Polymers from sugars and CO₂: ring-opening polymerisation and copolymerisation of cyclic carbonates derived from 2-deoxy-d-ribose

Abstract

We report the preparation of two anomeric cyclic carbonate monomers from CO2 and natural sugar 2-deoxy-d-ribose, their ring-opening polymerisation and copolymerisation with trimethylene carbonate to produce aliphatic polycarbonates with tunable properties.

Polymers from sugars and unsaturated fatty acids: ADMET polymerisation of monomers derived from d-xylose, d-mannose and castor oil

“…[18][19][20][21] We also recently reported a series of studies on the ROP of cyclic carbonates synthesised from sugars and CO 2 . [22][23][24] Other significant examples of sugar-based monomers polymerised via ROP are phosphodiesters 25,26 and β-lactams. [27][28][29][30][31] Beyond ROP and transesterification techniques, acyclic diene metathesis (ADMET) polymerisation is also a method of choice for the polymerisation of renewable monomers, including those derived from plant oils.…”

“…Previously mentioned 10-undecenoic acid was employed as it is known to confer flexibility to polymer backbonesin contrast with previously reported purely sugar-based polymers, characterised by elevated glass transition temperatures (T g ) but brittle behaviour. [22][23][24] D-Xylose and D-mannose were selected as substrates as they are relatively underutilised and can be easily obtained from abundant hemicellulose, which could be in turn derived from waste sources. The structural and stereochemical complexity of the original sugars was preserved in the resulting polymers and its effects on properties studied.…”

Post‐polymerization modification of bio‐based polymers: maximizing the high functionality of polymers derived from biomass

“…A large proportion of the literature associated with bio‐based polymers tends to be focused on the synthesis of polyurethanes, polycarbonates and, in particular, polyesters . Aside from their extremely useful and diverse properties, one common aspect to all of these materials is that the chemical functionality required to synthesize them can be found in a wide range of bio‐based platform molecules (as an example, a particularly good overview on bio‐based platform molecules from a lignocellulosic feedstock is given by Isikgor and Becer) .…”

Advancements in six-membered cyclic carbonate (1,3-dioxan-2-one) synthesis utilizing carbon dioxide as a C1 source

“…29 Very recently, the same research team prepared a novel Dmannose-based cyclic carbonate 6 from natural sugar Dmannose 5 and CO 2 using their standard reaction conditions and successfully applied this monomer in the synthesis of polycarbonates 7 via a controlled organocatalytic ring-opening polymerization (Scheme 5). 30,31 In 2016, Bobbink and co-workers reported an innovative example of six-membered cyclic carbonate 9 preparation Scheme 4 Buchard's synthesis of six-membered cyclic carbonates 4. through a carbene-catalyzed xation of CO 2 onto corresponding 1,3-diol 8. The reaction was performed at the atmospheric pressure of CO 2 in the presence of over stoichiometric amounts of n BuBr and Cs 2 CO 3 to produce expected carbonate 2 in yield of 51% (Scheme 6).…”