Controlling the crystallinity and solubility of functional PCL with efficient post-polymerisation modification

Cinzia Clamor,Andrew P Dove,Peter M Wright,Beatrice N Cattoz,Rachel K O'Reilly

doi:10.1039/d0py01535k

Cinzia Clamor, Andrew P Dove + Show 3 more

Open Access

https://doi.org/10.1039/d0py01535k

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Abstract

Varying the size of an alkyl side-chain group, installed by thiol–ene addition of alkylthiols to poly(ε-allyl caprolactone), the semi-crystallinity and lipophilicity of functional PCLs could be modulated to achieve divergent physico-chemical properties.

Highlights

Post-polymerisation modifications represent an attractive strategy for the preparation of polymers bearing a diverse range of functionalities from a single monomer, enabling the introduction of functional moieties that are incompatible with ring-opening polymerisation conditions.[24,25,26]
The synthesis of the lipophilic polyesters was obtained via ring-opening polymerisation of an allyl-functional caprolactone monomer which was subsequently functionalised via thiol–ene addition using a range of commercially available alkyl thiols
DPP was chosen as a catalyst since it was found to efficiently catalyse the ring-opening polymerisation (ROP) of CL and afford polymers with high molecular weight and narrow dispersities.[12]

Summary

Introduction

Post-polymerisation modifications represent an attractive strategy for the preparation of polymers bearing a diverse range of functionalities from a single monomer, enabling the introduction of functional moieties that are incompatible with ring-opening polymerisation conditions.[24,25,26] In particular, the use of simple and robust thiol-based click chemistries has attracted considerable attention owing to their rapid reactivity, orthogonality and versatility of conjugation, allowing the incorporation of a wide range of substituents on the polymer backbone through reaction with terminal alkenes (thiol–ene)[27,28,29] and terminal alkynes (thiol–yne).[30,31] the thiol–ene addition has been explored in materials chemistry for the preparation of elastomers,[32] nanoparticles,[33] and tissue engineering scaffolds[34] exploiting the versatility of this chemistry to obtain different materials with tuneable properties. The effect of alkyl chain length on bulk polymer properties was investigated, and demonstrates the potential to tune solubility and crystallinity of poly(ε-caprolactone) in a simple and efficient fashion.

Results

Conclusion