Benzaldehyde‐functional cellulose paper sheets have been synthesized via tosylation of cellulose (Whatman No 5) followed by addition of p‐hydroxy benzaldehyde. Via UV‐induced Paterno–Büchi [2+2] cycloaddition reactions, these aldehyde functional surfaces are grafted with triallylcyanurate, trimethylolpropane allyl ether, and vinyl chloroacetate. In the following, allyl‐functional polymers (poly(butyl acrylate), pBA, Mn = 6990 g mol−1, Đ = 1.12 and poly(N‐isopropyl acrylamide), pNIPAAm, Mn = 9500 g mol−1, Đ = 1.16) synthesized via reversible addition fragmentation chain transfer polymerization are conjugated to the celloluse surface in a UV‐induced grafting‐to approach. With pBA, hydrophobic cellulose sheets are obtained (water contact angle 116°), while grafting of pNIPAAm allows for generation of “smart” surfaces, which are hydrophilic at room temperature, but that become hydrophobic when heated above the characteristic lower critical solution temperature (93° contact angle). The Paterno–Büchi reaction has been shown to be a versatile synthetic tool that also performs well in grafting‐to approaches whereby its overall performance seems to be close to that of radical thiol‐ene reactions.
