title: A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes.
abstract: Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic nature of the monomer is conserved. The resulting polymer, polynorbornene, has a very high glass transition temperature, Tg, and interesting optical and electrical properties. However, the polymerization of functional norbornenes by this mechanism is complicated by the fact that the endo substituted norbornene monomer has, in general, a very low reactivity. Furthermore, the separation of the endo substituted monomer from the exo monomer is a tedious task. Here, we present a simple protocol for the polymerization of substituted norbornenes (endo:exo ca. 80:20) bearing either a carboxylic acid or a pendant double bond. The process does not require that both isomers be separated, and proceeds with low catalyst loadings (0.01 to 0.02 mol%). The polymer bearing pendant double bonds can be further transformed in high yield, to afford a polymer bearing pendant epoxy groups. These simple procedures can be applied to prepare polynorbornenes with a variety of functional groups, such as esters, alcohols, imides, double bonds, carboxylic acids, bromo-alkyls, aldehydes and anhydrides.
authors.affiliation: Department of Chemistry, Université de Sherbrooke.
authors.forename: Basile
authors.initials: B
authors.lastname: Commarieu
authors.affiliation: Department of Chemistry, Université de Sherbrooke.
authors.forename: Jonathan
authors.initials: J
authors.lastname: Potier
authors.affiliation: Department of Chemistry, Université de Sherbrooke.
authors.forename: Moubarak
authors.initials: M
authors.lastname: Compaore
authors.affiliation: Department of Chemistry, Université de Sherbrooke.
authors.forename: Raphael
authors.initials: R
authors.lastname: de Boever
authors.affiliation: Department of Chemistry, Université de Sherbrooke.
authors.forename: Regis
authors.initials: R
authors.lastname: Imbeault
authors.affiliation: Department of Chemistry, Université de Sherbrooke; jerome.claverie@usherbrooke.ca.
authors.forename: Jerome P
authors.initials: JP
authors.lastname: Claverie
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000032:analysis*; D002264:Carboxylic Acids; D002384:Catalysis; D007094:Imides / Q000032:analysis; D007536:Isomerism; D008968:Molecular Conformation; D009636:Norbornanes; D058105:Polymerization; D011108:Polymers / Q000737:chemistry*
chemical_list: D001643:Bridged Bicyclo Compounds; D002264:Carboxylic Acids; D007094:Imides; D009636:Norbornanes; D011108:Polymers; C046060:2-norbornene