Post-polymerisation modification of bio-derived unsaturated polyester resins via Michael additions of 1,3-dicarbonyls

TY - JOUR

T1 - Post-polymerisation modification of bio-derived unsaturated polyester resins via Michael additions of 1,3-dicarbonyls

AU - Farmer, T. J.

AU - Clark, J. H.

AU - Macquarrie, D. J.

AU - Ogunjobi, J. K.

AU - Castle, R. L.

N1 - This is an author produced version of a paper published in Polymer Chemistry. Uploaded in accordance with the publisher's self-archiving policy.

PY - 2016/2/28

Y1 - 2016/2/28

N2 - Post-polymerisation modification of α,β-unsaturated polyesters (UPEs) is useful to deliver polymers with tuneable properties and applications different from their parent backbone. Bio-derivable itaconate unsaturated polyesters, with a range of co-monomers, were modified via a heterogeneously catalysed microwave-assisted Michael addition of pendants, acetylacetone (Hacac) and dimethyl malonate (DMM), to the polymer backbones with very short reaction times. Differential scanning calorimetry analysis showed an increase in the glass-transition temperatures of most of the saturated polyesters considered. Solubility and complexation studies demonstrated metal chelating abilities of the acetylacetone pendant can be retained, even following tethering to a polyester backbone. Additionally, it is demonstrated for the first time that Michael addition with Hacac and DMM can be used to reverse Ordelt saturation, an unwanted side-reaction in the synthesis of UPEs.

AB - Post-polymerisation modification of α,β-unsaturated polyesters (UPEs) is useful to deliver polymers with tuneable properties and applications different from their parent backbone. Bio-derivable itaconate unsaturated polyesters, with a range of co-monomers, were modified via a heterogeneously catalysed microwave-assisted Michael addition of pendants, acetylacetone (Hacac) and dimethyl malonate (DMM), to the polymer backbones with very short reaction times. Differential scanning calorimetry analysis showed an increase in the glass-transition temperatures of most of the saturated polyesters considered. Solubility and complexation studies demonstrated metal chelating abilities of the acetylacetone pendant can be retained, even following tethering to a polyester backbone. Additionally, it is demonstrated for the first time that Michael addition with Hacac and DMM can be used to reverse Ordelt saturation, an unwanted side-reaction in the synthesis of UPEs.

KW - bio-based polymer

KW - unsaturated polyester

KW - itaconate polyester

KW - Michael addition

KW - Ordelt saturation

UR - http://www.scopus.com/inward/record.url?scp=84958952919&partnerID=8YFLogxK

U2 - 10.1039/c5py01729g

DO - 10.1039/c5py01729g

M3 - Article

AN - SCOPUS:84958952919

SN - 1759-9954

VL - 7

SP - 1650

EP - 1658

JO - Polymer Chemistry

JF - Polymer Chemistry

IS - 8

ER -