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Mr Oliver Patrick Hewitson

Postgraduate Research Student

Academic and research departments

Department of Chemistry.


ROHANI BINTI ABU BAKAR, YUMAN LI, OLIVER PATRICK HEWITSON, PETER J. ROTH, JOSEPH LOUIS KEDDIE (2022)Azide Photochemistry in Acrylic Copolymers for Ultraviolet Cross-Linkable Pressure-Sensitive Adhesives: Optimization, Debonding-on-Demand, and Chemical Modification, In: ACS applied materials & interfaces14(26)pp. 30216-30227 ACS

Pressure-sensitive adhesives (PSAs) are usually made from viscoelastic, high-molecular weight copolymers, which are fine-tuned by adjusting the comonomer ratios, molecular weights, and cross-link densities to optimize the adhesion properties for the desired end-use. To create a lightly cross-linked network, an ultraviolet (UV) photoinitiator can be incorporated. Here, we present the first use of perfluorophenylazide chemistry to control precisely a polyacrylate network for application as a PSA. Upon UV irradiation, the highly reactive nitrene from the azide moiety reacts with nearby molecules through a C–H insertion reaction, resulting in cross-linking via covalent bonding. This approach offers three benefits: (1) a means to optimize adhesive properties without the addition of an external photoinitiator; (2) the ability to switch off the tack adhesion on demand via a high cross-linking density; and (3) a platform for additional chemical modification. A series of poly(n-butyl acrylate-co-2,3,4,5,6-pentafluorobenzyl acrylate) or poly(PFBA-co-BA) copolymers was synthesized and modified post-polymerization into the photo-reactive poly(n-butyl acrylate-co-4-azido-2,3,5,6-tetrafluorobenzyl acrylate) (azide-modified poly(PFBA-co-BA)) with various molar contents. When cast into films, the azide-modified copolymers with a high azide content achieved a very high shear resistance after UV irradiation, whereas the tack and peel adhesion decreased strongly with increasing azide content, indicating that excessive cross-linking occurred. These materials are thus photo-switchable. However, in the low range of azide content, an optimum probe tack adhesion energy was obtained in films with a 0.3 mol% azide content, where a long stress plateau (indicating good fibrillation) with a high plateau stress was observed. An optimum peel adhesion strength was achieved with 0.5 mol% azide. Thus, the adhesion was finely controlled by the degree of cross-linking of the PSA, as determined by the azide content of the copolymer chain. Finally, as a demonstration of the versatility and advantages of the materials platform, we show an azide–aldehyde–amine multicomponent modification of the azide copolymer to make a dye-functionalized film that retains its adhesive properties. This first demonstration of using azide functionality has enormous potential for functional PSA design.