The breath figure (BF) process has been widely used to prepare patterned porous films. The mechanism remains to be further elucidated, especially how polymer architectures affect the stability of water droplets and the pore structure. Polystyrenes (PS) was functionalized with a series of polar groups both in chain middle and chain end, which was synthesized by using difunctional atom transfer radical polymerization (ATRP) initiators with the combination of nucleophilic substitution of the end bromine. It is found that PS with polar groups, which help to reduce interfacial tension, tends to form regular patterns at low concentration and to generate multilayered pores. The coalescence resistance measurement was performed to characterize the stabilization of water droplets from polymers by precipitation. The results show opposite trend with the results of the BF process, indicating a minor role played by polymer precipitation on microdroplets stabilization. We reveal that addition of only an oxyethyl group in the chain middle of PS contributes to the formation of ordered patterns. This study helps to shed light on the impact of polymer architectures on the self-assembly behavior in the BF process.atom transfer radical polymerization, breath figure, interfacial tension, isoporous pattern, polar groups
| INTRODUCTIONIsoporous materials have found their applications in many areas such as templates, 1,2 sensors, 3-5 cell culture, 6-8 and separation. [9][10][11] In addition to the self-assembly of block copolymers, 12 the breath figure (BF) method has received great attention for its simplicity and economy to prepare isoporous films. [13][14][15][16] Since the first report of condensing droplets by Lord Rayleigh in 1911, 17 the BF method uses volatile solvents to induce vapor condensation, leaving porous imprints after the total evaporation of solvents and droplets. The stability of water droplets and their rearrangement by Marangoni convection and thermocapillary force ensure the formation of honeycomb patterns. [18][19][20][21][22][23][24][25][26][27][28][29][30][31] Up to now, a lot of polymers with different topological structures have been investigated in the BF process, including star-shaped polymers, 18,32,33 dendrimers, 34 comb-like polymers, 35 rod-coil block copolymers, 36,37 and linear polymers. [38][39][40][41][42][43] Apart from topology, the chemical composition of polymers also shows great impact on their self-assembly behavior. Ji et al. reported that the Di Zhou and Bai-Heng Wu contributed equally to this work.