Ring‐Opening Metathesis Polymerization of Norbornene‐Based Monomers Obtained via the Passerini Three Component Reaction

Abstract

Ring‐opening metathesis polymerization is a robust method to synthesize a variety of polymers by using ring‐strained molecules as monomers, e.g., norbornenes. However, the synthesis of monomers with multiple functional groups remains a challenge, albeit peptide functional norbornenes have previously been used. Here, the Passerini three component reaction is exploited to synthesize norbornenes with two variable functional groups varying in bulkiness and distance from the polymerizable alkene. The results indicate that the functional groups do not affect the kinetics of the polymerization, whereas the length of the linker has a minor effect. Furthermore, a diblock‐type copolymer is synthesized in a one‐pot fashion, also indicating good control of the polymerization process. The thermal properties of all polymers are evaluated, highlighting the effect of monomer composition. This synthetic approach can be transferred to a variety of compounds, thus promising highly diverse polymers with complex compositions and architectures.

One‐Pot Synthesis of Thiocarbamates

“…ROMP has shown excellent tolerance towards a range of functional groups, [54,55] while our fundamental interest in the coupling of multicomponent reactions with polymer synthesis has found this approach versatile and highly efficient. [56,57] It is noted that sulfur-bearing monomers are known to be particularly challenging in several chain-growth polymerizations, e. g. in radical processes. However, with ROMP this difficulty can be overcome, e. g. recently dithiocarbamate-functional norbornene monomers were polymerized by ROMP in a controlled way, obtaining macroinitiators capable of initiating reversible-addition-fragmentation chain-transfer (RAFT) polymerization.…”

Modern Trends in Polymerization-Induced Self-Assembly

“…Most ring-opening polymerizations (ROP), such as ring-opening metathesis polymerization (ROMP) and ROP of lactones, lactams, cyclic ethers, etc., proceed through an ionic mechanism. ROMP polymerization of cyclic monomers containing C=C bonds is initiated typically by metal alkylidene complexes M=CR(R ′ ) such as Ru-based Grubbs catalysts of 1-3 generation (G1-G3) [272][273][274][275][276][277][278][279][280][281][282][283]. Various functional norbornenes are the most frequently used monomers in ROMP, which usually proceeds through living mechanisms, giving rise to block copolymer synthesis [284,285].…”