Postpolymerization modification of polynorbornene side chains via tetramethyl guanidine promoted esterification

Abstract

We demonstrate that polynorbornene containing primary activated bromide moieties is a novel chemically modifiable platform for postpolymerization modification. Polymer P0 was synthesized via ring‐opening metathesis polymerization of monomer 1 with the assistance of Grubbs third generation (G‐III) catalyst. Subsequently, nucleophilic substitution was conducted by mixing P0 with n‐caproic acid, sorbic acid, m‐toluic acid or 4‐nitrobenzoic acid in the presence of 1,1,3,3‐tetramethylguanidine (TMG) under mild and stoichiometric condition to generate functionalized polymers P1–P4. NMR results approved full conversion of the reactive sites and exemplified the “click” nature of TMG promoted esterification. Thermal stability and glass transition behaviors of all the polymer samples were investigated by thermal gravimetric analysis and differential scanning calorimetry. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3733–3740

Castor Oil-Based Bioplastics via Polyesterification: Synthesis, Characterization, and Functionalization

“…Nucleophilic substitution is an extensively investigated reaction throughout the development of organic chemistry, and recent publications reflect its impact on polymer synthesis. For example, Rebert, 36 Bai et al, 37−39 Xu et al, 40 and Wang et al 41 employed organobase-catalyzed esterification to realize polycondensation and post-polymerization modification, demonstrating tremendous potential of this synthetic tool in structural control (e.g., functionality, topology, and sequence). In particular, Bai et al 29 synthesized a series of biobased functional polymers via tetramethyl guanidine-promoted polyesterification under mild conditions by using 10undecenoic acid (0) as a starting material, an abundantly available renewable resource derived from castor oil.…”

“…Nucleophilic substitution is an extensively investigated reaction throughout the development of organic chemistry, and recent publications reflect its impact on polymer synthesis. For example, Rebert, Bai et al, − Xu et al, and Wang et al employed organobase-catalyzed esterification to realize polycondensation and post-polymerization modification, demonstrating tremendous potential of this synthetic tool in structural control ( e.g. , functionality, topology, and sequence).…”