Synthesis and characterization of size-tunable core-shell structural polyacrylate-graft-poly(acrylonitrile-ran-styrene) (ASA) by pre-emulsion semi-continuous polymerization

The core-shell polymeric polyacrylate-graft-poly(acrylonitrile-ran-styrene) (ASA) has been explored for the polymer industry due to its excellent properties. However, it has been a longstanding challenge to synthesize large size-tunable particles by the conventional batch polymerization. In this paper, an accurate method, i.e. pre-emulsion semi-continuous polymerization, is applied to prepare ASA polymeric particles, which makes a series of different particle sizes (100–450 nm) of the crosslinked poly(butyl acrylate) (PBA) inner core coated with a hard shell using the poly(acrylonitrile-ran-styrene) (AS) copolymer. Specifically, the feed modes and proportion of seed are investigated to tune the particle size. The results show that the PBA seed microsphere in pre-emulsion semi-continuous polymerization is enlarged by accurate feed rate, but not in batch polymerization. A possible mechanism for the growth of the PBA core is proposed that secondary particles from homogeneous nucleation in semi-continuous feed mode is less than that of batch mode, which attenuate the impact on the growth of core particle. The size and morphology of resulting particles are characterized using various analytical techniques including the transmission electron microscopy (TEM), the scanning electron microscopy (SEM) and the dynamic light scattering (DLS). Core-shell separates phase corresponding to different glass transition temperatures is evaluated using differential scanning calorimeter (DSC) analyses indirectly. Moreover, the mechanical properties including impacts and tensile strengths are also analyzed. This study thus highlights a detailed strategy to tune polymeric particles related to different properties and the nucleating mechanism of seed emulsion polymerization that governs structure, particle size and distribution of ASA polymer with a bespoke structure for various application.