The last challenge for living anionic polymerization of 1,3-cyclohexadiene with the s-butyllithium/cyclopentyl methyl ether system

Natori, Itaru; Natori, Shizue; Jang, Taehee; Ogino, Kenji

doi:10.1016/j.polymer.2022.124821

Cited by 4 publications

(2 citation statements)

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“…Recently, new initiators for the anionic polymerization of vinyl monomers, , and isocyanates, − were investigated, and some “forgotten” monomers were revisited and studied through modern anionic polymerization techniques. , Lee and co-workers reported a novel dimeric self-associated sodium diphenylamide (NaDPA) as a robust chain-end-protective initiator for the initiator-transfer anionic polymerization (ITAP) of n -hexyl isocyanate (HIC) in the absence or presence of sodium additives. The ITAP offers precise control over a wide range of molecular weights due to the improved livingness caused by the chain-end protection of NaDPA.…”

Section: Current Status Of Living Carbanionic Polymerizationmentioning

confidence: 99%

Quo Vadis Carbanionic Polymerization?

et al. 2022

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Living anionic polymerization will soon celebrate 70 years of existence. This living polymerization is considered the mother of all living and controlled/living polymerizations since it paved the way for their discovery. It provides methodologies for synthesizing polymers with absolute control of the essential parameters that affect polymer properties, including molecular weight, molecular weight distribution, composition and microstructure, chain-end/in-chain functionality, and architecture. This precise control of living anionic polymerization generated tremendous fundamental and industrial research activities, developing numerous important commodity and specialty polymers. In this Perspective, we present the high importance of living anionic polymerization of vinyl monomers by providing some examples of its significant achievements, presenting its current status, giving several insights into where it is going (Quo Vadis) and what the future holds for this powerful synthetic method. Furthermore, we attempt to explore its advantages and disadvantages compared to controlled/living radical polymerizations, the main competitors of living carbanionic polymerization.

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Section: Current Status Of Living Carbanionic Polymerizationmentioning

confidence: 99%

Quo Vadis Carbanionic Polymerization?

et al. 2022

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“…In general, it fully meets the requirements of its use as anionic polymerization solvent and in post-treatment separation technologies. For example, Natori et al 16 recently reported that the controlled anionic polymerization of 1,3-cyclohexadiene with alkyl lithium/ether was achieved for the first time. The type of ether is the main factor affecting the polymerization result.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, kinetic study and characterization of C5‐dienes/styrene copolymers via living anionic polymerization in cyclopentyl methyl ether solvent

Fu,

Yang,

Xiong

et al. 2023

Polymer International

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Abstract1,3‐Dienes/styrene sequence‐controlled copolymers are widely used as thermoplastic elastomers, transparent impact resin and synthetic rubber and other materials. In this work, the binary anionic copolymerization of styrene (S) and C5‐dienes including 1,3‐pentadiene (P, E/Z = 65/35) and isoprene (I) were studied in cyclopentyl methyl ether (CPME) ‘green’ solvent using n‐BuLi as initiator, and the effects of copolymerization monomer ratio and polar additive (PA) on the copolymerization kinetics and monomer sequence distributions were investigated. The kinetic analysis results showed that all copolymerization systems were the first‐order reaction and the C5‐dienes/S could be quantitatively consumed. The addition of S or I was conducive to the efficient conversion of P. Although the addition of PAs had little effect on the polymerization rate, it had a great influence on the microstructure and sequence distribution of the copolymer. 1H NMR tracking analysis showed that, for S/P copolymerization with different feeding ratios 1/3 < fP < 2/3, the instant composition FP in the copolymer remained relatively constant at 15% < FP < 35% when the monomer conversion rate was below 60%, and thus the inevitable formation of P microblocks in subsequent polymerization sequences was observed. Additionally, similar sequence distributions were obtained in the case of I/P copolymerization systems. By contrast, S/I copolymerization conformed to the typical random copolymerization pattern, and the copolymerization activity of S was slightly higher than that of the I in CPME. The use of strong PAs such as 2,2‐di(2‐tetrahydrofuran)propane directly resulted in a change of monomer sequence from a random pattern to a gradual block pattern. Moreover, the 3,4‐isoprene branch units were much more sensitive to solvent and PA than 1,2‐pentadiene units for C5‐dienes; also Fourier transform infrared and DSC analysis verified the microstructure and sequence analysis results mentioned above. In addition, the results of gel permeation chromatography showed that the copolymerization process in CPME had excellent controllable characteristics. © 2023 Society of Industrial Chemistry.

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Design strategies, surface functionalization, and environmental remediation potentialities of polymer-functionalized nanocomposites

Betrehem

Ali

et al. 2022

Chemosphere

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The last challenge for living anionic polymerization of 1,3-cyclohexadiene with the s-butyllithium/cyclopentyl methyl ether system

Cited by 4 publications

References 84 publications

Quo Vadis Carbanionic Polymerization?

Quo Vadis Carbanionic Polymerization?

Synthesis, kinetic study and characterization of C5‐dienes/styrene copolymers via living anionic polymerization in cyclopentyl methyl ether solvent

Design strategies, surface functionalization, and environmental remediation potentialities of polymer-functionalized nanocomposites

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