Polymers from Plant Oils

190 Pages·2015·2.602 MB·English

by  Alessandro Gandini, Talita Lacerda

Polymers from Plant Oils
Alessandro Gandini
and
Talita Martins Lacerda
A Smithers Group Company
Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom
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http://www.polymer-books.com
First Published in 2015 by
Smithers Rapra Technology Ltd
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
©Smithers Information Ltd., 2015
All rights reserved. Except as permitted under current legislation no part
of this publication may be photocopied, reproduced or distributed in any
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the prior permission from the copyright holder.
A catalogue record for this book is available from the British Library.
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within the text and the author and publishers apologise if
any have been overlooked.
ISBN: 978-1-90903-090-9 (hardback)
978-1-91024-241-4 (softback)
978-1-90903-091-6 (ebook)
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P
reface
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 20th 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 19th 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.
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Polymers from Plant Oils
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).
iv
C
ontents
1 Introduction ...............................................................................................1
1.1 Setting the Stage ..............................................................................1
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
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
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
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Polymers from Plant Oils
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
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
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
7 Diels–Alder Reactions and Polycondensations Applied to Vegetable
Oils and their Derivatives .......................................................................135
vi
Contents
8 Conclusions and Perspectives .................................................................145
Abbreviations ....................................................................................................147
Index ..............................................................................................................153
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Polymers from Plant Oils
viii
1
Introduction
1.1 Setting the Stage
World production of major oilseeds has increased from 331 million tonnes to 529
million tonnes in the last decade, whereas the harvested area has increased from 186
million acres to 234 million acres in the same period. According to the United States
Department of Agriculture (USDA), soybean oilseeds represent over half of the total
production of oilseeds and are mainly grown in Brazil, USA and Argentina; followed by
rapeseed (grown in European Union (EU)-27, Canada and China), cottonseed (China
and India) and sunflower oilseeds (Ukraine, EU-27 and Russia). Figure 1.1 shows
the total production projection of major oilseeds around the world for 2014/2015.
2014/2015 Total Oilseed Production
34.92
117.18
57.26
37.35
Production (MMT)
97.07
59.08 - 128
20.36 - 59.08 World Total:
59.08
528.9 MMT
8.45 - 20.36
1.86 - 8.45
Source: PSD Online (Upload: November 10, 2014)
0 - 1.86
(http://www.fas.usda.gov/psdonline)
Figure 1.1 Total production of oilseeds 2014/2015.
Reproduced with permission from United States Department of Agriculture
http://www.fas.usda.gov/psdonline
©United States Department of Agriculture [1]
1