Low T_g, strongly segregated, ABA triblock copolymers: a rheological and structural study

ABA triblock copolymers can form microphase separated structures where the B blocks form bridges between A domains, leading to reversible networks interesting for a variety of applications such as pressure sensitive adhesives or thermoplastic elastomers. However, a major drawback of these systems is their rapid loss of mechanical properties upon temperature increase. A potential way to circumvent this limitation would be to design ABA triblock copolymers that keep their microphase separation at high temperatures. In this paper, we report on all-soft ABA triblock copolymers having a poly(n-butyl acrylate) (PnBA) central block and poly(heptafluorobutyl acrylate) (PHFBA) outer blocks. By introducing fluorinated units, the incompatibility between the blocks is largely increased, allowing strong segregation between the block domains, which preserve the microphase separation up to high temperatures despite the low glass transition temperature of the blocks, as shown by temperature dependent SAXS measurements. We study the properties of different copolymers, with similar PHFBA volume fractions but different block lengths. Linear shear rheology measurements revealed the presence of a second, low frequency, plateau whose onset and length depend on the PnBA and PHFBA length, respectively. This plateau also persists up to higher temperatures for longer PHFBA blocks.