Synthesis of Linear Polyesters from Monomers Based on 1,18-(Z)-Octadec-9-enedioic Acid and Their Biodegradability

Abstract

A new family of bio-based linear polyesters from oleic acid was developed by a bulk polymerization process. First, efficient chemical pathways were selected to synthesize three monomer derivatives from 1,18-(Z)-octadec-9-enedioic acid, allowing the synthesis of four polyesters that differ by the number of double bonds along the polymer backbone. After the analysis of the structure of the polymers, their thermal properties and their biodegradability were investigated. It was shown that the melting temperature of the polyesters increased with the decrease in the unsaturation content in the repeat units of the polymers and they have very low glass-transition temperatures. A biodegradation process was also highlighted for poly­(1,18-(Z)-octadec-9-enylene 1,18-(Z)-octadec-9-enedioate) and poly­(1,18-octadecylene 1,18-octadecanedioate). Based on their thermal features, these biodegradable polyesters can represent an alternative of the synthetic polymers derived from petroleum hydrocarbons, such as low-density polyethylene.

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

“… On the basis of T m values in the resultant long chain aliphatic polyesters prepared by ADMET polymerization and subsequent (exhaustive) hydrogenation and polycondensation, , the effect of methylene length toward the thermal property was demonstrated; the value reached a constant value (Figure b) . Very recently, synthesis of linear polyesters based on 1,18-( Z )-octadec-9-enedioic acid, natural unsaturated fatty diacid presented in its esterified form, was reported by Roumanet et al In particular, poly­(1,18-octadecylene 1,18-octadecanedioate) prepared from 1,18-octadecanedioic acid and 1,18-octadecane diol possess high melting temperature ( T m = 100 °C), a possibility for these polyesters as an alternative of the petroleum-based synthetic polymers was suggested . A biodegradation process was also highlighted for the resultant polyesters such as poly­(1,18-( Z )-octadec-9-enylene 1,18-( Z )-octadec-9-enedioate) and poly­(1,18-octadecylene 1,18-octadecanedioate) …”

“…In particular, as focused on in this Perspective, development of advanced polyesters, which display tunable mechanical properties and biodegradability, from so-called bio-based monomers by precise polymerization techniques attracts considerable attention. − Plant oils, ,− ,− generally obtained as fatty acids or fatty acid methyl esters by chemical modifications, have been considered as a useful renewable feedstock especially for synthesis of the (semicrystalline) aliphatic polyesters, whereas many studies have thus been known for synthesis of polyesters from the other renewable resources such as lignin, sugars, ,,− and terpenes. ,, As described below, study on efficient conversion of plant oils, such as isomerization alkoxycarbonylation, olefin metathesis (including so-called ethenolysis) routes, or new catalysts for the transesterification, attracts considerable attention.…”

Continuous Flow Z‐Stereoselective Olefin Metathesis: Development and Applications in the Synthesis of Pheromones and Macrocyclic Odorant Molecules**

“…Analytical data for this compound were identical with those reported in the literature. 10  Scale up of the reaction with Ru-4 (10 mmol scale)…”

“…Recently, we described the synthesis of a cost-effective Z-selective cyclometalated Ru-catalyst Ru-4 9 featuring an unsymmetrical unsaturated NHC (U2-NHC) ligand accessible through a multicomponent process. 10 Apart from its high versatility and excellent Z-selectivity demonstrated in self-, cross-and ring-openingpolymerization metathesis, the novel cyclometalated catalyst Ru- 4 showed impressive robustness in reactive media affording good fidelity of high Z-selectivity over time, surpassing previously described Rucatalysts. This sought-after feature led us to focus our attention on the development of a continuous flow Z-selective process.…”

Balancing Degradability and Physical Properties of Amorphous Poly(d,l‐lactide) by Making Blends

“…The ester functional groups in polymer backbone repeat units can be hydrolyzed under appropriate environments leading to the breakage of the polymer chain (fragmentation) followed by bio‐assimilation of fragmented oligomers and monomers to carbon dioxide (CO 2 ), water, and biomass. [ 4–9 ] This two‐step process is called biodegradation. The first step of biodegradation, the process of fragmentation to oligomers and monomers, is highly critical for the whole process of biodegradation as long macromolecule chains with high molar mass cannot be bio‐assimilated.…”