Polymers from sugars and CO2

Ring-opening polymerisation and copolymerisation of cyclic carbonates derived from 2-deoxy-d-ribose

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Abstract

Bio-based aliphatic polycarbonates (APCs) are attractive synthetic materials for biomedical applications because of their biodegradabilty and biocompatability properties. A high yielding 3-step process that utilises CO2 as a C1 synthon is presented for converting raw sugar, 2-deoxy-D-ribose into a novel 6-membered cyclic carbonate for ring-opening polymerisation (ROP) into carbohydrate-based APCs. The α- and β-anomers of the monomer could be isolated and revealed very different polymerisability, as rationalised by DFT calculations. Whereas the β-anomer could not be polymerised under the conditions tested, organocatalytic homopolymerisation of the α-anomer, in solution at room temperature (rt) or under melt conditions, yielded highly insoluble polycarbonates, composed of both cyclic and linear topologies, and exhibiting a glass transition temperature (Tg) of ∼58 °C. Random copolymers with controllable incorporation of this new sugar monomer were prepared with trimethylene carbonate (TMC) at rt in the bulk or in solution with Mn up to 64 000 g mol−1. With increasing sugar content, the Tg values of the copolymers increased and their thermal degradability was enhanced, giving access to a new class of APCs with tailored properties.
Original languageEnglish
Pages (from-to)2093-2104
JournalPolymer Chemistry
Volume8
Issue number13
DOIs
Publication statusPublished - 15 Mar 2017

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polycarbonate
Ribose
Carbonates
Ring opening polymerization
Polycarbonates
Sugars
Polymerization
Copolymerization
Polymers
Deoxy Sugars
Copolymers
Monomers
Temperature
Transition Temperature
Carbohydrates
Homopolymerization
Discrete Fourier transforms
Glass
Hot Temperature
Topology

Cite this

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title = "Polymers from sugars and CO2: Ring-opening polymerisation and copolymerisation of cyclic carbonates derived from 2-deoxy-d-ribose",
abstract = "Bio-based aliphatic polycarbonates (APCs) are attractive synthetic materials for biomedical applications because of their biodegradabilty and biocompatability properties. A high yielding 3-step process that utilises CO2 as a C1 synthon is presented for converting raw sugar, 2-deoxy-D-ribose into a novel 6-membered cyclic carbonate for ring-opening polymerisation (ROP) into carbohydrate-based APCs. The α- and β-anomers of the monomer could be isolated and revealed very different polymerisability, as rationalised by DFT calculations. Whereas the β-anomer could not be polymerised under the conditions tested, organocatalytic homopolymerisation of the α-anomer, in solution at room temperature (rt) or under melt conditions, yielded highly insoluble polycarbonates, composed of both cyclic and linear topologies, and exhibiting a glass transition temperature (Tg) of ∼58 °C. Random copolymers with controllable incorporation of this new sugar monomer were prepared with trimethylene carbonate (TMC) at rt in the bulk or in solution with Mn up to 64 000 g mol−1. With increasing sugar content, the Tg values of the copolymers increased and their thermal degradability was enhanced, giving access to a new class of APCs with tailored properties.",
author = "Gregory, {Georgina L.} and Gabriele Kociok-Kohn and Antoine Buchard",
year = "2017",
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publisher = "Royal Society of Chemistry",
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T2 - Ring-opening polymerisation and copolymerisation of cyclic carbonates derived from 2-deoxy-d-ribose

AU - Gregory, Georgina L.

AU - Kociok-Kohn, Gabriele

AU - Buchard, Antoine

PY - 2017/3/15

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N2 - Bio-based aliphatic polycarbonates (APCs) are attractive synthetic materials for biomedical applications because of their biodegradabilty and biocompatability properties. A high yielding 3-step process that utilises CO2 as a C1 synthon is presented for converting raw sugar, 2-deoxy-D-ribose into a novel 6-membered cyclic carbonate for ring-opening polymerisation (ROP) into carbohydrate-based APCs. The α- and β-anomers of the monomer could be isolated and revealed very different polymerisability, as rationalised by DFT calculations. Whereas the β-anomer could not be polymerised under the conditions tested, organocatalytic homopolymerisation of the α-anomer, in solution at room temperature (rt) or under melt conditions, yielded highly insoluble polycarbonates, composed of both cyclic and linear topologies, and exhibiting a glass transition temperature (Tg) of ∼58 °C. Random copolymers with controllable incorporation of this new sugar monomer were prepared with trimethylene carbonate (TMC) at rt in the bulk or in solution with Mn up to 64 000 g mol−1. With increasing sugar content, the Tg values of the copolymers increased and their thermal degradability was enhanced, giving access to a new class of APCs with tailored properties.

AB - Bio-based aliphatic polycarbonates (APCs) are attractive synthetic materials for biomedical applications because of their biodegradabilty and biocompatability properties. A high yielding 3-step process that utilises CO2 as a C1 synthon is presented for converting raw sugar, 2-deoxy-D-ribose into a novel 6-membered cyclic carbonate for ring-opening polymerisation (ROP) into carbohydrate-based APCs. The α- and β-anomers of the monomer could be isolated and revealed very different polymerisability, as rationalised by DFT calculations. Whereas the β-anomer could not be polymerised under the conditions tested, organocatalytic homopolymerisation of the α-anomer, in solution at room temperature (rt) or under melt conditions, yielded highly insoluble polycarbonates, composed of both cyclic and linear topologies, and exhibiting a glass transition temperature (Tg) of ∼58 °C. Random copolymers with controllable incorporation of this new sugar monomer were prepared with trimethylene carbonate (TMC) at rt in the bulk or in solution with Mn up to 64 000 g mol−1. With increasing sugar content, the Tg values of the copolymers increased and their thermal degradability was enhanced, giving access to a new class of APCs with tailored properties.

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