Influence of polymerization conditions on the molecular weight and polydispersity of polyepichlorohydrin

The influence of the relevant reaction conditions on the molecular weight and polydispersity during the cationic ring-opening polymerization of epichlorohydrin has been studied using an experimental design. The polymerization was conducted in the presence of an alcohol (diol and triol), a Lewis acid at two temperatures (5 °C and 25 °C), and with two monomer addition rates. FT-IR spectra were used for the chemical characterization of the polymer, and MALDI-TOF mass spectrometry was used to determine the oligomeric composition and the masses of the initiator or transfer agent. The FT-IR showed the characteristic peaks of polyepichlorohydrin, and the mass spectra indicate that the alcohol was incorporated in the polymer structure. The MW and polydispersity were determined using gel permeation chromatography. We observed that the two most significant parameters that affected MW were the monomer addition rate and the reaction temperature, whereas polydispersity was most strongly affected by the monomer addition rate.