Polyethylene-like materials from plant oils

Abstract

<jats:p> Polyethylene (PE) is the most important synthetic polymer material produced. Its excellent material properties arise from crystalline interactions in its hydrocarbon chains. This simple concept inspires studies of materials based on alternative non-fossil feedstocks and with additional traits such as a non-persistent nature. Renewable seed oil or microalgae oil lipids can serve as a feedstock for long-chain difunctional monomers. Catalytic conversion of their unsaturated fatty acids by e.g. isomerizing carbonylation or olefin metathesis yields long-chain monomers X-(CH <jats:sub>2</jats:sub> ) <jats:sub>n</jats:sub> -X with 18–26 carbon atoms and terminal dicarboxy, diol or diamine groups (X), and ultralong-chain PE telechelics with 48 carbon atoms. These can be polymerized to polyesters, polycarbonates and other (ultra)long-chain polycondensates. These in many cases possess PE-like solid-state structure and properties. Unlike PE, they contain in-chain functional groups that can potentially enhance degradability. The crystalline and hydrophobic nature of the polymers decelerates degradation strongly compared to rapidly degrading shorter chain analogues. Our preliminary findings suggest that a non-persistent nature can be achieved for these materials. This review article is based on a lecture held at the Royal Society Discussion Meeting on Science to enable the circular economy. </jats:p> <jats:p>This article is part of a discussion meeting issue ‘Science to enable the circular economy’.</jats:p>

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

“…An important advance is the development of long‐chain polyesters from such starting materials that can mimic important properties of polyethylene, while offering degradability. [ 129 , 130 ] Remarkably, polyesters 19,19 and 23,23 were prepared on 100 g scale; the necessary dimethyl‐1,19‐nonadecanedioate monomer was directly prepared from technical‐grade high oleic sunflower oil. Such polyesters offer suitable mechanical properties (elongation at break >600 %; Young's modulus of 400 MPa) for non‐wovens or extruded transparent films.…”

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

“…The catalytic conversion of unsaturated fatty acids by isomerizing carbonylation or olefin metathesis yields (ultra)long-chain AB-type monomers bearing terminal dicarboxyl, diol, or diamine groups [ 84 ]. These vegetable oil-based monomers can be polymerized to polyesters, polycarbonates, and other (ultra)long-chain polycondensates, corresponding to polyethylene-like materials with an additional non-persistent feature.…”

“…The unsaturated pendant groups allowed the conduction of a further step of post-polymerization crosslink-ing [82], as well as post-polymerization chemical modifications, such as bromination, epoxidation, and cross-metathesis [83]. The catalytic conversion of unsaturated fatty acids by isomerizing carbonylation or olefin metathesis yields (ultra)long-chain AB-type monomers bearing terminal dicarboxyl, diol, or diamine groups [84]. These vegetable oil-based monomers can be polymerized to polyesters, polycarbonates, and other (ultra)long-chain polycondensates, corresponding to polyethylene-like materials with an additional non-persistent feature.…”

Fettsäuren und Fettsäurederivate als nachwachsende Plattformmoleküle für die chemische Industrie

“…[128] Ein bedeutender Fortschritt ist die Entwicklung von langkettigen Polyestern, deren Eigenschaften denen des Po-lyethylens ähneln, die gleichzeitig aber (biologisch) abbaubar sind. [129,130] Bemerkenswerterweise lassen sich die Polyester 19,19 und 23,23 schon in 100-g-Maßstäben herstellen, wobei sich das dafür notwendige 1,19-Nonadecandisäuredimethylester-Monomer direkt aus technischem Sonnenblumençl mit hohem Ölsäuregehalt herstellen lässt. Solche Polyester weisen die notwendigen mechanischen Eigenschaften (Dehnung bei Bruch > 600 %; Youngs Modul von 400 MPa) für Vliesstoffe oder fließgepresste Filme auf.…”