Entropically-driven macrolide polymerizations for the synthesis of aliphatic polyester copolymers using titanium isopropoxide

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Entropically-driven macrolide polymerizations for the synthesis of aliphatic polyester copolymers using titanium isopropoxide

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2019-03-11

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Hillmyer, Marc A
hillmyer@umn.edu

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Abstract

Thermal and mechanical properties of sustainable aliphatic polyesters can be tuned through the synthesis of copolymers. The synthesis of two 14-membered macrolides are reported: a cyclic tetraester with alternating lactic acid (LA) and 3-hydroxypropionic acid (3HP) units and a cyclic diester with alternating glycolic acid (GA) and 2-methyl-1,3-propanediol (2MD) units. Ring-opening transesterification polymerization (ROTEP) of these macrolides to yield poly(LA-stat-3HP) and poly(GA-alt-2MD), respectively, were found to be modestly endothermic (ΔHp° = 2.0 kJ mol-1 and 0.5 kJ mol-1, respectively) and endoentropic (ΔSp° = 27 J mol-1 K-1 and 23 J mol-1 K-1, respectively). Inexpensive and non-toxic titanium isopropoxide Ti(Oi-Pr)4 functions as an active catalyst for these entropically-driven ROTEPs, achieving high conversions (> 90%) in under 1 h. The polymerizations exhibit control over molar mass with dispersity values < 1.7. P(GA-alt-2MD) is an amorphous polymer with a low glass transition temperature near −30 °C. P(LA-co-3HP) exhibits a glass transition temperature up to 13 °C and depending on the regioregularity, exhibits a melting temperature up to 96 °C.

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Macromolecules 2019, 52, 2371−2383. DOI: 10.1021/acs.macromol.9b00065
http://doi.org/10.1021/acs.macromol.9b00065

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National Science Foundation

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Amador, Adrian G; Watts, Annabelle; Neitzel, Angelika, E; Hillmyer, Marc A. (2019). Entropically-driven macrolide polymerizations for the synthesis of aliphatic polyester copolymers using titanium isopropoxide. Retrieved from the Data Repository for the University of Minnesota (DRUM), https://doi.org/10.13020/6qe9-kv23.
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File View/OpenDescriptionSize
Readme.txtReadme8.86 KB
Primary Data Files.zipAll Data Files (zip)30.99 MB
Crystallography data.zipCrystallography data: The crystal structures obtained for samples (.cif and reports)835.45 KB
DSC data.zipDifferential Scanning Calorimetry (DSC) data for each sample (.txt)2.6 MB
ESI data.zipElectrospray Ionisation (ESI) mass spectrometry data for monomers (.csv)36.1 KB
GCMS data.zipGas chromatography-mass spectrometry (GCMS) data (.xls)5.97 MB
HPLC data.zipHigh performance liquid chromatography (HPLC) data (.csv)160.34 KB
Kinetics and thermodynamics.zipKinetics and thermodynamics data of the polymerization (.csv)6.23 MB
MALDI data.zipMatrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) data (.csv)537.98 KB
NMR data.zipNuclear magnetic resonance (NMR) spectroscopy data for each sample (.fid)12.35 MB
Rheology data.zipRheology data: the time-temperature superposition (TTS) shifted data for the sample (.csv )5.89 KB
SEC data.zipSize exclusion chromatography (SEC) data (.csv)2.15 MB
TGA data.zipThermogravimetric analysis (TGA) (.csv)432.5 KB

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