Search

This work explores for the first time the enzymatic synthesis of poly(butylene-co-e-caprolactone) (PBSCL) copolyesters in bulk using commercially available monomers (dimethyl succinate (DMS), 1,4-butanediol (BD), and e-caprolactone (CL)). A preliminary kinetic study was carried out which demonstrated the higher reactivity of DMS over CL in the condensation/ring opening polymerization reaction, catalyzed by Candida antarctica lipase B. PBSCL copolyesters were obtained with high molecular weights and a random microstructure, as determined by 13C NMR. They were thermally stable up to 300 °C, with thermal stability increasing with the content of CL in the copolyester. All of them were semicrystalline, with melting temperatures and enthalpies decreasing up to the eutectic point observed at intermediate compositions, and glass transition temperatures decreasing with the content of CL in the copolyester. The use of CALB provided copolyesters free from toxic metallic catalyst, which is very useful if the polymer is intended to be used for biomedical applications. Peer Reviewed Objectius de Desenvolupament Sostenible::11 - Ciutats i Comunitats Sostenibles

Diblock copolymers (PPDLx-b-pPAAy) were prepared from ω-pentadecalactone and l -glutamic acid or l -lysine amino acids by ring opening polymerization initiated by amino groups. Telechelic amino-ended poly(ω-pentadecalactone) with a length of 15–20 repeating units was firstly synthesized by enzymatic polymerization by means of CALB and then used as macroinitiator for the polymerization of the N-carboxyanhydrides of the two α-amino acids conveniently protected as benzyl and eN-carbobenzoxy derivatives, respectively. The molecular weight of the polypeptide block was accurately controlled by adjusting the amino acid/macroinitiator ratio used in the feed. Copolymers with Mn ranging between ∼5000 and ∼40,000 g·mol−1 and varying ester/peptide ratio were obtained and characterized in detail by GPC and NMR spectroscopy. The thermal properties of these copolymers were evaluated by TGA and DSC, and their structure in the solid-state including their response to heating, were examined by FTIR and XRD at variable temperature. It was shown that the polypentadecalactone segment was crystallized for all compositions and that the polypeptide counterpart adopted a two-dimensional hexagonal packing of α-helices at temperatures above melting of the polyester block. SAXS revealed the presence of a biphasic nanostructure with a repeating distance of 27 nm for the case of glutamic-based copolymers. It was demonstrated that both glutamic and lysine-based PPDLx-b-pPAAy copolymers could self-assemble in well-shaped nanospheres with a diameter in the ∼200–400 nm range and a negative zeta-potential.

Robust and flexible free-standing films made of spin-coated poly(lactic acid) (PLA) and poly(3,4-ethylenedioxythiophene) (PEDOT) nanolayers have been prepared. A steel sheet coated with a sacrificial layer of PEDOT:poly(styrenesulfonate) (PSS) and a spin-coated nanolayer of PLA was used as working electrode for the anodic polymerization of 3,4-ethylenedioxythiophene monomer. The latter was only successfully accomplished when rounded-shape nanoperforations of average diameter 49¿±¿14¿nm were introduced into PLA layers, which was achieved by combining the phase segregation processes undergone by immiscible PLA:poly(vinyl alcohol) (PVA) mixtures with selective solvent etching to remove PVA domains. Nanoperforations allowed the utilization of the semiconducting PEDOT:PSS sacrificial layer to immobilize the electropolymerized PEDOT chains. Morphological and topographical studies show the templating effect of PEDOT layers. In addition of flexibility and mechanical strength, free-standing 5-layered films present good electrochemical activity, evidencing their potential ability to reversibly exchange ions with the medium. These properties offer important advantages with respect to those of neat PLA and supported PEDOT films, as has been illustrated by cell culture and protein adsorption assays. Cell cultures evidenced the superior behavior of 5-layered films as bioactive platforms for fibroblast and epithelial cells proliferation, while adsorption assays reflected their potential as selective bioadhesive surfaces for protein separation

Monomers obtained from renewable feedstocks have emerged as a sustainable alternative to petroleum derived polymers. One of the biomass derived polyesters that has recently been gaining attention as an alternative to petrochemical polyethylene terephtalate (PET) for food and beverage packaging applications is poly(ethylene furanoate) (PEF). However, similar to PET, PEF is not biodegradable or compostable and its end-of-life options must be thus considered to avoid contributing to the accumulation of plastic waste. In this manuscript, PEF films were first produced using thermo-compression, an industrially relevant processing method, and their thermal, mechanical, and barrier properties were determined and compared to those of PET and other biopolyesters to ascertain their suitability for food packaging. Thereafter, the chemical glycolysis of PEF film waste was investigated using a sustainable and thermally stable acid–base organocatalyst. After succesfully deconstructing PEF into bis(2-hydroxyethyl)-furan-2,5-dicarboxylate (BHEF), the obtained BHEF diester was used to resynthesize PEF using the same catalyst to generate a new biopolyester with similar thermal properties to the virgin one in a closed-loop cycle., The authors thank for technical and human support provided by IZO-SGI SGIker of UPV/EHU and European funding (ERDF and ESF). Authors gratefully acknowledge financial support from Spanish Ministry of Science and Innovation (MICI) through projects MAT2017-83373-R and RTI 2018-097249-B-C21.

Cyclic oligomers of isomannide 2,5-furandicarboxylate were synthesized using the high dilution condensation method. A mixture of dimer, trimer, and tetramer species largely enriched in dimer was obtained. These cyclic oligomers were made to react with oligo(butylene 2,5-furandicarboxylate) in bulk at 220 °C by ring opening polymerization using Sn(Oct)2 as a catalyst. A series of random poly(butylene 2,5-furandicarboxylate) copolyesters containing isomannide in a range of 5–50 mol % and with weight-average molecular weights between 30,000 and 50,000 g·mol–1 were prepared. These copolyesters started to decompose above 300 °C, and only those containing less than 10 mol % of isomannide showed signs of crystallinity. They displayed glass-transition temperatures in the 40–100 °C range with values increasing steadily with the content in isomannide. At difference with poly(butylene 2,5-furandicarboxylate) homopolyester that is reluctant to undergo hydrolysis, the isomannide-containing copolyesters were noticeably degraded by water, much more rapidly when exposed to lipases.

Cyclic oligomers of hexamethylene furanoate and hexamethylene terephthalate were obtained from 1,6-hexanediol and the corresponding methyl esters using Candida antarctica lipase B (CALB) enzyme catalyst. HPLC, MALDI-TOF MS, and NMR analyses showed that mixtures composed from cyclic dimer up to heptamer were obtained almost quantitatively. Subsequently, these cycles were polymerized by ring opening polymerization (ROP) mediated by CALB to obtain semicrystalline polymers. In addition, we demonstrated that the polymers obtained from the ROP process could be transformed into cyclic oligomers in high yields using enzymatic cyclodepolymerization, thereby recycling the polymer in a circular biosynthetic path.

Sugar-based polyesters derived from sorbitol and isohexides were obtained via solvent-free enzymatic catalysis. Pendant hydroxyl groups, coming from the sorbitol units, were present along the polyester backbone, whereas the two isohexides, namely, isomannide and isoidide dimethyl ester monomers, were selected to introduce rigidity into the polyester chains. The feasibility of incorporating isomannide as a diol compared to the isoidide dimethyl ester as acyl-donor via lipase-catalyzed polycondensation was investigated. The presence of bicyclic units resulted in enhanced Tg with respect to the parent sorbitol-containing polyester lacking isohexides. The different capability of the two isohexides to boost the thermal properties confirmed the more flexible character provided by the isoidide diester derivative. Solvent-borne coatings were prepared by cross-linking the sugar-based polyester polyols with polyisocyanates. The increased rigidity of the obtained sugar-based polyester polyols led to an enhancement in hardness of the resulting coatings.

Poly(ethylene succinate) (PES) with weight-average molecular weight above 60,000 g mol-1 was efficiently obtained by enzymatic ring opening polymerization of cyclic oligo(ethylene succinate)s c(ES)n, which in turn were prepared by lipase-catalysed cyclocondensation in solution of dimethyl succinate and ethylene glycol. The methodology was demonstrated to be also applicable to the synthesis of high molecular weight PES-copolyesters containing butylene succinate, e-hydroxycaproate or L-lactate units with a random distribution.

Three series of polyalkanoates (adipates, suberates and sebacates) were synthesized using as monomers three sugar-based bicyclic diols derived from D-glucose (Glux-diol and isosorbide) and D-mannose (Manx-diol). Polycondensations were conducted in the melt applying similar reaction conditions for all cases. The aim was to compare the three bicyclic diols regarding their suitability to render aliphatic polyesters with enhanced thermal and mechanical properties. The ensuing polyesters had molecular weights (Mw) in the 25,000–50,000 g mol-1 range with highest values being attained for Glux-diol. All the polyesters started to decompose above 300 °C and most of them did not display perceivable crystallinity. On the contrary, they had glass transition temperatures much higher than usually found in homologous polyesters made of alkanediols, and showed a stress– strain behavior consistent with their Tg values. Glux-diol was particularly effective in increasing the Tg and to render therefore polyesters with high elastic modulus and considerable mechanical strength.

The synthesis, characterization and comparative evaluation of properties of two series of cationic PBS copolyesters bearing respectively ammonium and tributylphosphonium side groups, are reported. The copolyesters with contents in ionic units up to 50 mole-% as well as the fully ionic homopolyesters were prepared by polycondensation in the melt catalyzed by CALB or TBT. Their Mn ranged between 20,000 and 5000 g mol-1 depending of composition and the type of ionic group that is involved. All the copolyesters were non-water soluble and showed good thermal stability. They were semicrystalline with melting temperatures and enthalpies decreasing with the ionic contents. The interactions interplayed by the ionic groups restricted largely the molecular mobility and caused a significant increase in the melt viscosity and glass transition temperature of PBS and a decrease in crystallization rate. Both ammonium and phosphonium containing PBS copolyesters were able to be coupled with sulfonated PBS to generate ionic polymer blends with modified crystallizability. The presence of both ammoniums and phosphoniums provided PBS with remarkable antimicrobial activity against gram-positive and gram-negative bacteria.

Bacterial polyesters such as polyhydroxyalkanoates (PHAs) are of great interest for a large number of applications both because of their properties and because they come from renewable resources, despite having a higher cost than commodity polymers. Their foaming—although it presents some difficulties—could be an option to increase their competitiveness. In this work, two strategies have been studied to enhance the poly(3-hydoxybutyrate-co-4-hydroxybutyrate) (P3HB4HB) foamability by extrusion foaming. The effect of the cooling system (water-quenching or air-cooling), chain extender (CE) addition and chemical blowing agent (CBA) amount were evaluated. Density, cellular morphology, mechanical and thermal properties were studied. Optimal density reduction was achieved with use of CE and 3–4 wt.% of CBA masterbatch. The most effective strategy on density reduction was the addition of CE, while the water quenching had only a slight influence on the samples in which CE was not present. CE addition decreased the viscosity and the degradation rate of the polymer, thus leading to lighter foams with larger cells but with equal or even slightly better resistance to compressive and tensile stress, in general terms.

Multifunctional electrospun scaffolds were prepared from two polylactide (PLA) grades having slightly different d-lactide content (4.2 wt % and 2.0 wt %). Triclosan (TCS), ketoprofen (KTP), and p-coumaric acid (CUM) were selected as bactericide, anti-inflammatory, and antioxidant agents, respectively. Single, binary, and ternary drug-loaded microfibers having a unimodal diameter distribution could be prepared using a common chloroform:acetone:dimethylsulfoxide mixture and similar operational parameters (i.e., voltage, flow rate, and tip-collector distance). FTIR spectra were sensitive to the low amount of drugs loaded and even showed slight differences in PLA conformation. DSC heating scans clearly demonstrated the ability of electrospinning to induce molecular orientation of PLA and also the nucleation effect of incorporated drugs to induce crystallization. Thus, crystallinity of binary drug-loaded scaffolds was significantly higher than observed for unloaded samples. Release behavior of the three drugs from loaded scaffolds and PLA matrices in PBS:ethanol medium was evaluated. A rapid release was always detected, together with partial drug retention which was higher when the more stereoregular PLA matrix was employed. A strong bactericidal effect was found when scaffolds were loaded with 3 wt/vol % of TCS, but incorporation of a small percentage of KTP (i.e., 1 wt/vol %) had a bacteriostatic effect even in the absence of TCS. The inherent cytotoxicity of TCS could be well neutralized by enhancing cell viability by incorporation of CUM and/or KTP. Multifunctional electrospun scaffolds were prepared from two polylactide (PLA) grades having slightly different d-lactide content (4.2 wt % and 2.0 wt %). Triclosan (TCS), ketoprofen (KTP), and p-coumaric acid (CUM) were selected as bactericide, anti-inflammatory, and antioxidant agents, respectively. Single, binary, and ternary drug-loaded microfibers having a unimodal diameter distribution could be prepared using a common chloroform:acetone:dimethylsulfoxide mixture and similar operational parameters (i.e., voltage, flow rate, and tip-collector distance). FTIR spectra were sensitive to the low amount of drugs loaded and even showed slight differences in PLA conformation. DSC heating scans clearly demonstrated the ability of electrospinning to induce molecular orientation of PLA and also the nucleation effect of incorporated drugs to induce crystallization. Thus, crystallinity of binary drug-loaded scaffolds was significantly higher than observed for unloaded samples. Release behavior of the three drugs from loaded scaffolds and PLA matrices in PBS:ethanol medium was evaluated. A rapid release was always detected, together with partial drug retention which was higher when the more stereoregular PLA matrix was employed. A strong bactericidal effect was found when scaffolds were loaded with 3 wt/vol % of TCS, but incorporation of a small percentage of KTP (i.e., 1 wt/vol %) had a bacteriostatic effect even in the absence of TCS. The inherent cytotoxicity of TCS could be well neutralized by enhancing cell viability by incorporation of CUM and/or KTP.

Biotechnologically accessible 1,4-butanediol and vegetal oil-based diethyl sebacate were copolymerized with bicyclic acetalized d-glucose derivatives (Glux) by polycondensation both in the melt at high temperature and in solution at mild temperature mediated by polymer-supported Candida antarctica lipase B (CALB). Two series of random copolyesters (PBxGluxySeb and PBSebxGluxy) were prepared differing in which d-glucose derivative (Glux diol or Glux diester) was used as comonomer. The three parent homopolyesters PBSeb, PBGlux, and PGluxSeb were prepared as well. Both methods were found to be effective for polymerization although significant higher molecular weights were achieved by melt polycondensation. The thermal properties displayed by the copolyesters were largely dependent on composition and also on the functionality of the replacing Glux unit. The thermal stability of PBSeb was retained or even slightly increased after copolymerization with Glux, whereas crystallinity and melting temperature were largely depressed. On the contrary, the glass-transition temperature noticeably increased with the content in Glux units. PGluxSeb distinguished in displaying both Tg and Tm higher than PBSeb because a different crystal structure is adopted by this homopolyester. The hydrolytic degradability of PBSeb in water was enhanced by copolymerization, in particular, when biodegradation was assisted by lipases.

The use of NMR spectroscopy in solution to investigate the chemical structure of engineering poly(alkylene terephthalate)s such as poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), and poly(butylene terephthalate) (PBT) is reviewed. Chemical defects present in the polyester chain, such as oxydialkylene units, as well as accompanying side products such as cyclic oligomers generated in the polycondensation, are well detected in 1H NMR spectra. The technique is also demonstrated to be effective for identifying, and even for quantifying in certain cases, the end groups of these polyterephthalates, including those that are generated in small amounts as a consequence of thermal degradation. The application of NMR to the study of the chemical microstructure of copolyesters derived from such polyterephthalates is also reviewed for its unique ability to determine comonomeric sequence lengths and degree of randomness (R). Copolyesters synthesized by either melt polycondensation or entropically driven ring opening polymerization, in addition to those prepared by solid-state modification or melt blending, are the object of this review.

Electrospun scaffolds from an amino acid containing poly(ester urea) (PEU) were developed as promising materials in the biomedical field and specifically in tissue engineering applications. The selected poly(ester urea) was obtained with a high yield and molecular weight by reaction of phosgene with a bis(alpha-aminoacy1)-alpha,omega-dioldiester monomer. The polymer having L-Ieucine, 1,6-hexanediol and carbonic acid units had a semicrystalline character and relatively high glass transition and melting temperatures. Furthermore it was highly soluble in most organic solvents, an interesting feature that facilitated the electrospinning process and the effective incorporation of drugs with bactericidal activity (e.g. biguanide derivatives such as clorhexidine and polyhexamethylenebiguanide) and enzymes (e.g. alpha-chymotrypsin) that accelerated the degradation process. Continuous micro/nanofibers were obtained under a wide range of processing conditions, being diameters of electrospun fibers dependent on the drug and solvent used.; Poly(ester urea) samples were degradable in media containing lipases and proteinases but the degradation rate was highly dependent on the surface area, being specifically greater for scaffolds with respect to films. The high hydrophobicity of new scaffolds had repercussions on enzymatic degradability since different weight loss rates were found depending on how samples were exposed to the medium (e.g. forced or non-forced immersion). New scaffolds were biocompatible, as demonstrated by adhesion and proliferation assays performed with fibroblast and epithelial cells. (C) 2014 Elsevier B.V. All rights reserved.

2,3-O-Methylene-L-threitol (Thx) is a cyclic carbohydrate-based diol prepared by acetalization and subsequent reduction of the naturally occurring tartaric acid. The structure of Thx consists of a 1,3-dioxolane ring with two attached primary hydroxyl groups. Two series of partially bio-based poly(butylene terephthalate) (PBT) copolyesters were prepared using Thx as a comonomer by melt polycondensation (MP) and solid-state modification (SSM). Fully random copolyesters were obtained after MP using mixtures of Thx and 1,4-butanediol in combination with dimethyl terephthalate. Copolyesters with a unique block-like chemical microstructure were prepared by the incorporation of Thx into the amorphous phase of PBT by SSM. The partial replacement of the 1,4-butanediol units by Thx resulted in satisfactory thermal stabilities and gave rise to an increase of the Tg values, this effect was comparable for copolyesters prepared by MP and SSM. The partially bio-based materials prepared by SSM displayed higher melting points and easier crystallization from the melt, due to the presence of long PBT sequences in the backbone of the copolyester. The incorporation of Thx in the copolyester backbone enhanced the hydrolytic degradation of the materials with respect to the degradation of pure PBT.

Poly(alkylene terephthalate)s, PET and PBT in particular, are materials of great relevance and growing projection in the thermoplastic field but are today almost totally produced from fossil resources. The current huge consumption of these polyesters necessitates urgent actions addressed to make them renewable by using naturally-occurring raw materials. Among the different approaches that are being followed to develop bio-based poly(terephthalate)s, the use of bicyclic carbohydrate-derived difunctional compounds as building-blocks is receiving much attention in the last few years because partially renewable polyesters with high Tg may be thus obtained. This review presents a critical account of the terephthalate homopolymers and copolymers that have been synthesized using the two types of carbohydrate-based bicyclic monomers, isohexides and diacetals, explored to date. The properties displayed by the novel bio-based poly(terephthalate)s in relation to the bicyclic structure of the used monomers are comparatively reviewed and their potential as emergent materials for thermoplastic applications is evaluated.

The carbohydrate-based diol 2,4:3,5-di- O -methylene- D -mannitol (Manx) has been used to obtain aliphatic polyesters. Manx is a symmetric bicyclic compound consisting of two fused 1,3-dioxane rings and bearing two primary hydroxyl groups. In terms of sti ff ness, it is comparable to the widely known isosorbide, but it a ff ords the additional advantages of being much more reactive in polycondensation and capable of producing stereoregular polymers with fairly high molecular weights. A fully bio-based homopolyester (PManxS) has been synthesized by polycondensation in the melt from dimethyl succinate and Manx. The high thermal stability of PManxS, its relatively high glass transition temperature ( T g =68 ° C) and elastic modulus, and its enhanced sensitivity to the action of lipases point to PManxS as a polyester of exceptional interest for those applications where biodegradability and molecular sti ff ness are priority requirements. In addition, random copolyesters (PB x Manx y S) covering a broad range of compositions have been obtained using mixtures of Manx and 1,4-butanediol in the reaction with dimethyl succinate. All PB x Manx y S were semicrystalline and displayed T g values from − 29 to +51 ° C steadily increasing with the content in Manx units. The stress − strain behavior of these copolyesters largely depended on their content in Manx and they were enzymatically degraded faster than PBS.

Mixtures of the dimethyl esters of adipic acid and 2,3:4,5-di-O-methylene-galactaric acid (Galx) were made to react in the melt with either 1,6-hexanediol or 1,12-dodecanediol to produce linear polycyclic copolyesters with aldarate unit contents varying from 10 up to 90 mole %. The copolyesters had weight–average molecular weights in the ∼35,000–45,000 g mol−1 range and a random microstructure, and were thermally stable up to nearly 300 °C. They displayed Tg in the -50 to -7 °C range with values largely increasing with the content in galactarate units. All the copolyesters were semicrystalline with Tm between 20 and 90 °C but only those made from 1,12-dodecanediol were able to crystallize from the melt at a crystallization rate that decreased as the contents in the two comonomers approached each other. Copolyesters containing minor amounts of galactarate units adopted the crystal structure characteristic of aliphatic polyesters but a new crystal polymorph was formed when the cyclic sugar units became the majority. Stress–strain parameters were sensitively affected by composition of the copolyesters with the mechanical behavior changing from flexible/ductile to stiff/brittle with the replacement of adipate units by the galactarate units.

A series of poly(ethylene terephthalate) terpolyesters containing varying amounts of both 1,4-cyclohexylenedimethylene and isosorbide units were prepared by melt phase polycondensation. These terpolymers were obtained with high molecular weights and polydispersities around 2.0–2.5. The nuclear magnetic resonance data revealed that they were all random terpolymers and that small amounts of isosorbide were lost during the polycondensation reaction. Thermal data showed that terpolymers with 90 mol% of ethylene units were crystalline, whereas the two other series containing 80 and 70 mol% were unable to crystallize from the melt. For the three series studied, it was observed that the glass transition temperature increased steadily with the content of isosorbide units, and that they had similar thermal stability.

2,4:3,5-Di-O-methylene-D-mannitol, abbreviated as Manx, is a D-mannitol-derived compound with the secondary hydroxyl groups acetalized with formaldehyde. The bicyclic structure of Manx consists of two fused 1,3-dioxane rings, with two primary hydroxyl groups standing free for reaction. A homopolyester made of Manx and dimethyl terephthalate as well as a set of copolyesters of poly(butylene terephthalate) (PBT) in which 1,4-butanediol was replaced by Manx up to 50% were synthesized and characterized. The polyesters had Mw in the 30 000−52 000 g mol−1 range and a random microstructure and were thermally stable up to nearly 370 °C. They displayed outstanding high Tg with values from 55 to 137 °C which steadily increased with the content in Manx. Copolyesters containing up to 40% of Manx were semicrystalline and adopted the crystal structure of PBT. Their stress− strain parameters were sensitively affected by the presence of carbohydrate-based units with elongation at break decreasing but tensile strength and elastic moduli steadily increasing with the degree of replacement.

The synthesis of a series of poly(ester amide)s constituted by glycolic acid, adipic acid, and different ratios of 1,3-pentanediamine and 1,5-pentanediamine units was studied and the derived copolymers were characterized. Thermal polycondensation between the potassium adipate salt and the appropriate ratio of N,N′-bis(chloroacetyl)-1,3-pentanediamine and N,N′-bis(chloroacetyl)-1,5-pentanediamine was proved to be effective, proceeded with high yield, and rendered samples with moderate molecular weight for carefully controlled competitive thermal degradation reactions. Physical properties were highly dependent on the final composition. In particular, crystallinity and thermal stability decreased with 1,3-pentanediamine unit content, that is, with the incorporation of lateral ethyl groups into the main chain. The presence of these units also changed solubility in solvents like methanol and degradability in a protease K enzymatic medium. Specifically, incorporation of 1,3-pentanediamine units led to a gradual increase in degradability. All poly(ester amide)s were able to establish intermolecular hydrogen bonding interactions, which in semicrystalline samples pointed to typical sheet structures of polyamides according to X-ray diffraction and infrared spectroscopic data. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40102.

The backbone of poly(butylene terephthalate) (PBT) was modified with 2,4:3,5-di- O -methylene- D -glucitol (Glux) using solid-state modification (SSM). The obtained copolyest- ers proved to have a non-random overall chemical microstruc- ture. The thermal properties of these semicrystalline, block- like, Glux-based materials were extraordinary, showing higher melting points, and glass transition temperatures compared with other sugar-based copolyesters prepared by SSM. These remarkable thermal properties were a direct result of the inher- ently rigid structure of Glux and the relatively slow randomiza- tion of the block-like chemical microstructure of the Glux- based copolyesters in the melt. SSM proved to be a versatile tool for preparing partially biobased copolyesters with superior thermal properties

Electrospun scaffolds constituted by different mixtures of two biodegradable polyesters are prepared. Specifically, materials with well differentiated properties can be derived from the blending of hydrophilic polyglycolide (PGA) and hydrophobic poly(e-caprolactone) (PCL), which are also two of the most applied polymers for biomedical uses. Electrospinning conditions are selected in order to get homogeneous and continuous fibers with diameters in the nano/micrometric range. These conditions are also applied to load the different scaffolds with curcumin (CUR) and polyhexamethylene biguanide (PHMB) as hydrophobic and hydrophilic bactericide compounds, respectively. Physicochemical characterization of both unloaded and loaded scaffolds is performed and involved Fourier transform infrared and 1H NMR spectroscopies, morphological observations by scanning electron microscopy, study of thermal properties through calorimetry and thermogravimetric analysis, and evaluation of surface characteristics through contact angle measurements. Release behavior of the loaded scaffolds is evaluated in two different media. Results point out a well differentiated behavior where the delivery of CUR and even PHMB are highly dependent on the PGA/PCL ratio, the capability of the medium to swell the polymer matrix, and the diffusion of the selected solvent into the electrospun fibers. All samples show a bactericide effect in both hydrophilic cell culture and hydrophobic agar media.

The two cyclic acetals, 2,3-di-O-methylene-l-threitol and dimethyl 2,3-di-O-methylene-l-threarate, were used for the synthesis of two series of PBS copolyesters differing in which unit, butylene or succinate, was replaced, in addition of the corresponding parent homopolyesters. Polycondensation reactions were carried out in the melt affording polymers with satisfactory molecular weights. Copolyesters were prepared with contents in tartaric acid-based units over the whole range of compositions and they all had a random chemical microstructure. The physical properties of the novel copolyesters varied widely depending not only on their composition but also on the type of unit that was replaced. They showed higher glass transition (Tg), lower melting temperatures (Tm), and lower crystallinity compared to the parent PBS homopolyester. Regarding mechanical properties, the presence of the stiff cyclic acetal units in the PBS chain caused an increase in the elongation at break and also a reduction in both elastic modulus and tensile strength of the polyester. Upon copolymerization the PBS notably increased its hydrolytic degradability and more slightly its susceptibility to be degraded by lipases.

An overview on the synthesis, structure and properties of polyamides and aromatic copolyesters produced by using monomers derived from carbohydrates is provided. Two examples are selected for illustration: (a) aliphatic polyamides prepared from aldaric acids and (b) aromatic copolyesters containing alditols units. Polycondensation in solution of n-alkanediamines ( n taking even values from 6 to 12) with activated pentaric (l- arabino and xylo) and hexaric ( galacto and d- manno) acids bearing the secondary hydroxyl groups protected as methyl ether, afforded linear polyaldaramides PA- nSu with Mw oscillating between 25 000 and 150 000 g mol−1. They are stable above 300°C and are semicrystalline even so only PA- nMn are stereoregular. Melting temperatures of PA- nSu range between 140 and 230°C and most of them are able to crystallize from the melt at a rate that increases with the length of the polymethylene segment. Both melting and glass transition temperatures decrease with the content in sugar units. Spherulitic films, oriented fibers and lamellar single crystals could be obtained from PA -nSu. All these polyamides seem to adopt a common crystal structure made of hydrogen-bonded sheets with the sugar residue skewed to attain an efficient side-by-side packing of the polymer chains. Aromatic homopolyesters and copolyesters derived from terephthalic acid and mixtures of butylene glycol and O-methylated alditols were prepared by polycondensation in the melt with Mw in the 20 000–50 000 g mol−1 range and a random microstructure. The thermal properties of PBT containing alditols units are very depending on the sugar constitution and copolyester composition. In general they are thermally stable above 300°C and display crystallinity for contents in alditols up to 30%. Melting temperatures decrease with the content in alditols whereas an opposite trend is observed for glass transition temperatures. The crystalline structure of PBT is preserved in the crystalline copolyesters whereas a different crystal lattice is adopted by homopolyesters entirely made of alditol units. In general, polyamides and polyesters containing sugar derived units are widely soluble in organic solvents, markedly hydrophilic and more susceptible to hydrolysis than their parent polymers.

The preparation of cyclic ethylene and butylene 2,5-furandicarboxylate oligoesters and their conversion to furan-based polyesters poly(ethylene furanoate) (PEF) and poly(butylene furanoate) (PBF) by ring-opening polymerization (ROP) are described. The cyclic oligoesters were obtained in high yields by both high dilution condensation and thermal cyclodepolymerization methods, and they consisted of mixtures of small size species. Cyclic dimer, trimer and tetramer oligoesters were isolated by semipreparative chromatography and found to be crystalline compounds melting within the 140–200 °C range. ROP catalyzed by Sn(Oct) 2 of both mixtures and individual species afforded PEF and PBF with weight-average molecular weights between 50,000 and 60,000 g mol −1 . Polymerization rate was found to be higher for butylene than for ethylene cyclic oligofuranoates, and also to increase slightly as cycle size decreased. The thermal properties of PEF and PBF prepared by ROP were in full agreement with those reported for these polyesters obtained by melt polycondensation.

Poly(butylene 2,5-furandicarboxylate-co-succinate) copolyesters (coPBFxSy) have been synthesized by ring opening polymerization (ROP). Cyclic butylene 2,5-furandicarboxylate and butylene succinate oligomer mixtures, to be used as monomers for ROP, were prepared by high dilution condensation and enzymatic cyclization reactions, respectively. Two different catalytic systems, tin dioctanoate and supported Candida antarctica lipase B (CALB), were used for polymerization. Thus two series of copolyesters covering the whole range of compositions were prepared and their properties comparatively examined. In both cases, random copolyesters with compositions close to those used in their respective feeds were obtained. The influence of composition on reaction kinetics with respect to time and temperature was evaluated for the two series. Chemically catalyzed ROP rendered copolyesters with Mw in the ~50 000–65 000 g mol-1 range, whereas values between 15 000 and 45 000 g mol-1 were attained when the ROP reaction was assisted by CALB. The thermal behavior of coPBFxSy obtained by ROP was similar to that reported for such copolymers prepared by melt polycondensation. They all start to decompose above 300 °C and display melting enthalpy and temperatures that decrease with copolymerization, attaining minimum values when the comonomer contents are approximate to balance. On the contrary, the glass-transition temperature increased almost linearly with the content of butylene furandicarboxylate units, covering the whole range of values between those of the two parent homopolyesters. Small deviations in thermal properties observed between the two series could be attributed to their differences in molecular weights. Hydrolytic and enzymatic degradation studies revealed that coPBFxSy became more degradable with increasing content of succinic units, whereas the homopolyester PBF remained practically unaffected when incubated under similar conditions.