Mechanistic Insights on the Anionic Polymerization of Aliphatic Aldehydes

Martin, Barbara Y.; Schutz, Louis; Claverie, Jérôme P.

doi:10.1021/acs.macromol.1c01003

Cited by 3 publications

(4 citation statements)

References 45 publications

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“…In this contribution, under mild conditions (1% BF 3 •Et 2 O or InBr 3 , at 25 °C for 30 mins), the copolymerization of B to E with 1 manifested the high efficiency and afforded copolymers of P1B to P1E with M n of 2.5 ~18.3 kDa, Ð of 1.4 ~1.5 (Supplementary Table 2), and alternating sequences according to NMR spectra (Supplementary Figs. [58][59][60][61]. Generally, the synthesis of high-molecular-weight polymers through the cationic polymerization is a major challenge because of the high activity of the cationic propagating species that can cause various side reactions.…”

Section: Resultsmentioning

confidence: 99%

“…Plenty of aldehydes can be extracted directly from plants or synthesized by the dehydrogenation of renewable alcohols 56,57 . However, except formaldehyde, other aldehydes are quite difficult to carry out chain (co) polymerization due to their low enthalpy of polymerization according to previous studies 58,59 . In this study, we employed 56 commercially available aldehydes bearing multifarious substituents to deliver a family of polyesters incorporating the aldehyde-anhydride alternating sequence.…”

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confidence: 99%

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A recyclable polyester library from reversible alternating copolymerization of aldehyde and cyclic anhydride

Zhang,

Guo,

Zhang

et al. 2023

Nat Commun

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Our society is pursuing chemically recyclable polymers to accelerate the green revolution in plastics. Here, we develop a recyclable polyester library from the alternating copolymerization of aldehyde and cyclic anhydride. Although these two monomer sets have little or no thermodynamic driving force for homopolymerization, their copolymerization demonstrates the unexpected alternating characteristics. In addition to readily available monomers, the method is performed under mild conditions, uses common Lewis/Brønsted acids as catalysts, achieves the facile tuning of polyester structure using two distinct monomer sets, and yields 60 polyesters. Interestingly, the copolymerization exhibits the chemical reversibility attributed to its relatively low enthalpy, which makes the resulting polyesters perform closed-loop recycling to monomers at high temperatures. This study provides a modular, efficient, and facile synthesis of recyclable polyesters using sustainable monomers.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

A recyclable polyester library from reversible alternating copolymerization of aldehyde and cyclic anhydride

Zhang,

Guo,

Zhang

et al. 2023

Nat Commun

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“…We recently became interested in a family of self-immolative polymers based on aliphatic polyaldehydes that can cleanly evaporate under mild conditions. 24 However, the absence of living characteristics during the polymerization prevented us from preparing amphiphilic copolymers, which could later be used to stabilize a nanomaterial dispersion.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Thus, in this work, we explore the design of an ephemeral polymeric surfactant, which is an amphiphilic oligomer that cleanly depolymerizes into gaseous monomers. We recently became interested in a family of self-immolative polymers based on aliphatic polyaldehydes that can cleanly evaporate under mild conditions . However, the absence of living characteristics during the polymerization prevented us from preparing amphiphilic copolymers, which could later be used to stabilize a nanomaterial dispersion.…”

Section: Introductionmentioning

confidence: 99%

Ephemeral Amphiphilic Polyamines that Evaporate When Triggered─Implications for the Fabrication of Electronic Inks

Martin

Claverie

2022

ACS Appl. Polym. Mater.

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Without surfactants, nanomaterials tend to be aggregated in the liquid state. However, the presence of surfactants in the solid state can negatively impact the mechanical, electronic, and optical properties of the nanomaterial. Here, we have explored the design of an ephemeral surfactant, that is to say a surfactant, which is stable in solution but can be depolymerized in the solid phase and then be evaporated. The reaction of glyoxal with a 1,3diamine leads to an unprecedented ladder polyamine (LPA), which depolymerizes into evaporable monomers as soon as it is in contact with acid. These LPA oligomers were found to be amphiphilic and could be used to stabilize a dispersion of polymer nanoparticles (NPs) in water. Once dipped in a slightly acidic solution, the dried polymer film was found to be devoid of the LPA surfactant. This concept was used to fabricate an electronic ink based on multiwalled carbon nanotubes (MWCNTs) whereby the LPA depolymerization was triggered by a photoacid generator. After applying the ink on a glass substrate, the conductivity of the MWCNT films was low, due to the charge transfer resistance created by the interfacial surfactant. Once exposed to light, the surfactant depolymerized and evaporated, and the film recovered its native conductivity. We envision that these ephemeral surfactants could become useful assets in the fabrication of electronic inks.

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