Ziegler-Natta polymerization of alpha-olefins in the presence of non-polymerizing olefins

Abstract

A method is presented for increasing molecular weight and/or stereoregularity of poly(alpha-olefins) by polymerizing alpha-olefins in the presence of 1) a Ziegler-Natta catalyst system and 2) at least one non-polymerizing olefin which is not polymerizable under the polymerization conditions.

We claim:  
     
         1 . A method of polymerizing alpha-olefins having three or more carbon atoms comprising a polymerization step performed in the presence of 1) a Ziegler-Natta catalyst system and 2) at least one non-polymerizing olefin which is not polymerizable under the polymerization conditions.  
     
     
         2 . The method of  claim 1  wherein said non-polymerizing olefin is selected from the group consisting of secondary, tertiary and quaternary olefins.  
     
     
         3 . The method of  claim 1  wherein said non-polymerizing olefin is selected from the group consisting of secondary, tertiary and quaternary cyclic internal olefins.  
     
     
         4 . The method of  claim 3  wherein said non-polymerizing olefin comprises a substituted or unsubstituted cyclohexene ring.  
     
     
         5 . The method of  claim 3  wherein said non-polymerizing olefin is selected from the group consisting of: 3-carene, 2-carene, alpha-pinene, beta-pinene and 1-methylcyclohexene.  
     
     
         6 . The method of  claim 5  wherein said non-polymerizing olefin is 3-carene.  
     
     
         7 . The method of  claim 1  wherein said non-polymerizing olefin does not bind irreversibly to a catalyst of the Ziegler-Natta catalyst system.  
     
     
         8 . The method of  claim 1  wherein said non-polymerizing olefin is effective in amounts of less than 8 mole percent of the combined amounts of alpha-olefin reactants plus non-polymerizing olefins.  
     
     
         9 . The method of  claim 1  wherein said non-polymerizing olefin is characterized by an IVnp/IVmo for 7.4 mole percent of 1.7 or greater.  
     
     
         10 . The method of  claim 1  wherein said non-polymerizing olefin is characterized by an Mw:np/Mw:mo for 5.6 mole percent of 2.0 or greater.  
     
     
         11 . The method of  claim 1  additionally comprising the step of removing said non-polymerizing olefin from a polymerized product of said polymerization step.  
     
     
         12 . The method of  claim 11  wherein said non-polymerizing olefin removed from said polymerized product is reused in a subsequent polymerization step.  
     
     
         13 . The method of  claim 1  wherein the amount of non-polymerizing olefins present during said polymerization step is at least 0.5 mole percent of the combined amounts of alpha-olefin reactants plus non-polymerizing olefins.  
     
     
         14 . The method of  claim 13  wherein the amount of non-polymerizing olefins present during said polymerization step is between 0.5 mole percent and 14 mole percent of the combined amounts of alpha-olefin reactants plus non-polymerizing olefins.  
     
     
         15 . The method of  claim 13  wherein the amount of non-polymerizing olefins present during said polymerization step is between 0.5 mole percent and 8 mole percent of the combined amounts of alpha-olefin reactants plus non-polymerizing olefins.  
     
     
         16 . The method of  claim 13  wherein said non-polymerizing olefin is selected from the group consisting of secondary, tertiary and quaternary olefins.  
     
     
         17 . The method of  claim 13  wherein said non-polymerizing olefin is selected from the group consisting of secondary, tertiary and quaternary cyclic internal olefins.  
     
     
         18 . The method of  claim 17  wherein said non-polymerizing olefin comprises a substituted or unsubstituted cyclohexene ring.  
     
     
         19 . The method of  claim 17  wherein said non-polymerizing olefin is selected from the group consisting of: 3-carene, 2-carene, alpha-pinene, beta-pinene and 1-methyl-cyclohexene.  
     
     
         20 . The method of  claim 19  wherein said non-polymerizing olefin is 3-carene or 2-carene.  
     
     
         21 . The method of  claim 13  wherein said non-polymerizing olefin does not bind irreversibly to a catalyst of the Ziegler-Natta catalyst system.  
     
     
         22 . The method of  claim 13  wherein said non-polymerizing olefin is effective in amounts of less than 8 mole percent of the combined amounts of alpha-olefin reactants plus non-polymerizing olefins.  
     
     
         23 . The method of  claim 13  wherein said non-polymerizing olefin is characterized by an IVnp/IVmo for 7.4 mole percent of 1.7 or greater.  
     
     
         24 . The method of  claim 13  wherein said non-polymerizing olefin is characterized by an Mw:np/Mw:mo for 5.6 mole percent of 2.0 or greater.  
     
     
         25 . The method of  claim 13  additionally comprising the step of removing said non-polymerizing olefin from a polymerized product of said polymerization step.  
     
     
         26 . The method of  claim 25  wherein said non-polymerizing olefin removed from said polymerized product is reused in a subsequent polymerization step.  
     
     
         27 . A reaction mixture comprising 1) at least one alpha-olefin monomer having three or more carbon atoms and 2) at least one second olefin characterized by an IVnp/IVmo for 7.4 mole percent of 1.7 or greater.  
     
     
         28 . The reaction mixture of  claim 27  wherein the amount of second olefins is at least 0.5 mole percent of the combined amounts of alpha-olefin reactants plus second olefins.  
     
     
         29 . The reaction mixture of  claim 27  wherein the amount of second olefins is between 0.5 mole percent and 14 mole percent of the combined amounts of alpha-olefin reactants plus second olefins.  
     
     
         30 . A reaction mixture comprising 1) at least one alpha-olefin monomer having three or more carbon atoms and 2) at least one second olefin characterized by an Mw:np/Mw:mo for 5.6 mole percent of 2.0 or greater.  
     
     
         31 . The reaction mixture of  claim 30  wherein the amount of second olefins is at least 0.5 mole percent of the combined amounts of alpha-olefin reactants plus second olefins.  
     
     
         32 . The reaction mixture of  claim 30  wherein the amount of second olefins is between 0.5 mole percent and 14 mole percent of the combined amounts of alpha-olefin reactants plus second olefins.  
     
     
         33 . A reaction mixture comprising 1) at least one alpha-olefin monomer having three or more carbon atoms and 2) at least one second olefin selected from the group consisting of secondary, tertiary and quaternary cyclic internal olefins having no primary olefin groups.  
     
     
         34 . The reaction mixture of  claim 33  wherein said second olefin comprises a substituted or unsubstituted cyclohexene ring.  
     
     
         35 . The reaction mixture of  claim 34  wherein said second olefin is selected from the group consisting of: 3-carene, 2-carene, alpha-pinene, beta-pinene and 1-methyl-cyclohexene.  
     
     
         36 . The reaction mixture of  claim 35  wherein said second olefin is 3-carene or 2-carene.  
     
     
         37 . The reaction mixture of  claim 34  wherein the amount of second olefins is at least 0.5 mole percent of the combined amounts of alpha-olefin reactants plus second olefins.  
     
     
         38 . The reaction mixture of  claim 34  wherein the amount of second olefins is between 0.5 mole percent and 14 mole percent of the combined amounts of alpha-olefin reactants plus second olefins.