halogen atom, a C 3 -C 10  alkyl 5 group which may be halogenated, a C 6 -Cl 0  aryl group which may be halogenated, a C 2 -C 10  alkenyl group, a C 7 -C 40 -arylalkyl group, a.C 7 -C 40  alkylaryl group, a C 8 -C 40  arylalkenyl group, a —NR′ 2 , —SR′, —OR:, —OSiR′ 3  or —PR′ 2  radical, wherein R: is one of a halogen atom, a C 1 -C 10  alkyl group, or a C 6 -C 10  aryl group;  
         R 4  to R 7  are identical or different and are hydrogen, as defined for R 3  or two or more adjacent radicals R 5  to R 7  together with the atoms connecting them form one or more rings;  
         
           
             
             
                 
                 
             
           
         
         —B(R 14 )—, —Al(R 14 )—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO 2 —, —N(R 14 )—, —CO—, —P(R 14 )—, or —P(O)(R 14 )—, or an amidoborane radical;  
         wherein: R 14 , R 15 and R 16  are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20  alkyl group, a C 1 -C 20  fluoroalkyl or silaalkyl group, a C 6 -C 30  aryl group, a C 6 -C 30  fluoroaryl group, a C 1 -C 20  alkoxy group, a C 2 -C 20  alkenyl group, a C 7 -C 40  arylalkyl group, a C 8 -C 40  arylalkenyl group, a C 7 -C 40  alkylaryl group, or R 14  and R 15 , together with the atoms binding them, form a cyclic ring;  
         or, R 13  is represented by the formula:  
         
           
             
             
                 
                 
             
           
         
         wherein: R 17  to R 24  are as defined for R 1  and R 2 , or two or more adjacent radicals R 17  to R 24 , including R 20  and R 21 , together with the atoms connecting them form one or more rings;  
         M 2  is one or more carbons, silicon, germanium or tin;  
         R 8 , R 10  and R 12  are identical or different and have the meanings stated for R 4 to R 7 ;and  
         R 9  and R 11  are identical or different and are each a Group IVA radical having from 2 to 20 carbon atoms or are each a primary, secondary or tertiary butyl group, an aryl group, an isopropyl group, trialkyl silyl group, or a fluoroalkyl group.  
       
     
     
         2 . The process of  claim 1  wherein R 3  are identical C 3 -C 10  alkyl groups.  
     
     
         3 . The process of  claim 1  wherein R 4  to R 7  are hydrogen atoms.  
     
     
         4 . The process of  claim 1  wherein the monomers are selected from C 2 -C 14  olefins.  
     
     
         5 . The process of  claim 1  wherein the monomers are selected from ethylene, propylene, 1-butene and 1-hexene.  
     
     
         6 . A polymer comprising propylene units prepared by the process of  claim 1 .  
     
     
         7 . The process of  claim 1  wherein the monomers consist essentially of propylene.  
     
     
         8 . The process of  claim 1  wherein M 1  is selected from titanium, zirconium and hafnium.  
     
     
         9 . The process of  claim 1  wherein M 1  is zirconium.  
     
     
         10 . The process of  claim 1  wherein R 3  are identical C 3  alkyl groups.