Thermoresponsive Behavior of Mixtures of Epoxy Functionalized Oligo(ethylene glycol) Methacrylate Copolymers

Abstract

Thermoresponsive random copolymers based on 2‐(2‐methoxyethoxy)ethyl methacrylate (MEO2MA) and oligo(ethylene glycol) methyl ether methacrylate (OEG8‐9MA) are synthesized by atom transfer radical polymerization (ATRP). In a second step, they are used as macroinitiators for the ATRP of glycidyl methacrylate (GMA), introducing a short end‐block with epoxy functionalities that allows the connection of the thermoresponsive polymers to a variety of molecules, surfaces, or particles. The resulting epoxy functionalized terpolymers exhibit lower critical solution temperatures (LCST), which can be adjusted by changing the feed monomer ratio of MEO2MA and OEG8‐9MA. Binary blends show one or two cloud points depending on the blend composition. A model for the polymer collapse in one mixed particle or in two different particles as function of composition is proposed. magnified image

Post-polymerization modification reactions of poly(glycidyl methacrylate)s

“…[30][31][32][33][34] The synthesis of the backbone itself is not discussed and the reader is referred to a number of important publications in this regard. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Other polymer backbones that carry a side-chain epoxide functionality are important as is seen in the works of Harth, Dove, He, Siegwert, and Theato. [35][36][37][38][39][40] However, these backbones are outside the scope of the present review as we limit ourselves to PGMA polymers only.…”

“…In fact, PGMA can be easily synthesised from its commercially available and inexpensive monomer, glycidyl methacrylate, by free radical polymerization processes (Scheme 1). [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Stability-wise, the puried homopolymer can be stored at room temperature and under ambient conditions for years without compromising its structural integrity. In this way, it differs from other reactive scaffolds like alkene and alkynecarrying which can crosslink during polymerisation if the Ezzah M. Muzammil is a Master student from Nanyang Technological University (NTU) in the Division of Chemistry and Biological Chemistry.…”

“…Of course, co-polymerization is possible with any other acrylate or methacrylate monomer to further diversify the range of structures and applications of the nal materials. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] When required, the epoxy side chains of PGMA can be subjected to a nucleophilic ring-opening reaction under a variety of conditions to afford functionalised polymers (Scheme 2). The wide range of chemistry available allows one to freely choose the nature of the functional group and the manner of the ring-opening reaction.…”

Dual Responsiveness of a Tunable Thermosensitive Polypeptide

“…Strategies have focused on introducing small fractions of comonomers with reactive side chains that can be grafted postpolymerization, including alkynes 9,10 and allyl pendant functionalities. 11 Hydroxyl terminated oligo(ethylene glycol) methacrylate monomers have been incorporated, with 2-hydroxyethyl methacrylate, both as a functional handle and as a modifier to tune the copolymer's lower critical solution temperature (LCST) properties. 12 Short ester oligo(ethylene glycol) side chains have also been used to confer thermoresponsiveness to polypeptides with defined α-helical secondary structure.…”

Thermoresponsive Nanodevices in Biomedical Applications

“…LCST molecular weight non‐dependent thermoresponsive polymers like PNIPAm are usually synthesized with FRP since the weight distribution is not affecting the T CP , but this presents a huge drawback to achieve a sharp and controlled transition temperature in molecular weight dependent polymers like PVCL, POEGMA, etc. It is known that mixtures of polymers like POEGMA of different sizes or high weight distribution give broader transitions in comparison with the well defined ones …”