Three di-block copolymers polymethylene-b-poly(methyl methacrylate) (PM-b-PMMA) with different chain segment ratio were synthesized via the combination of living polymerization of ylides and atomic transfer radical polymerization (ATRP). Honeycomb-patterned films of such diblock copolymers were fabricated via static breath-figure method with four different solvents, respectively. The morphology of such porous film was observed by scanning electron microscopy (SEM). The effects of solvents, concentration, PMMA segment and PM∶PMMA ratio of diblock copolymers on the pore size and its distribution were investigated. Honeycomb-patterned films containing polyole?n segment with nanometer (520 nm) and micrometer pore (1.1 μm) were successfully fabricated via the static breath-?gure (BF) method using carbon disulfide and dichloromethane as solvent at the concentration of 3 wt%. The pore size of honeycomb film increased with the decrease of polymer concentration. The length of PMMA segment and the PM∶PMMA ratio of diblock copolymers play an important role in the morphology of polymer ?lm.

Key words: polyolefin, block copolymer, breath-figure, honeycomb-patterned film