Tetrabutylammonium fluoride initiated anionic ring-opening polymerizations of N–sulfonyl aziridines

Wang, Haixin; Li, Jie; Li, Zhenjiang; Liu, Bo; Chen, Kai; Zhang, Zhihao; Hu, Yongzhu; Zhou, Fangyuan; Li, Yongqiang; Guo, Kai

doi:10.1016/j.eurpolymj.2020.109999

Cited by 8 publications

(6 citation statements)

References 39 publications

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“…TsMAz was chosen as a representative sulfonylaziridine as it is the most studied sulfonylaziridine monomer. Recent work by Guo and co-workers showed that halides are capable of initiating sulfonylaziridine AROP, and therefore, we mostly focused on ILs with bistriflimide anions so as to avoid halide-containing ILs . Solutions of the initiators were prepared in DMF using KHMDS and BuN( H )Ts , respectively.…”

Section: Resultsmentioning

confidence: 99%

“…Recent work by Guo and co-workers showed that halides are capable of initiating sulfonylaziridine AROP, and therefore, we mostly focused on ILs with bistriflimide anions so as to avoid halidecontaining ILs. 24 Solutions of the initiators were prepared in DMF using KHMDS and BuN(H)Ts, respectively. The initiators were separately prepared in DMF to avoid reactions between KHMDS (which deprotonated the initiator) and the ILs before being added to the IL solutions of TsMAz.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Sulfonylaziridines are typically polymerized in polar, aprotic solvents such as DMSO and DMF. The related sulfonylazetidines have also been reported to polymerize in NMP. − Recently, the copolymerization of a sulfonylaziridine with phthalic anhydride to a poly(ester amide) was reported, and the grafting of polysulfonamides from cellulose, with applications in oil–water separations, was demonstrated …”

Section: Introductionmentioning

confidence: 99%

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Anionic Ring-Opening Polymerizations of N-Sulfonylaziridines in Ionic Liquids

et al. 2022

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The anionic ring-opening polymerization (AROP) of sulfonylaziridines in ionic liquids (ILs) is reported. In imidazolium ILs, the polymerization of 2-methyl-N-tosylaziridine (TsMAz) is not controlled due to poor solubility at higher degrees of polymerization and apparent solvent-transfer reactions. In the phosphonium IL [P6,6,6,14][Tf2N], the polymerization of TsMAz is controlled and living, and capable of sequential block copolymer synthesis. The polymerization of TsMAz is first-order with respect to monomer in ILs, with rates slower than observed in traditional aprotic polar solvents (e.g., DMF). Molecular dynamics simulations were used to compare DMF vs IL solutions consisting of BuN(K)Ts (as a model for the propagating chain end). The molecular dynamics simulations suggest better monomer/anion organization in DMF and poorer mobilities in the ILs; both are consistent with observed reduction in polymerization rates in the ILs compared to DMF.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Anionic Ring-Opening Polymerizations of N-Sulfonylaziridines in Ionic Liquids

et al. 2022

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“…[12][13][14] In contrast, aziridines activated with electron-withdrawing groups on the nitrogen (typically sulfonyl groups), polymerize anionically to form linear polymers, of which many have been reported. 9,10,[15][16][17][18][19][20][21][22][23][24] Recently, bissulfonyl aziridines are also nding application in step-growth polymerizations. For example, Yoon and Zhang independently reported a series of bis(N-sulfonyl aziridine) monomers, which can be polymerized with various dinucleophiles such as dicarboxylic acids, diphenols, dithiols and diamines.…”

Section: Introductionmentioning

confidence: 99%

Rapid synthesis of functional poly(ester amide)s through thiol–ene chemistry

West

Rupar

2023

RSC Adv.

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“…42 Well-defined polysulfonamides can be obtained in a short time (20 min) using phosphazene superbase. Other catalysts, such as N-heterocyclic olefins 43 and tetrabutylammonium fluoride, 44 have demonstrated catalytic efficiency in this anionic polymerization. However, the organocatalytic initiating systems are not well-developed, with initiators are limited to activated amines, 42 unprotected amino alcohols, 45 and tosyl azide.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast organocatalytic ring‐opening polymerization of N‐sulfonyl aziridine in the melt

Chen

Wang

Zhu

et al. 2021

Journal of Polymer Science

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An ultrafast approach for controlled synthesis of well-defined polysulfonamides is established through organocatalytic anionic ring-opening polymerization (ROP) of N-sulfonyl aziridine in the melt. Several different organobases are investigated, and it is found that N,N,N 0 ,N 00 ,N 00pentamethyldiethylenetriamine (PMDETA) catalyzed ROP of 2-methyl-Ntosylaziridine (TsMAz) gives the desired polymer, while 1,4-diazabicyclo[2.2.2] octane (DABCO) and 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) initiate the polymerization along with initiator to produce uncontrolled polymers. Using PMDETA as the catalyst, poly(2-methyl-N-tosylaziridine) with molecular weight over 100 kg/mol can be synthesized in less than 90 s. Various initiators, including carboxylic acid, N-sulfonyl amide, unactivated amine, phenol, and thiol, are applicable for this protocol to give the molecular weight and endgroup controlled polymers under the open-flask condition. Combining this ultrafast ROP with ring-opening metathesis polymerization (ROMP), a brush copolymer is facile synthesized. This approach allows the ultrafast metal-free synthesis of polysulfonamide and expands the scope of initiators for the ROP of N-sulfonyl aziridines.

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Tetrabutylammonium fluoride initiated anionic ring-opening polymerizations of N–sulfonyl aziridines

Cited by 8 publications

References 39 publications

Anionic Ring-Opening Polymerizations of N-Sulfonylaziridines in Ionic Liquids

Anionic Ring-Opening Polymerizations of N-Sulfonylaziridines in Ionic Liquids

Rapid synthesis of functional poly(ester amide)s through thiol–ene chemistry

Ultrafast organocatalytic ring‐opening polymerization of N‐sulfonyl aziridine in the melt

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