Copolymerization of Cyclic Phosphonate and Lactide: Synthetic Strategies toward Control of Amphiphilic Microstructure

James Beament, Thomas Wolf, Jens C. Markwart, Frederik R. Wurm, Matthew D. Jones, Antoine Buchard

Research output: Contribution to journalArticle

Abstract

Controlling the microstructure of polymers through chemical reactivity is key to control the material properties of synthetic polymers. Herein we investigate the ring-opening copolymerization of a mixture of lactide and 2ethyl-2-oxo-1,3,2-dioxaphospholane, promoted by an aluminum pyrrolidine monophenolate complex or 1,8diazabicyclo[5.4.0]undec-7-ene (DBU). This monomer mixture provides fast access to amphiphilic copolymers. The reaction conditions control the copolymer microstructure, which has been determined via a combination of 1H and 31P NMR spectroscopy. The choice of initiator has a profound impact: both initiators produce tapered block copolymers but with reverse monomer selectivity. While the aluminum initiator favors the cyclic phosphonate monomer, DBU favors lactide polymerization. Moreover, a sequential control of temperature facilitates the preparation of block copolymers in one pot. Thermal properties measured by TGA and DSC correlate to copolymer architectures. This methodology is the first report of copolymerization between cyclic phosphonates and lactide and opens the possibility to tune the thermal properties, solubility, and degradation rates of the resulting materials.
LanguageEnglish
Pages1220–1226
Number of pages7
JournalMacromolecules
Volume52
Issue number3
Early online date30 Jan 2019
DOIs
StatusPublished - 2019

Cite this

Copolymerization of Cyclic Phosphonate and Lactide: Synthetic Strategies toward Control of Amphiphilic Microstructure. / Beament, James; Wolf, Thomas; Markwart, Jens C.; Wurm, Frederik R.; Jones, Matthew D.; Buchard, Antoine.

In: Macromolecules, Vol. 52, No. 3, 2019, p. 1220–1226.

Research output: Contribution to journalArticle

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abstract = "Controlling the microstructure of polymers through chemical reactivity is key to control the material properties of synthetic polymers. Herein we investigate the ring-opening copolymerization of a mixture of lactide and 2ethyl-2-oxo-1,3,2-dioxaphospholane, promoted by an aluminum pyrrolidine monophenolate complex or 1,8diazabicyclo[5.4.0]undec-7-ene (DBU). This monomer mixture provides fast access to amphiphilic copolymers. The reaction conditions control the copolymer microstructure, which has been determined via a combination of 1H and 31P NMR spectroscopy. The choice of initiator has a profound impact: both initiators produce tapered block copolymers but with reverse monomer selectivity. While the aluminum initiator favors the cyclic phosphonate monomer, DBU favors lactide polymerization. Moreover, a sequential control of temperature facilitates the preparation of block copolymers in one pot. Thermal properties measured by TGA and DSC correlate to copolymer architectures. This methodology is the first report of copolymerization between cyclic phosphonates and lactide and opens the possibility to tune the thermal properties, solubility, and degradation rates of the resulting materials.",
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AB - Controlling the microstructure of polymers through chemical reactivity is key to control the material properties of synthetic polymers. Herein we investigate the ring-opening copolymerization of a mixture of lactide and 2ethyl-2-oxo-1,3,2-dioxaphospholane, promoted by an aluminum pyrrolidine monophenolate complex or 1,8diazabicyclo[5.4.0]undec-7-ene (DBU). This monomer mixture provides fast access to amphiphilic copolymers. The reaction conditions control the copolymer microstructure, which has been determined via a combination of 1H and 31P NMR spectroscopy. The choice of initiator has a profound impact: both initiators produce tapered block copolymers but with reverse monomer selectivity. While the aluminum initiator favors the cyclic phosphonate monomer, DBU favors lactide polymerization. Moreover, a sequential control of temperature facilitates the preparation of block copolymers in one pot. Thermal properties measured by TGA and DSC correlate to copolymer architectures. This methodology is the first report of copolymerization between cyclic phosphonates and lactide and opens the possibility to tune the thermal properties, solubility, and degradation rates of the resulting materials.

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