Synthesis of α-Bromine-Terminated Polystyrene Macroinitiator and Its Initiation of MMA Polymerization by ATRP

In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br_2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br_2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93. 8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate (MMA) in the presence of copper (I ) halogen and 2, 2' -bipyridine (bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1. 2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by ~1H NMR spectra.

Effect of Ink Molecular Weights and Annealing Conditions on Molecular Transfer Printing

The molecular transfer printing（MTP） technique has been invented to fabricate chemical patterns with high fidelity using homopolymer inks. In this work, we systematically studied the effects of the molecular weights of homopolymer inks and transfer conditions on the MTP process. We explored a large range of molecular weights（~3.5-56 kg·mol^（-1）） of hydroxyl-terminated polystyrene（PS-OH） and hydroxyl-terminated poly（methyl methacrylate）（PMMA-OH） in the MTP process, and found that the resulting chemical patterns on replicas from all five blends were functional and able to direct the assembly of films of the same blends. The transfer temperature and the film annealing sequences had an impact on the MTP process. MTP was sensitive to the transfer temperature and could only be performed within a certain temperature range, i.e. higher than the glass transition temperature（T_g） of copolymers and lower than the rearrangement temperature of the assembled domains. Pre-organization of the blend films was also necessary for MTP since the preferential wetting of PMMA domains at the replica surface might result in the formation of a PMMA wetting layer to prevent the presentation of underlying chemical patterns to the replica surface.