Polymers from Plant Oils

Unique state-of-the-art book on an important topic in renewable materials

The purpose of this monograph is to provide a thorough outlook on the topic related to the synthesis and characterization of original macromolecular materials derived from plant oils, an important part of the broader steadily growing discipline of polymers from renewable resources. The interest in vegetable oils as sources of biodiesel and materials has witnessed a remarkable growth of scientific and industrial interest since the beginning of the third millennium responding to the pressing drive to implement sustainability in the energy and materials sectors.

The book highlights the most relevant strategies being pursued to elaborate polymers derived from a variety of common oils, by direct activation or through chemical modifications yielding novel monomers. Because glycerol is the main byproduct of biodiesel production, it is treated here as the other logical source of macromolecular synthesis. Each of the different approaches is illustrated by an introductory layout of the underlying chemical mechanisms, followed by examples of notable achievements in terms of the properties and potential applications of the ensuing materials, which span a wide range of structures and performances. In particular, original pathways involving click-chemistry reactions as thiol-ene and Diels-Alder couplings and metathesis polymerizations are discussed and shown to reflect the involvement of a growing number of research programs worldwide.

Alessandro Gandini is a physical chemist who has taught and conducted research for the last fifty years at academic and other institutions in Switzerland, UK, Canada, USA, Cuba, France, Brazil and Portugal, after his first degree in Italy. His main scientific interests are polymer synthesis and characterization, with a special emphasis on polymers from renewable resources, photochemistry, and the physical chemistry of surfaces and interfaces. He has published more than 400 scientific contributions and is an Honorary Doctor of the Saint Petersburg Forestry Academy and of Havana University, and was invested with the Ermine decoration of Grenoble National Polytechnic Institute, France.

Talita M. Lacerda received her PhD degree in chemistry in 2012 from the São Carlos Institute of Chemistry, University of São Paulo, Brazil. After holding a post-doc position in Professor Alessandro Gandini's research group (2012-2016) and in Professor Michael Meier's research group (2013-2014), she moved in 2016 to the Biotechnology Department of Lorena School of Engineering, University of São Paulo. Her main research interests include the synthesis and chemical modification of polymers and the development of biocomposites based on renewable resources.

Preface to First Edition vii

Preface to the Second Edition ix

1 Introduction 1

1.1 Setting the Stage 1

References 7

2 Basic Chemical Notions 9

2.1 Drying Mechanism 9

2.2 Reactive Sites 11

2.2.1 Reactions of the Ester Group 12

2.2.2 Reactions of Unsaturated Bonds 13

References 19

3 Polymerisation of Pristine Oils and their Fatty Acids 23

3.1 Polymerisation of Unsaturated Oils and Fatty Acids 23

3.2 Specific Case of Castor Oil 26

References 31

4 Monomers and Polymers from Chemically Modified Plant Oils and their Fatty Acids 33

4.1 Epoxidised Structures 33

4.1.1 Direct Polymerisation 33

4.1.2 Reactions with Amines and Anhydrides 36

4.1.3 Acrylation Reactions 39

4.2 Polyol Structures for Polyurethanes 43

4.3 Polyisocyanates for Polyurethanes 47

4.4 Polyether and Polyester Diols for Thermoplastic Polyurethanes 49

4.5 Diols and Diacids for Linear Polyesters 51

4.6 Monomers for Linear Polyamides and Polycarbonates 57

4.7 Vinyl, Acrylic and Other Monomers for Linear Chain-growth Polymerisation 59

4.8 Monomers for Other, Less Common Linear Polymers 64

4.9 Special Cases of Castor Oil and Ricinoleic Acid 64

4.10 Special Case of Glycerol 69

References 73

5 Metathesis Reactions Applied to Plant Oils and Polymers Derived from the Ensuing Products 83

5.1 General Considerations 83

5.2 Metathesis Reactions as Tools for the Synthesis of Monomers and Polymers Derived from Vegetable Oils 87

5.2.1 Metathesis Reactions for Monomer Synthesis 87

5.2.2 Olefin Metathesis Applied to Polymer Synthesis 92

5.2.2.1 Acyclic Diene Metathesis Polymerisation 92

5.2.2.2 Acyclic Triene Metathesis Polymerisation 97

5.2.2.3 Ring-opening Metathesis Polymerisation 98

5.2.2.4 Special Cases of Acetal Metathesis Polymerisation and Alternating Diene Metathesis Polymerisation 101

References 104

6 Thiol-ene and Thiol-yne Reactions for the Transformation of Oleochemicals into Monomers and Polymers 109

6.1 General Considerations 109

6.2 Thiol-ene Reaction as a Tool for the Synthesis of Monomers and Polymers Derived from Vegetable Oils 112

6.2.1 Thiol-ene Reactions for Monomer Synthesis 112

6.2.2 Thiol-ene Reactions Applied to Polymer Synthesis 120

6.2.3 Thiol-ene Reactions for Chemical Modifications after Polymerisation 125

6.3 Thiol-yne Reaction as a Tool for the Synthesis of Monomers and Polymers Derived from Vegetable Oils 127

6.4 Final Considerations 130

References 130

7 Diels–Alder Reactions and Polycondensations Applied to Vegetable Oils and their Derivatives 135

References 142

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