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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
- Veröffentlichungsjahr: 2023
Furan Polymers and their Reactions Understand furan polymers and their roles in industrial production Furans are platform chemicals from biomass which have a range of functions in the production of solvents, biofuels, and monomers for industrial polymer synthesis. As the search for sustainable industrial processes makes biomass resources ever more vital, a more detailed understanding of these compounds and their industrial uses has never been more critical. Furan Polymers and their Reactions surveys these crucial compounds and their contributions to polymer synthesis. It discusses the biorefinery of furans, identifies furfural and 5-hydroxymethyl furfural as the key furan monomer precursors for different polymer synthetic processes, and analyzes all the major reactions furans undergo during these processes and the structures, properties and applications of the ensuing materials. The results are a vital contribution to the growing field of renewable industry. Furan Polymers and their Reactions readers will also find: * Detailed analysis of key polymerization reactions such as the Diels-Adler reaction, chain-growth and step-growth polymerizations, as well as the chemical modifications of some of these polymers. * An authorial team with decades of combined experience in furan chemistry and polymer synthesis Furan Polymers and their Reactions is an essential resource for researchers and professionals in industrial engineering, polymer science, and biotechnology, as well as for any industry professionals working with platform chemicals or polymer synthesis.
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Furan Polymers and their Reactions
Alessandro Gandini
Retired from the Polytechnic InstituteGrenobleFrance
Talita Martins Lacerda
University of São PauloLorenaBrazil
This edition first published 2024
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Hardback ISBN: 9781119888697; ePub ISBN: 9781119888703; ePDF ISBN: 9781119888680; oBook ISBN: 9781119888710
Cover Image: Courtesy of Talita Martins Lacerda
Cover design by Wiley
Set in 9.5/12.5pt STIXTwoText by Integra Software Services Pvt. Ltd, Pondicherry, India
Contents
Cover
Title Page
Copyright Page
Foreword
Preface
1 A Brief History
2 The Peculiar Chemical Features of the Furan Heterocycle and the Synthesis of Furfural and Hydroxymethylfurfural
2.1 Free Radical Reactions
2.2 Electrophilic Reactions
2.3 Photochemistry
2.4 Hydrolysis Reactions
2.5 The Diels–Alder Reaction
2.6 Furfural and Hydroxymethylfurfural as Industrial Commodities and as Building Blocks for Furan Monomers
3 Polymers from Furfural and Furfuryl Alcohol
3.1 Furfural Resins
3.2 Furfuryl Alcohol Resins
4 Polymers from Chain Polyaddition Reactions
4.1 Free Radical Systems
4.2 Cationic Systems
4.3 Anionic Systems
4.4 Stereospecific Systems
5 Polymers from Polycondensation (Step) Reactions
5.1 Polyesters
5.2 Polyamides
5.3 Polyurethanes
5.4 Polyureas, Polyparabanic Acids, Polybenzoxazines, polySchiff Bases, and Polyhydrazides
5.5 Conjugated Furan Oligomers and Polymers
5.6 Epoxy Resins
6 The Furan/Maleimide Diels–Alder Reaction Applied to Polymer Synthesis and Modification
6.1 Polycondensations (Step-growth Polymerizations)
6.2 Polymer Modification and Cross-linking
6.3 Miscellaneous Systems
6.4 A New Paradigm: Aromatics from Furans
7 Chemical and Biological Degradation
8 General Conclusions
Index
End User License Agreement
List of Tables
CHAPTER 04
Table 4.1 The effect of furan additives...
CHAPTER 05
Table 5.1 Summary of some representative...
Table 5.2 Comparison of some of the major...
Table 5.3 Thermal and mechanical data of...
Table 5.4 FDCA-based copolyesters bearing...
Table 5.5 Second-order rate constants and...
Table 5.6 Second-order rate constants and...
List of Illustrations
CHAPTER 02
Figure 2.1 The resonance-contributing...
Figure 2.2 The relative dienic and...
Figure 2.3 The addition modes of...
Figure 2.4 Two alternative termination...
Figure 2.5 Electrophilic substitution...
Figure 2.6 The mercury-sensitized...
Figure 2.7 The interactions of...
Figure 2.8 The structure of the...
Figure 2.9 The photochemical...
Figure 2.10 Photoinduced cyclodimerization...
Figure 2.11 The [π2+π2] photochemical...
Figure 2.12 The typical reactions associated...
Figure 2.13 The Diels–Alder reaction...
Figure 2.14 The DA reaction of furan...
Figure 2.15 The DA reaction of furan...
Figure 2.16 The aromatization of DA...
Figure 2.17 The conversion of C5 sugars...
Figure 2.18 The conversion of C6 sugars...
Figure 2.19 The most important monomers...
Figure 2.20 The general structure...
Figure 2.21 The most important monomers...
Figure 2.22 The generic structure...
Figure 2.23 Electrophilic condensation...
CHAPTER 03
Figure 3.1 The crystalline difuran...
Figure 3.2 The oily trifuran compound...
Figure 3.3 Tentative structure of a...
Figure 3.4 The base-catalyzed condensation...
Figure 3.5 The early linear structure...
Figure 3.6 The likely mechanism of the...
Figure 3.7 The optimized condition for...
Figure 3.8 The catalyzed hydrogenation...
Figure 3.9 FA seen as a compound with...
Figure 3.10 Two alternative condensation...
Figure 3.11 The ideal polymer structure...
Figure 3.12 The structure of the colorless...
Figure 3.13 The reaction of dimer model...
Figure 3.14 The reaction of FA-polymer...
Figure 3.15 A typical 1H NMR spectrum...
Figure 3.16 UV-visible spectra of (A)...
Figure 3.17 The sequence of steps leading...
Figure 3.18 Two model experiments showing...
Figure 3.19 The DA coupling reaction responsible...
Figure 3.20 The coupling of a growing...
Figure 3.21 Rigid artefacts prepared...
Figure 3.22 The cationic copolymerization...
Figure 3.23 Two systems involving the...
CHAPTER 04
Figure 4.1 The structure of the...
Figure 4.2 The charge-transfer...
Figure 4.3 The structure of the...
Figure 4.4 The alternating...
Figure 4.5 The competition...
Figure 4.6 Two alternative modes...
Figure 4.7 Examples of conjugated...
Figure 4.8 The stabilized structure...
Figure 4.9 Tetramer isolated in the...
Figure 4.10 The protonated furan...
Figure 4.11 The growing dihydrofuran...
Figure 4.12 Branched structures...
Figure 4.13 Conjugated moieties...
Figure 4.14 The two tetramers...
Figure 4.15 2-Vinyl furan (VF)...
Figure 4.16 The expected normal...
Figure 4.17 Two modes of C5 electrophilic...
Figure 4.18 The sequence of events...
Figure 4.19 The regular structure...
Figure 4.20 Synthesis of furan-terminated...
Figure 4.21 Synthesis of a block copolymer...
Figure 4.22 Grafted copolymer prepared...
Figure 4.23 Crosslinked polyVF resins...
Figure 4.24 The cationic polymerization...
Figure 4.25 The limiting structures...
Figure 4.26 The alternating copolymer...
Figure 4.27 The alternating copolymer...
Figure 4.28 The furan radical anion...
Figure 4.29 The alternating copolymer...
Figure 4.30 The monomer units present...
Figure 4.31 Linear crystalline polymers...
Figure 4.32 The structures of the 2-furan...
Figure 4.33 The two oxirane ring opening...
Figure 4.34 The polyFO structure arising...
Figure 4.35 Termination reaction with the...
Figure 4.36 Termination reaction with the...
Figure 4.37 The mechanism leading to the...
Figure 4.38 The uncatalyzed reaction of...
CHAPTER 05
Figure 5.1 Chemical structure...
Figure 5.2 Evolution of the number...
Figure 5.3 Condensation reaction...
Figure 5.4 Synthesis of difuran...
Figure 5.5 A set of furan polyesters...
Figure 5.6 General chemical route to...
Figure 5.7 Furan building blocks...
Figure 5.8 General representation...
Figure 5.9 The first reported synthesis...
Figure 5.10 Synthesis of FDCA-based...
Figure 5.11 Chemical structure of...
Figure 5.12 Schematic representation...
Figure 5.13 Oligoester synthesis from...
Figure 5.14 Synthesis of polyesters...
Figure 5.15 Chemical structures of 2,4-PBF...
Figure 5.16 Synthesis of a polyester from...
Figure 5.17 Molecular structures of...
Figure 5.18 Transpolycondensation reaction...
Figure 5.19 Photocrosslinking through...
Figure 5.20 Synthesis and photopolymerization...
Figure 5.21 Synthesis and ensuing polymerization...
Figure 5.22 Synthesis of (a) crosslinked...
Figure 5.23 Chemical structure of the...
Figure 5.24 General repeating unity...
Figure 5.25 Bisfuranic dicarboxylic...
Figure 5.26 Polymerization of difuran...
Figure 5.27 Aromatic polyamides prepared...
Figure 5.28 Furan-based diamines used for...
Figure 5.29 Synthesis of the furan-Kevlar...
Figure 5.30 Molecular structures of some...
Figure 5.31 Possible route for the...
Figure 5.32 Synthesis of poly...
Figure 5.33 Molecular structure...
Figure 5.34 Molecular structure...
Figure 5.35 Schematic representation...
Figure 5.36 Synthesis and polymerization...
Figure 5.37 Schematic representation...
Figure 5.38 The synthesis of 2-furyl...
Figure 5.39 The synthesis of 2-furfuryl...
Figure 5.40 The mechanism of formation...
Figure 5.41 The three furan diols and...
Figure 5.42 The structures of a selection...
Figure 5.43 TGA tracings for different...
Figure 5.44 The structures of three...
Figure 5.45 Dynamic mechanical behavior...
Figure 5.46 Stress-strain patterns...
Figure 5.47 Comparison between the...
Figure 5.48 Synthesis of a furan polyol...
Figure 5.49 The furan diisocyanate...
Figure 5.50 The synthesis of two furan...
Figure 5.51 Synthesis of 2,2-difurfuryl...
Figure 5.52 Synthesis of furan polyureas...
Figure 5.53 Synthesis of a furan-aliphatic...
Figure 5.54 Stress-strain plots for the...
Figure 5.55 Synthesis of furan polyureas...
Figure 5.56 Typical synthesis...
Figure 5.57 Typical furan-bearing...
Figure 5.58 The possible polymerization...
Figure 5.59 The types of crosslinked...
Figure 5.60 A benzoxazine incorporating...
Figure 5.61 Model mono- and bis-Schiff...
Figure 5.62 The fully conjugated...
Figure 5.63 The other three...
Figure 5.64 Synthesis of a...
Figure 5.65 Synthesis of furan-aliphatic...
Figure 5.66 Synthesis of a series...
Figure 5.67 A selection of the most...
Figure 5.68 The growth mechanism...
Figure 5.69 The photoluminescent...
Figure 5.70 Photochemical synthesis...
Figure 5.71 Polyelectrolyte chitosan...
Figure 5.72 PVA acetalyzed with the...
Figure 5.73 The monomer unit in the...
Figure 5.74 Anomalous monomer units...
Figure 5.75 The first reported synthesis...
Figure 5.76 Oligofurans bearing...
Figure 5.77 Structurally regular...
Figure 5.78 The monomer unit in...
Figure 5.79 The alternating motif...
Figure 5.80 The structure of the...
Figure 5.81 The diepoxy monomers...
Figure 5.82 Epoxy resins based on...
CHAPTER 06
Figure 6.1 Schematic illustration...
Figure 6.2 The mechanism of the...
Figure 6.3 An example of studied...
Figure 6.4 Progressive decrease...
Figure 6.5 Progressive increase...
Figure 6.6 The DA polycondensation...
Figure 6.7 The DA system involving...
Figure 6.8 The aliphatic and the...
Figure 6.9 Schematic representation...
Figure 6.10 DA cross-linking polycondensation...
Figure 6.11 Non-linear DA polycondensations...
Figure 6.12 The synthesis of a polyurethane...
Figure 6.13 The structure of a third-generation...
Figure 6.14 Double-click approach to the...
Figure 6.15 Relative DA reactivity of furan...
Figure 6.16 DA inter-polymer cross-linking.
Figure 6.17 The DA forward and reverse...
Figure 6.18 DA cross-linking and...
Figure 6.19 Dynamic-mechanical...
Figure 6.20 The DA/retro-DA system...
Figure 6.21 Furan-amidation of...
Figure 6.22 The double DA cycle:...
Figure 6.23 Thermally reversible...
Figure 6.24 DA healing process...
Figure 6.25 TPS furan modification...
Figure 6.26 Comparison of solvent...
Figure 6.27 Molding of the TPS...
Figure 6.28 Dynamic mechanical...
Figure 6.29 DA cross-linking of...
Figure 6.30 DA-reversible cross-linking...
Figure 6.31 Thiol-ene click reaction...
Figure 6.32 Two modes of exploiting...
Figure 6.33 Dynamic mechanical properties...
Figure 6.34 DA cross-linking of furan-modified...
Figure 6.35 Comparative effect of mixing time...
Figure 6.36 The generic structure of chitosan.
Figure 6.37 DA cross-linking furan-modified...
Figure 6.38 An example of triglyceride...
Figure 6.39 Synthesis of three monomers...
Figure 6.40 Linear DA thermally reversible...
Figure 6.41 Synthesis of a trifuran monomer...
Figure 6.42 Non-linear DA polymerization of...
Figure 6.43 Non-linear DA polycondensation...
Figure 6.44 Transamination and oxirane opening...
Figure 6.45 DA polymerization involving both...
Figure 6.46 The domains covered by biomedical...
Figure 6.47 The application of the DA reaction...
Figure 6.48 Hot spot (magnetic hyperthermia)...
Figure 6.49 Mechanical retro-DA reaction applied...
Figure 6.50 Stretching a polymer incorporating...
Figure 6.51 Stress-induced DA breaking and...
Figure 6.52 ROMP of a modified furan/maleic...
Figure 6.53 ROMP of a hydrolyzed furan/maleic...
Figure 6.54 Polymer formed in the ROMP of the...
Figure 6.55 The transformation of the furan/maleic...
Figure 6.56 The major products in the DA reaction...
Figure 6.57 The major products of the DA reaction...
CHAPTER 07
Figure 7.1 The sequence of initial...
Figure 7.2 A recent furan polyester...
Figure 7.3 The furan polyesters first...
Figure 7.4 The structure of random furan...
Figure 7.5 The monomers and oligoesters...
Guide
Cover
Title Page
Copyright Page
Table of Contents
Foreword
Preface
Begin Reading
Index
End User License Agreement
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Foreword
Furan Polymers and their Reactions surveys the chemistry of these crucial renewable heterocyclic compounds and their contributions to polymer synthesis with a large variety of their structures. This book discusses the biorefinery of furans, identifies furfural and 5-hydroxymethyl furfural as the key furan monomer precursors for different polymer synthetic processes, and analyzes all the major reactions the monomers undergo during these processes, as well as the structures, properties, modifications, and applications of the ensuing materials. The results are a vital contribution to the growing field of renewable macromolecular materials.
The book provides an up-to-date and detailed analysis of key polymerization reactions such as chain-growth and step-growth polymerizations and the furan/maleimide Diels–Alder reaction, both as a polycondensation tool and as one of the sources of the chemical modifications of polymers.
Furan Polymers and their Reactions is an essential resource and is highly recommended for researchers and professionals in industrial engineering, polymer science, and biotechnology, as well as for any industry professionals working with platform chemicals or polymer synthesis.
Kris MatyjaszewskiCarnegie Mellon UniversityPittsburgh, May 2023
Preface
Eons of evolution have gradually transformed biological structures and functions in all areas of life through increasing molecular complexity and interactions which provided specific adaptations by natural selection. The synthesis of macromolecules in both animal and vegetal species has fulfilled vastly different roles ranging from DNA for genetic information to cellulose and lignin for structural solidity, all being regularly renewed by appropriately adapted pathways in which solar energy is, directly or indirectly, the driving force. In the context of materials science, natural polymers have provided mankind for millennia with valuable sources of living support, including shelter, clothing, tools, and cultural artefacts, aided by technological adaptations, such as natural fiber weaving, papyrus- and then papermaking, leather tanning and construction ingenuities like waterproofing, gluing, as well as hunting and fishing aids. Although some chemistry was unknowingly involved in these activities, the actual suitable chemical modification of natural polymers only begun in the nineteenth century essentially with the preparation of cellulose esters, the vulcanization of rubber, the exploitation of natural resins for making adhesives and sealants, and the controlled drying of plant oils to prepare plastic sheets like linoleum. The major progress, however, occurred throughout the twentieth century because of the chemical revolution associated with the exploitation of fossil resources to prepare monomers and to implement their polymerizations and thus provide an array of synthetic macromolecular materials endowed of different properties and applications. This vigorous development, particularly during the second half of the century, which took the inaccurate name of “plastic revolution”, went for a large part to the detriment of the pursuit of research in the realm of renewable resources as providers of monomers and their polymers, with few novel contributions. This situation started changing toward the end of the century when the paradigm of sustainability begun to make its way within the general conscience in the wake of calls to reduce the dependence on materials and energy providers based on the use of dwindling petroleum and natural gas reserves and to reduce their negative ecological impact to the planet. Research on the alternative exploitation of renewable resources for the same purposes thus resurfaced first timidly, then progressively with more impetus in academy and industry as the century was coming to a close to welcome the new millennium.
This state of affairs is opening a bright scenario in which polymers from renewable resources are witnessing a spectacular growth in the twenty-first century because they represent the response of macromolecular science and technology to the challenges of fighting climate deregulation, together with the equally fundamental search for renewable energy resources, both presently dominated by the exploitation of fossil counterparts. A 2008 monograph provided the first comprehensive state of the art on these materials [1] and numerous reviews followed, with a recent overview of the topic [2] aimed at highlighting the incessant progresses and perspectives in all its domains. The topic is usually subdivided into three major approaches to the elaboration of materials from renewable resources, namely (i) the synthesis of important polymers which are traditionally prepared from fossil resources and can also be prepared now using the same monomers, but derived from renewable counterparts, (ii) the chemical modification of natural polymers to generate novel materials, and (iii) the exploitation of a variety of monomers and macromonomers derived from renewable resources to prepare original macromolecular structures with interesting, or unique, properties and promising applications.
Furans constitute a major class of potential monomers pertaining to the third approach, and this book’s title is a minimalist condensation of the important reality of polymers containing furan units derived from natural resources based on polysaccharides and sugars found worldwide as agricultural and forestry side-products, or available in sufficient quantities to justify their exploitation without affecting the food and feed requirements. Two compounds, furfural and hydroxymethylfurfural are readily prepared from these pentoses and hexoses and can be turned into a variety of monomers, thus generating a whole family of sustainable materials covering virtually all structures and properties already found in fossil-based polymers and even previously unattained performances. This situation is unique, since it cannot be achieved with other natural polymer like cellulose, starch, natural rubber and chitosan, or indeed with such natural monomers as terpenes and vegetable oils, because in all these contexts, their inherent chemical structures limits the breadth of polymer properties that can be obtained, notwithstanding the very impressive variety of materials which have and are being successfully prepared and which have so importantly enriched the domain of polymers from renewable resources.
Molecules and macromolecules incorporating the furan heterocycle have been known or synthesized since 1780 when 2-furoic acid was first prepared by Scheele, followed by furfural, furfuryl alcohol and furan itself in the nineteenth century, and by hydroxymethylfurfural and the first industrial furfuryl alcohol resins in the mid-twentieth century. The real event, however, that established furans as a widely recognized branch of chemistry was the publication in 1953 of a seminal book, The Furans, by A.P. Dunlop and F.N. Peters (ACS Monograph Series N° 119, Reinhold Publishing Co., New York), two high ranking industrial chemists working at the Quaker Oats Company, the progenitor of furfural and furfuryl alcohol. This monumental monograph of close to 900 pages and covering virtually all furan compounds known then, set the scenario for the development of furans in all major branches of chemistry, including organic synthesis, natural compounds, pharmaceuticals, industrial aspects (particularly for the production of furfural), and the nascent macromolecular field (particularly related to furfuryl alcohol resins). Although numerous book chapters, reviews and patents, based on much published research, have since been covering these topics, no other volume has appeared updating the general field of furans in such a comprehensive treatment. Indeed, the present book is no exception, because its purpose is confined to the area of furan polymers, with the specific message of highlighting the renewable character of these materials and hence providing a contribution to the enhancement of sustainability in the realm of macromolecular science. The field of furan polymers is less than a century old and much younger if one considers materials other than the by-now classic resins based on furfuryl alcohol. It seems fair to point out that serious interest in these materials only begun a few decades ago. Several reviews have covered this area since then but, given the rapid upsurge of important advances in different widening contexts, the need for a more comprehensive and updated monograph prompted us to write this book, which attempts to provide a systematic coverage, while giving more emphasis to recent progress, and to propose ideas about future perspectives and practical developments.
We thought it would be useful to begin with a brief historical sketch and with a chapter devoted to a concise reminder of the chemical peculiarities associated with the furan heterocycle because of their strong implications in determining the behavior and mechanisms of most of the types of polymerizations to be discussed. This introductory chapter is however not intended to cover the organic chemistry of furans, whose synthetic and reactivity aspects fall outside the scope of the book. We also decided to treat the polycondensation of furfuryl alcohol and the ensuing materials in a separate first chapter of the book’s main subject because of the unique historical and mechanistic features of what remains today the most important furan industrial material, although this primacy might not last much longer. The rest of the book is organized as in a classical polymer treatise, namely by treating chain- and step-growth systems separately. The properties and potential applications of these materials from renewable resources are outlined when the preparation of each of them is discussed, often comparing their features with those of traditional fossil-based counterparts or emphasizing their unique connotations. We wish to reiterate that the sustainability connotation permeating each section of the book is as essential an ingredient as its actual portrayal of a notable family of macromolecular materials.
References
1
Belgacem, M.N. and Gandini, A. (Eds.) (2008).
Monomers, polymers and composites from renewable resource
. Elsevier, Amsterdam.
2
Gandini, A. and Lacerda, T.M. (2022). Polymers from renewable resources: Macromolecular materials for the twenty-first century? In:
Macromolecular Engineering: From Precise Synthesis to Macroscopic Materials and Applications
, 2e (eds. K. Matyjaszewski, Y. Gnanou, N. Hadjichristidis, and M. Muthukumar). WILEY-VCH GmbH, Vol. 5, 1–77.
1 A Brief History
Furfural (F) industrial production, from pentose-rich oat hulls, begun in 1922 at the Quaker Oats cereal mill in Iowa, and soon after its first resins for molding and abrasive tools were on the market in the US. That was followed by furfuryl alcohol (FA) industrial production by the same company in 1934, through an efficient F reduction process, and its resins for the foundry business in 1958 became commercially available. In both instances, these materials were crosslinked polymers with useful thermal and mechanical properties, but little was known about their mechanisms of formation and ultimate structures. It is most likely that the resinification of both these furans was a frequent unwanted event when handling them from their earlier synthetic operations and isolation, given their sensitivity to accidental polymerization, particularly in acidic media. It is moreover particularly relevant to note that since the inception of a series of thermoplastic (cellulose esters) and thermoset (linoleum and vulcanized natural rubber) materials from renewable resources during the second half of the nineteenth century, these furan resins were the first novel materials being produced from renewable resources in the twentieth century. In another vein, F was converted into adiponitrile for the manufacture of Nylon 6,6 and in this du Pont process of 1949, the tetrahydrofuran intermediate was also later utilized to prepare poly(tetramethylene ether)glycol.
A very modest number of other interesting contributions to furan polymers can be found in the period going back to the late 1960s, whereas the following decade saw what should be considered as the beginning of serious research aimed at preparing and characterizing such materials and unravelling the mechanisms of their formation. The first review on furan polymers, published by one of us in 1977 [1], reflects this initial ferment, albeit underlining that much of it was not entirely gratifying in terms of scientific depth or practical success as far the properties of the ensuing materials. It can be argued that this state of affairs stemmed in part from the few and non-communicating groups scattered around the world, with only one laboratory at Havana University doing systematic work on the polymerization of alkenyl furans and other F-derived monomers. Examples of the paucity of research topics pointed out in that review reflected mostly the rare reports on furan polyesters and polyamides and the absence of studies on polyurethanes, epoxies and other relevant polycondensates. This problem mostly reflected the difficulty in efficiently preparing bifunctional monomers, which were difficult to attain from the monofunctional F and FA.
Some 10 years later, a second review [2] reflected a much-improved situation with a variety of novel investigations covering a wider domain of polymer syntheses and structures, suggesting that the 1980s had brought about a significant awakening concerning the interest of working on furan polymers. But the availability of bifunctional monomers persisted because of the difficulties associated with producing hydroxymethylfurfural (HMF) from hexoses in economically viable quantities.
The overall positive trend was however to continue, as reflected by a third review published a decade later [3], in which the sheer volume of available scientific literature on the subject (reflected by the more than 300 references) was as impressive as much of its scientific and applied quality. This advance was facilitated by the progress in the exploitation of HMF as a source of various bifunctional monomers well suited for the synthesis of polyesters, polyamides and polyurethanes, among other polycondensates.
The research aimed at optimizing the production of HMF became an international effort at the end of the twentieth century, with the primary aim consisting in using it to prepare the corresponding diacid, 2,5-furandicarboxylic acid (FDCA) as the priority monomer, although other difunctional homologues, such as the 2,5-bis(hydroxymethyl)furan (BHMF), were also actively sought, as discussed in a fourth review [4]. The success of this strategy and of other original approaches, notably the application of the Diels–Alder reaction, meant that within another quarter of a century, furan polymers have progressively become a household item to macromolecular scientists, as highlighted by a recent fifth review [5], which represented a skeletal work in progress for the writing of this comprehensive book, which attempts to provide a full picture, going from the pioneering investigations of some 50 years ago to the opening up of brilliant perspectives inspired by the most recent advances.
The numerous breakthroughs that took place in this relatively short saga are documented in detail in each chapter together with a deserved mention to the colleagues who were and are behind these achievements.
References
1
Gandini, A. (1977).
Adv. Polym. Sci
. 25: 47–96.
2
Gandini, A. (1986).
Encyclopedia Polym. Sci. Eng
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