Copolymerization of aziridines and cyclic anhydrides by metal-free catalysis strategy

Xia, Tian; Yue, Tian‐Jun; Gu, Ge‐Ge; Wan, Zhao‐Qian; Li, Zong-Lin; Ren, Wei‐Min

doi:10.1016/j.eurpolymj.2020.109900

“…Cyclic polymers were isolated in some cases where mono/bicyclic anhydrides and N-benzyl substituted aziridines were applied (TOF 1 -10 h -1 , 70 °C, 0.2 -1 mol%, Mn = 4.4 -34.1 kg/mol, Tg = 41 -126 °C, Td = 258 -311 °C). [239] As cyclic polymers formed by macrocyclisation during termination, applying higher BnOH loadings resulted in more linear chains. of PA/N-Ts-EI ROCOP.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

Heterocycle/Heteroallene Ring‐Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

Williams

¹

,

Plajer

²

2021

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Heteroatom‐containing polymers have strong potential as sustainable replacements for petrochemicals, show controllable monomer–polymer equilibria and properties spanning plastics, elastomers, fibres, resins, foams, coatings, adhesives, and self‐assembled nanostructures. Their current and future applications span packaging, house‐hold goods, clothing, automotive components, electronics, optical materials, sensors, and medical products. An interesting route to these polymers is the catalysed ring‐opening copolymerisation (ROCOP) of heterocycles and heteroallenes. It is a living polymerization, occurs with high atom economy, and creates precise, new polymer structures inaccessible by traditional methods. In the last decade there has been a renaissance in research and increasing examples of commercial products made using ROCOP. It is better known in the production of polycarbonates and polyesters, but is also a powerful route to make N‐, S‐, and other heteroatom‐containing polymers, including polyamides, polycarbamates, and polythioesters. This Review presents an overview of the different catalysts, monomer combinations, and polymer classes that can be accessed by heterocycle/heteroallene ROCOP.

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“…[237,238] Quantitative monomer alternation was achieved with Lewis base/alcohol organocatalysts.C yclic polymers were isolated in some cases when mono-/bicyclic anhydrides and N-benzylsubstituted aziridines were applied (TOF 1-10 h À1 ,708 8C, 0.2-1mol %, M n = 4.4-34.1 kg mol À1 , T g = 41-126 8 8C, T d = 258-311 8 8C). [239] As with cyclic polymers formed by macrocyclisation during termination, applying higher BnOH loadings resulted in more linear chains.…”

Section: Rocop Involving Aziridinesmentioning

confidence: 99%

Heterocycle/Heteroallene Ring‐Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

Williams

¹

,

Plajer

²

2021

View full text Add to dashboard Cite

Heteroatom‐containing polymers have strong potential as sustainable replacements for petrochemicals, show controllable monomer–polymer equilibria and properties spanning plastics, elastomers, fibres, resins, foams, coatings, adhesives, and self‐assembled nanostructures. Their current and future applications span packaging, house‐hold goods, clothing, automotive components, electronics, optical materials, sensors, and medical products. An interesting route to these polymers is the catalysed ring‐opening copolymerisation (ROCOP) of heterocycles and heteroallenes. It is a living polymerization, occurs with high atom economy, and creates precise, new polymer structures inaccessible by traditional methods. In the last decade there has been a renaissance in research and increasing examples of commercial products made using ROCOP. It is better known in the production of polycarbonates and polyesters, but is also a powerful route to make N‐, S‐, and other heteroatom‐containing polymers, including polyamides, polycarbamates, and polythioesters. This Review presents an overview of the different catalysts, monomer combinations, and polymer classes that can be accessed by heterocycle/heteroallene ROCOP.

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“…The ROAP of the unsubstituted aziridine or the less nucleophilic N-alkyl aziridines with cyclic anhydrides generated uncontrolled products owing to the unavoidable zwitterionic side reactions. [24][25][26] Only the electrophilic N-sulfonyl aziridines were found to copolymerize with cyclic anhydrides in a controllable manner. 27 As far as we know, there is no report on the synthesis of semi-aromatic PEAs via the ROP of the corresponding cyclic (ester-amide)s. In this work, we intend to report a facile modular synthetic pathway for eight-membered cyclic (ester-amide)s starting from readily available phthalic anhydride (PA) and β-amino alcohols (M1-M5, Scheme 1B), investigate their organocatalytic ROP, and obtain a series of semi-aromatic PEAs with tunable and enhanced thermal stability while retaining their inherent degradability.…”

Section: Introductionmentioning

confidence: 99%

Facile synthesis of eight-membered cyclic(ester-amide)s and their organocatalytic ring-opening polymerizations

Guo

¹

,

Xiong

²

,

Shi

³

et al. 2022

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Copolymerization of aziridines and cyclic anhydrides by metal-free catalysis strategy

Cited by 14 publications

References 48 publications

Heterocycle/Heteroallene Ring‐Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

Heterocycle/Heteroallene Ring‐Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

Heterocycle/Heteroallene Ring‐Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

Facile synthesis of eight-membered cyclic(ester-amide)s and their organocatalytic ring-opening polymerizations

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