Stereospecific cationic RAFT polymerization of bulky vinyl ethers and stereoblock poly(vinyl alcohol) via mechanistic transformation to radical RAFT polymerization of vinyl acetate

Uchiyama, Mineto; Satoh, Kotaro; Kamigaito, Masami

doi:10.1016/j.giant.2021.100047

Cited by 31 publications

(28 citation statements)

References 69 publications

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“…The fast interconversion between the cationic and dormant species enables control of the molecular weight of the resulting polymer via the DT process, as in cationic reversible addition‐fragmentation chain transfer (RAFT) polymerizations with other systems. [ 38–45 ] In particular, when the amount of TfOH is very low in comparison to thioacetal, the molecular weight of the resulting polymer is practically defined by the feed ratio of the monomer and thioacetal and is close to the calculated value assuming that one polymer chain is generated from one molecule of thioacetal. Thus, a thioacetal unit can quantitatively afford a poly(vinyl ether) chain.…”

Section: Introductionmentioning

confidence: 57%

Hybridization of Step‐/Chain‐Growth and Radical/Cationic Polymerizations Using Thioacetals as Key Components for Triblock, Periodic and Random Multiblock Copolymers with Thermoresponsiveness

Uchiyama

Osumi

Satoh

et al. 2021

Macromol. Rapid Commun.

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A novel strategy for synthesizing a series of multiblock copolymers is developed by combining radical/cationic step‐growth polymerizations of dithiols and divinyl ethers and chain‐growth cationic degenerative chain‐transfer (DT) polymerizations of vinyl ethers using thioacetals as key components. The combination of radical step‐growth polymerization and a cationic thiol‐ene reaction or cationic step‐growth polymerization enables the synthesis of a series of macro chain‐transfer agents (CTAs) composed of poly(thioether) and thioacetal groups at different positions. The resulting products are 1) bifunctional macro CTAs with thioacetal groups at both chain ends, 2) periodic macro CTAs periodically having thioacetal groups in the main chain, and 3) random macro CTAs randomly having thioacetal groups in the main chain. Subsequently, the obtained macro CTAs are used for chain‐growth cationic DT polymerization of methoxyethyl vinyl ether (MOVE) to result in 1) triblock, 2) periodic, and 3) random multiblock copolymers consisting of poly(thioether) and poly(MOVE) segments. All these triblock and multiblock copolymers composed of hydrophobic poly(thioether) and hydrophilic poly(MOVE) segments show an amphiphilic tendency to form characteristic micelles in aqueous solutions. In addition, due to the thermoresponsive poly(MOVE) segments, the obtained copolymers exhibit lower critical solution temperatures that depend on the segment sequences and lengths.

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Section: Introductionmentioning

confidence: 57%

Hybridization of Step‐/Chain‐Growth and Radical/Cationic Polymerizations Using Thioacetals as Key Components for Triblock, Periodic and Random Multiblock Copolymers with Thermoresponsiveness

Uchiyama

Osumi

Satoh

et al. 2021

Macromol. Rapid Commun.

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“…Simultaneous control of stereoregularity and molecular weight of polymers is beneficial in polymer synthesis but it is difficult to achieve [48]. The use of RAFT (reversible addition-fragmentation chain transfer) agents has made simultaneous control feasible and different dithiocarbamate compounds have been investigated as RAFT agent [49].…”

Section: Application Of Dithiocarbamate Compounds As Raft Agent In Po...mentioning

confidence: 99%

“…Nitrogen-containing dithiocarbamates are now being used as the most effective RAFT agent with reduced bulky attachment when compared to other RAFT agents [50]. The presence of nitrogen in the dithiocarbamate compound stabilizes the cationic intermediate due to the fact that nitrogen is an electron-donating atom [48,50]. Dithiocarbamate was also used as both emulsifier and RAFT agent in the polymerization of stable latex of vinyl acetate polymer [51].…”

Section: Application Of Dithiocarbamate Compounds As Raft Agent In Po...mentioning

confidence: 99%

The Versatility in the Applications of Dithiocarbamates

Ajiboye

Marzouki

Onwudiwe

2022

IJMS

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Dithiocarbamate ligands have the ability to form stable complexes with transition metals, and this chelating ability has been utilized in numerous applications. The complexes have also been used to synthesize other useful compounds. Here, the up-to-date applications of dithiocarbamate ligands and complexes are extensively discussed. Some of these are their use as enzyme inhibitor and treatment of HIV and other diseases. The application as anticancer, antimicrobial, medical imaging and anti-inflammatory agents is examined. Moreover, the application in the industry as vulcanization accelerator, froth flotation collector, antifouling, coatings, lubricant additives and sensors is discussed. The various ways in which they have been employed in synthesis of other compounds are highlighted. Finally, the agricultural uses and remediation of heavy metals via dithiocarbamate compounds are comprehensively discussed.

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“…In 2021, Kamigaito reported the employment of cationic RAFT polymerization to achieve stereospecific LCP of bulky vinyl ethers ( Figure ) with Lewis acid catalysts. [ 107 ] The tacticity control was realized by the stereospecific propagation based on the steric hinderance of bulky substituents on VEs and counteranions generated from catalysts (e.g., BF 3 ·OEt 2 or EtAlCl 2 ) at −78 °C. affording isotactic‐rich PVEs of predetermined molecular weights.…”

Section: Emerging Initiation/controlling Systems For Lcpmentioning

confidence: 99%

Recent Advances in Living Cationic Polymerization with Emerging Initiation/Controlling Systems

Chen

Zhang

Jin

et al. 2021

Macromol. Rapid Commun.

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While the conventional living cationic polymerization (LCP) provided opportunities to synthesizing well‐defined polymers with predetermined molecular weights, desirable chemical structures and narrow dispersity, it is still important to continuously innovate new synthetic methods to meet the increasing requirements in advanced material engineering. Consequently, a variety of novel initiation/controlling systems have be demonstrated recently, which have enabled LCP with spatiotemporal control, broadened scopes of monomers and terminals, more user‐friendly operations and reaction conditions, as well as improved thermomechanical properties for obtained polymers. In this work, recent advances in LCP is summarized with emerging initiation/controlling systems, including chemical‐initiated/controlled cationic reversible addition‐fragmentation chain transfer (RAFT) polymerization, photoinitiated/controlled LCP, electrochemical‐controlled LCP, thionyl/selenium halide‐initiated LCP, organic acid‐assisted LCP, and stereoselective LCP. It is hoped that this summary will provide useful knowledge to people in related fields and stimulate new ideas to promote the development and application of LCP in both academia and industry.

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Stereospecific cationic RAFT polymerization of bulky vinyl ethers and stereoblock poly(vinyl alcohol) via mechanistic transformation to radical RAFT polymerization of vinyl acetate

Cited by 31 publications

References 69 publications

Hybridization of Step‐/Chain‐Growth and Radical/Cationic Polymerizations Using Thioacetals as Key Components for Triblock, Periodic and Random Multiblock Copolymers with Thermoresponsiveness

Hybridization of Step‐/Chain‐Growth and Radical/Cationic Polymerizations Using Thioacetals as Key Components for Triblock, Periodic and Random Multiblock Copolymers with Thermoresponsiveness

The Versatility in the Applications of Dithiocarbamates

Recent Advances in Living Cationic Polymerization with Emerging Initiation/Controlling Systems

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