Renewable Poly(Thioether‐Ester)s from Fatty Acid Derivatives via Thiol‐Ene Photopolymerization

Abstract

Partially bio-based poly(thioether-ester)s were obtained in high conversion from thiol-ene photopolymerization of fatty dienes with dithiols utilizing mild, solventless reaction conditions. Fatty dienes were synthesized by esterification of 9-decenoic acid, a terminally unsaturated medium-chain fatty acid that can be obtained from ethenolysis of oleic acid, with ethylene glycol and 9-decen-1-ol to yield bio-based dienoic monomers amenable to subsequent thiol-ene polymerization. Polycondensation with 1,2-ethanedithiol (EDT) and 1,3-propanedithiol (PDT) gave a series of semicrystalline poly(thioether-ester) s with degrees of polymerization that ranged from 29 to 85, polydispersity indices between 2.81 and 4.38, and glass transitions from −36.8 to −25.7 C. The polymers were elastic at room temperature, with EDT-linked materials exhibiting greater elasticity than the corresponding PDTlinked polymers. All polymers were thermally stable below 320 C, with 10% mass loss (T 10 ) occurring above 338 C. Enthalpies of fusion increased with higher relative crystallinity and were greater than the corresponding enthalpies of crystallization. The polymers were soluble in nonpolar solvents such as chloroform and THF but resisted dissolution in more polar solvents with dielectric constants above 10. Furthermore, the polymers were susceptible to acidic hydrolysis but resisted basic hydrolysis at room temperature. J Am Oil Chem Soc (2019) 96: 825-837 826 J Am Oil Chem Soc J Am Oil Chem Soc (2019) 96: 825-837 a RCC = renewable carbon content = (renewable carbons) / (total carbons) in repeat unit (see Scheme 1). b Ð = polydispersity index = M w /M n . c DP = average degree of polymerization = M n /repeat unit MW. d Values in parentheses represent standard deviation from the reported mean (n = 3). 828 J Am Oil Chem Soc J Am Oil Chem Soc (2019) 96: 825-837

Renewable Aliphatic Polyesters from Fatty Dienes by Acyclic Diene Metathesis Polycondensation

“…Lastly, it is likely that 4 – 6 were semicrystalline in nature since both T c and T g were observed. Further evidence supporting the claim of semicrystallinity was the opaque appearance of 4 – 6 , which was attributed to the differing refractive indices of the crystalline and amorphous domains contained within the polymers (Moser et al, ).…”

“…Monomers 1 – 3 were prepared (Fig. ) via p TsOH‐catalyzed esterification of 9DA with a stoichiometric excess of alcohol in refluxing toluene (Moser, ; Moser et al, ). Elimination of water using a Dean‐Stark apparatus facilitated high conversion (≥94% after 16 hours).…”

“…Other examples are limited to polyolefins derived from copolymerization of 9DA with ethene and propene as well as polymerization of cyclic 9DA‐derived amides to give polyamides (Kaminsky and Fernandez, ; Mudiyanselage et al, ). In another example, linear, aliphatic poly(thioether‐ester)s were prepared via thiol‐ene polymerization of α,ω‐dienes derived from 9DA (Moser et al, ). Lastly, diesters arising from esterification of both 9DA and UDA with various alcohols were reduced to α,ω‐diethers, which were in turn polymerized to the corresponding polyethers by both ADMET and thiol‐ene methodologies (Dannecker et al, ).…”

Production of Industrially Useful and Renewable p‐Cymene by Catalytic Dehydration and Isomerization of Perillyl Alcohol

“…As part of our continuing efforts to produce aliphatic polyesters from renewable starting materials (Moser et al, 2019, 2020), we were originally attempting to esterify 9‐decenoic acid with 4 in the presence of catalytic p TsOH in refluxing toluene to give the corresponding tris ‐unsaturated perillyl decenoate as a monomer for subsequent acyclic diene metathesis polymerization and thiol‐ene photochemical polycondensation. The esterification procedure had proven simple and effective for several previous condensations involving different alcohol/acid combinations (Moser, 2014; Moser et al, 2019, 2020), but in this case the expected ester was not observed. Instead, a mixture comprised of 4 , unreacted 9‐decenoic acid, and a curiously high amount of 1 (31%) was noted.…”

High strength, acid‐resistant composites from canola, sunflower, or linseed oils: Influence of triglyceride unsaturation on material properties

“…14,21,22 23,24 Similar reactivity of triglyceride derivatives with sulfur radicals has also been reported by the thiol-ene reaction. [25][26][27][28][29][30][31][32][33] Triglyceride-sulfur materials prepared by inverse vulcanization have proven highly effective as adsorbents for water purification, as cathode materials in Li-S batteries, 34 and as fertilizers. Less work has been done to elucidate the mechanical strength and chemical resilience of triglyceride-sulfur composites, though significant progress on elucidating monomer composition-mechanical property relationships has been made for high sulfur-content materials in general.…”