Time-temperature superposition for kinetic mapping of solventless autocatalytic addition of diisocyanates and macrodiols.

The migration of chemicals from polyurethane (PUR) is a concern in many applications, such as adhesives for food packaging. Low molecular weight catalysts, which are prone to migration, need to be eliminated from PUR, in particular those containing Sn or other metals. This is difficult partly due to many uncertainties of autocatalytic polyaddition between isocyanates and polyols. Hexamethylene and tolylene diisocyanates, HDI and TDI, are often reacted with macrodiols to produce prepolymers for PUR. This study measures isocyanate contents during the polyaddition of HDI and TDI with excess macrodiols. Ester-based macrodiols were reacted between 60 °C and 90 °C using 1 : 0.3 and 1 : 0.5 molar ratios to form OH-terminated prepolymers. Time-temperature superposition (TTS) was used to process the values of unreacted isocyanate fractions from several temperatures. Presumed activation energies and kinetic data scatter implied that polymerization has a distinct initial phase of conversion of unreacted diisocyanate into monofunctional adducts by addition to macrodiols, followed by more complex processes. Utilization of the activation energy from the initial phase and TTS application might allow the prediction of kinetic trends without the need for a large volume of accurate data. Such kinetic mapping should be useful for developing catalyst-free PUR with low levels of migrating chemicals.

Conversion of fatty acid methyl esters into dibasic esters by metathesis and their lubricant properties.

Biodiesel plants are struggling to find value added applications for fatty acid methyl esters (FAME). One option for FAME valorization would be dibasic esters, which can be transesterified with 2-ethylhexyl (2EH) or other alcohols to produce lubricant basestocks and achieve the most widespread viscosity grades VG46 and VG32. Biocatalytic, metathesis and other synthetic pathways are available to produce dibasic esters. Using a ruthenium-based catalyst, methyl oleate was converted into monounsaturated dibasic ester by metathesis and reached VG22 after transesterification with 2EH in this investigation. Synthesized 2EH esters of other dibasic acids showed distinct viscometric trends. Their correlation implied that FAME from gondoic and erucic acids should result in VG32 and VG46 respectively, if converted into 2EH dibasic esters. Pour points demonstrated excellent low temperature fluidity and resistance to heat thinning when monounsaturation was retained. Oxidative stability properties remained acceptable, volatility was lower than that of VG46 mineral oils. Mixed alcohols, acids and esters can also be used for meeting VG specifications or achieving higher biobased contents. Currently petrochemical ester basestocks dominate in high performance hydraulic fluids (HF). However, fractionation of FAME into high-erucic/gondoic esters in biodiesel plants can produce a valuable biobased feedstock for large volume manufacture of HF and other lubricants.

Non-destructive inspection of food and technical oils by terahertz spectroscopy.

Quality control and non-destructive monitoring are of notable interest of food and pharmaceutical industries. It relies on the ability of non-invasive inspection which can be employed for manufacturing process control. We hereby apply terahertz (THz) time-domain spectroscopy as non-destructive technique to monitor pure and degraded oils as well as hydrocarbon chemicals. Significant differences in the spectra of refractive index (RI) and absorption coefficient arising from the presence of ester linkages in the edible and technical oils were obtained. Explicit increase from 1.38 to 1.5 of the RI in all THz spectrum range was observed in hydrocarbons and mono-functional esters with the increase of molar mass. This fact is in contrast of RI dependence on molar mass in multi-functional esters, such as Adipate or vegetable oils, where it is around 1.54. Degradation products, Oleic Acid (OA) and water in particular, lead only to some changes in absorption coefficient and RI spectra of vegetable oils. We demonstrate that complex colloidal and supramolecular processes, such as dynamics of inverse micelles and oil hydrolysis, take part during oil degradation and are responsible for non-uniform dependence of optical properties on extent of degradation.

Lipid Layers on Nanoscale Surface Topography: Stability and Effect on Protein Adsorption.

Herein, we report the coating of a surface with a random nanoscale topography with a lipid film formed by an anchoring stearic acid (SA) monolayer and phospholipid (DPPC) layers. For this purpose, different procedures were used for phospholipid coating, including adsorption from solution, drop deposition, and spin-coating. Our results reveal that the morphology of the obtained lipid films is strongly influenced by the topography of the underlying substrate but also impacted by other factors, including the coating procedure and surface wettability (modulated by the presence of SA). These coated surfaces showed a remarkable antifouling behavior toward proteins, with different yields of repellency (Yrp) depending on the amount/organization of DPPC on the nanostructured substrate. The interaction between the proteins and phospholipids involves a partial detachement of the film. The use of characterization techniques with different charcateristics (accuracy, selectivity, analysis depth) did not reveal any obvious vertical heterogenity of the probed interface, indicating that the lipid film acts as a nonfouling coating on the whole surface, including the outermost part (nanoprotrusions) and deeper regions (valleys).

Self-assembly of fatty acids on hydroxylated Al surface and effects of their stability on wettability and nanoscale organization.

The self-assembly of fatty acids (FA) on the surfaces of inorganic materials is a relevant way to control their wetting properties. While the mechanism of adsorption on model flat substrate is well described in the literature, interfacial processes remain poorly documented on nanostructured surfaces. In this study, we report the self-assembly of a variety of FA on a hydroxylated Al surface which exhibits a random nanoscale organization. Our results revealed a peculiar fingerprint due to the FA self-assembly which consists in the formation of aligned nanopatterns in a state of hierarchical nanostructuration, regardless of the molecular structure of the FA (chain length, level of unsaturation). After a significant removal of adsorbed FA using UV/O3 treatment, a complete wetting was reached, and a noticeable disturbance of the surface morphology was observed, evidencing the pivotal role of FA molecules to maintain these nanostructures. The origin of wetting properties was investigated prior to and after conditioning of FA-modified samples taking into account key parameters, namely the surface roughness and its composition. For this purpose, the Wenzel roughness, defined as the third moment of power spectral density, was used, as it is sensitive to high spatial frequency and thus to the obtained hierarchical level of nanostructuration. Our results revealed that no correlation can be made between water contact angles (θ(w)) and the Wenzel roughness. By contrast, θ(w) strongly increased with the amount of -CHx- groups exhibited by adsorbed FA. These findings suggest that the main origin of hydrophobization is the presence of self-assembled molecules and that the surface roughness has only a small contribution to the wettability.

Ordered nanostructures on a hydroxylated aluminum surface through the self-assembly of fatty acids.

We investigate the mechanism of self-assembly of fatty acids (FA) and methyl oleate on an Al oxy-hydroxide surface with a view to deciphering the role and nature of interfacial processes (adsorption, chemical binding, molecular organization, etc.). For this purpose, we focus on parameters related to intrinsic properties of molecules, namely the level of unsaturation and the nature of the head group (carboxylic acid or ester). After the FA adsorption, the presence of coordinative bonded carboxylate species on the Al oxy-hydroxide surface is demonstrated by means of PM-IRRAS analysis. We observe that contact of methyl oleate with the surface leads to its chemical transformation through a saponification reaction. As a consequence, it binds to the surface in a manner similar to that for fatty acids. Through an innovative mode of atomic force microscopy (AFM), the organization of the adsorbed molecules is demonstrated. Our results reveal the existence of highly ordered nanostructures guided by the FA self-assembly. The size of these nanostructures was determined with accuracy, suggesting that it exceeds one FA monolayer. By contrast, no organization was observed with methyl oleate.