Atkinson, Rachel
(2021)
Terpene-derived, hard-soft block copolymers as sustainable thermoplastic elastomers.
PhD thesis, University of Nottingham.
Abstract
The work described in this thesis is focused on the development of sustainable, hardsoft, block copolymers, via reversible addition-fragmentation chain transfer (RAFT) polymerisation. A wide range of terpene (meth)acrylate monomers are investigated, some novel and some previously reported, and a number of block copolymer materials have been produced. The syntheses of these materials are described in detail and some further, application-focused, materials testing has been carried out.
Chapter 1 introduces the core concepts involved in this work, particularly: polymer theory, sustainability and sustainable polymer synthesis, block copolymer synthesis and block copolymer applications.
Chapter 2 exploresthe polymerisation of terpene (meth)acrylate monomers, derived from α-pinene, β-pinene and limonene. Free radical polymerisations have been carried out and discussed, followed by a more in-depth study of the polymerisation of these monomers via RAFT polymerisation. RAFT polymerisation has been used to synthesise both homopolymers and hard-soft diblock copolymers, and some initial material properties such as phase separation are investigated.
Chapter 3 focuses on the development of the diblock copolymers discussed in Chapter 2, to produce hard-soft-hard, ABA triblock copolymers; a particularly useful structure of hard-soft block copolymer, used in thermoplastic elastomers. The primary focus of this chapter is the combination of α-pinene methacrylate and butyl acrylate-based polymers and the investigation of their material properties, but alternative terpene-derived monomers are also considered.
Chapter 4 introduces several new (meth)acrylate monomers, derived from geraniol and β-pinene. The synthesis, polymerisation and subsequent block copolymerisation of these monomers is reported, and introductory investigation into the morphologies and material properties of these materials has been undertaken.
Chapter 5 focuses on acrylamide polymerisation, specifically the renewably sourced monomer, N-isobornyl acrylamide, which when polymerised exhibits a very high Tg. The benefits and limits of this new monomer are considered. Again, ABA triblock copolymers containing poly(butyl acrylate) as the soft, central block have been produced.
The tensile and adhesive testing of materials in this thesis was carried out by Matthew Elsmore, under the supervision of Dr Davide de Focatiis at the University of Nottingham. The industrial optimisation and scale up of α-pinene-OH and β-pineneOH was carried out by Dr Maria Pin-No at Cornelius Specialities Ltd. The nopinyl methacrylate and acrylate syntheses were carried out and optimised by Sean Smith, under the supervision of Prof. Robert Stockman at the University of Nottingham. The N-isobornyl acrylamide synthesis, optimisation, scale up, and free radical polymerisations discussed in this thesis were carried out by Rhona Savin, under the supervision of Prof. Robert Stockman and Prof. Steve Howdle at the University of Nottingham. Small angle X-ray scattering measurements were carried out at Diamond Light Source, in collaboration with Prof. Paul Topham and Dr Matthew Derry from the Aston University, and Dr Daniel Toolan from the University of Sheffield.
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