Lubricating and Waxy Esters, V: Synthesis, Crystallization, and Melt and Flow Behaviors of Branched Monoesters Incorporating 9-Decenol and 9-Decenoic Acid

Abstract

Branched derivatives of waxy monoesters incorporating 9-decenol and 9-decenoic acid were synthesized using epoxidation and ring-opening esterification. The reactions were conducted at two different temperatures and monitored over time. The crystallization, melting, and viscosity of the compounds were all controlled strongly as a function of incremental branching. Isomerism was shown to be critically important: an OH group at the end of the hydrocarbon chain completely suppressed crystallization, whereas its isomer with a terminal acyl chain did not. The structure of the linear monoesters were shown to provide the templates for crystallization, melting, and flow behavior, whereas the branching effect extended but could not erase the effect of the base molecular architecture. These compounds present a large range of properties that are suitable for a variety of applications ranging from waxes to lubricants.

Engineering Green Lubricants IV: Influence of Structure on the Thermal Behavior of Linear and Branched Aliphatic Fatty Acid-Derived Diesters

“…At the Trent Center for Biomaterials Research, we have already reported on the low temperature flow properties of several series of linear and branched monoesters and diesters with the aim of understanding and predicting the molecular features that result in superior lubricants. − Notably, we have found that branched diesters possess exceptional low temperature and flow properties, whereas the crystallization and melting points of the diesters scale predictably as functions of the total chain length and diol chain length. , Our reports, however, have thus far not systematically reported on the thermal stability of these materials. Similarly, although the thermal stabilities of many biobased materials can be found in the literature, predictable correlations between molecular structures of vegetable oil-derived materials and their thermal stability are still lacking.…”

Engineering Green Lubricants I: Optimizing Thermal and Flow Properties of Linear Diesters Derived from Vegetable Oils

“…A significant body of knowledge addressing the shortcomings of biobased ester materials exists within the literature. The crystallization and melting points of esters, for example, can be suppressed by introducing intra- and intermolecular elements such as chain length mismatch, unsaturation, , double bond position and configuration, , and branching − to sterically hinder crystal packing. Similarly, the viscosity of ester compounds may be varied by alterations to their molecular architectures, for example, varying acid and/or fatty alcohol chain lengths, the degree of saturation, , double bond configuration, and molecular polarity .…”

“…The Trent Centre for Biomaterials Research is conducting a comprehensive study of the structure–function relationships of simple and complex ester materials in an attempt to address part of this gap. Already, a series of studies on the changes to physical properties resulting from structural modifications such as branching along the ester backbone, chain length mismatch, asymmetry, and saturation have been presented for monoesters, ,,,, diacid-derived diesters, and structured TAG oligomers . In this paper, we extend our contribution by reporting the changes to the crystallization and melting behaviors and flow properties of a template series of symmetric diesters (chemical formula (C 17 H 33 COO) 2 [CH 2 ] n ) as a function of the methylene spacer units between the two ester moieties (given by the diol chain length, n ).…”

Engineering Green Lubricants II: Thermal Transition and Flow Properties of Vegetable Oil-Derived Diesters

“…Many examples of branched vegetable oil-derived esters demonstrating excellent low temperature properties for lubricant applications have been reported within the literature, − including branched jojoba-like monoesters − and diesters prepared at the Trent Centre for Biomaterials Research (TCBR) which demonstrated low temperature flow properties comparable to, or even better than, those in the literature. Furthermore, it has been observed at the TCBR that the structural features of the precursor esters such as symmetry and total chain length imparted strong lingering effects on the thermal properties of their branched derivatives. , Consequently, the significant potential of the branched esters for use in high end lubricant formulations, as well as the fundamental knowledge that can be gained for the custom design of a vast range of biobased materials (e.g., phase change materials and functional waxes) with tailored crystallization, melting and flow behaviors motivates the investigation of molecular structure on the physical properties of a larger collection of precursor ester homologues.…”

“…Furthermore, it has been observed at the TCBR that the structural features of the precursor esters such as symmetry and total chain length imparted strong lingering effects on the thermal properties of their branched derivatives. 14,15 Consequently, the significant potential of the branched esters for use in high end lubricant formulations, as well as the fundamental knowledge that can be gained for the custom design of a vast range of biobased materials (e.g., phase change materials and functional waxes) with tailored crystallization, melting and flow behaviors motivates the investigation of molecular structure on the physical properties of a larger collection of precursor ester homologues.…”