A novel borinate ester copolymer for Poly(Frustrated Lewis pair) gels

• Published in: Polymer (Guilford) Vol. 242; p. 124576
• Main Authors: Wang, Meng, Holland, Jordan, Horton, Thomas A.R., Yolsal, Utku, Shaver, Michael P.
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 01-03-2022; Elsevier BV
• Subjects: Boron; Chemical perception; Chemoreception; Copolymers; Crosslinking; Cyclic ethers; Drug delivery; Elasticity; Ethers; Fluorination; Frustrated Lewis pairs; Gelation; Gels; Mechanical properties; Network formation; Physical properties; Polymeric Lewis acids; Polymers; Polystyrene; Polystyrene resins; Rheological properties; Rheology; Steric hindrance; Stimuli responsive materials; Styrene; Styrenes; Cyclic ethers; Rheology; Stimuli responsive materials; Polymeric Lewis acids; Frustrated Lewis pairs
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2022.124576

The versatile chemistry of boronic acid and boronate ester containing polymers has led to key applications in drug delivery, chemical sensing, and dynamic materials. However, their use in polymeric Frustrated Lewis pairs (FLP) remains unreported. In this paper we report the synthesis of a novel fluorinated borinate ester copolymer which, when combined with a suitable Lewis basic copolymer, generates polymeric FLP networks capable of responsive gelation. The borinate ester moiety, bis(pentafluorophenyl)borinic acid tetrafluorophenyl ester, was affixed to a polystyrene copolymer by a two-step post-polymerisation modification, which can be easily upscaled and purified. The Gutmann-Beckett method suggests these fluorinated borinate ester moieties are amongst the most Lewis acidic boron-containing polymers reported to date. Upon mixing with a Lewis basic copolymer poly(styrene-co-p-diphenylphosphino styrene), gelation cannot be achieved due to steric hindrance around the Lewis centres. However, network formation can be triggered by addition of small molecules such as diethylazodicarboxylate (DEAD) and cyclic ethers. The physical parameters and nature of the crosslinks of the gels prepared from different crosslinkers were probed by rheology. All networks demonstrated strong elastic behaviour, corresponding to covalently crosslinked materials. DEAD crosslinked gels displayed different behaviour to those triggered by cyclic ethers, indicating that mechanism of small molecule activation also plays an important role in the mechanical properties of poly(FLP) gels.
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•Synthesis of novel borinate ester copolymer as a polymeric Lewis acid.•Polymeric Frustrated Lewis pairs of borinate esters and phosphines form responsive gels.•Tunable crosslinks with cyclic ethers and azos alter rheology and reactivity.