Solvent and catalyst-free modification of hyperbranched polyethyleneimines by ring-opening-addition or ring-opening-polymerization of <i>N</i>-sulfonyl aziridines

Li, Zhunxuan; Chen, Rui; Wang, Ying; Zhu, Linlin; Luo, Wenyi; Zhang, Zhen; Hadjichristidis, Nikos

doi:10.1039/d1py00125f

Cited by 19 publications

(11 citation statements)

References 59 publications

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Section: Resultsmentioning

confidence: 99%

“…Herein, the formed tertiary amine moiety may serve as the organobase to catalyze the ring-opening polymerization of bis(N-sulfonyl aziridine) in toluene or tetrahydrofuran, as we previously reported. 32 The structure of polymer P1 was characterized by NMR analysis, and the results are present in Fig. 1.…”

Section: Synthesis Of Chiral Bis(2-substituted N-sulfonyl Aziridine) ...mentioning

confidence: 99%

“…The electron-withdrawing effect of the sulfonyl group further stabilizes the evolving aza-anion at the growing chain end by delocalization, and propagation continues via sulfonamide anions. Among these two kinds of aziridines, N-sulfonyl aziridines have received considerable attention in recent years, and significant progress has been made by Wurm, Taton, Rupar, et al [17][18][19][20][21][22][23][24][25][26][27][28] Our group employed 2-azaallyl anions, carboxylic acids, cellulose fibers, and hyperbranched polyethyleneimine as the (macro)initiators for the ring-opening polymerization of N-sulfonyl aziridines, respectively, achieving architectural and functionalized poly(N-sulfonyl aziridine) s. [29][30][31][32][33][34][35] However, the polymeric materials based on N-sulfonyl aziridines are still rare, and the chemical structure of the obtained polymers is restricted to polyethyleneimine-derived skeletons.…”

Section: Introductionmentioning

confidence: 99%

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Catalyst-free aziridine-based step-growth polymerization: a facile approach to optically active poly(sulfonamide amine)s and poly(sulfonamide dithiocarbamate)s

2022

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis Of Chiral Bis(2-substituted N-sulfonyl Aziridine) ...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Catalyst-free aziridine-based step-growth polymerization: a facile approach to optically active poly(sulfonamide amine)s and poly(sulfonamide dithiocarbamate)s

2022

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“…Organocatalytic systems, using an organic superbase, such as N -heterocyclic carbene and phosphazene, and an amine initiator ( N -benzyl sulfonamide, trimethylsilyl azide, or unprotected aminoalcohols), have been developed toward the metal-free synthesis of polysulfonamides. Our group recently employed carboxylic acids, cellulose fibers, and hyperbranched polyethyleneimine as the (macro)initiators for the organocatalytic ROP of N -sulfonyl aziridines, respectively, achieving architectural and functionalized poly( N -sulfonyl aziridine)s. − Despite the achievements for the ROP of N -sulfonyl aziridines, the chemical structure of the obtained polysulfonamides is restricted to polyethyleneimine-derived skeletons.…”

Section: Introductionmentioning

confidence: 99%

Organocatalytic Synthesis of Polysulfonamides with Well-Defined Linear and Brush Architectures from a Designed/Synthesized Bis(N-sulfonyl aziridine)

et al. 2021

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We report a new synthetic methodology for polysulfonamides with well-defined linear and brush architectures by organocatalytic polymerizations. A new monomer, bis(2,3-disubstituted N-sulfonyl aziridine), has been rationally designed/ synthesized and used in step-growth polymerization with various bisnucleophiles (dicarboxylic acids, diphenols, and dithiols). The branches or cross-linkages derived from the ring-opening polymerization of N-sulfonyl aziridines are suppressed using this specific bis(aziridine) monomer, resulting in a well-controlled linear polysulfonamide architecture. The synthesized polysulfonamides emit blue fluorescence in solution and exhibit excellent thermal properties with decomposition temperature at 5% weight loss (T d,5% ) up to 360.0 °C and glass-transition temperature (T g ) ranging from 62.5 to 199.2 °C. Furthermore, a fast one-pot cascade approach has been developed toward polysulfonamide brush copolymers with a well-controlled grafted chain length.

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“…We recently reported a solvent-and catalyst-free modification of hyperbranched polyethyleneimine (PEI) by ROP of N-sulfonyl aziridines. 54 The tertiary amino group of PEI was supposed to catalyze the melt polymerization of N-sulfonyl aziridines. Although this modification method is efficient and easy-handing, the polymerization is not well controlled, and the initiators are very limited.…”

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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Solvent and catalyst-free modification of hyperbranched polyethyleneimines by ring-opening-addition or ring-opening-polymerization of N-sulfonyl aziridines

Abstract: An easy, efficient, and solvent/catalyst-free synthetic methodology was developed for the modification of hyperbranched polyethyleneimines (PEI) by ring-opening-addition or ring-opening-polymerization of N-sulfonyl aziridines. Under melting and open-flask conditions, the nucleophilic...

Cited by 19 publications

References 59 publications

Catalyst-free aziridine-based step-growth polymerization: a facile approach to optically active poly(sulfonamide amine)s and poly(sulfonamide dithiocarbamate)s

Catalyst-free aziridine-based step-growth polymerization: a facile approach to optically active poly(sulfonamide amine)s and poly(sulfonamide dithiocarbamate)s

Organocatalytic Synthesis of Polysulfonamides with Well-Defined Linear and Brush Architectures from a Designed/Synthesized Bis(N-sulfonyl aziridine)

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

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