Emulsion Polymerization of Acrylonitrile in Aqueous Methanol

Polyacrylonitrile (PAN) is the most widely utilized precursor for carbon fiber (CF) production. Though the CF market is growing, increased adoption is impeded by the high cost of the primary raw material, acrylonitrile (AN). AN is manufactured today via propylene ammoxidation, which produces several byproducts (hydrogen cyanide, acetonitrile, acrolein) that require multi-step separations to produce polymerization-grade AN. Recently, a new approach to manufacture bio-based AN from sugars was proposed based on catalytic nitrilation, which produces AN from C3-acrylate esters at >98% yield with alcohol and water as coproducts. The proposed nitrilation process included a 2-stage separation and purification scheme for AN recovery. Here, we hypothesize that in addition to offering a green alternative to propylene ammoxidation with higher product yield, nitrilation of methyl acrylate to produce AN could also enable direct AN polymerization without the proposed separation steps, since water can act as the solvent and MeOH as the chain transfer agent (CTA). Because AN, water, and MeOH form a ternary azeotrope, the heat duty required for separation is substantial and removal of this separation step reduces the heat demand significantly. To that end, we report AN polymerization via emulsion polymerization in aqueous methanol at varying concentrations of CTA. High molecular weight, low polydispersity (e.g., 331.7 kDa, PDI = 1.88) PAN copolymers were produced from AN-MeOH-water emulsions, in the absence of additional CTAs. These PAN copolymers demonstrated thermal properties and carbon mass yields comparable to PAN copolymers prepared via conventional emulsion polymerization. By polymerizing AN in aqueous MeOH, the alcohol acts as the CTA, obviating the need for toxic, malodorous thiol-based CTAs (mercaptans). Utilizing the MeOH coproduct as the CTA results in a substantial heat demand reduction for the overall nitrilation process by 35%, leading to a 40% reduction imported process electricity demand, as the heat-intensive distillation steps required post-ammoxidation and previously proposed post-nitrilation are avoided. This polymerization method offers the opportunity to reduce the energy requirements of renewable AN production to improve both the sustainability and overall economics of bio-based CF precursor production.