Clean synthesis of linear and star amphiphilic poly(?-caprolactone)-: Block -poly(ethyl ethylene phosphonate) block copolymers: Assessing self-assembly and surface activity

Article abstract of DOI:10.1039/d0gc00819b

Anionic ring-opening polymerization (AROP) of 2-ethyl-2-oxo-1,3,2-dioxaphospholane (EP) has been utilized to create alternative hydrophilic moieties for utilization in surfactants. The current "go-to" hydrophilic unit is poly(ethylene glycol) (PEG), but this is non-biodegradable and there is some evidence that its use can lead to accumulation of toxic by-products. We have created new approaches leading to water-dispersible, fully degradable amphiphilic block copolymers. Our approach utilized poly(?-caprolactone)-based macroinitiators in a solvent free process with organocatalyst DBU. We have prepared a comprehensive set of novel amphiphilic PCL-b-PEP block copolymers including linear diblock, triblock and star diblock copolymers characterized by SEC, ¹H and ³¹P NMR and MALDI-TOF analyses. Supercritical carbon dioxide (scCO₂) was exploited to efficiently extract the residual EP monomer leading to significantly increased gravimetric yields of purified product compared to conventional techniques such as dialysis. The self-assembly of the amphiphilic copolymers in water was investigated by DLS and cryo-TEM and their surface-activity as a function of concentration was investigated by tensiometry showing behavior that matches or exceeds commercially available surfactants.

Full text of DOI:10.1039/d0gc00819b

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2020, DOI: 10.1039/D0GC00819B.
Volume 20
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May 2018
Pages 1919-2160
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Paul T. Anastas et al.
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Green Chemistry
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