Synthesis of Bio-Based Aliphatic Polyesters from Plant Oils by Efficient Molecular Catalysis: A Selected Survey from Recent Reports

Abstract

Recent development in efficient synthesis of (unsaturated) 1,ω-fatty acid diesters (and the diols), which can be used as monomers for synthesis of long chain aliphatic polyesters, especially by Pd-catalyzed isomerization alkoxycarbonylation, Ru-catalyzed olefin metathesis (self-metathesis and cross metathesis), and the tandem olefin metathesis and the ester hydrogenation from plant oils (unsaturated fatty acid esters such as methyl oleate, methyl linoleate, etc.) have been summarized. Recent development for synthesis of (semicrystalline) long chain aliphatic polyesters by polycondensation of 1,ω-dicarboxylic acids and the diols, dehydrogenation polycondensation of the diols or carbonylation polycondensation of the ω-alken-1-ol, and acyclic diene metathesis (ADMET) polymerization of nonconjugated 1,ωdiene (and the tandem ADMET polymerization and hydrogenation system for synthesis of saturated polyester) have also been reviewed. Depolymerization of these long chain aliphatic polyesters was also demonstrated (by olefin metathesis, treatment with alcohols, etc.). Catalyst development for these reactions (more active, under mild conditions) plays a key role in efficient synthesis.

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

“…One can mention, for instance, many possible routes to convert fatty-acid-based monomers into polyolefins with the most diverse pendant groups along the polymer chain via radical polymerization [ 99 ]. Nomura and Awang reviewed the many contributions available based on the synthesis of 1,ω-fatty acid diesters and diols, which can be used as monomers for the synthesis of long-chain aliphatic polyesters by numerous routes [ 100 ]. A facile route for semi-aromatic polyamides from dimethyl 9-octadecenedioate and p -xylylenediamine or diethylenetriamine was reported, leading to materials with good thermal and mechanical properties [ 101 ].…”

Ethylene/Myrcene Copolymers as New Bio-Based Elastomers Prepared by Coordination Polymerization Using Titanium Catalysts

“…The development of sustainable polymers from bio-renewable feedstocks − has been an important subject not only in polymer chemistry but also in catalysis and synthetic chemistry. − It has been considered that the precision polymerization technique plays a key role for the purpose, − and many studies have thus been reported concerning the so-called bio-based (aliphatic) polyesters prepared from renewable resources (plant oils etc. ). − Monoterpenes, consisting of two isoprene units, are promising renewable monomers − due to their natural abundance and reactive conjugated 1,3-diene framework (like isoprene). Indeed, β-myrcene (myrcene) can be polymerized via radical, − anionic, , or coordination (catalytic) polymerization, − and especially there have been reports for copolymerization with styrene on the relevance of styrene-butadiene (SBR) or styrene-isoprene rubbers .…”

Enzymatic recycling of polymacrolactones

“…1 Some of them are also biobased which is an added value for in the near future fossil fuel resources may become exhausted. 2–4 Within these biobased polymers are polymacrolactones or polymacrolides (PMLs). They are polyesters with similar properties to polyethylene, and are usually obtained by ring opening polymerization (ROP) of large ring size lactones which contain 12 or more atoms in the ring and are called macrolactones (MLs).…”