Aliphatic Long‐Chain C₂₀ Polyesters from Olefin Metathesis

Abstract

Self-metathesis of undecenoic acid with [(PCy3)2Cl2Ru=CHPh] (2), followed by exhaustive hydrogenation yielded pure 1,20-eicosanedioic acid (5) (>99%) free of side-products from isomerization. Polycondensation with eicosane-1,20-diol (6), formed by reduction of the diol, yielded polyester 20,20 (Tm = 108 °C). By comparison, the known ADMET polymerization of undec-10-enyl undec-10-enoate (7), and subsequent exhaustive polymer-analogous hydrogenation yielded a polyester (poly-8) with irregular structure of the ester groups in the polymer chain (-O(C=O)- vs. -C(=O)O-) (Tm = 103 °C). Hydrogenation of secondary dispersions of poly-7 yielded aqueous dispersions of the long-chain aliphatic polyester poly-8.

Plant Oil‐Based Long‐Chain C26 Monomers and Their Polymers

“…The melting temperature of PE 12,12 was consistent with the values obtained by Barbiroli et al41 and was lower than the T m values of polyesters PE 26,26 and PE 12,26 . In all instances, the melting temperatures are compatible with those observed for other long‐chain aliphatic polyesters16, 17, 25, 42 and comparable to T m values of low‐density polyethylene. For example, the melting temperature of PE 26,26 is lower than the T m value of the polyester PE 30,30 prepared by Cho and Lee42 and higher than the T m of polyesters PE 19,19 and PE 23,23 obtained by Mecking16 and his team.…”

“…Recent contributions in this field include, for instance, the study of Petrović et al15 on high‐molecular‐weight linear polyesters from the methyl ester of 9‐hydroxynonanoic acid prepared by ozonolysis of castor oil and methanolysis of triglycerides. Moreover, Mecking and co‐workers16, 17 have investigated aliphatic long‐chain C 19 and C 23 monomers generated via carbonylation of methyl oleate and ethyl erucate, respectively, and C 20 monomers prepared via self‐metathesis of undecenoic acid and its derivatives.…”

Accessing Monomers, Surfactants, and the Queen Bee Substance by Acrylate Cross‐Metathesis of Long‐Chain Alkenones

“…From the profile presented in Table 1, we could predict what were to be the major products from this reaction. For instance, cross-metathesis with methyl acrylate was expected to produce the diester undeca-2,9-dienedioate (1) as the major single compound (37.8%, Table 2), representing a suitable monomer with which to access polymers like polyesters (for an example of biobased long-chain polyester synthesis, see [37]) and polyamides [23]. Approximately 7% was predicted be the (1) U K ′ 37 = C 37:2 (C 37:2 + C 37:3 ) U K ′ 37 = 0.033T • C + 0.044 Scheme 2 Cross-metathesis of major isolated Isochrysis alkenones with methyl acrylate methyl ester of the so-called queen substance of the honey bee, methyl 9-oxodec-2-enoate (methyl ODA, 2), derived from the methyl 37:3 alkenone and of value for agricultural purposes [27].…”

Synthesis of Bio-Based Poly(lactic acid-co-10-hydroxy decanoate) Copolymers with High Thermal Stability and Ductility

“…Miller et al [13] developed several thermoplastic materials, poly(alkylene 4-hydroxybenzoates), poly(alkylene vanillates) and poly(alkylene syringates), with good thermal properties, the monomers of which are derived from lignin. Mecking's group selected isomerized alkoxycarbonylation of fatty acids with long-chain linear monomers containing a C19-C23 alkyl chain length to prepare fully renewable polyester by polycondensation [14]. Barrett and his members had prepared several photocurable polyesters based on different polyols and itaconic acids from photoactive renewable monomers [15].…”