Structural analysis of cross-linked poly(vinyl alcohol) using high-field DNP-NMR

Poly(vinyl alcohol) (PVOH) is a water-soluble synthetic polymer, widely used in materials for functional films and moldings, fiber fabric sizing agents, paper coating resins, and adhesives. PVOH is mainly applied in the form of an aqueous solution, yet after its application, insolubility (water resistance) is required. To achieve this, additives are introduced. These additives used with PVOH are cross-linking agents which react with the hydroxyl groups and modified functional groups in PVOH. Because of the poor reactivity of unmodified PVOH, it does not react with cross-linking agents that have functional reactive groups. Therefore, modified PVOH that reacts with a cross-linking agent more successfully is required. These chemical bonding sites are so low in abundance that it is difficult to characterize the cross-linking structure. Solid-state 13C NMR is a powerful technique that can be used for the structural analysis of a polymer material. However, its sensitivity is low, hence it is difficult to determine crosslinking in a polymer, as it makes up only a small proportion of the product. Therefore, solid-state 13C NMR sensitivity can be enhanced by high-field dynamic nuclear polarization (DNP) using strong electron polarization. In this study, the reaction of acetoacetylated PVOH with a cross-linking agent, adipic dihydrazide, was analyzed. This crosslinked PVOH is the most popular vinyl alcohol polymer on the commercial market. The sensitivity enhanced 13C NMR spectra reveal that the carbonyl of the acetoacetyl group of PVOH crosslinks with adipic hydrazide by forming an imine bond (>C <svg xmlns="http://www.w3.org/2000/svg" version="1.0" width="13.200000pt" height="16.000000pt" viewBox="0 0 13.200000 16.000000" preserveAspectRatio="xMidYMid meet"><metadata> Created by potrace 1.16, written by Peter Selinger 2001-2019 </metadata><g transform="translate(1.000000,15.000000) scale(0.017500,-0.017500)" fill="currentColor" stroke="none"><path d="M0 440 l0 -40 320 0 320 0 0 40 0 40 -320 0 -320 0 0 -40z M0 280 l0 -40 320 0 320 0 0 40 0 40 -320 0 -320 0 0 -40z"/></g></svg> N–) this study also shows that the product has only seven crosslinking sites per molecular chain with a polymerization degree of 1000 and is water resistant.