Biopolymers from Vegetable Oils via Catalyst- and Solvent-Free “Click” Chemistry: Effects of Cross-Linking Density

Abstract

New monomers were prepared by introducing the azide groups in castor, canola, corn, soybean, and linseed oils. Polymerization of the azidated oils with alkynated soybean oil under thermal "click" chemistry conditions (without using a solvent or a catalyst) yielded fully cross-linked elastomers (1-5) of almost the same density (1.05 × 10(-3) kg/m(3)). The degree of cross-linking gradually increased from the castor-derived polymer (220 mol/m(3)) to the linseed-derived polymer (683 mol/m(3)). A systematic correlation between the degree of cross-linking and the thermal and mechanical properties was observed in these biopolymers. Tensile strength (0.62-3.39 MPa) and glass transition temperature (-5 to 16 °C) increased and the linear thermal expansion coefficient decreased in the series from the canola-derived polymer (2) to the linseed-derived polymer (5). The castor-derived polymer (1) that possesses an additional hydroxyl group per fatty acid chain behaved differently.

Effects of different epoxidation methods of soybean oil on the characteristics of acrylated epoxidized soybean oil-co-poly(methyl methacrylate) copolymer

“…According to Hazer and coworkers [26][27][28][29][30][31][32][33], vegetable oils were autooxidized by exposure to sunlight or daylight in air for a given time to produce epoxides, peroxides, peroxides, and hydroperoxides in the molecular chains and were also graft copolymerized by free radical polymerization with other materials such as methyl methacrylate and styrene. Recently, the vegetable oil-based polymers have been prepared by cationic, olefin metathesis and condensation polymerization reactions, including the use of 'click' chemistry and carbon dioxide [5,[34][35][36][37]. Acrylation of epoxidized vegetable oils is one of the interesting techniques for preparing the vegetable oil-based polymers.…”

Biorefineries – factories of the future

“…Due to economic reasons in 2004 Metabolix began to produce PHB also from plants (Jacquel et al, 2008). Soybean and linseed oils were used as substrates for monomers to produce elastomers (Hong et al, 2012) and ethylene from bioethanol (KBBE Report, 2010). In the United States, $ 310 billion was spend on bioplastics in 2002.…”

Monomers and polymers from plant oils via click chemistry reactions

“…Alternatively, Shah and coworkers reported that alkynated plant oils are also accessible from the corresponding epoxidized derivatives taking advantage of the HIGHLIGHT propensity of the epoxy rings to undergo ring-opening nucleophilic addition. 81,82 A real challenge for the near future is definitively to develop new methods (e.g., catalytic dehydrogenation of alkenes) to directly transform fatty acids into alkyne derivatives under sustainability criteria.…”