Preparation of high‐strength, high‐modulus PVA fiber by synthesis of syndiotacticity‐rich high molecular weight PVA polymers with VAc and VBz via emulsifier‐free emulsion polymerization

Abstract

Different vinyl acetate (VAc) and vinyl benzoate (VBz) monomer ratios have been chosen as monomers to create high polymerization degree (Pn) and high syndiotacticity‐diad content (S‐diad) poly(vinyl alcohol) (PVA) polymers via emulsifier‐free polymerization in order to address the problem of limited mechanical capabilities of PVA fibers prepared with low Pn and low S‐diad polymer. The variations in hydrogen bonding, Pn, S‐diad, and viscosity of different PVA polymers were investigated and evaluated using Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, gel permeation chromatography, and a viscosity tester. Moreover, various PVA fibers with high strength and modulus have been manufactured using a synthetic polymer as the raw material for dry‐wet spinning. The effect of Pn and S‐diad on the mechanical and thermal characteristics of PVA fibers is evaluated using a variety of characterization techniques, such as the scanning electron microscope, differential scanning calorimetry, thermogravimetric analyzer, X‐ray diffraction, and tensile tester. As the ratio of VBz monomer increased, the results suggested that VBz may have a considerable impact on the Pn and S‐diad of PVA polymers, the OH vibration absorption peak reduced from 3491 to 3442 cm−1; the Pn increased from 2112 to 17,704; and the S‐diad rose from 51.2% to 60.1%. In addition to the fact that Pn and S‐diad significantly increased the fibers' strength and modulus, the crystallinity increased from 41.8% to 51.7%, and the orientation degree rose from 87.5% to 91.7%, as Pn and S‐diad increased; the tensile strength and highest elastic modulus increased from 9.71 ± 0.3 cN/dtex to 12.74 ± 0.5 cN/dtex (increased of 31.2%) and 264.52 ± 9.3 cN/dtex to 338.41 ± 8.6 cN/dtex (increased of 27.9%); the elongation at break decreased from 5.63 ± 0.3% to 2.92 ± 0.2%.