Fatty Acids and their Derivatives as Renewable Platform Molecules for the Chemical Industry

Abstract

Oils and fats of vegetable and animal origin remain an important renewable feedstock for the chemical industry. Their industrial use has increased during the last 10 years from 31 to 51 million tonnes annually. Remarkable achievements made in the field of oleochemistry in this timeframe are summarized herein, including the reduction of fatty esters to ethers, the selective oxidation and oxidative cleavage of C–C double bonds, the synthesis of alkyl‐branched fatty compounds, the isomerizing hydroformylation and alkoxycarbonylation, and olefin metathesis. The use of oleochemicals for the synthesis of a great variety of polymeric materials has increased tremendously, too. In addition to lipases and phospholipases, other enzymes have found their way into biocatalytic oleochemistry. Important achievements have also generated new oil qualities in existing crop plants or by using microorganisms optimized by metabolic engineering.

Bimolecular Coupling in Olefin Metathesis: Correlating Structure and Decomposition for Leading and Emerging Ruthenium−Carbene Catalysts

“…7 Of major importance, therefore, is the breakthrough performance of cyclic (alkyl)(amino) carbene derivatives (CAAC; Chart 1 ). 8 The CAAC catalysts show unprecedented productivity in the transformation of renewable fatty acids into α-olefins by cross-metathesis with ethylene (“ethenolysis”), 9 − 12 as first reported by Bertrand and Grubbs in 2015, 10 and in macrocyclization via ring-closing metathesis 11 − 13 (mRCM). The latter process is of highly topical interest for the production of antiviral drugs.…”

The Prospering of Macromolecular Materials Based on Plant Oils within the Blooming Field of Polymers from Renewable Resources

“…The large number of naturally available oils and the wide array of possible chemical modifications that can be performed are therefore the keys that allow researchers to continuously achieve a myriad of fascinating molecular structures based on triglycerides. In fact, oils and fats of vegetable and animal origin make up the greatest proportion of the consumption of renewable raw materials in the chemical industry [23,30]. A widely accepted notion asserts that the fossil-based chemical industry is perfectly consolidated-in terms of technology, investments, and profits-to provide the commodities, fine chemicals, and specialties on which our modern society stands [31].…”

“…In industrial processing, vegetable oils are converted to glycerol plus fatty acids, methyl esters, and fatty alcohols, and subsequent chemical modification steps are often conducted in order to obtain the specific chemicals of interest. Those reactions mainly consist of tackling the unsaturated bonds, as in the case of epoxidation, hydroformylation, dimerization, thiol-ene coupling, oxidative cleavage (ozonolysis), olefin metathesis, pericyclic reactions, and radical additions, as well as transition-metal catalyzed and Diels-Alder syntheses to aromatic compounds [6,23,32]. Among the chemicals of interest, one finds non-exhaustively, soaps, surfactants, emollients, pesticide formulations, and lubricants [23,[31][32][33][34][35][36].…”

“…Those reactions mainly consist of tackling the unsaturated bonds, as in the case of epoxidation, hydroformylation, dimerization, thiol-ene coupling, oxidative cleavage (ozonolysis), olefin metathesis, pericyclic reactions, and radical additions, as well as transition-metal catalyzed and Diels-Alder syntheses to aromatic compounds [6,23,32]. Among the chemicals of interest, one finds non-exhaustively, soaps, surfactants, emollients, pesticide formulations, and lubricants [23,[31][32][33][34][35][36]. Rios and coworkers described the synthesis of new lubricant molecules from castor oil by conducting an initial step of esterification of ricinoleic acid with 2-ethylhexanol, followed by epoxidation and ring-opening of the oxirane rings [37].…”

“…A further section is dedicated to the most recent contributions related to composites made of vegetable oil-based continuous phases, which was addressed a few years ago in the monograph published by Zhang et al [22] Finally, the specific use of tung oil and its main fatty acid as a source of original polymers, copolymers, and nanocomposites is discussed in greater detail in terms of mechanisms, structures, properties, and possible applications. It is important to mention here a very recent contribution by Biermann and collaborators [23], reviewing the use of fatty acids and their derivatives as a source of low molecular weight products, such as fatty alcohols, ethers, amines, among others, and polymers. The authors carefully presented the synthetic routes involved in the preparation of fatty acid-based commodities, including a final section on enzymatic and microbial transformations.…”