The effect of side chain spacer length on the thermoresponsive behaviour of poly(methylamide acrylate)s

Alexander Rajakanthan; Paul Wilson; Kristian Kempe

doi:10.1039/d3py00154g

The effect of side chain spacer length on the thermoresponsive behaviour of poly(methylamide acrylate)s

Alexander Rajakanthan, Paul Wilson, Kristian Kempe

Research output: Contribution to journal › Article › Research › peer-review

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Abstract

We report the synthesis of three methylamide acrylate monomers with varying spacer length between the polymerizable acrylate and pendant amide functionalities; methylamide ethyl acrylate (MAmEA), methylamide propyl acrylate (MAmPA) and methylamide butyl acrylate (MAmBA). Each monomer was subsequently polymerised via redox-initiated reversible addittion-fragmentation chain transfer (RRAFT) to yield well-defined homopolymers with differing physicochemical properties. All homopolymers were found to be amorphous, and thermally degrade via a two-step decomposition process. Whilst P(MAmEA) and P(MAmPA) were found to be soluble in aqueous solution between 30-80 °C, P(MAmBA) showed a lower critical solution temperature (LCST) behaviour. Detailed aqueous solubilty studies performed on P(MAmBA) revealed that the cloud point temperature (T_cp) could be tuned based on the degree of polymerisation (DP_n), concentration and nature of the aqueous media, highlighting its potential use as a water-soluble, thermoresponsive polymer in a range of applications.

Original language	English
Pages (from-to)	2054-2062
Number of pages	9
Journal	Polymer Chemistry
Volume	14
Issue number	17
DOIs	https://doi.org/10.1039/d3py00154g
Publication status	Published - 7 May 2023

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458119799-oaAccepted author manuscript, 1.11 MB

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title = "The effect of side chain spacer length on the thermoresponsive behaviour of poly(methylamide acrylate)s",

abstract = "We report the synthesis of three methylamide acrylate monomers with varying spacer length between the polymerizable acrylate and pendant amide functionalities; methylamide ethyl acrylate (MAmEA), methylamide propyl acrylate (MAmPA) and methylamide butyl acrylate (MAmBA). Each monomer was subsequently polymerised via redox-initiated reversible addittion-fragmentation chain transfer (RRAFT) to yield well-defined homopolymers with differing physicochemical properties. All homopolymers were found to be amorphous, and thermally degrade via a two-step decomposition process. Whilst P(MAmEA) and P(MAmPA) were found to be soluble in aqueous solution between 30-80 °C, P(MAmBA) showed a lower critical solution temperature (LCST) behaviour. Detailed aqueous solubilty studies performed on P(MAmBA) revealed that the cloud point temperature (Tcp) could be tuned based on the degree of polymerisation (DPn), concentration and nature of the aqueous media, highlighting its potential use as a water-soluble, thermoresponsive polymer in a range of applications.",

author = "Alexander Rajakanthan and Paul Wilson and Kristian Kempe",

note = "Funding Information: The authors acknowledge the technical assistance of the University of Warwick Polymer Characterisation RTP team. P.W. thanks the Royal Society and Tata companies for the award of a University Research Fellowship (URF\R1\180274). K.K. gratefully acknowledges the award of an ARC Future Fellowship (FT190100572) from the Australian Research Council (ARC). A.R. wishes to acknowledge the Monash Graduate Scholarship and Monash International Tuition Scholarship. Publisher Copyright: {\textcopyright} 2023 The Royal Society of Chemistry.",

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AU - Rajakanthan, Alexander

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N1 - Funding Information: The authors acknowledge the technical assistance of the University of Warwick Polymer Characterisation RTP team. P.W. thanks the Royal Society and Tata companies for the award of a University Research Fellowship (URF\R1\180274). K.K. gratefully acknowledges the award of an ARC Future Fellowship (FT190100572) from the Australian Research Council (ARC). A.R. wishes to acknowledge the Monash Graduate Scholarship and Monash International Tuition Scholarship. Publisher Copyright: © 2023 The Royal Society of Chemistry.

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N2 - We report the synthesis of three methylamide acrylate monomers with varying spacer length between the polymerizable acrylate and pendant amide functionalities; methylamide ethyl acrylate (MAmEA), methylamide propyl acrylate (MAmPA) and methylamide butyl acrylate (MAmBA). Each monomer was subsequently polymerised via redox-initiated reversible addittion-fragmentation chain transfer (RRAFT) to yield well-defined homopolymers with differing physicochemical properties. All homopolymers were found to be amorphous, and thermally degrade via a two-step decomposition process. Whilst P(MAmEA) and P(MAmPA) were found to be soluble in aqueous solution between 30-80 °C, P(MAmBA) showed a lower critical solution temperature (LCST) behaviour. Detailed aqueous solubilty studies performed on P(MAmBA) revealed that the cloud point temperature (Tcp) could be tuned based on the degree of polymerisation (DPn), concentration and nature of the aqueous media, highlighting its potential use as a water-soluble, thermoresponsive polymer in a range of applications.

AB - We report the synthesis of three methylamide acrylate monomers with varying spacer length between the polymerizable acrylate and pendant amide functionalities; methylamide ethyl acrylate (MAmEA), methylamide propyl acrylate (MAmPA) and methylamide butyl acrylate (MAmBA). Each monomer was subsequently polymerised via redox-initiated reversible addittion-fragmentation chain transfer (RRAFT) to yield well-defined homopolymers with differing physicochemical properties. All homopolymers were found to be amorphous, and thermally degrade via a two-step decomposition process. Whilst P(MAmEA) and P(MAmPA) were found to be soluble in aqueous solution between 30-80 °C, P(MAmBA) showed a lower critical solution temperature (LCST) behaviour. Detailed aqueous solubilty studies performed on P(MAmBA) revealed that the cloud point temperature (Tcp) could be tuned based on the degree of polymerisation (DPn), concentration and nature of the aqueous media, highlighting its potential use as a water-soluble, thermoresponsive polymer in a range of applications.

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The effect of side chain spacer length on the thermoresponsive behaviour of poly(methylamide acrylate)s

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The effect of side chain spacer length on the thermoresponsive behaviour of poly(methylamide acrylate)s

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Expanding the toolbox of synthetic stealth polymers

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