Use Of A Combination Chain Transfer And Activating Agent To Control Molecular Weight And Optical Density Of Pd Catalyzed Norbornene Polymers

Abstract

A method of controlling the molecular weight of poly(cyclic) olefin (norbornene-type) polymers and activating the polymerization thereof with a single material is provided. Such method include adding a chain transfer/activating agent to a mixture of monomer(s), catalyst, solvent and an optional cocatalyst and polymerizing the mixture to form a polymer. It is shown that the amount of chain transfer/activating agent in the mixture can serve to control the molecular weight of the resulting polymer, its percent conversion or both, and in some embodiments the optical density of the resulting polymer.

1 . A method of polymerizing poly(cyclic) olefin monomers, comprising:
 combining a monomer composition comprising one or more poly(cyclic) olefin monomers, a palladium catalyst complex, and a chain transfer/activating agent to form a mixture; and   polymerizing the mixture to form a polymer.   
     
     
         2 . The method of  claim 1 , where the chain transfer/activating agent provides for activating the palladium catalyst complex for forming a palladium hydride-containing moiety. 
     
     
         3 . The method of  claim 1 , where the chain transfer/activating agent comprises an acid. 
     
     
         4 . The method of  claim 3 , where the acid is formic acid. 
     
     
         5 . The method of  claim 4 , where the formic acid and the palladium catalyst complex interact to form a palladium formate intermediate. 
     
     
         6 . The method of  claim 5 , where the formic acid serves as a chain transfer/activating agent and a catalyst activating agent. 
     
     
         7 . The method of  claim 6 , where the catalyst complex comprises at least one phosphorous containing moiety. 
     
     
         8 . A reaction mixture comprising:
 one or more poly(cyclic) olefin monomers;   a palladium catalyst complex;   an optional co-catalyst; and   a chain transfer/activating agent (CTAA).   
     
     
         9 . The reaction mixture of  claim 8 , where the palladium catalyst complex is essentially phosphorous-free. 
     
     
         10 . The reaction mixture of  claim 9 , where at least one of the one or more poly(cyclic) olefin monomers is HFANB. 
     
     
         11 . The reaction mixture of  claim 9 , where at least one of the one or more poly(cyclic) olefin monomers is MeOAcNB. 
     
     
         12 . The reaction mixture of  claim 9 , where the CTAA is formic acid. 
     
     
         13 . The reaction mixture of  claim 12 , further comprising an amount of CTAA that is from 1 to 25% of the total monomer loading to the reaction mixture. 
     
     
         14 . The reaction mixture of  claim 12 , where the one or more poly(cyclic) olefin monomers are at least two distinct types of norbornene-type monomers.