Synthesis of dual-responsive polymer via convertible RAFT and ring-opening polymerizations in one-pot

Wang, Changhui; Fan, Yunshan; Zhang, Ze; Chen, Qian-Bao; Zeng, Tianyou; Meng, Qingyong; You, Ye‐Zi

doi:10.1016/j.apsusc.2019.01.033

Cited by 14 publications

(9 citation statements)

References 37 publications

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“…Followed by the AROP of A and PET-RAFT of B, monomers C and D were added, and AROP and PET–RAFT were conducted respectively to yield the heptablock copolymer. You et al also showed that AIBN catalyzed RAFT polymerization of NIPMAm and TPPCl catalyzed AROP of MT can be carried out in one pot using TTC RAFT agent to synthesize block-like copolymers based on the discrepancy between the rate of polymerization of the two monomers . The polymerization of MT is initiated at both sides of the TTC, and the polymerization of NIPMAm takes place on the −R side of the TTC.…”

Section: Block Copolymers From Vinyl Polymersmentioning

confidence: 99%

“…You et al also showed that AIBN catalyzed RAFT polymerization of NIPMAm and TPPCl catalyzed AROP of MT can be carried out in one pot using TTC RAFT agent to synthesize block-like copolymers based on the discrepancy between the rate of polymerization of the two monomers. 178 The polymerization of MT is initiated at both sides of the TTC, and the polymerization of NIPMAm takes place on the −R side of the TTC. The long induction period of PMT polymerization allows for the homopolymerization of NIPMAm, which slowed down significantly as the PS started to polymerize, giving access to block-like copolymer.…”

Section: Raft First: Combined Approaches For Block Copolymer Synthesismentioning

confidence: 99%

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Linear Block Copolymer Synthesis

et al. 2022

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Block copolymers form the basis of the most ubiquitous materials such as thermoplastic elastomers, bridge interphases in polymer blends, and are fundamental for the development of high-performance materials. The driving force to further advance these materials is the accessibility of block copolymers, which have a wide variety in composition, functional group content, and precision of their structure. To advance and broaden the application of block copolymers will depend on the nature of combined segmented blocks, guided through the combination of polymerization techniques to reach a high versatility in block copolymer architecture and function. This review provides the most comprehensive overview of techniques to prepare linear block copolymers and is intended to serve as a guideline on how polymerization techniques can work together to result in desired block combinations. As the review will give an account of the relevant procedures and access areas, the sections will include orthogonal approaches or sequentially combined polymerization techniques, which increases the synthetic options for these materials.

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Section: Block Copolymers From Vinyl Polymersmentioning

confidence: 99%

Section: Raft First: Combined Approaches For Block Copolymer Synthesismentioning

confidence: 99%

Linear Block Copolymer Synthesis

et al. 2022

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“…Based on the RAFT versatility, recent years have seen an expansion of using various RAFT agents beyond traditional thermally initiated radical polymerizations . One emerging direction is the use of RAFT agents that facilitate other classes of polymerization such as anionic ring‐opening polymerization (AROP) and cationic RAFT polymerization, in synergy with radical mediated RAFT polymerization, to enable dual copolymerization strategies and access unique copolymer compositions . Another emerging research area is the exploitation of the versatile photochromic behavior of RAFT agents for photo‐controlled polymerization upon direct photo‐fragmentation of the R‐group of the RAFT agent by UV/Vis irradiation (following the iniferter mechanism) or through a photocatalyst (photoinduced‐electron/energy transfer) .…”

Section: Figurementioning

confidence: 99%

Orthogonal Cationic and Radical RAFT Polymerizations to Prepare Bottlebrush Polymers

et al. 2020

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An orthogonal combination of cationic and radical RAFT polymerizations is used to synthesize bottlebrush polymers using two distinct RAFT agents. Selective consumption of the first RAFT agent is used to control the cationic RAFT polymerization of a vinyl ether monomer bearing a secondary dormant RAFT agent, which subsequently allows side-chain polymers to be grafted from the pendant RAFT agent by a radical-mediated RAFT polymerization of a different monomer, thus completing the synthesis of bottlebrush polymers. The high efficiency and selectivity of the cationic and radical RAFT polymerizations allow both polymerizations to be conducted in one-pot tandem without intermediate purification. Reversible addition-fragmentation chain-transfer (RAFT)has grown in the last 20 years as one of the most versatile polymerization techniques, enabling the control of molecular weight distribution, branched architecture, and chemical functionality for a wide range of polymeric systems. [1] Based on the RAFT versatility, recent years have seen an expansion of using various RAFT agents beyond traditional thermally initiated radical polymerizations. [2] One emerging direction is the use of RAFT agents that facilitate other classes of polymerization such as anionic ring-opening polymerization (AROP) [3] and cationic RAFT polymerization, [4] in synergy with radical mediated RAFT polymerization, to enable dual copolymerization strategies [4b,d, 5] and access unique copolymer compositions. [3c, 4b] Another emerging research area is the exploitation of the versatile photochromic behavior of RAFT agents for photo-controlled polymerization upon direct photo-fragmentation of the R-group of the RAFT agent by UV/Vis irradiation (following the iniferter mechanism) [6] or through a photocatalyst (photoinduced-electron/energy transfer). [7] In particular, Xu and Boyer demonstrated the wavelength dependency of selectively photo-activated RAFT agents [6b, 8] to allow selective RAFT control for orthogonal polymerizations, where an unselected yet activatable RAFT agent remains dormant during photo-controlled radical polymerization with another RAFT agent. [9] Such selective RAFT processes had been previously untapped owing to inherent difficulties in suppressing chain transfer activity of reactive RAFT agents. [10] Through selective photo-fragmentation, Matyjaszewski, Boyer, and co-workers elegantly demonstrated an orthogonal iniferter-RAFT polymerization. [9b] In their case (Figure 1 a), a RAFT-agent-bearing methacrylate monomer was first polymerized orthogonally to produce a linear polymeric chain with pendant RAFT agents remaining intact during the polymerization of the methacrylate unit. The pendant RAFT Figure 1. Generalized structure of a RAFT agent and comparison of two-step syntheses of bottlebrush macromolecules via orthogonal RAFT in a) previous work [9b] and b) this work.

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“…Wang and co-workers employed a combined reversible addition-fragmentation with chain transfer (RAFT) and anionic ring opening polymerization (AROP) strategy to copolymerize PPS with N -isopropylmethacrylamide (NIPMAM). 18 However, this resulted in some incorporation of the NIPMAM into the PS block. Developing facile synthetic techniques that allow for synthesizing PS containing block copolymers, especially those with epoxides, through sequential addition of monomer would allow for finer control over copolymer physical properties and increase access to these materials.…”

Section: Introductionmentioning

confidence: 99%