The hydrolytic behavior of N,N’-(dimethylamino) ethyl acrylate-functionalized polymeric stars

Well-deﬁned N,N’-(dimethylamino)ethyl acrylate (DMAEA) functionalized polymeric stars have been synthesized via an arm-ﬁrst approach. Utilizing reversible addition–fragmentation chain transfer polymerization, linear homopolymers (PEGA, PHEA) were chain extended with DMAEA and a divinyl crosslinker to produce a series of crosslinked polymeric stars. These stars were characterized using a range of techniques including NMR, SEC, DLS and TEM analysis. The hydrolytic behavior of the DMAEA when tethered within a micellar core was investigated by1 H NMR spectroscopy and was found to be strongly dependent on temperature. At elevated temperatures either a higher crosslinking density or a longer arm length was found to oﬀer greater protection to the amine resulting in slower hydrolysis, with hydrolysis found to level oﬀ at a lower ﬁnal percentage hydrolysis. In contrast, the composition and nature of the arm was found to have little impact on the hydrolysis, with the same trends relating to the eﬀect of temperature and crosslinking density observed with a linear (HEA) and a brush (PEGA) arm. Additionally, the release of DMAE from the polymeric stars was successfully conﬁrmed through the use of an enzymatic assay, producing a concentration of DMAE in good agreement with the theoretical concentration based on the 1H NMR spectroscopic analysis.

URI

http://hdl.handle.net/10454/15422

Version

Published version

Citation

Rolph MS, Pitto-Barry A and O’Reilly RK (2017) The hydrolytic behaviour of N,N’- (dimethylamino)ethyl acrylate-functionalized polymeric stars. Polymer Chemistry. 8(34): 5060- 5070.

Link to Version of Record

https://doi.org/10.1039/c7py00219j

Type

Article