Spontaneous copolymerization of phthalic anhydride with aziridine or 2-methylaziridine

Pooley, S. Amalia; Canessa, Guido S.; Rivas, B. L.

doi:10.1016/0014-3057(94)00204-5

“…Poly(ester‐amide)s, the formal products of anhydride/aziridine ROCOP, combine the biodegradability of polyesters with the thermal and mechanical properties of polyamides—these desirable features have resulted in applications ranging from drug delivery systems to hydrogels, composite matrices, and tissue engineering scaffolds [236] . In some cases, anhydride/aziridine ROCOP was spontaneous, but was characterized by poor control over the molar mass and amine linkages [237, 238] . Quantitative monomer alternation was achieved with Lewis base/alcohol organocatalysts.…”

Section: Rocop Involving Aziridinesmentioning

confidence: 99%

“… [236] In some cases, anhydride/aziridine ROCOP was spontaneous, but was characterized by poor control over the molar mass and amine linkages. [ 237 , 238 ] Quantitative monomer alternation was achieved with Lewis base/alcohol organocatalysts. Cyclic polymers were isolated in some cases when mono‐/bicyclic anhydrides and N ‐benzyl‐substituted aziridines were applied (TOF 1–10 h −1 , 70 °C, 0.2‐1 mol %, M n =4.4–34.1 kg mol −1 , T g =41–126 °C, T d =258–311 °C).…”

Section: Rocop Involving Aziridinesmentioning

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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“…[174] Replacing aziridine with N-alkyl aziridine still could not control the copolymerization process, resulting in low-MW copolymers. [175][176][177] N-sulfonyl aziridines, compared to N-alkyl aziridine, were found more suitable for ROP because the strong electronwithdrawing sulfonyl group weakens the nucleophilicity of the nitrogen in aziridine. [178] The Hadjichristidis group recently utilized phosphazene organobase to mediate the alternating ROCOP of N-sulfonyl aziridines and cyclic anhydrides, affording copolymers with M n s over 35 kDa and Đs less than 1.1 (Scheme 11a).…”

Section: Aziridine/anhydride or Epoxidementioning

confidence: 99%

“…Early studies showed that aziridine copolymerized with anhydrides to form alternating insoluble poly(ester‐ alt ‐amides) with polyamine linkages [174] . Replacing aziridine with N ‐alkyl aziridine still could not control the copolymerization process, resulting in low‐MW copolymers [175–177] …”

Section: Copolymerization Of Binary Monomer Mixturesmentioning

confidence: 99%

Recent Advances in Sequence‐Controlled Ring‐Opening Copolymerizations of Monomer Mixtures

Wang

¹

,

Huo

²

,

Xie

³

et al. 2023

Chemistry An Asian Journal

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Transforming renewable resources into functional and degradable polymers is driven by the ever‐increasing demand to replace unsustainable polyolefins. However, the utility of many degradable homopolymers remains limited due to their inferior properties compared to commodity polyolefins. Therefore, the synthesis of sequence‐defined copolymers from one‐pot monomer mixtures is not only conceptually appealing in chemistry, but also economically attractive by maximizing materials usage and improving polymers’ performances. Among many polymerization strategies, ring‐opening (co)polymerization of cyclic monomers enables efficient access to degradable polymers with high control on molecular weights and molecular weight distributions. Herein, we highlight recent advances in achieving one‐pot, sequence‐controlled polymerizations of cyclic monomer mixtures using a single catalytic system that combines multiple catalytic cycles. The scopes of cyclic monomers, catalysts, and polymerization mechanisms are presented for this type of sequence‐controlled ring‐opening copolymerization.

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“…[236] In some cases,anhydride/ aziridine ROCOP was spontaneous,but was characterized by poor control over the molar mass and amine linkages. [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.

show abstract

Spontaneous copolymerization of phthalic anhydride with aziridine or 2-methylaziridine

Cited by 11 publications

References 16 publications

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

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

Recent Advances in Sequence‐Controlled Ring‐Opening Copolymerizations of Monomer Mixtures

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

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