Fabrication of 2D Block Copolymer Brushes via a Polymer‐Single‐Crystal‐Assisted‐Grafting‐to Method

Block copolymer brushes are of great interest due to their rich phase behavior and value‐added properties compared to homopolymer brushes. Traditional synthesis involves grafting‐to and grafting‐from methods. In this work, a recently developed “polymer‐single‐crystal‐assisted‐grafting‐to” method is applied for the preparation of block copolymer brushes on flat glass surfaces. Triblock copolymer poly(ethylene oxide)‐b‐poly(l‐lactide)‐b‐poly(3‐(triethoxysilyl)propyl methacrylate) (PEO‐b‐PLLA‐b‐PTESPMA) is synthesized with PLLA as the brush morphology‐directing component and PTESPMA as the anchoring block. PEO‐b‐PLLA block copolymer brushes are obtained by chemical grafting of the triblock copolymer single crystals onto a glass surface. The tethering point and overall brush pattern are determined by the single crystal morphology. The grafting density is calculated to be ≈0.36 nm−2 from the atomic force microscopy results and is consistent with the theoretic calculation based on the PLLA crystalline lattice. This work provides a new strategy to synthesize well‐defined block copolymer brushes. A recently developed “polymer‐single‐crystal‐assisted‐grafting‐to” method is applied for the preparation of block copolymer brushes on flat glass surfaces. Poly(ethylene oxide)‐b‐poly(l‐lactide) diblock copolymer brushes are obtained by chemical grafting of triblock copolymer poly(ethylene oxide)‐b‐poly(l‐lactide)‐b‐poly(3‐(triethoxysilyl)propyl methacrylate) single crystals onto a glass surface. This work provides a new strategy to synthesize well‐defined block copolymer brushes.