Graft copolymers of hydroxyethyl cellulose by a 'grafting to' method

15N labelling as a powerful characterisation tool in 'click' polymer chemistry

Fanny Joubert, Osama Musa, David R. W. Hodgson, Neil R. Cameron

Research output: Contribution to journalArticleResearchpeer-review

3 Citations (Scopus)

Abstract

We demonstrate how 15N labelling can be used to probe the success of 'grafting to' processes, through the preparation of well-defined graft copolymers of hydroxyethyl cellulose by combining RAFT polymerisation and copper-catalysed azide-alkyne cycloaddition (CuAAC). Using synthesised alkyne-functionalised chain transfer agents, short-chain (DP = 10) poly(N-vinylpyrrolidone) (PVP) and poly(N-isopropyl acrylamide) (PNIPAAM) were prepared in high conversion in a controlled manner (ÐM of ∼1.4 and 1.2 respectively). Separately, partially 15N-labelled N3-HEC was synthesised and characterised using solid state 13C, 15N CP-MAS NMR and FTIR spectroscopies. Alkyne-terminated PVP and PNIPAAM were grafted at different graft densities onto partially 15N-labelled N3-HEC using the click reaction. The hybrid HEC-g-polymer materials were fully characterised using solid state 13C and 15N CP-MAS NMR and FTIR spectroscopies. While 13C and FTIR spectroscopies gave indirect or weak evidence of CuAAC coupling, the cycloaddition of the alkyne-terminated polymers with N3-HEC was proven unambiguously by 15N solid state NMR spectroscopy. This indicates the utility of 15N labelling for probing the coupling efficiency of CuAAC reactions when employed in 'grafting to' processes with cellulosic substrates.
Original languageEnglish
Pages (from-to)1567-1575
Number of pages9
JournalPolymer Chemistry
Volume6
Issue number9
DOIs
Publication statusPublished - 7 Mar 2015
Externally publishedYes

Cite this

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title = "Graft copolymers of hydroxyethyl cellulose by a 'grafting to' method: 15N labelling as a powerful characterisation tool in 'click' polymer chemistry",
abstract = "We demonstrate how 15N labelling can be used to probe the success of 'grafting to' processes, through the preparation of well-defined graft copolymers of hydroxyethyl cellulose by combining RAFT polymerisation and copper-catalysed azide-alkyne cycloaddition (CuAAC). Using synthesised alkyne-functionalised chain transfer agents, short-chain (DP = 10) poly(N-vinylpyrrolidone) (PVP) and poly(N-isopropyl acrylamide) (PNIPAAM) were prepared in high conversion in a controlled manner ({\DH}M of ∼1.4 and 1.2 respectively). Separately, partially 15N-labelled N3-HEC was synthesised and characterised using solid state 13C, 15N CP-MAS NMR and FTIR spectroscopies. Alkyne-terminated PVP and PNIPAAM were grafted at different graft densities onto partially 15N-labelled N3-HEC using the click reaction. The hybrid HEC-g-polymer materials were fully characterised using solid state 13C and 15N CP-MAS NMR and FTIR spectroscopies. While 13C and FTIR spectroscopies gave indirect or weak evidence of CuAAC coupling, the cycloaddition of the alkyne-terminated polymers with N3-HEC was proven unambiguously by 15N solid state NMR spectroscopy. This indicates the utility of 15N labelling for probing the coupling efficiency of CuAAC reactions when employed in 'grafting to' processes with cellulosic substrates.",
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Graft copolymers of hydroxyethyl cellulose by a 'grafting to' method : 15N labelling as a powerful characterisation tool in 'click' polymer chemistry. / Joubert, Fanny; Musa, Osama; Hodgson, David R. W.; Cameron, Neil R.

In: Polymer Chemistry, Vol. 6, No. 9, 07.03.2015, p. 1567-1575.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Graft copolymers of hydroxyethyl cellulose by a 'grafting to' method

T2 - 15N labelling as a powerful characterisation tool in 'click' polymer chemistry

AU - Joubert, Fanny

AU - Musa, Osama

AU - Hodgson, David R. W.

AU - Cameron, Neil R.

PY - 2015/3/7

Y1 - 2015/3/7

N2 - We demonstrate how 15N labelling can be used to probe the success of 'grafting to' processes, through the preparation of well-defined graft copolymers of hydroxyethyl cellulose by combining RAFT polymerisation and copper-catalysed azide-alkyne cycloaddition (CuAAC). Using synthesised alkyne-functionalised chain transfer agents, short-chain (DP = 10) poly(N-vinylpyrrolidone) (PVP) and poly(N-isopropyl acrylamide) (PNIPAAM) were prepared in high conversion in a controlled manner (ÐM of ∼1.4 and 1.2 respectively). Separately, partially 15N-labelled N3-HEC was synthesised and characterised using solid state 13C, 15N CP-MAS NMR and FTIR spectroscopies. Alkyne-terminated PVP and PNIPAAM were grafted at different graft densities onto partially 15N-labelled N3-HEC using the click reaction. The hybrid HEC-g-polymer materials were fully characterised using solid state 13C and 15N CP-MAS NMR and FTIR spectroscopies. While 13C and FTIR spectroscopies gave indirect or weak evidence of CuAAC coupling, the cycloaddition of the alkyne-terminated polymers with N3-HEC was proven unambiguously by 15N solid state NMR spectroscopy. This indicates the utility of 15N labelling for probing the coupling efficiency of CuAAC reactions when employed in 'grafting to' processes with cellulosic substrates.

AB - We demonstrate how 15N labelling can be used to probe the success of 'grafting to' processes, through the preparation of well-defined graft copolymers of hydroxyethyl cellulose by combining RAFT polymerisation and copper-catalysed azide-alkyne cycloaddition (CuAAC). Using synthesised alkyne-functionalised chain transfer agents, short-chain (DP = 10) poly(N-vinylpyrrolidone) (PVP) and poly(N-isopropyl acrylamide) (PNIPAAM) were prepared in high conversion in a controlled manner (ÐM of ∼1.4 and 1.2 respectively). Separately, partially 15N-labelled N3-HEC was synthesised and characterised using solid state 13C, 15N CP-MAS NMR and FTIR spectroscopies. Alkyne-terminated PVP and PNIPAAM were grafted at different graft densities onto partially 15N-labelled N3-HEC using the click reaction. The hybrid HEC-g-polymer materials were fully characterised using solid state 13C and 15N CP-MAS NMR and FTIR spectroscopies. While 13C and FTIR spectroscopies gave indirect or weak evidence of CuAAC coupling, the cycloaddition of the alkyne-terminated polymers with N3-HEC was proven unambiguously by 15N solid state NMR spectroscopy. This indicates the utility of 15N labelling for probing the coupling efficiency of CuAAC reactions when employed in 'grafting to' processes with cellulosic substrates.

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M3 - Article

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SP - 1567

EP - 1575

JO - Polymer Chemistry

JF - Polymer Chemistry

SN - 1759-9954

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ER -