Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources

Abstract

Oligomeric polyether polyols were obtained through the acid‐catalyzed ring‐opening polymerization of epoxidized methyl oleate and the subsequent partial reduction of ester groups to give primary alcohols. The oligomers were characterized with titration, spectroscopic techniques (Fourier transform infrared and nuclear magnetic resonance), matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, size exclusion chromatography, and differential scanning calorimetry. Depending on the degree of reduction, polyols of different hydroxyl content values were obtained and were reacted with 4,4′‐methylenebis(phenyl isocyanate) to yield polyurethanes. These materials, which were characterized by differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis, could behave as hard rubbers or rigid plastics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 634–645, 2006

Oleic and Undecylenic Acids as Renewable Feedstocks in the Synthesis of Polyols and Polyurethanes

“…Low molecular weight polyols (up to 1,200 Da) were prepared from EMO through cationic polymerization in the presence of 0.5%wt. HSbF 6 at room temperature and the further partial reduction of the carboxylate groups to hydroxyl moieties using lithium aluminum hydride as a reducing agent [41]. The catalyst was completely soluble in EMO at room temperature, and the oligomerization was performed homogeneously in the absence of solvent, making it an advantageous process from an environmental viewpoint.…”

“…A series of segmented and non-segmented crosslinked PUs were synthesized from the above mentioned polyols using MDI or L-lysine diisocyanate (LDI) as coupling agents and 1,3-propanediol as a chain extender [41,43]. Segmented PUs are elastomeric block copolymers that generally exhibit a phase-segregated morphology made up of soft rubbery segments and hard glassy or semicrystalline segments.…”

Synthesis and Characterization of Polyurethanes Made from Copolymers of Epoxidized Natural Oil and Tetrahydrofuran

“…Not many literature have appeared on making oligomeric/polymeric polyols from natural oil and its derivatives. One of the examples is the work done by Lligadas et al 8 ,…”

Copolymers of tetrahydrofuran and epoxidized vegetable oils: application to elastomeric polyurethanes

“…33 Polyol formation by ring-opening polymerization of epoxidised methyloleate (EMO) and epoxidized soybean oil (ESO) have been studied using HSbF 6 50 and BF 3 .OEt 2 in dichloromethane respectively. 34,35 Polyether polyols derived from ESO exhibited thermally stable (>340 ˚C) highly cross-linked structures with glass transition temperatures between -16 and -48 ˚C. 35 After hydrolysis these cross-linked structures could be converted into hydrogels.…”

“…35 After hydrolysis these cross-linked structures could be converted into hydrogels. Polyols (900-1200 55 g/mol) derived from HSbF 6 mediated ring-opening of EMO were reacted with 4,4'-methylene diphenyldiisocyanate (MDI) to make hard polyurethane rubbers, 34 while reaction with larger polyols (~7000 g/mol) furnished more flexible materials. or PO is the higher yield of polymers achievable (85-90%) compared to homopolymerization alone.…”