Polyvinyl alcohol-waterborne blocked-based polyurethane composite surface sizing agents for enhancing mechanical performance of specialty paper

Efficient improvement of paper strength while optimized sizing technique remains challenging and fascinating since specialty paper are required to low-cost, high printing quality and environmental sustainability. Herein, a novel controlled reactivity polyester glycol-based cross-linker (TBPU) applied in paper surface sizing was exploited by simple two-steps polymerization and blending process. An end-blocked structure design strategy of containing densely distributed multiple soft segments and active hydrogen nucleophilic segments (Butanone oxime, MEKO as end closure units) in isocyanate dispersion was achieved to address the scarcity of mechanical properties and the inconvenient in surface-sizing progress. TBPU can block the NCO groups in IPDI segments at 60 °C, and NCO groups can be deblocked at the temperature higher than 110 °C, which endow TBPU with latent cross-linking property. Afterward, we took advantage of the structural feature of polyhydroxy compounds and the adhesion to cellulose via using polyvinyl alcohol (PVA) as a blending component to form TBPU/PVA emulsion. The organization of NCO groups react with hydroxyl groups, carbamate groups cross-linked with hydrogen bonds, and crystallized PCL segments generates phase-separated hierarchical domains. Serving as high-reactivity paper-sizing fillers capable of cross-linking and disintegration under an external change of temperature, the hierarchical domains can strengthen the specialty papers and enhance their water resistance and ink adhesion. The influences of TBPU content, PVA content and NCO/OH molar ratio on the physicochemical properties of the resultant emulsions and sized paper have been investigated. As a result, the paper sized with TBPU-1.6/PVA emulsion exhibit a tensile index of ≈107.19 Nm/g, a tearing index of ≈11.79 m N • m2/g, a folding resistance of ≈4511 s, an optimum blending temperature of 70 °C and exceptional cooperation ratio with PVA and TBPU (4.0 wt%, 3.0 wt%), which are 1.649 times, 1.966 times, and 2.652 times than those of untreated papers (65 Nm/g, 6 m N • m2/g, 1701 s). Furthermore, sizing liquid can be conveniently applied and recycled due to their excellent environmental friendliness and Biodegradability, this work provides a promising solution for optimizing surface sizing technology.