Crystalline lamellar films with honeycomb structure from comb-like polymers of poly(2-long-alkyl-2-oxazoline)s.

Comb-like copolymers are usually structured by grafting polymeric side chains onto main polymer chain. There are few reports of comb-on-comb polymers in which dense secondary side chains are grafted onto primary side chain. In this work, we synthesized comb polymers with grafted-on-graft side chains (c-PEI-g-Acyl) via an effective acylation reaction of comb polymers possessing polyethyleneimine (PEI) side chain with long-alkyl acyl chlorides. For comparison, we also synthesized homopolymers l-PEI-g-Acyls via reaction of linear PEI with long-alkyl acyl chlorides. Then, we investigated their crystalline feature in the film formation by XRD, DSC and SEM, and found that the polymers tend to form hexagonal lamella structures with bilayer alkyl spacing. The comb polymers c-PEI-g-Acyls and linear polymers l-PEI-g-Acyls were used in preparation of honeycomb film by the "breath-figure" process by dropping chloroform solution of the polymers on substrate. Different to many honeycomb polymeric films which are supported by amorphous phase, interestingly, our polymers easily afford honeycomb films which are supported by crystalline lamellae frames under higher humidity condition. It was found that the comb polymers of c-PEI-g-Acyls with longer PEI primary side chain and long alkyl secondary side chain have advantages in producing honeycomb film than linear polymers of l-PEI-g-Acys.