One‐Pot Catalytic Copolymerization of Unsaturated Plant Oils or Fatty Acid Methyl Esters with Ethylene

Abstract

Until now natural fatty acid esters with their internal CC‐bonds cannot be used as substrates for catalytic polymerization reactions. It is always necessary to convert them to terminal unsaturated fatty acid esters first. Therefore, we now developed a two‐catalyst system consisting of an isomerization catalyst and a Brookhart polymerization catalyst. With this system of isomerizing copolymerization (IsoCoP) it is possible to copolymerize high oleic plant oils or fatty acid methyl esters with ethylene in a one‐pot reaction. The resulting polymers have molecular weights above 30 kDa and can contain more than 20 weight percent plant oils. The copolymers of fatty acid methyl esters are soluble in organic solvents. The predominant part of the copolymers from plant oils is usually soluble. The insoluble fraction is soluble after hydrolysis indicating a rare cross‐linking of polyolefin chains by triglycerol units. The catalytic system is effective yielding polymers with a productivity of up to 100 kg polymer per mole catalyst and pretty robust. Plants oils need to be purified only by a simple filtration over alumina before copolymerization. Practical Application: The possibility to copolymerize plant oils with ethylene leads to a new class of polymers and may enhance the usage of plant oils for plastics greatly. The new polymers might be used, e.g., for tackifiers or primers. High oleic plant oils as well as unsaturated fatty acid methyl esters can be directly copolymerized with ethylene by a combination of an isomerization catalyst with a Brookhart polymerization catalyst.

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

“…Finally worth mentioning is a one‐pot catalytic copolymerization of 2 b or plant oils with ethylene using an isomerization catalyst and a Brookhart polymerization catalyst at the same time. [176] …”

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

“…Another recent contribution is related to the preparation of ABA triblock copolyolefins from lauryl acrylate and triacetic acid lactone, leading to materials that are suitable for high-performance pressure-sensitive adhesives [ 80 ]. Isomerizing copolymerization was used to copolymerize high-oleic oils or fatty acid methyl esters with ethylene in a one-pot reaction [ 81 ]. The isolated polyolefins had Mn values higher than 30 kDa, comprising more than 20 wt.% of plant oils.…”

Fettsäuren und Fettsäurederivate als nachwachsende Plattformmoleküle für die chemische Industrie

“…Zum Abschluss dieses Abschnitts ist auch noch die katalytische Eintopf-Copolymerisation von 2 b oder Pflanzençlen mit Ethen unter der gleichzeitiger Benutzung eines isomerisierenden Katalysators und eines Brookhart-Polymerisationskatalysators erwähnenswert. [176]…”

“…Weiterhin wurde eine nachhaltige Aufreinigung über überkritische CO 2 ‐Extraktion eingeführt, welche die Rückgewinnung von nicht umgesetztem 17 b ermöglicht. Zum Abschluss dieses Abschnitts ist auch noch die katalytische Eintopf‐Copolymerisation von 2 b oder Pflanzenölen mit Ethen unter der gleichzeitiger Benutzung eines isomerisierenden Katalysators und eines Brookhart‐Polymerisationskatalysators erwähnenswert [176] …”