Polymerization and Manufacture of Polyoxymethylene

Water‐Degradable Oxygen‐Rich Polymers with AB/ABB Units from Fast and Selective Copolymerization

“…We sought to use the depolymerization of trioxymethylene (TOM) for releasing formaldehyde copolymerized with cyclic anhydrides, based on the well-established reversible reaction "TOM* * formaldehyde". [38] We used commercially available glutaric anhydride (GA) as a representative cyclic anhydride, which can be produced from succinic acid, a DOE's top 12 biomass-derived compound, [39] through two intermediate chemicals of γ-butyrolactone and glutaric acid (Scheme S1). [40] Under the optimized reaction conditions (at 100 °C, with [TOM] 0 : [GA] 0 : [catalyst] = 100 : 450 : 1, for 5 min), the common inorganic strong acid of concentrated sulfuric acid (~98 % H 2 SO 4 ) achieved the alternating copolymerization of GA (A) and formaldehyde (B), affording the copolymer with exclusive AB type of repeating units, a molecular weight (M n ) of 10.1 kDa, and a dispersity (Ð = M w /M n ) of 1.5 (entry 1 in Table 1).…”

“…We sought to use the depolymerization of trioxymethylene (TOM) for releasing formaldehyde copolymerized with cyclic anhydrides, based on the well‐established reversible reaction “TOM⇌formaldehyde” [38] . We used commercially available glutaric anhydride (GA) as a representative cyclic anhydride, which can be produced from succinic acid, a DOE's top 12 biomass‐derived compound, [39] through two intermediate chemicals of γ‐butyrolactone and glutaric acid (Scheme S1) [40] .…”

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

“…Prominently, all of these aldehydes can be made from readily available feedstocks, and some of the aldehydes such as 2 to 7, 10 to 13, 19 to 21, and 55 can be extracted directly from plants. The promotion of novel strategies for converting aldehydes into sustainable polymers is eminently luscious but remains challenging 58,64 . In our strategy, the application of such sweeping substrates represents an exceptional polymer synthetic method for assembling aldehydes.…”

“…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.…”

“…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.…”