Micro and nano cellular amorphous polymers (PMMA, PS) in supercritical CO2 assisted by nanostructured CO2-philic block copolymers – One step foaming process

Microcellular foaming of commodity amorphous polymers, poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) was studied in supercritical CO2 via a batch one-step process in the presence of block copolymers able to change their foaming behaviour and therefore the porous structures. Triblock (styrene-co-butadiene-co-methylmethacrylate SBM, methylmethacrylate-co-butylacrylate-co-methylmethacrylate MAM) terpolymers were blended to PS or PMMA by extrusion. They showed advantages compared to classical PS-PMMA polymer blends in terms of cell size control and reduction of cell size. Foaming is carried out on bulk injection molded samples which were saturated under high pressures of CO2 (300 bars) at different temperatures (25° C to 80 °C) and different depressurization rates (pressure drop rates from 150 bar/min to 12 bar/min). Very distinct cellular structures and densities were controlled by varying either the copolymer type or the foaming conditions (T,P). Cell sizes ranged from 0.2 μm to 200 μm, and densities from 0.30 g/cm3 to 1 g/cm3 in the polymers considered. Particularly, when triblock copolymers were able to self organize (nanostructuring) in a polymer matrix, they became phase separated at a nanometer level, presenting nanostructured polymers matrixes. To conclude the study, a possible nanostructuring mechanism is suggested based on the interplay between rubbery and highly CO2-philic blocks/rigid and less CO2-philic blocks. It is demonstrated that block copolymer additives are a good pathway towards micro and ultra microcellular supercritical CO2 foaming of amorphous polymers.

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► Nanostructured block copolymers act as nucleating agents for foaming processes in amorphous polymers using ScCO2.
► PS and PMMA can be foamed using one-step ScCO2 foaming processes.
► Adding nanostructured block copolymers in amorphous matrixes reduces cell sizes and increases cell densities.