New bio-based monomers: tuneable polyester properties using branched diols from biomass

Abstract

A family of monomers, including 2,5-hexandiol, 2,7-octandiol, 2,5-furandicarboxylic acid (FDCA), terephthalic acid (TA), and branched-chain adipic and pimelic acid derivatives, all find a common derivation in the biomass-derived platform molecule 5-(chloromethyl)furfural (CMF). The diol monomers, previously little known to polymer chemistry, have been combined with FDCA and TA derivatives to produce a range of novel polyesters. It is shown that the use of secondary diols leads to polymers with higher glass transition temperatures (T) than those prepared from their primary diol equivalents. Two methods of polymerisation were investigated, the first employing activation of the aromatic diacids via the corresponding diacid chlorides and the second using a transesterification procedure. Longer chain diols were found to be more reactive than the shorter chain alternatives, generally giving rise to higher molecular weight polymers, an effect shown to be most pronounced when using the transesterification route. Finally, novel diesters with high degrees of branching in their hydrocarbon chains are introduced as potential monomers for possible low surface energy materials applications.

Biocatalytic Production of Amino Carbohydrates through Oxidoreductase and Transaminase Cascades

“…Visualization of the TLC plates was achieved by UV light or staining with ab asic potassium permanganate solution. 1 Ha nd 13 CNMR spectra were recorded with aB ruker AV-400 (Germany) instrument at 20 8C( see Supporting Information). 1,2,3,4-Di-O-isopropylidene-a-d-galactopyranose (1.5 g, 5.7 mmol) was dissolved in EtOAc (38 mL) and iodoxybenzoic acid (4.8 g, 17 mmol) was added.…”

“…To date, most applications of plant carbohydrates begin by deconstructing polysaccharides to monomers for fermentation to fuels and platform chemicals. [9][10][11][12][13] An emerging area of research aims to utilize the versatility and ensuingu seful properties of native structures present in plant carbohydrates instead of degrading the structurest o monomers. [6,7] For example, diacids, diamines,a nd AB monomers (e.g.,m olecules containing both carboxylic acid and amino groups)a re required for polyamide synthesis, [8] andd iacids and diols for polyester synthesis.…”

“…[6,7] For example, diacids, diamines,a nd AB monomers (e.g.,m olecules containing both carboxylic acid and amino groups)a re required for polyamide synthesis, [8] andd iacids and diols for polyester synthesis. [9][10][11][12][13] An emerging area of research aims to utilize the versatility and ensuingu seful properties of native structures present in plant carbohydrates instead of degrading the structurest o monomers. [14][15][16][17] Bifunctional carbohydrates (e.g.,d iacids, diamines, or AB monomers) from native carbohydrate structures are among the desired products.…”

Biotic and Abiotic Synthesis of Renewable Aliphatic Polyesters from Short Building Blocks Obtained from Biotechnology

“…[14] As an example, poly(propylene dicarboxylate) polyesters < 0.5 0.8 [118] with molar masses lower than 2500 gmol À1 are synthesized from the uncatalyzed esterification of 1,3-PDO and SA or AA. The molar mass depends on the [COOH]/[OH] molarr atio, according to the Carothers law.…”

“…[118] Nevertheless, some high-temperature reactions in solution have also been reported for less soluble aromatic polyesters. The reactionb etween diacyl chlorides and aliphatic diols or diphenolic compounds commonly takes place in solution and at low or moderate temperature (mostly below 100 8C).…”