Synthesis of polybutadiene nanoparticles by emulsion polymerization: The effect of electrolyte and initiator type on particle size and reaction kinetics

Abstract

Emulsion polymerization of the butadiene (Bu) was performed in the presence of disproportionate potassium rosinate (DPR) as anionic emulsifier, potassium hydroxide (KOH), and potassium carbonate (K2CO3) as electrolytes, and three different initiators including potassium persulfate (KPS), 2,2′-azobisisobutyronitrile (AIBN) or 4,4′-azobis(4-cyanovaleric acid) (ACVA, also known as VAZO) at 70 °C. Latexes were prepared with a solid content of about 30 wt%. The particle size and its distribution were measured by dynamic light scattering (DLS) analysis, while the polymerization conversion was determined gravimetrically at different time intervals. Results on the emulsion polymerization of Bu in the presence of KOH and K2CO3 co-electrolytes showed that adding KOH to the reaction media decreases the polymerization rate. Positive effect of co-electrolytes on the control over polybutadiene latex (PBL) particles size and its distribution was also confirmed, where K2CO3 played roles as electrolyte and pH buffer and KOH served double roles as electrolyte and alkaline supplier of the reaction media. Complete solubility of the AIBN in Bu resulted in higher rate of polymerization in the presence of AIBN in comparison to other initiators, i.e., VAZO or KPS. The results showed that initiator type plays a significant role on the formation of PBL nanoparticles and kinetics of the polymerization. The kinetic studies revealed that emulsion polymerization of Bu follows case 1 (i.e., $$\bar{n}$$ ≪0.5, where $$\bar{n}$$ indicates average number of the propagating chains per particle) of the Smith-Ewart kinetics.