Among various biomass‐based components, both lignin and glycerol are important, since they are abundantly produced as by‐products in industrial processes. Accordingly, in the present study, new types of crosslinked epoxy resins were synthesized from lignin and glycerol. Polymers derived from two types of lignin‐based crosslinked epoxy resins were prepared through two‐step reactions, ester‐carboxylic acid derivative preparation followed by crosslinked epoxy resin preparation, in order to establish a crosslinked epoxy resin system in which glycerol units were included. The resins obtained were labeled as follows: series 1, lignosulfonate‐glycerol polyacid (Ser1LSGLYPA); and series 2, glycerol diglycidyl ether (Ser2GLYDGE). The functional groups of the resins were analyzed using Fourier transform infrared spectrometry. The thermal properties of the resins were analyzed using differential scanning calorimetry and thermogravimetry. The glass transition temperature of the crosslinked epoxy resins increased with increasing LSGLYPA and GLYDGE contents for Ser1LSGLYPA and Ser2GLYDGE, respectively. The thermal degradation temperature for Ser1LSGLYPA and Ser2GLYDGE did not show significant change, suggesting that the crosslinked epoxy resins were thermally stable. The mass residue at 500 °C was not affected by the changes of LSGLYPA and GLYDGE contents. Copyright © 2009 Society of Chemical Industry

Commercial availability of fatty acid methyl ester (FAME) from palm oil targeted for biodiesel offers a good feedstock for the production of structurally well‐defined polyols for polyurethane applications. The effect of molecular weight (MW), odd and even carbon numbers, and the linear and branched structure reactants used in the ring‐opening reaction of epoxidized fatty acid methyl ester (E‐FAME) on the properties of polyols was investigated. Conversions of E‐FAME to PolyFAME polyols were confirmed by Fourier transform infrared analysis, oxirane oxygen content, and hydroxyl number. Gel permeation chromatography (GPC) calibrated against polyether polyols as a standard and vapor pressure osmometry were used for MW determination. GPC chromatograms of PolyFAME polyols clearly demonstrated the formation of oligomers during ring‐opening reactions. MW, and odd and even carbon numbers in a structure of linear diols and branched diol used in the syntheses of PolyFAME polyols did not have an effect on crystallinity, glass transition, or melt temperatures measured using Differential scanning calorimetry (DSC). PolyFAME polyols ring‐opened with water, methanol, and 1,2‐propanediol contained secondary hydroxyl groups, whereas PolyFAME polyols ring‐opened with linear diols contained a mixture of primary and secondary hydroxyl groups. It was found that the concentration of primary hydroxyl groups increased significantly by increasing the number of carbons from C2 to C3 in the linear diols. The viscosity of PolyFAME polyols also increased with the MW of linear diols used in the E‐FAME ring‐opening reaction. These findings would be beneficial for formulators in choosing the most cost effective polyols for polyurethane formulations.

Model palm olein natural oil polyols (NOPs) with varying ratios of primary to secondary hydroxyls were synthesized, characterized, and evaluated in reaction kinetics study with isocyanate in formation of polyurethanes. Reaction rate constants and activation energies associated with primary and secondary hydroxyls of NOPs were quantified. The kinetic study in toluene shows that the NOP containing primary hydroxyls have three times higher reaction rate constants in noncatalyzed reaction with 4,4′‐diphenylmethane diisocyanate (4,4′‐MDI) compared to the model NOP containing only secondary hydroxyls, which is associated with higher activation energy of secondary hydroxyls. However, the difference in reaction rate constants of primary and secondary hydroxyls in NOPs diminished in the reactions catalyzed with dibutyltin dilaurate. Bulk polymerization reaction confirms the kinetics results in toluene, showing that the model NOP containing primary hydroxyls reached gel time at a faster rate. Evaluation of elastomers from bulk polymerization shows low degree of phase separation of hard and soft segments for elastomers based on the model NOPs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42955.

Polyester polyols from renewable resources have gained significant interest in the field of polyurethane chemistry. Two sets of segmented TPUs were prepared from crystalline and amorphous azelate polyols, 4,4′‐methylenebis(phenyl isocyanate), and 1,4‐butanediol as a chain extender at a mole ratio of 1:2:1, respectively. Bio‐1,3‐propanediol (1,3‐PDO) and 1,5‐pentanediol (PTDO) were used to prepare crystalline azelate polyols, while 1,2‐propanediol (1,2‐PDO) and 2,2′‐dimethyl‐1,3‐propanediol (NPG) were used to prepare amorphous azelate polyols. All TPUs displayed clear glass transition temperatures (T gs) in between −36 and − 24 °C, associated with azelate polyols soft segments, which are decreasing with increasing diols chain lengths in azelate polyols. TPUs based on crystalline azelate polyols exhibited higher mechanical properties and better heat resistance in comparison to their counter parts. Besides, TPU based on 1,3‐PDO azelate showed lower percentage of hysteresis indicating lower heat build‐up. This is essentially good for TPUs that are to be used in dynamic applications such as rollers and wheels. Hence, the study on structure–property correlation of the crystalline and amorphous azelate polyols and their effect on TPUs properties suggest that crystalline azelate polyols are suitable for dynamic application of TPU, and amorphous azelate polyols are suitable for coatings and adhesives applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47890.