Andreia F. Sousa

The quest for sustainable polyesters – insights into the future

Polyesters from renewable resources are an expanding area with a burgeoning scientific activity, nevertheless little has been reviewed about this particular class of polymers. The present appraisal intends to contribute to fill this literature gap by reviewing recent aspects related to the most promising renewable-based polyesters. Emphasis will be placed on bio-based polyesters that, given their comparable properties, may replace polymers derived from fossil fuel feedstock, and on bio-based polyesters with completely innovative properties for novel applications. Furthermore, the sources of renewable monomers will also be reviewed, together with the most relevant eco-friendly synthetic approaches used in polycondensation reactions leading to polyesters.

Biobased polyesters and other polymers from 2,5-furandicarboxylic acid: a tribute to furan excellency

Motivated by the general concern about sustainability and environmental issues, an intense search for renewable-based polymers has grown exponentially in recent years. This search definitely spotlighted polyesters derived from 2,5-furandicarboxylic acid, among other polymers, as some of the most promising, especially due to the resemblance of this renewable monomer to the well-known petroleum-based terephthalic acid, as well as owing to the possibility of preparing innovative materials. The huge number of recent papers and patents about this family of polymers explore aspects as diverse as synthesis with other renewable-based monomers, leading to the preparation of materials with enhanced thermo-mechanical, biodegradability and liquid crystalline properties, among other features. Additional aspects pursued in such studies are innovation in the synthetic approaches or their optimisation, as well as the development of applications for everyday-life objects for example packaging materials, especially bottles, textiles, coating, and toners, among many other uses. Despite this intense activity, little has been reviewed recently about this unique family of polyesters or derived polymers, as the only reviews on the subject date back to the last century. In this perspective, the present review aims at contributing to filling this literature gap, covering recent aspects related with challenges in developing polyesters, polyamides, or other polymers from 2,5-furandicarboxylic acid and their precursors. Emphasis is placed on monomer synthesis, polymerisation reactions, catalysts and applications.

Synthesis and Characterization of Novel Biopolyesters from Suberin and Model Comonomers

The synthesis of novel polyesters from model long-chain aliphatic monomers and from suberin reactive aliphatic fragments was conducted using mild polycondensation or polytransesterification conditions. The ensuing polyesters were characterized by means of various techniques. When mixtures of simple suberin-like monomers were used, the ensuing polyesters had very regular structures, with melting temperatures around 80 degrees C and glass transitions below room temperature. This first systematic study of the exploitation of suberin as a precursor to novel aliphatic polyesters confirmed the huge potential of using this abundant renewable resource to prepare macromolecular materials for promising applications.

Suberin isolation from cork using ionic liquids: characterisation of ensuing products

Cholinium alkanoates, a class of benign ionic liquids, were demonstrated to efficiently extract suberin domains from cork. A detailed characterisation of the extracted material has yet to be attained. In the present study the significance of the alkylic chain length of the anion and the ionic liquids basicity was investigated. The results obtained emphasise cholinium hexanoates selection; it proved to be a straightforward process, also ensuring the recyclability and reusability of the ionic liquid. The extracted suberinic material has been thoroughly characterised for the first time by ATR-FTIR, NMR, GC-MS and thermal analyses. Data showed that it is mainly composed of oligomeric or polymeric aliphatic esterified structures, resulting from suberin partial cleavage. More than 40 wt% of the extracted suberinic material was found to be cross-linked. Even though, the composing monomeric units were similar to those usually identified in suberin samples obtained by the conventional extraction processes. These data pave the way for advanced studies of suberin monomers/oligomers as building-blocks for the development of novel biopolymers and biomaterials.

New unsaturated copolyesters based on 2,5-furandicarboxylic acid and their crosslinked derivatives

The synthesis and characterisation of a novel family of unsaturated polyesters (UPs) and their crosslinked resins (UPRs) based on 2,5-furandicarboxylic acid (FDCA) are reported. Their original features stem from the use of FDCA as the aromatic monomer, and also from the fact that UPs are entirely based on renewable resources, oppositely to most reported materials which are typically based on petrochemicals or instead they are derived from both petrochemicals and a percentage of renewables. Additionally, instead of styrene, 2-hydroxyethylmethacrylate (HEMA) was used as the reactive solvent to obtain the UPRs. These novel resins showed adequate thermal and mechanical behavioural tendencies similar to petrochemical ones, namely high glass transition temperature (up to 104 °C) and good thermal stability (up to 230 °C). These characteristics enhance their prospects of being a successful renewable-based material.

Synthesis of aliphatic suberin-like polyesters by ecofriendly catalytic systems

A rapid and ecofriendly microwave assisted p-dodecylbenzenesulfonic acid (DBSA) emulsion polycondensation of long-chain suberin model comonomers was successfully carried out for the first time. Microwave irradiation reduced drastically the reaction time to only 15 min, compared with the DBSA/water polycondensation under conventional heating. Bulk polycondensation using CALB lipase or Bi(OTf)3 were also carried out with isolation yields up to 93% and number-average molecular weights up to around 7300.

Ex Situ Reconstitution of the Plant Biopolyester Suberin as a Film

Biopolymers often have unique properties of considerable interest as a basis for new materials. It is however not evident how to extract them from plants without destroying their chemical skeleton and inherent properties. Here we report the ex situ reconstitution of the biopolyester suberin as a new waterproof and antimicrobial material. In plant cell walls, suberin, a cross-linked network of aromatic and aliphatic monomers, builds up a hydrophobic protective and antimicrobial barrier. Recently we succeeded in extracting suberin from the plant cell wall using the ionic liquid cholinium hexanoate. During extraction the native three-dimensional structure of suberin was partially preserved. In this study, we demonstrate that this preservation is the key for its ex situ reconstitution. Without any chemical additives or purification, the suberin composing macromolecules undergo self-association on the casting surface forming a film. Suberin films obtained show barrier properties similar to those of the suberin barrier in plants, including a potentially broad bactericidal effect.

Unveiling the dual role of the cholinium hexanoate ionic liquid as solvent and catalyst in suberin depolymerisation

Disruption of the three-dimensional network of suberin in cork by cholinium hexanoate leads to its efficient and selective isolation. The reaction mechanism, which likely involves selective cleavage of some inter-monomeric bonds in suberin, was still unanswered. To address this question, the role of the ionic liquid during suberin depolymerisation and during cleavage of standard compounds carrying key chemical functionalities was herein investigated. A clear demonstration that the ionic liquid catalyses the hydrolysis of acylglycerol ester bonds was attained herein, both experimentally and computationally (DFT calculations). This behaviour is related to cholinium hexanoate capacity to activate the nucleophilic attack of water. The data showed also that the most favourable reaction is the hydrolysis of acylglycerol ester bonds, with the C2 position reporting the faster kinetics, whilst most of the linear aliphatic esters remained intact. The study emphasises that the ionic liquid plays the dual role of solvent and catalyst and leads to suberin efficient extraction through a mild depolymerisation. It is also one of the few reports of ionic liquids as efficient catalysts in the hydrolysis of esters.

Solvation of alkane and alcohol molecules. Energy contributions

In this work we conduct a systematic ab initio study of the solvation of small alkane, monoalcohol and diol molecules, in polar solvents with different properties. A choice of basis set suitable for the type of compounds under study is presented. The various components of the solvent–solute interaction and the cavitation energy are treated individually and their variation with chain length and introduction of hydroxy groups assessed. The use of solute molecules in which controlled changes are imposed allows for an estimation of the relative contributions, thus eliminating accidental error cancellation.

Determination of the Hydroxy and Carboxylic Acid Groups in Natural Complex Mixtures of Hydroxy Fatty Acids by 1H Nuclear Magnetic Resonance Spectroscopy

The use of trichloroacetyl isocyanate (TAI) to mark both hydroxyl and carboxyl groups borne by the hydrolysis or methanolysis of suberin fragments (a complex mixture of hydroxy fatty acids), allowed the quantitative assessment of the ratio between carboxyl and hydroxy groups, as well as the ratio between primary and secondary hydroxy groups, to be carried out reliably by 1H nuclear magnetic resonance (NMR) spectroscopy. All the samples thus analyzed displayed an excess of CO2H (or CO2CH3) functions with respect to the OH counterparts, albeit to a variable extent, depending on the procedure adopted to isolate the suberin fragments. The precise knowledge of the molar ratio of these two reactive moieties is fundamental for the correct utilization of suberin monomers in polymerization reactions leading to aliphatic polyesters.