The invention provides polyester polyol compositions and resin blends, useful as components of polyurethane and polyisocyanurate polymers, produced from cyclohexane oxidation reaction byproducts, such as water extracts and non-volatile distillation residues from the reaction. Such byproducts of industrial processes for preparation of adipic acid and caprolactam, important intermediates in the production of various types of nylon, have hitherto largely been used only as fuels. The present invention provides value-added products, methods for making, and methods for using the byproduct-derived polyester polyol compositions. For example, the invention provides polyurethane (PU) and/or polyisocyanurate (PIR) polymers made using the polyol compositions and polyfunctional isocyanates. The PU and PIR polymers can be used as adhesives, binders (e.g., for wood fibers), coatings (e.g., for controlled release fertilizers), and foams.