RESUMEN
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[double bond, length as m-dash]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.
RESUMEN
By controlling both the kind of ion and the ionic strength of electrolytes in an emulsion polymerization system of vinyl pivalate containing about 1% sodium lauryl sulfate as a surfactant, nanoparticles of polyvinylpivalate having a diameter of about 25 nm were successfully prepared. The use of high concentrations of lithium chloride and lithium sulfate (approximately 1.0 mol L(-1)) prevented the nanoparticles from aggregating and produced nanoparticles sizes of 25-50 nm. Ammonium acetate and sodium acetate, on the other hand, accelerated the aggregate of the nanoparticles. These phenomena were examined in detail and found to be similar to the Hofmeister phenomena and the combination rule proposed by Craig et al.