Nucleophilic "X"-Yne polymerisation for material synthesis

Giannantonio, Daniele ORCID: 0009-0008-5234-0337 (2025). Nucleophilic "X"-Yne polymerisation for material synthesis. University of Birmingham. Ph.D.

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Abstract

Polymeric materials shape the world we live in, and imagining our reality without them seems an impossible task. However, concerns about their sustainability are rapidly arising since most of them are synthesised from crude oil derivatives and accumulate in the environment with little known consequences.
The inclusion of bio-based renewable monomers into polymer structures represents a significant and valuable effort in building more sustainable materials. However, attention must be placed on the polymerisation method too, to adhere to green chemistry principles. Current step-growth polymerisation techniques succeed in including heteroatoms into polymer backbones aiming to introduce new reactivity handles, but they often require harsh reaction conditions such as high temperature. On the other hand, polymerisations proceeding via chain-growth mechanism occur at lower temperatures but produce mostly carbon-carbon based backbones.
The goal of this thesis was to leverage the nucleophilic addition of heteroatoms to activated alkynes, i.e.the thiol- and hydroxyl-yne click reactions, to synthesize a new range of polymers. In light of its simplicity and selectivity, this reaction has been successfully employed to yield designer polyesters, both linear and crosslinked, with tuneable thermomechanical properties and controlled degradability. Moreover, the same approach could be expanded into the production of polyester amides from bio-sourced monomers to access a novel class of amino acids-based polymers.

Type of Work:

Thesis (Doctorates > Ph.D.)

Award Type:

Doctorates > Ph.D.

Supervisor(s):