Contents

Cover

Title page

Copyright page

Preface to First Edition

Preface to the Second Edition

Chapter 1: Introduction

1.1 Setting the Stage
References

Chapter 2: Basic Chemical Notions

2.1 Drying Mechanism
2.2 Reactive Sites
References

Chapter 3: Polymerisation of Pristine Oils and their Fatty Acids

3.1 Polymerisation of Unsaturated Oils and Fatty Acids
3.2 Specific Case of Castor Oil
References

Chapter 4: Monomers and Polymers from Chemically Modified Plant Oils and their Fatty Acids

4.1 Epoxidised Structures
4.2 Polyol Structures for Polyurethanes
4.3 Polyisocyanates for Polyurethanes
4.4 Polyether and Polyester Diols for Thermoplastic Polyurethanes
4.5 Diols and Diacids for Linear Polyesters
4.6 Monomers for Linear Polyamides and Polycarbonates
4.7 Vinyl, Acrylic and Other Monomers for Linear Chain-growth Polymerisation
4.8 Monomers for Other, Less Common Linear Polymers
4.9 Special Cases of Castor Oil and Ricinoleic Acid
4.10 Special Case of Glycerol
References

Chapter 5: Metathesis Reactions Applied to Plant Oils and Polymers Derived from the Ensuing Products

5.1 General Considerations
5.2 Metathesis Reactions as Tools for the Synthesis of Monomers and Polymers Derived from Vegetable Oils
References

Chapter 6: Thiol-ene and Thiol-yne Reactions for the Transformation of Oleochemicals into Monomers and Polymers

6.1 General Considerations
6.2 Thiol-ene Reaction as a Tool for the Synthesis of Monomers and Polymers Derived from Vegetable Oils
6.3 Thiol-yne Reaction as a Tool for the Synthesis of Monomers and Polymers Derived from Vegetable Oils
6.4 Final Considerations
References

Chapter 7: Diels-Alder Reactions and Polycondensations Applied to Vegetable Oils and their Derivatives

References

Index

End User License Agreement

List of Illustrations

Chapter 1

Figure 1.1 Total production of oilseeds 2017/2018 (Mt).
Scheme 1.1 Generic structure of a natural triglyceride component of vegetable oils in which R₁, R₂ and R₃ are fatty-acid chains
Scheme 1.2 Structures of the most common fatty acids

Chapter 2

Scheme 2.1 Reactions involved in the oxido-polymerisation of unsaturated fatty acid and the corresponding oils
Scheme 2.2 Kinetic system associated with oxido-polymerisation
Scheme 2.3 Readily exploitable reactive sites in unsaturated triglycerides
Scheme 2.4 Mechanism of the transesterification reaction in acid conditions
Scheme 2.5 Progressive epoxidation of unsaturated triglycerides applied to trioleate
Scheme 2.6 Hydroformylation of methyl oleate
Scheme 2.7 Two possible routes for the dimerisation of oleic moieties [2]
Scheme 2.8 Principle of the thiol-ene reaction
Scheme 2.9 Ozonolysis of castor oil, followed by reduction and hydrolysis
Scheme 2.10 Mechanism of the ozonolysis reaction [19]
Scheme 2.11 General olefin metathesis reaction
Scheme 2.12 illustrates some applications of this reaction to transformation of castor oil-derived undecenal into aliphatic macrodiols for polycondensation reactions.
Scheme 2.12 Mechanisms of metathesis pathways applied to undecenal [23]

Chapter 3

Scheme 3.1 Mechanism of acid-catalysed Diels–Alder coupling between unsaturated oils [1]
Scheme 3.2 Polymerisation of polyunsaturated structures by superacids [1]
Scheme 3.3 Cationic copolymerisation by boron trifluoride etherate (BFE) of an unsaturated triglyceride and a mixture of styrene and divinylbenzene [2–5]
Scheme 3.4 Mechanism for the cationic crosslinking of tung oil [8]
Scheme 3.5 General molecular structure of castor oil
Scheme 3.6 Copolyester based on castor oil and various comonomers [11, 12]
Scheme 3.7 Process leading to a waterborne polyurethane based on castor oil. DMPA: 2,2-Dimethoxy-2-phenylacetophenone [16]
Scheme 3.8 Self-condensation of ricinoleic acid
Scheme 3.9 Polycondensation of ricinoleic acid in the presence of diols [19]
Scheme 3.10 Non-linear polycondensation of ricinoleic acid with pentaerythritol [20, 21]
Scheme 3.11 The synthesis of ABA triblock copolyesters based on ricinoleic acid and L-lactide. ROP: Ring-opening polymerisation [23]

Chapter 4

Scheme 4.1 Cationic photocrosslinking of epoxidised linseed oil [1–3]
Scheme 4.2 Cationic polymerisation of epoxidised methyl oleate and subsequent partial reduction of ester groups of the product into primary OH groups (X=CH₂OH, or COOCH₃). THF: Tetrahydrofuran [9]
Scheme 4.3 Epoxidized soybean oil for the preparation of epoxy thermoset [12].
Scheme 4.4 Reaction of epoxidised linseed oil with diamines [13]
Scheme 4.5 Monomers used to prepare epoxy resins based on terminally epoxidised derivatives of fatty acids [18]
Scheme 4.6 Two-step acrylation of an oxirane moiety incorporated into a triglyceride chain [25, 26]
Scheme 4.7 Partially acrylated epoxidised soybean oil followed by its maleation [29]
Scheme 4.8 Synthesis of novel epoxydised fatty acids from unsaturated vegetable oils as exemplified by the specific case of soybean oil. CTAB: Cetyltrimethylammonium bromide [30]
Scheme 4.9 Monomers used in the study of new epoxy resins. EGS: Glycidyl ester of epoxidised soybean oil fatty acid and EEW: epoxy equivalent weight [30]
Scheme 4.10 Different mechanistic pathways leading to incorporation of OH groups in triglyceride chains through their unsaturations [31]
Scheme 4.11 Mechanism of conversion of an oxirane moiety into a primary OH group through carbonatation [37]
Scheme 4.12 Synthesis of several vegetable oil-based polyols with residual unsaturations [45]
Scheme 4.13 Alternative routes explored to convert triglycerides and their fatty acids into polyisocyanates. Adapted from S. Miao, P. Yong, Z. Su and S. Zhang, Acta Biomaterialia, 2014, 10, 1692 [46]
Scheme 4.14 Structures of diester diols from the study by Cramail and co-workers [56]
Scheme 4.15 Transformation of plant oils into their corresponding diesters, diols and diacids. BDTPMB: Bis(ditertiarybutylphosphinomethyl)benzene [63]
Scheme 4.16 Three routes leading to the ROP of PDL. e-ROP: Enzymatic ring-opening polymerisation [71]
Scheme 4.17 Synthesis of linear polyesters with dangling aliphatic chains using different fatty acids. DMF: Dimethylformamide [73]
Scheme 4.18 Linear aliphatic polyesters incorporating epoxide functions [77]
Scheme 4.19 Homopolymerisation of an epoxide-carboxylic monomer. PMA: Propylene glycol monomethyl ether acetate; TBABr: tetrabutylammonium bromide; and TPPB: tetraphenylphosphonium bromide [78]
Scheme 4.20 Synthesis of diacids and diamines from vegetable fatty acid methyl esters [60–62]
Scheme 4.21 Synthesis of VO by transvinylation [91]
Scheme 4.22 Random free-radical copolymerisation of VL with VAc
Scheme 4.23 Synthesis of saturated fatty acid methacrylates and their atom transfer radical polymerisation. PMDETA: N,N,N′,N′,N″-Pentamethyldiethylenetriamine and TEA: triethylamine [110]
Scheme 4.24 The three unsaturated fatty-acid methacrylates (b, c, d) and the alcohol used for their synthesis (a) [117]
Scheme 4.25 Two ways of preparing fatty acid-bearing oxazolines, and their cationic polymerisation [122]
Scheme 4.26 ‘Chemical flowchart’ from castor ricinoleic triglyceride to polyamide (PA) 11
Scheme 4.27 Introduction of a vinyl end-group onto polyricinoleic acid by immobilised Candida antarctica lipase [126]
Scheme 4.28 Preparation of segmented polyurethanes from polyricinoleic acid. DMAc: dimethylacetamide [127]
Scheme 4.29 Synthesis of bis-cyclic carbonate macromonomers based on methyl 10-undecenoate. TBD: 1,5,7-Triazabicyclo[4.4.0]dec-5-ene and UndBdA: undecenylbisdiamide [128]
Scheme 4.30 Preparation of various polyhydroxyurethanes. IPDA: Isophorone diamine [128]
Scheme 4.31 Linear growth of oligoglycerols catalysed by a nucleophilic agent
Scheme 4.32 Model structure of a hyperbranched polyglycerol
Scheme 4.33 Processes of glycerol conversion into value-added chemicals
Scheme 4.34 Reaction mechanism for the catalytic dehydration of glycerol to acrolein

Chapter 5

Scheme 5.1 a) Cross-metathesis; b) self-metathesis; c) ring-closing metathesis; and d) ring-opening metathesis [1]
Scheme 5.2 Representative mechanism of the metathesis reaction for olefin [4, 5]
Scheme 5.3 Most commonly used ruthenium-based olefin metathesis catalysts [5]
Scheme 5.4 Self-metathesis and cross-metathesis reactions
Scheme 5.5 Synthesis of a C₃₀ α,ω-diester derived from ω-hydroxy palmitic acid. TEA: Triethylamine [14]
Scheme 5.6 Cross-metathesis of methyl 10-undencenoate and dimethyl maleate [20]
Scheme 5.7 Synthetic route to amino esters by sequential metathesis and hydrogenation reactions [18, 24]
Scheme 5.8 Synthesis of renewable AB-type monomers via the Lossen rearrangement, cross-metathesis, and subsequent deprotection. DBU: 1,8-Diazabicyclo[5.4.0]undec-7-ene [25]
Scheme 5.9 The ADMET polymerisation reaction
Scheme 5.10 Long-spaced polyacetals (upper scheme) and polycarbonates (lower scheme) by ADMET copolymerisation and subsequent hydrogenation [44]
Scheme 5.11 Structure of the monomer used to prepare novel renewable polyurethanes. DBTDL: Dibutyltin dilaurate and THF: tetrahydrofuran [47]
Scheme 5.12 ADMET route to prepare renewable polyamides [16]
Scheme 5.13 Synthesis of branched macromolecules via ATMET polymerisation with a chain stopper [52]
Scheme 5.14 ROMP reaction of cyclopentene (schematic)
Scheme 5.15 ROMP of norbornene-modified castor oil and cyclooctene [57]
Scheme 5.16 Preparation of ROMP-susceptible monomers from castor oil. LAH: Lithium aluminum hydride [61]
Scheme 5.17 Acetal interchange reaction a) and the same principle applied to polymerisation by the acetal metathesis polymerisation mechanism b)
Scheme 5.18 Proposed mechanism for ALTMET polymerisation with the first step as a reversible ADMET reaction (I) and the second step an irreversible insertion of the diacrylate (II) [65]
Scheme 5.19 Synthesis of a diene and a diacrylate to be copolymerised further to give AB-alternating copolymers by ALTMET polymerisation [68]

Chapter 6

Scheme 6.1 General thiol-ene coupling reaction
Scheme 6.2 Examples of substrates susceptible to hydrothiolation via a base/nucleophile-mediated process [5]
Scheme 6.3 Thiol-ene free-radical mechanism. AIBN: Azobisisobutyronitrile [5]
Scheme 6.4 Thiol-ene reactions leading to fatty-acid based monomers for polyester synthesis [12, 13]
Scheme 6.5 Monomers synthesised via thiol-ene reaction to be used further in reversible Diels–Alder polymerisations. DCC: N,N’-Dicyclohexylcarbodiimide and DMAP: 4-dimethylaminopyridine [17, 18]
Scheme 6.6 Synthesis of a renewable diisocyanate via the thiol-ene click reaction. THF: Tetrahydrofuran [27]
Scheme 6.7 Carboxyl monomers from sunflower oil and castor oil [19, 29]
Scheme 6.8 Synthesis of new fatty acid-derived monomers for the preparation of polyamides [30]
Scheme 6.9 Reaction of aminated grapeseed oil with epoxidised linseed oil. AGSO: Amino-grafted soybean oil and ELO: epoxidised linseed oil [31]
Scheme 6.10 General thiol-ene polymerisation
Scheme 6.11 Ene and thiol monomers for the synthesis of polyesters and polyanhydrides [33]
Scheme 6.12 Copolymerisation of different ratios of derivatives of fatty acids and a derivative of ferulic acid via the thiol-ene addition with 1,4-butanedithiol [34]
Scheme 6.13 Monomers and polyethylene-like polymers derived from castor oil. DMSO: Dimethyl sulfoxide [39]
Scheme 6.14 Monomers synthesised for the preparation of renewable polythioethers [40]
Scheme 6.15 Enzymatic polymerisation of globalide followed by thiol-ene post-polymerisation modification [45]
Scheme 6.16 Post-polymerisation modification of DecEnOx-derived polymers [47]
Scheme 6.17 Radical-mediated mechanism of the thiol-yne click reaction [49]
Scheme 6.18 Synthesis of fatty acid-derived polyols starting from 10-undecenoic acid and oleic acid. DMPA: 2,2-Dimethoxy-2-phenylacetophenone [50]
Scheme 6.19 Application of thiol-ene and thiol-yne reactions of propargylic fatty ester and propargylic fatty diester with mercaptoethanol [52]

Chapter 7

Scheme 7.1 Diels-Alder and retro-Diels–Alder reactions
Scheme 7.2 Diels–Alder equilibrium between furan and maleimide end groups in a stepwise macromolecular synthesis
Scheme 7.3 Typical thermally reversible Diels–Alder polymerisation with a difuran monomer prepared from a derivative of vegetable oils [9, 10]
Scheme 7.4 Non-linear Diels–Alder polycondensation between an oil-based trisfuran and a BM. TCE: 1,1,2,2-Tetrachloroethane [11]
Scheme 7.5 Double insertion of furfurylamine into epoxidised linseed oil [12]
Scheme 7.6 Linear Diels–Alder polymerisation of a difuran product with an aromatic bismaleimide [12]
Scheme 7.7 Non-linear Diels–Alder polymerisation of the trisfuran with an aromatic bismaleimide [12]
Scheme 7.8 Crosslinking of tung oil with different bismaleimide through Diels–Alder (DA) intermolecular couplings (a) and its aminolysis followed by linear DA polymerisation of the ensuing fatty acid furan amides (b) [13]

This edition first published 2019 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA
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Library of Congress Cataloging-in-Publication Data
Names: Gandini, Alessandro, author. | Lacerda, Talita Martins, author.
Title: Polymers from plant oils / Alessandro Gandini and Talita M. Lacerda.
Description: 2nd edition. | Hoboken, NJ : John Wiley & Sons, Inc., 2018. | Includes bibliographical references and index. |
Identifiers: LCCN 2018044842 (print) | LCCN 2018046235 (ebook) | ISBN 9781119555827 (ePub) | ISBN 9781119555339 (ePDF) | ISBN 9781119555797 (hardcover)
Subjects: LCSH: Vegetable oils–Industrial applications. | Plant polymers. | Polymerization. | Biomass chemicals. | Renewable natural resources.
Classification: LCC TP680 (ebook) | LCC TP680 .G28 2018 (print) | DDC 665.3–dc23 LC record available at https://lccn.loc.gov/2018044842

Preface to First Edition

Vegetable (or plant) oils, shown here as plant triglycerides, constitute one of the most abundant variety of renewable resources on our planet. They have been exploited by humans for millennia for three major purposes: food and feed, energy sources and precursors to useful products and materials. Ancient utilisations and applications (empirical by definition) contributed to ensure: daily sustenance for people and animals; comfort through heating and illumination; development of protective, writing and artistic coatings in the form of film-forming materials that ‘dried in air’. They were then adopted as pristine natural compounds, though in some instances other components were mixed with them, as in the case of inks and lacquers. Simple chemical transformations carried out empirically were also developed, as in the manufacture of soaps simulating the process applied to animal fats.

Unraveling of their chemical structure, and hence understanding of their reactivity, favoured more rational processing and widened the range of applications throughout the twentieth century. Another more important ‘revolution’ has begun at the start of the third millennium with expansion of the research/development of biofuels and macromolecular materials.

This book is devoted exclusively to the latter realm, with particular emphasis on recent trends, progress, achievements and perspectives, with broad treatment of the subject, including inks, paints and coatings, in addition to the more conventional bulk thermoplastic and thermosetting polymers.

In the field of film-forming materials, use of alkyd resins incorporating plant oils or their derivatives has been a standard practice for a century, but no major qualitative advance was introduced until recently. The same applies for bulk polymers based on vegetable oils, of which linoleum (first commercialised in the middle of the nineteenth century) was for a long time the only important representative of these materials. Nylon 11 (commercialised under the name of Rilsan based on castor oil as a precursor) has been an important addition to this small family from the 1950s onwards. In other words, vegetable oils represented a very modest presence as basic constituents of macromolecular materials up to about a decade ago, but the situation has evolved radically since then.

The purpose of this book is to highlight this impressive and promising ongoing trend, which is also occurring in all other areas of the novel burgeoning domain of polymers from renewable resources.

We wish to thank most heartedly Joan Gandini for her constant help in improving the language and style of the manuscript. The authors kindly acknowledge FAPESP for T.M.L.’s post-doctoral fellowship (2012/00124-9) and CNPq for A.G’s visiting professorship (Science Without Borders programme, PVE 401656/2013-6).

February 2015

Preface to the Second Edition

The publishers of the first edition of this book (2015), Smithers Rapra, relinquished their copyright to the authors who prepared the present second edition for publication under the auspices of Scrivener Publishing. There are no qualitative changes in the contents of this edition with respect to the first, which we still considered quite appropriate, whereas our attention focused on bringing up to date a number of issues related to recent relevant facts and important contributions. We feel that the topic of the book has maintained a high level of interest, as judged by the continuing flow of publications and new materials being developed by both academic and industrial research activities throughout the world. We trust therefore that the message contained in the original preface remains fully justified.

The authors kindly acknowledge FAPESP for financial support (2017/16062-6).

Alessandro Gandini and Talita M. Lacerda
August 2018