Abstract: Polyesters synthesized through the alternating copolymerization of epoxides and cyclic anhydrides compose a growing class of polymers that exhibit an impressive array of chemical and physical properties. Because they are synthesized through the chain-growth polymerization of two variable monomers, their syntheses can be controlled by discrete metal complexes, and the resulting materials vary widely in their functionality and physical properties. This polymer-focused review gives a perspective on the current state of the field of epoxide/anhydride copolymerization mediated by discrete catalysts and the relationships between the structures and properties of these polyesters.

Abstract: Cutin, a polyester composed mostly of oxygenated fatty acids, serves as the framework of the plant cuticle. The same types of cutin monomers occur across most plant lineages, although some evolutionary trends are evident. Additionally, cutins from some species have monomer profiles that are characteristic of the related polymer suberin. Compositional differences likely have profound structural consequences, but little is known about cutin's molecular organization and architectural heterogeneity. Its biological importance is suggested by the wide variety of associated mutants and gene-silencing lines that show a disruption of cuticular integrity, giving rise to numerous physiological and developmental abnormalities. Mapping and characterization of these mutants, along with suppression of gene paralogs through RNA interference, have revealed much of the biosynthetic pathway and several regulatory factors; however, the mechanisms of cutin polymerization and its interactions with other cuticle and cell wall components are only now beginning to be resolved.

Abstract: Nowadays, the synthesis of (semi)aromatic polymers from lignin derivatives is of major interest, as aromatic compounds are key intermediates in the manufacture of polymers and lignin is the main source of aromatic biobased substrates. Phenols with a variety of chemical structures can be obtained from lignin deconstruction; among them, vanillin and ferulic acid are the main ones. Depending on the phenol substrates, different chemical modifications and polymerization pathways are developed, leading to (semi)aromatic polymers covering a wide range of thermomechanical properties. This review discusses the synthesis and properties of thermosets (vinyl ester resins, cyanate ester, epoxy, and benzoxazine resins) and thermoplastic polymers (polyesters, polyanhydrides, Schiff base polymers, polyacetals, polyoxalates, polycarbonates, acrylate polymers) prepared from vanillin, ferulic acid, guaiacol, syringaldehyde, or 4-hydroxybenzoic acid.

Abstract: Aliphatic polyester block polymers constitute a highly useful and amazingly versatile class of self-assembled materials. Analogous to styrenic block polymers in both design and function, the property profiles of these degradable materials can be precisely tailored by altering the chemical structure of the components. Driven by this ideal, we have examined the impact of n-alkyl substituents on the polymerization thermodynamics and kinetics of substituted δ-valerolactone monomers and developed guiding design principles based on critical structure–property relationships in the resulting aliphatic polyesters. Under bulk room temperature conditions the polymerization rate depends strongly on substituent position and exhibits a more modest dependence on alkyl length (from −CH3 to −(CH2)8CH3). The enthalpy and entropy of polymerization are significantly influenced by substituent position, but both are largely insensitive to n-alkyl length. However, the physical properties of the resulting aliphatic polyesters de...

Abstract: The first effective organopolymerization of the biorenewable “non-polymerizable” γ-butyrolactone (γ-BL) to a high-molecular-weight metal-free recyclable polyester is reported. The superbase tert-Bu-P4 is found to directly initiate this polymerization through deprotonation of γ-BL to generate reactive enolate species. When combined with a suitable alcohol, the tert-Bu-P4-based system rapidly converts γ-BL into polyesters with high monomer conversions (up to 90 %), high molecular weights (Mn up to 26.7 kg mol−1), and complete recyclability (quantitative γ-BL recovery).

Abstract: Recent studies on the enzymatic degradation of synthetic polyesters have shown the potential of polyester hydrolases from thermophilic actinomycetes for modifying or degrading polyethylene terephthalate (PET). TfCut2 from Thermobifida fusca KW3 and LC-cutinase (LCC) isolated from a compost metagenome are remarkably active polyester hydrolases with high sequence and structural similarity. Both enzymes exhibit an exposed active site in a substrate binding groove located at the protein surface. By exchanging selected amino acid residues of TfCut2 involved in substrate binding with those present in LCC, enzyme variants with increased PET hydrolytic activity at 65°C were obtained. The highest activity in hydrolyzing PET films and fibers were detected with the single variant G62A and the double variant G62A/I213S. Both variants caused a weight loss of PET films of more than 42% after 50 h of hydrolysis, corresponding to a 2.7-fold increase compared to the wild type enzyme. Kinetic analysis based on the released PET hydrolysis products confirmed the superior hydrolytic activity of G62A with a fourfold higher hydrolysis rate constant and a 1.5-fold lower substrate binding constant than those of the wild type enzyme. Mono-(2-hydroxyethyl) terephthalate is a strong inhibitor of TfCut2. A determination of the Rosetta binding energy suggested a reduced interaction of G62A with 2PET, a dimer of the PET monomer ethylene terephthalate. Indeed, G62A revealed a 5.5-fold lower binding constant to the inhibitor than the wild type enzyme indicating that its increased PET hydrolysis activity is the result of a relieved product inhibition by mono-(2-hydroxyethyl) terephthalate. Biotechnol. Bioeng. 2016;113: 1658-1665. © 2016 Wiley Periodicals, Inc.

Abstract: The compatibility of thermally reduced graphene (TRG) with multiblock copolyesters, composed of poly(butylene terephthalate) (PBT) segments and poly(tetramethylene ether) glycol segments, was examined in detail. The morphology observed by optical microscopy and scanning electron microscopy showed that the compatibility was enhanced with increasing content of the PBT segment in the polyester. This compatibility behavior was analyzed quantitatively, by using the percolation threshold of electrical conductivity, and then further analyzed by using the Hansen solubility parameters to provide a general quantitative guideline to predict the compatibility of TRG with various polymers. The results suggest that the total solubility parameter, δT, value of TRG is larger than 24.0 (MPa)½, and thus that the compatibility with polymer is enhanced as the δT value of a polymer increases toward 24.0 (MPa)½. However, this prediction does not fit well in the presence of a comonomer such as acrylic acid, which has a ...

Abstract: TfCut2 from Thermobifida fusca KW3 and the metagenome-derived LC-cutinase are bacterial polyester hydrolases capable of efficiently degrading polyethylene terephthalate (PET) films. Since the enzymatic PET hydrolysis is inhibited by the degradation intermediate mono-(2-hydroxyethyl) terephthalate (MHET), a dual enzyme system consisting of a polyester hydrolase and the immobilized carboxylesterase TfCa from Thermobifida fusca KW3 was employed for the hydrolysis of PET films at 60°C. HPLC analysis of the reaction products obtained after 24 h of hydrolysis showed an increased amount of soluble products with a lower proportion of MHET in the presence of the immobilized TfCa. The results indicated a continuous hydrolysis of the inhibitory MHET by the immobilized TfCa and demonstrated its advantage as a second biocatalyst in combination with a polyester hydrolase for an efficient degradation oft PET films. The dual enzyme system with LC-cutinase produced a 2.4-fold higher amount of degradation products compared to TfCut2 after a reaction time of 24 h confirming the superior activity of his polyester hydrolase against PET films.

Abstract: Renewable, biodegradable polymers, such as aliphatic polyesters, based on sustainable sources have attracted considerable interest as alternatives to petroleum-based polymers. One limiting factor in the development of aliphatic polyesters as replacements for these materials has been their relatively low glass transition temperatures (Tg). For example, commercially available poly(lactic acid) has a Tg of approximately 60 °C. Epoxide/anhydride copolymerizations offer an alternative to the ring-opening polymerization of lactones for the synthesis of aliphatic polyesters and allow for tuning of polymer properties through two distinct monomer sets. We synthesized six partially or fully renewable tricyclic anhydrides and copolymerized them with propylene oxide (PO) and cyclohexene oxide (CHO). By varying both the epoxide and the anhydride, we were able to tune the Tg of the resulting polymers over a nearly 120 °C range from 66 °C to an exceptionally high 184 °C. Polymers produced with PO had a lower range of Tg...

Abstract: cis,cis-Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis-muconate is synthesized and subsequently incorporated into poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the ...

Abstract: Polyester biomaterials are used in tissue engineering as scaffolds for implantation of tissues developed in vitro. An ideal biodegradable elastomer for cardiac tissue engineering exhibits a relatively low Young’s modulus, with high elongation and tensile strength. Here we describe a novel polyester biomaterial that exhibits improved elastic properties for cardiac tissue engineering applications. We synthesized poly(octamethylene maleate (anhydride) 1,2,4-butanetricarboxylate) (124 polymer) prepolymer gel in a one-step polycondensation reaction. The prepolymer was then molded as desired and exposed to ultraviolet (UV) light to produce a cross-linked elastomer. 124 polymer exhibited highly elastic properties under aqueous conditions that were tunable according to the UV light exposure, monomer composition, and porosity of the cured elastomer. Its elastomeric properties fell within the range of adult heart myocardium, but they could also be optimized for higher elasticity for weaker immature constructs. The ...

Abstract: Poly(dodecylene 2,5-furanoate) (PDoF) is a novel alipharomatic polyester which was prepared by combining a long chain glycol as the monomer (1,12-dodecamethylene glycol) and 2,5-furan dicarboxylic acid (FDCA), which can be derived from biomass. A variation of the well-known two-step polycondensation method was applied for the preparation of PDoF. The glass transition temperature of this polyester, which was recorded by using fast scanning calorimetry (FSC) is observed at −5 °C. The melting temperature is about 111 °C while the equilibrium melting temperature was extrapolated through Hoffman–Week plots to 127.3 ± 0.2 °C. New insights in the complex melting behavior were obtained by employing conventional and temperature modulated calorimetry. The crystallization kinetics in isothermal and nonisothermal modes were investigated by means of Avrami and Lauritzen–Hoffman models and model-free kinetics. The thermal stability of PDoF was reduced in comparison with previously studied furanoates, as a result of the...

Abstract: Glass fiber-reinforced polyester composite (GFRPs) scraps from manufacturing of polyester laminates were pyrolyzed at 500, 550 and 600°C in an 70 Kg innovative batch pilot plant that processes whole parts. The presence of a hydraulic guard guarantees the safety of the process. The influence of the maximum process temperature on yields and chemical-physical properties of pyrolysis products was investigated: the oil fraction was analysed by GC-MS, Viscometer and XRF, while the gas fraction was monitored online during the entire pyrolysis process by µ-GC. Substantial fractions of methane (20.7 vol %) and hydrogen (11.5 vol %) were produced. The solid residue (glass fibers covered by a thin carbonaceous layer) underwent an oxidative process at 500 and 600°C at different residence times to provide clean glass fibers free of organic residues. The effects of both pyrolysis and oxidative step on the glass fibers, obtained in different process conditions, were evaluated by SEM and Raman spectroscopy.

Abstract: Petroleum based epoxy and polyester based thermoset resins can be used to produce high-quality polymer concrete. However, petroleum based resources are finite and this has necessitated the development of thermoset bioresins to be used as polymer concrete. Furfuryl alcohol (FA), a thermoset bioresin, is derived from lignocellulosic biomass and it can be polymerized into polyfurfuryl alcohol (PFA) in the presence of an acid catalyst. The highly exothermic polymerization reactions involving conversion of FA to PFA can be used to fabricate PFA based concrete with rock-like structure. The PFA based polymer concrete offers the broadest range of chemical resistance against acid and alkali over all other types of polymer concrete which are based upon different thermoset polymeric systems. In this review paper, we have discussed the formulations (incorporation of aggregates, fillers, and resin) and properties (especially compressive and flexural) of epoxy and polyester based polymer concrete. In another section, we have given the mechanical, thermal, and water resistance properties of PFA based biopolymer, biocomposites, nanocomposites, and polymer concrete. Lastly, we have tried to explore whether PFA can be used successfully as biopolymer concrete or not.