2020
DOI: 10.1021/acs.macromol.0c00417
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Cascade Reactions in Chain-Growth Polymerization

Abstract: While the design and implementation of cascade reactions in organic chemistry and enzymatic biosynthesis flourished in the past decades, cascade reactions in polymerization remain an emerging concept with exciting opportunities. Cascade polymerization techniques can be used to generate polymers in which unique structures and functionalities are incorporated in the backbone of polymers, making them powerful tools to address the ever-increasing demand for new materials with improved functionality and sustainabil… Show more

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Cited by 29 publications
(23 citation statements)
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“…Therefore, we turned our attention to light‐mediated polymerization techniques, as recent works have demonstrated that they are versatile tools to mediate controlled polymerization following radical, [34–42] cationic, [43–47] and metathesis pathways [48–50] at ambient temperature (Figure 1B) [51] . In particular, we envisioned that the photoinduced electron/energy transfer‐reversible addition/fragmentation chain transfer (PET‐RAFT) polymerization developed by Boyer and co‐workers [52–56] could be employed to mediate the radical ring‐opening cascade copolymerization (rROCCP) [57, 58] of the macrocyclic allylic sulfone with acrylates or acrylamides (Figure 1C). Unlike the polymerization that is thermally initiated by azobisisobutyronitrile (AIBN), which requires high temperatures (80–100 °C) to maintain a sufficiently high rate of propagation, PET‐RAFT can be performed at mild temperatures, thereby enabling favorable comonomer reactivity ratios in copolymerization [59] .…”
Section: Introductionmentioning
confidence: 99%
“…Therefore, we turned our attention to light‐mediated polymerization techniques, as recent works have demonstrated that they are versatile tools to mediate controlled polymerization following radical, [34–42] cationic, [43–47] and metathesis pathways [48–50] at ambient temperature (Figure 1B) [51] . In particular, we envisioned that the photoinduced electron/energy transfer‐reversible addition/fragmentation chain transfer (PET‐RAFT) polymerization developed by Boyer and co‐workers [52–56] could be employed to mediate the radical ring‐opening cascade copolymerization (rROCCP) [57, 58] of the macrocyclic allylic sulfone with acrylates or acrylamides (Figure 1C). Unlike the polymerization that is thermally initiated by azobisisobutyronitrile (AIBN), which requires high temperatures (80–100 °C) to maintain a sufficiently high rate of propagation, PET‐RAFT can be performed at mild temperatures, thereby enabling favorable comonomer reactivity ratios in copolymerization [59] .…”
Section: Introductionmentioning
confidence: 99%
“…73 Cascade polymerizations can also generate conjugated polymers with more diverse structures (e.g., the metathesis and metallotropy polymerization). 74,75 For homopolymers, however, less controlled polymerizations might be utilized (e.g., the free radical polymerization of PGA, see Fig. 9), which could significantly increase the polymer scope.…”
Section: Discussionmentioning
confidence: 99%
“…Cyclopolymers comprise in‐chain ring repeating units to potentially serve as unique functional polymers with multiple nanopores, for example, a high glass transition temperature or rigid polymers and selective molecular recognition materials by their cyclic units. [ 1–9 ] Cyclopolymers are generally obtained from cyclopolymerization of bifunctional monomers such as divinyl monomers via an alternating process of intramolecular cyclization and intermolecular propagation. [ 1 ] Promotion of the intramolecular cyclization step is particularly important to realize cyclopolymerization without intermolecular linking of polymers and/or macroscopic gelation; the efficient cyclization involves a spatially adjacent placement of two olefins in cyclopolymerization of divinyl monomers.…”
Section: Methodsmentioning
confidence: 99%
“…Recent advances in polymerization systems and design strategies of monomers [ 3–6 ] have opened possibilities to synthesize cyclo(co)polymers with large in‐chain rings and/or well‐defined primary structures (e.g., monomer sequence) via cyclopolymerization. [ 21–31 ] One promising approach is to use template molecules for controlling bond formation to on‐target structures.…”
Section: Methodsmentioning
confidence: 99%