Synthesis of Diblock and Triblock Polymers from Cyclooctadiene and Norbornene Via ROMP in Miniemulsion

Abstract

The synthesis of diblock and triblock linear polyolefins via ring opening metathesis polymerization (ROMP) in an aqueous nanoparticle dispersion is presented. The different block polyolefins are synthesized from the cyclic olefins 1,5‐cyclooctadiene and norbornene (NB), using a water‐soluble TEGylated ruthenium alkylidene catalyst, yielding the structures PCOD‐b‐PNB, PNB‐b‐PCOD, and PCOD‐b‐PNB‐b‐PCOD. High monomer conversion (>90%), monitored by NMR, is achieved in relatively short times (≈1 h) for the polymerization of each block. The livingness of the system, essential to obtain block copolymers, is confirmed by gel permeation chromatography. Latex particles' size during the multiple steps range between 90 and 150 nm. The results demonstrate that it is possible to obtain nanoparticle latexes from ROMP‐based monomers with block copolymer architectures, creating the opportunity to copolymerize olefins bearing different functional groups for the synthesis of new materials.

RAFT‐Mediated Polymerization‐Induced Self‐Assembly

“…Theoretically, any RDRP technique or living polymerization technique can be selected to produce these block copolymer nanoobjects by PISA. Indeed, nitroxide‐mediated polymerization (NMP), atom‐transfer radical polymerization (ATRP), Cu‐mediated controlled polymerization, iodine‐transfer polymerization (ITP), organotellurium‐mediated radical polymerization (TERP), Co‐mediated radical polymerization, ring‐opening metathesis polymerization (ROMP), or reversible complexation‐mediated polymerization (RCMP) have been successfully implemented. However, RAFT‐mediated PISA remains the most employed strategy.…”

Enzyme‐Responsive Polymer Nanoparticles via Ring‐Opening Metathesis Polymerization‐Induced Self‐Assembly

“…PISA has largely involved radical polymerizations, and more recently photoinitiation, which has been shown to improve the precision in targeting a specific morphology . PISA has recently been extended to ring‐opening metathesis polymerization‐induced self‐assembly (ROMPISA) . Ring‐opening metathesis polymerization (ROMP) allows for the polymerization of a wide range of functional monomers, and utilization in PISA should in turn yield functionalized, well‐defined nanostructures in situ.…”

Ethylene‐Coordinative Chain‐Transfer Polymerization‐Induced Self‐Assembly (CCTPISA)

“…PISA is conceptually transposable to any living polymerization techniques. Pioneered with RDRP using RAFT by Ferguson et al., [21] PISA has indeed also been recently applied to non‐radical based polymerization techniques [24] such as ring opening metathesis polymerization, [25–27] anionic ring opening polymerization of N ‐carboxyanhydride [28,29] or Ni‐catalyzed isocyanide, [30] or allene polymerization [31] …”