Thin polymer films with different level of complexity prepared by surface-initiated ATRP

In the present study, the fabrication and characterization of thin polymer films with different level of complexity by surface initiated polymerization (SIP) was investigated. Poly(glycidyl methacrylate) (PGMA) was utilized as macromolecular anchoring polymer layers. The SIP macroinitiators were synthesized on the substrate surface by the reaction between epoxy groups of PGMA and carboxy functionality of bromoacetic acid (BAA) or 2-bromo-2-methylpropionic acid (BPA). Homogeneous uniform surfaces, gradient surfaces, one-component heterogeneous surfaces, two-component heterogeneous surfaces and patterned surfaces were synthesized based on the macromolecular anchoring layer approach.; First of all, tuning of the PGMA anchoring layer thickness and variation of surface initiators density were discussed. Styrene was used as a model system to study the surface initiated ATRP process. Different surface concentrations of BAA were used in the grafting experiments to acquire knowledge about the relationship between the amount of surface initiator and the rate of the grafted layer formation.; Next, a high-throughput combinatorial approach for the synthesis of tethered polymer layers with thickness and grafting density gradients was developed. This approach was also adopted to study the fundamentals of the kinetics of SI-ATRP of styrene. The effect of surface initiator density, monomer concentration, polymerization temperature and catalyst concentration on the kinetics of grafted films growth was systematically investigated.; One-component heterogeneous surfaces were synthesized based on self-assembly of phase-separated ultrathin polymer blend films and SI-ATRP. By changing the content of PGMA in PGMA/PMMA thin films, films with different heterogeneous morphologies were obtained. SIP of styrene amplified the heterogeneous PGMA patterns. SI-ATRP of pentafluorostyrene was also performed to generate (ultra)hydrophobic surfaces.; Next, the fabrication of two component heterogeneous surfaces utilizing the phase-separation phenomena in ultrathin polymer blend films (PS-COOH/PMMA) and the combination of "grafting-to" and "grafting-from" method was discussed. The segregated brushes demonstrated non-uniform surface response by studying the morphologies after treating with selective solvents and protein adsorption.; Finally, a novel approach to precisely regulate the growth of patterned surfaces through the combination of Capillary Force Lithography and SIP was described. This approach is based on the employment of PS as a resist material for SIP in an aqueous polymerization media.