Abstract: A free radical or controlled radical polymerization process of atom or group transfer radical polymerization. The process comprises radically polymerizing one or more radically (co)polymerizable monomers in the presence of a polymerization system. The one or more radically (co)polymerizable monomers comprise at least one or more radically (co)polymerizable diene monomers. The polymerization system comprises: an initiator having one or more radically transferable atoms or groups; a transition metal-ligand complex catalyst, wherein the ligand comprises any C-, N-, O-, P- or S-containing ligand which coordinates with the transition metal; an optional reducing agent capable of regenerating the lower oxidation state of the transition metal catalyst; and an optional organic solvent or water capable of solubilizing the transition metal-ligand complex catalyst. (Co)polymers produced by the free radical or controlled radical polymerization process of atom or group transfer radical polymerization.

Abstract: A free radical or controlled radical polymerization process of atom or group transfer radical polymerization. The process comprises radically polymerizing one or more radically (co)polmerizable monomers in the presence of a polymerization system. The one or more radically (co)polymerizable monomers comprise at least one or more radically (co)polymerizable diene monomers. The polymerization system comprises: an initiator having one or more radically transferable atoms or groups; a transition metal-ligand complex catalyst, wherein the ligand comprises any C-, N-, O-, P- or S-containing ligand which coordinates with the transition metal; an optional reducing agent capable of regenerating the lower oxidation state of the transition metal catalyst; and an optional organic solvent or water capable of solubilizing the transition metal-ligand complex catalyst. (Co)polymers produced by the free radical or controlled radical polymerization process of atom or group transfer radical polymerization.

Abstract: The disclosure discloses initiating systems for the radical polymerization of alkenes, and especially fluorine substituted alkenes. The polymerization is catalyzed by a metal carbonyl, preferably manganese carbonyl. The polymerization is initiated directly from alkyl halides at room temperature under visible white light. The polymers also allow the synthesis of block copolymers. The process comprises polymerizing at least one alkene monomer in the presence of a halide radical initiator, carbonyl catalyst and a solvent, under reaction conditions and for a time sufficient to polymerize the at least one alkene monomer to form a polymer. The present disclosure provides a method for living polymerization of alkene monomers which provides a high level of macromolecular control over the polymerization process and which leads to uniform and controllable polymeric products.

Abstract: A process is described comprising polymerizing at least one unsaturated monomer (e.g., fluorine substituted alkene monomer) in the presence of a hypervalent iodide radical initiator and a solvent, under reaction conditions and for a time sufficient to polymerize the at least one unsaturated monomer to form a polymer. The present disclosure provides a method for living polymerization of unsaturated monomers (e.g., fluorine substituted alkene monomers), which provides a high level of macromolecular control over the polymerization process and which leads to uniform and controllable polymeric products. The present disclosure also provides a method of functionalization of organic substrates with a CF3 or perfluoro (RF) group.

Abstract: A process is described comprising polymerizing at least one unsaturated monomer (e.g., fluorine substituted alkene monomer) in the presence of an azide radical initiator and a solvent, under reaction conditions and for a time sufficient to polymerize the at least one unsaturated monomer to form a polymer. The present disclosure provides a method for the synthesis of polymers with 100% azide chain end functionality, for living/controlled radical polymerization of unsaturated monomers (e.g., fluorine substituted alkene monomers) and for the synthesis of complex polymer architectures, using azide click reactions.