Renewable Polymers from Itaconic Acid
Trotta, Jacob Thomas
Itaconic acid (IA) is a biorenewable compound that is generated inexpensively and in large amounts by the fermentation of biomass. While a variety of structurally diverse polymers have been accessed from IA, continued exploration of efficient syntheses and polymerizations of novel monomers could lead to the development of sustainable materials that can help reduce society’s dependence of petroleum (Chapter 1). We show that from β-monomethyl itaconate, an IA derivative, we can utilize a selective addition strategy that allows access to both α-methylene-γ-butyrolactone (MBL, tulipalin A) and α-methylene-γ,γ-dimethyl-γ-butyrolactone (Me2MBL), which serve as high value biorenewable analogues to petroleum-derived methyl methacrylate. Subsequent polymerization of both Me2MBL and MBL through reversible addition-fragmentation chain-transfer (RAFT) polymerization generates well defined poly(Me2MBL) (PMe2MBL) and poly(MBL) (PMBL) polymers. Through physiochemical characterization, we show that PMe2MBL has desirable properties comparable with known PMBL materials (Chapter 2). We then extend our strategy to produce triblock polymers using PMBL end blocks with an IA-derived polyester mid-block. Using catalytic, solvent-free, and high yielding transformations from an itaconate source, we efficiently synthesize a saturated diol, a saturated diester, and an unsaturated diester. Subsequent step-growth polycondensation polymerizations of these monomers leads to polyesters with relatively high molar masses (> 10 kg/mol). Chain-end functionalization and chain-extension of the saturated polyesters with MBL then provides access to an almost completely IA-derived triblock polymer thermoplastic. Alternatively, we show that thiol-ene cross-linking of unsaturated polyesters allows access to thermosets with tunable mechanical properties based on the cross-linking density. In most cases, high isolated yields, high atom economies, and low process mass intensities for these reactions reflect green and sustainable processes (Chapter 3). We then explore sustainable methods for the oxidation of MBL to its oxide, MBLO. Ring-opening polymerizations of MBLO to PMBLO is performed and gives access to a new, biorenewable, and amorphous polyether that exhibits a high glass transition temperature (106 °C). Comparisons with other common polyethers highlights the potential utility of this new material, and the polymerization of similar renewable epoxide monomers are studied (Chapter 4).
butyrolactone; itaconic acid; polyether; step-growth; thermoplastic; thermoset; Polymer chemistry
Fors, Brett P.
Collum, David B.; Coates, Geoffrey
Chemistry and Chemical Biology
Ph.D., Chemistry and Chemical Biology
Doctor of Philosophy
Attribution 4.0 International
dissertation or thesis
Except where otherwise noted, this item's license is described as Attribution 4.0 International