Novel organosoluble polynorbornene bearing a polar, pendant, ester‐bridged epoxy group via living ring‐opening metathesis polymerization

Abstract

A novel organosoluble polynorbornene bearing a polar, pendant, ester‐bridged epoxy group [poly(oxiran‐2‐ylmethyl 2‐methylbicyclo[2.2.1]hept‐5‐ene‐2‐carboxylate) (polyOMMC)] was prepared via the living ring‐opening metathesis polymerization (ROMP) of active norbornenes with a Ru catalyst. PolyOMMC exhibited excellent solubility in a variety of solvents. The number‐average molecular weight of polyOMMC linearly increased with the [M]/[I] ratio (where [M] is the monomer concentration and [I] is the initiator concentration), and a narrow polydispersity of 1.09–1.19 was observed; this was considered a living polymerization. When ROMP of oxiran‐2‐ylmethyl 2‐methylbicyclo[2.2.1]hept‐5‐ene‐2‐carboxylate with [M]/[I] = 350 was carried out at 30 °C in CH2Cl2, the number‐average molecular weight (7.01 × 104; polydispersity index = 1.07) was close to the calculated molecular weight (7.28 × 104), and a diblock copolymer was observed after the addition of another monomer ([M]/[I] = 350) with an increase in the number‐average molecular weight (1.60 × 105; polydispersity index = 1.11), which was close to the calculated molecular weight (1.61 × 105). The modified polynorbornenes retained good solubility in methylene chloride, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, N,N‐dimethylacetamide, and N‐methyl‐2‐pyrrdione. High‐performance polynorbornenes with active epoxy groups could be designed with great potential for applications in photoresists, UV curing, and elastomers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4428–4434, 2006

Phosphonated homopolymers and copolymers via ring opening metathesis polymerization: T g tuning, flame resistance, and photolithography

“…Monomer 2 showed characteristic peak of epoxy at 912 cm −1 , and the peak at 1725 cm −1 was attributed to CO of the ester group . The isomers of endo and exo were calculated by NMR based on 1.8 ∼ 2.4 ppm (monomer 1 ) and 6.1–6.3 ppm (monomer 2 ) respectively . It was found that the endo/exo ratio of monomer 1 was 1/1 and 2/1 for monomer 2 , which were consistent with the findings in references very well …”

“…(28)], especially when flexibility is tuned by adjusting the chemical structures of macromolecular backbones. Besides, an epoxy‐containing norbornene monomer with rising potentials as a new crosslinker in resin industry was also used in this study . A second aim of this contribution is to test the flame retardance and photo resistance of PCPs for the promising industrial applications.…”

“…Monomer 1 and 2 were synthesized via Diels–Alder addition using either diethyl vinylphosphonate or glycidyl methacrylate with cylcopentadiene. Monomer 1 is a phosphonated component, 2 is epoxy‐containing and showing increasing interest in the preparation of advanced epoxy curing resins . Besides, the recent developed thiol‐epoxy “click” chemistry by Khan and coll.…”

The controlled homogeneous organic solution polymerization of new hydrophilic cationic exo‐7‐oxanorbornenes via ROMP with RuCl2(PCy3)2CHPh in a novel 2,2,2‐trifluoroethanol/methylenechloride solvent mixture

“…This is due in part to their relative ease of handling/storage as well as their high functional group tolerance. Indeed, a wide range of monomers bearing a broad spectrum of functionality have been successfully polymerized via ROMP employing Grubbs' catalyst 8–17. However, Grubbs' catalyst is not tolerant of all functionality.…”

Back Cover: A Highly Efficient, Clean‐Surface, Porous Platinum Electrocatalyst and the Inhibition Effect of Surfactants on Catalytic Activity (Chem. Eur. J. 1/2013)

“…Interest in polymers of cyclic olefins such as bicyclo[2.2.1]hept‐2‐ene(norbornene) and its derivatives has increased dramatically over the past decade. Norbornene (NBE) and its derivatives are commonly polymerized via four well‐known polymerization mechanisms with various transition‐metal‐containing catalysts: cationic polymerization,1 radical polymerization,2 ring‐opening metathesis polymerization (ROMP),3–15 and vinyl‐addition polymerization 16–22. Among them, vinylic polymerization has drawn more attention because it yields a special polynorbornene (PNBE) with a 2,3‐connected structure, which contains intact bicyclic units and is rotationally strongly constrained 23–25.…”