Azide Photochemistry in Acrylic Copolymers for Ultraviolet Cross-Linkable Pressure-Sensitive Adhesives: Optimization, Debonding-on-Demand, and Chemical Modification

作者：R. A. Bakar, Yuman Li, Oliver P. Hewitson, Peter J. Roth, Joseph L. Keddie · 发表于：ACS Applied Materials & Interfaces · 年份：2022 · DOI：10.1021/acsami.2c07385 · 被引用次数：23 · 研究领域：Photopolymerization techniques and applications、Photochromic and Fluorescence Chemistry、Luminescence and Fluorescent Materials

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 were 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 the increase in azide cont...