Tapered copolymers of styrene and 4‐vinylbenzocyclobutene via carbanionic polymerization for crosslinkable polymer films

Well‐defined polystyrene homopolymers with surface‐adhesive triethoxysilyl end group were synthesized via living carbanionic polymerization, epoxide end‐functionalization and subsequent hydrosilylation with triethoxysilane. Grafting‐to performance of polymers with various molecular weight ( M n = 3000–14,000 g mol −1 ) to a silicon surface was examined in dependence of reaction time, polymer concentration, solvent and number of alkoxysilyl end groups. Crosslinkable polymers for surface modification were synthesized by statistical carbanionic copolymerization of 4‐vinylbenzocyclobutene (4‐VBCB) and styrene, followed by epoxide end‐functionalization and triethoxysilane modification ( M n = 4000–14,000 g mol −1 ). The copolymers were characterized by 1 H‐NMR, THF‐SEC, and matrix‐assisted laser desorption and ionization time‐of‐flight mass spectrometry. In situ 1 H‐NMR kinetic studies in cyclohexane‐ d 12 provided information regarding the monomer gradient in the polymer chains, with styrene being the more reactive monomer ( r s = 2.75, r 4‐VBCB = 0.23). Thin polymer films on silicon wafers were prepared by grafting‐to surface modification under conditions derived for the polystyrene homopolymer. The traceless, thermally induced crosslinking reaction of the benzocyclobutene units was studied by DSC in bulk as well as in 3–6 nm thick polymer films. Crosslinked films were analyzed by atomic force microscopy, ellipsometry, and nanoindentation, showing smooth polymer films with an increased modulus. © 2019 The Authors. Journal of Polymer Science published by Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58 , 181–192