Issue 37, 2021

The influences of monomer structure and solvent on the radical copolymerization of tertiary amine and PEGylated methacrylates

Abstract

Tertiary Amine Methacrylates (TAMAs), such as 2-(N,N-diethylamino)ethyl methacrylate (DEAEMA) and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA), and PEGylated (macro)monomers, such as 2-ethoxyethyl methacrylate (EEMA1) and poly(ethylene glycol) methyl ether methacrylates with 9 and 23 units (PEGMA9 and PEGMA23, respectively), are two families of monomers frequently used in the synthesis of stimuli-responsive and biocompatible materials. They, along with methyl (MMA) and butyl (BMA) methacrylate, were used to synthesize a minilibrary of copolymers, namely poly(DEAEMA-co-EEMA1), poly(DEAEMA-co-PEGMA23), poly(DMAEMA-co-PEGMA9), poly(DMAEMA-co-PEGMA23), poly(DEAEMA-co-MMA), and poly(BMA-co-PEGMA9). The rate of copolymerization increased as the length of the PEG-side chain is decreased, and was higher for DEAEMA compared to DMAEMA systems. The estimated values of the reactivity ratios are: rDEAEMA = 0.61 ± 0.06 and rEEMA1 = 0.92 ± 0.09, rDEAEMA = 0.71 ± 0.15 and rPEGMA23 = 1.05 ± 0.21, rDMAEMA = 0.83 ± 0.01 and rPEGMA9 = 1.08 ± 0.02, rDMAEMA = 0.52 ± 0.09 and rPEGMA23 = 0.76 ± 0.14, and rBMA = 0.55 ± 0.13 and rPEGMA9 = 0.38 ± 0.09; p-dioxane at 70 °C: rDEAEMA = 0.91 ± 0.12 and rPEGMA9 = 0.75 ± 0.09; and tetrahydrofuran at 66 °C: rDEAEMA = 0.96 ± 0.13 and rPEGMA9 = 0.81 ± 0.11. While there was no difference in relative reactivity between the two amine-functional monomers when copolymerized with PEGylated methacrylates, the increased relative activity of the TAMAs compared to BMA is attributed to the formation of a cyclic intermediate. Additionally, as the PEG side-chain length is extended, the reactivity ratios for the amino monomers decreased. Finally, although a higher content of DEAEMA is incorporated in the copolymer for the poly(DEAEMA-co-MMA) when a more polar solvent is used, no differences were observed in the Mayo–Lewis plots for the poly(DEAEMA-co-PEGMA23) using p-dioxane, tetrahydrofuran and ethanol.

Graphical abstract: The influences of monomer structure and solvent on the radical copolymerization of tertiary amine and PEGylated methacrylates

Supplementary files

Article information

Article type
Paper
Submitted
04 Jun 2021
Accepted
24 Aug 2021
First published
24 Aug 2021

Polym. Chem., 2021,12, 5289-5302

The influences of monomer structure and solvent on the radical copolymerization of tertiary amine and PEGylated methacrylates

P. Quiñonez-Angulo, R. A. Hutchinson, Á. Licea-Claveríe, E. Saldívar-Guerra and I. Zapata-González, Polym. Chem., 2021, 12, 5289 DOI: 10.1039/D1PY00750E

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