Synthetic Design of Polyester Electrolytes Guided by Hydrophobicity Calculations

Abstract

Partition coefficients (LogP) help to quantify hydrophobicity, which can be used to guide the design of polymer electrolytes with targeted properties. Thus, this study combined synthetic experiments and molecular modeling to produce polyester electrolytes that solubilize lithium salts. These polyester electrolytes were derived from natural sources and polymerized with different ratios of polyols (diglycerol, glycerol, and diethylene glycol) and citric acid in the presence of lithium salts (LiTf and LiTFSI). The Fisher esterification produced homogeneous, cross-linked films with high optical transparency, whereas the lithium salts increased glass transition temperatures. The LogP values of monomers and the resulting polyesters were predicted using cheminformatics tools and indicate changing diglycerol to glycerol or diethylene glycol alters the hydrophobicity. Comparison of different molecular modeling methods with predicted LogP values demonstrate that LogP values are a reliable means of tailoring physical and chemical properties of these polymer electrolytes. Additionally, LogP values greatly benefit from being extremely less expensive from a computational standpoint as well as more convenient for calculating precursory quantitative information.

Predicting Monomers for Use in Polymerization‐Induced Self‐Assembly

“…[13] Although it has only recently adapted for polymer science,the versatility of LogP oct values has facilitated assessment of condensation polymerizations, [14] UV-cured films, [15] postpolymerization modifications, [16] polymer electrolytes, [17] and crystallization-driven self-assembly (CDSA). Forseveral decades,this metric has served as akey predictor of drug solubility for the pharmaceutical industry.…”

“…Forseveral decades,this metric has served as akey predictor of drug solubility for the pharmaceutical industry. [13] Although it has only recently adapted for polymer science,the versatility of LogP oct values has facilitated assessment of condensation polymerizations, [14] UV-cured films, [15] postpolymerization modifications, [16] polymer electrolytes, [17] and crystallization-driven self-assembly (CDSA). [18] During initial efforts to switch the focus from small, drug-like molecules to larger polymeric structures,n ormalizing LogP oct values with surface area (SA) minimized end-group effects and molecular weight differences.…”

Functionalization of polyesters with multiple B vitamins

“…To predict solubility, computational octanol–water partition coefficients (LogP oct ) were calculated (Supporting Information Fig. S7) and normalized with surface area . LogP oct values provide an accurate assessment of polarity and indicate hydrophobic (positive LogP oct ) or hydrophilic (negative LogP oct ) molecules and polymers .…”

“…Through a combination of moderate heat and mild acidic conditions, Fischer esterification converts OH and COOH groups to an ester and a water molecule . This equilibrium process also benefits from reduced pressure, azeotropic distillation, or high surface area films to facilitate removal of water. In the case of citric acid (CA), the acidity of CA negates the need for catalysts, such as para ‐toluenesulfonic acid .…”

Predicting Monomers for Use in Polymerization‐Induced Self‐Assembly

“…For several decades, this metric has served as a key predictor of drug solubility for the pharmaceutical industry . Although it has only recently adapted for polymer science, the versatility of Log P oct values has facilitated assessment of condensation polymerizations, UV‐cured films, post‐polymerization modifications, polymer electrolytes, and crystallization‐driven self‐assembly (CDSA) . During initial efforts to switch the focus from small, drug‐like molecules to larger polymeric structures, normalizing Log P oct values with surface area (SA) minimized end‐group effects and molecular weight differences …”