RAFT Polymerisation of Renewable Terpene (Meth)acrylates and the Convergent Synthesis of Methacrylate-Acrylate-Methacrylate Triblock Copolymers

Rachel Atkinson; Olivia Monaghan; Matthew Elsmore; Paul Topham; Daniel T.W. Toolan; Matthew Derry; Vincenzo Taresco; Robert Stockman; Davide De Focatiis; Derek J. Irvine; Steven Howdle

doi:10.1039/D1PY00326G

RAFT Polymerisation of Renewable Terpene (Meth)acrylates and the Convergent Synthesis of Methacrylate-Acrylate-Methacrylate Triblock Copolymers

Rachel Atkinson, Olivia Monaghan, Matthew Elsmore, Paul Topham, Daniel T.W. Toolan, Matthew Derry, Vincenzo Taresco, Robert Stockman, Davide De Focatiis, Derek J. Irvine, Steven Howdle^*

^*Corresponding author for this work

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Abstract

Terpenes are ideal candidates for sustainable polymer feedstocks because of their natural abundance and availability from existing waste streams. Previously, we have shown that a range of terpene(meth)acrylate monomers can be synthesised from the most commonly available terpenes (α-pinene, β-pinenene and limonene) and these readily undergo radical polymerisation. We now report the synthesis of well-defined polymers and precise di- and multiblock copolymer architectures by use of RAFT control. A very wide range of Tg values are observed for the terpene (meth)acrylate homopolymers, from -3 °C for poly(limonene acrylate), up to +168 °C for poly(α-pinene methacrylate), and we exploit these to create renewably-sourced hard-soft block copolymers. We also report the synthesis of difunctional poly(α- and β-pinene methacrylate) macro-RAFT agents and the preparation of ABA triblock copolymers. Promising adhesive properties are observed for a triblock copolymer comprised of poly(α-pinene methacrylate) and poly(butyl acrylate) blocks. A range of fully terpene-based triblock copolymers containing poly(limonene acrylate) soft blocks are also reported.

Original language	English
Pages (from-to)	3177-3189
Number of pages	13
Journal	Polymer Chemistry
Volume	12
Issue number	21
Early online date	5 May 2021
DOIs	https://doi.org/10.1039/D1PY00326G
Publication status	Published - 7 Jun 2021

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This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

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10.1039/D1PY00326GLicence: CC BY 3.0

RAFT Polymerisation of Renewable Terpene (Meth)acrylates
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
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Atkinson, R., Monaghan, O., Elsmore, M., Topham, P., Toolan, D. T. W., Derry, M., Taresco, V., Stockman, R., De Focatiis, D., Irvine, D. J., & Howdle, S. (2021). RAFT Polymerisation of Renewable Terpene (Meth)acrylates and the Convergent Synthesis of Methacrylate-Acrylate-Methacrylate Triblock Copolymers. Polymer Chemistry, 12(21), 3177-3189. https://doi.org/10.1039/D1PY00326G

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title = "RAFT Polymerisation of Renewable Terpene (Meth)acrylates and the Convergent Synthesis of Methacrylate-Acrylate-Methacrylate Triblock Copolymers",

abstract = "Terpenes are ideal candidates for sustainable polymer feedstocks because of their natural abundance and availability from existing waste streams. Previously, we have shown that a range of terpene(meth)acrylate monomers can be synthesised from the most commonly available terpenes (α-pinene, β-pinenene and limonene) and these readily undergo radical polymerisation. We now report the synthesis of well-defined polymers and precise di- and multiblock copolymer architectures by use of RAFT control. A very wide range of Tg values are observed for the terpene (meth)acrylate homopolymers, from -3 °C for poly(limonene acrylate), up to +168 °C for poly(α-pinene methacrylate), and we exploit these to create renewably-sourced hard-soft block copolymers. We also report the synthesis of difunctional poly(α- and β-pinene methacrylate) macro-RAFT agents and the preparation of ABA triblock copolymers. Promising adhesive properties are observed for a triblock copolymer comprised of poly(α-pinene methacrylate) and poly(butyl acrylate) blocks. A range of fully terpene-based triblock copolymers containing poly(limonene acrylate) soft blocks are also reported.",

author = "Rachel Atkinson and Olivia Monaghan and Matthew Elsmore and Paul Topham and Toolan, {Daniel T.W.} and Matthew Derry and Vincenzo Taresco and Robert Stockman and {De Focatiis}, Davide and Irvine, {Derek J.} and Steven Howdle",

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Atkinson, R, Monaghan, O, Elsmore, M, Topham, P, Toolan, DTW, Derry, M, Taresco, V, Stockman, R, De Focatiis, D, Irvine, DJ & Howdle, S 2021, 'RAFT Polymerisation of Renewable Terpene (Meth)acrylates and the Convergent Synthesis of Methacrylate-Acrylate-Methacrylate Triblock Copolymers', Polymer Chemistry, vol. 12, no. 21, pp. 3177-3189. https://doi.org/10.1039/D1PY00326G

TY - JOUR

T1 - RAFT Polymerisation of Renewable Terpene (Meth)acrylates and the Convergent Synthesis of Methacrylate-Acrylate-Methacrylate Triblock Copolymers

AU - Atkinson, Rachel

AU - Monaghan, Olivia

AU - Elsmore, Matthew

AU - Topham, Paul

AU - Toolan, Daniel T.W.

AU - Derry, Matthew

AU - Taresco, Vincenzo

AU - Stockman, Robert

AU - De Focatiis, Davide

AU - Irvine, Derek J.

AU - Howdle, Steven

N1 - This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

PY - 2021/6/7

Y1 - 2021/6/7

N2 - Terpenes are ideal candidates for sustainable polymer feedstocks because of their natural abundance and availability from existing waste streams. Previously, we have shown that a range of terpene(meth)acrylate monomers can be synthesised from the most commonly available terpenes (α-pinene, β-pinenene and limonene) and these readily undergo radical polymerisation. We now report the synthesis of well-defined polymers and precise di- and multiblock copolymer architectures by use of RAFT control. A very wide range of Tg values are observed for the terpene (meth)acrylate homopolymers, from -3 °C for poly(limonene acrylate), up to +168 °C for poly(α-pinene methacrylate), and we exploit these to create renewably-sourced hard-soft block copolymers. We also report the synthesis of difunctional poly(α- and β-pinene methacrylate) macro-RAFT agents and the preparation of ABA triblock copolymers. Promising adhesive properties are observed for a triblock copolymer comprised of poly(α-pinene methacrylate) and poly(butyl acrylate) blocks. A range of fully terpene-based triblock copolymers containing poly(limonene acrylate) soft blocks are also reported.

AB - Terpenes are ideal candidates for sustainable polymer feedstocks because of their natural abundance and availability from existing waste streams. Previously, we have shown that a range of terpene(meth)acrylate monomers can be synthesised from the most commonly available terpenes (α-pinene, β-pinenene and limonene) and these readily undergo radical polymerisation. We now report the synthesis of well-defined polymers and precise di- and multiblock copolymer architectures by use of RAFT control. A very wide range of Tg values are observed for the terpene (meth)acrylate homopolymers, from -3 °C for poly(limonene acrylate), up to +168 °C for poly(α-pinene methacrylate), and we exploit these to create renewably-sourced hard-soft block copolymers. We also report the synthesis of difunctional poly(α- and β-pinene methacrylate) macro-RAFT agents and the preparation of ABA triblock copolymers. Promising adhesive properties are observed for a triblock copolymer comprised of poly(α-pinene methacrylate) and poly(butyl acrylate) blocks. A range of fully terpene-based triblock copolymers containing poly(limonene acrylate) soft blocks are also reported.

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U2 - 10.1039/D1PY00326G

DO - 10.1039/D1PY00326G

M3 - Article

SN - 1759-9954

VL - 12

SP - 3177

EP - 3189

JO - Polymer Chemistry

JF - Polymer Chemistry

IS - 21

ER -

RAFT Polymerisation of Renewable Terpene (Meth)acrylates and the Convergent Synthesis of Methacrylate-Acrylate-Methacrylate Triblock Copolymers

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