Plant-Based Nonactivated Olefins: A New Class of Renewable Monomers for Controlled Radical Polymerization

Abstract

In light of fossil fuel depletion and a general necessity for sustainable development, the synthesis of polymers from renewable resources is gaining more and more importance, yet industrially relevant radical polymerizations still struggle with the incorporation of renewable resources as the number of natural molecules containing suitable double bonds is limited. Herein, we present the sustainable synthesis of nonactivated allylic and olefinic carbonate monomers from renewable resources in a solventless one-pot transesterification reaction. We subsequently confirm the first controlled radical copolymerization of such challenging nonactivated monomers with vinyl acetate, in which molecular weights above 10 000 g·mol–1 were reached. The controlled nature of the copolymerizations was verified by the low dispersities obtained and the linear increase in molecular weights with conversion. The so-prepared copolymers were purified using sustainable extractions by supercritical carbon dioxide (scCO2), which allowed recovery of up to 58% of unused monomer. Using FT-IR and NMR spectroscopy, the incorporation of the renewable monomers into the copolymer in up to 49 mol % was confirmed, which is the highest reported to date. The combination of a sustainable double bond functionalization pathway with controlled radical polymerizations highlights the potential of radical polymerizations in the quest for renewable polymers and introduces a new set of monomers for this technique.

Organic–inorganic hybrid coating materials derived from renewable soybean oil and amino silanes

“…In recent years, the use of renewable resources to replace petroleum as a raw material in the preparation of coating materials has received considerable attention because of the demands placed on fossil feedstocks and environmental issues. [1][2][3][4] Vegetable oils, as renewable resources, have unique chemical structures containing hydroxyls, esters, unsaturated sites, and other functional groups, and these can be modied to make low molecular weight polymeric materials for a range of versatile applications. [5][6][7][8][9] Acetoacetyl chemistry is interesting to use to prepare thermoset resins because acetoacetate functional groups can react with various groups, [10][11][12][13] including aldehydes, 14 isocyanates, 15 acrylates, 16 and amines.…”

“…Fig. S2 †) 1. H NMR (CDCl 3 , 400 MHz): d (ppm) ¼ 5.25 (s, 1H), 4.46-4.29 (m, 10H), 4.29-4.08 (m, 4H), 3.53-3.42 (m, 10H), 3.02-2.88 (m, 10H), 2.83-2.52 (m, 11H), 2.37-2.19 (m, 15H), 1.79-1.45 (m, 13H), 1.45-1.05 (m, 54H), 0.94-0.78 (m, 9H…”

Hybrid polyhydroxyurethanes: How to overcome limitations and reach cutting edge properties?

“…Synthesis of prepolymers with dangling cyclic carbonate groups via radical polymerization [129][130][131] The team of Detrembleur also performed the synthesis of several allyl-and vinyl-cyclic carbonate monomers as well as their polymerization either by cobalt-mediated radical polymerization or free and controlled radical polymerizations. [132,133] NIPUs from the reaction of acrylic cyclic carbonates and amines were also prepared by Figovsky et al. They evaluated the UV-stability of these coatings over time.…”

Einblick: Polymere und Nachhaltigkeit

“…4) Katalysatoren werden in ihrer Aktivität geschaltet wie in der Natur Enzyme. 5) Eine besondere aktuelle Einsatz-möglichkeit der intelligenten Polymere ist der 4-D-Druck.…”