Organic catalysis for polymerisation

668 Pages·2019·20.674 MB·English

by  Dove, Andrew Peter, Naumann, Stefan, Sardon, Haritz

Organic Catalysis for Polymerisation
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Polymer Chemistry Series
Editor-in-chief:
Ben Zhong Tang, The Hong Kong University of Science and Technology,
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7 Series editors:
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80 Alaa S. Abd-El-Aziz, University of Prince Edward Island, Canada
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17 Jianhua Dong, National Natural Science Foundation of China, China
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97 Jeremiah A. Johnson, Massachusetts Institute of Technology, USA
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3 Toshio Masuda, Shanghai University, China
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0. Christoph Weder, University of Fribourg, Switzerland
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g | Titles in the series:
c.or 1: Renewable Resources for Functional Polymers and Biomaterials
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s.r 2: Molecular Design and Applications of Photofunctional Polymers and
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u Materials
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s:// 3: Functional Polymers for Nanomedicine
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htt 4: Fundamentals of Controlled/Living Radical Polymerization
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o 5: Healable Polymer Systems
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01 6: Thiol-X Chemistries in Polymer and Materials Science
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er 7: Natural Rubber Materials: Volume 1: Blends and IPNs
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m 8: Natural Rubber Materials: Volume 2: Composites and Nanocomposites
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5 10: Polymeric Materials with Antimicrobial Activity: From Synthesis to
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on Applications
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e 11: Phosphorus-Based Polymers: From Synthesis to Applications
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bli 12: Poly(lactic acid) Science and Technology: Processing, Properties,
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P Additives and Applications
13: Cationic Polymers in Regenerative Medicine
14: Electrospinning: Principles, Practice and Possibilities
15: Glycopolymer Code: Synthesis of Glycopolymers and their Applications
16: Hyperbranched Polymers: Macromolecules in-between Deterministic
Linear Chains and Dendrimer Structures
17: Polymer Photovoltaics: Materials, Physics, and Device Engineering
18: Electrical Memory Materials and Devices
19: Nitroxide Mediated Polymerization: From Fundamentals to
Applications in Materials Science
20: Polymers for Personal Care Products and Cosmetics
21: Semiconducting Polymers: Controlled Synthesis and Microstructure
22: Bio-inspired Polymers
23: Fluorinated Polymers: Volume 1: Synthesis, Properties, Processing and
Simulation
24: Fluorinated Polymers: Volume 2: Applications
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25: Miktoarm Star Polymers: From Basics of Branched Architecture to
Synthesis, Self-assembly and Applications
26: Mechanochemistry in Materials
27: Macromolecules Incorporating Transition Metals: Tackling Global
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00 Challenges
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8-F 28: Molecularly Imprinted Polymers for Analytical Chemistry Applications
73 29: Photopolymerisation Initiating Systems
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01 30: Click Polymerization
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78 31: Organic Catalysis for Polymerisation
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Organic Catalysis for
Polymerisation
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9/ Andrew Dove
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1 University of Birmingham, UK
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oi:1 Email: [email protected]
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or Haritz Sardon
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s.rs University of the Basque Country UPV/EHU, Spain
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1 Stefan Naumann
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10. PrintISBN:978-1-78801-184-6
oi: PDFISBN:978-1-78801-573-8
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or PrintISSN:2044-0790
sc. ElectronicISSN:2044-0804
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57 Preface
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oi: Polymers are ubiquitous in our daily lives. They have revolutionized almost
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c. as packaging or other single-use products, to those with longer lifetimes
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s.r suchasclothingorconstruction,throughtohighervaluematerialsthatare
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pu componentsinhighvalueproductssuchasplasticelectronicsorhealthcare
s:// applications. As may be expected from the age of petroleum, a majority of
p
htt polymersthatarecommonlyusedarederivedfrompetrochemicalresources.
n
8 o Inevitably, with the high current focus on sustainable sourcing of polymers
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0 and the need for reducing plastic waste that enters and persists in the en-
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er vironment, when polymers enter the public consciousness, discussions
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e quickly turn to the consideration of their negative points over the many
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No positives in a blessing-and-curse style of argument.
15 Whilethebenefitsofpolymersareclearlyunderstood,themajorpointsof
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o criticism focus on the environmental impact of the polymers, from their
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she end-of-lifetreatmentsthatincludelimitedrecycling,burningtoproduceCO2
bli andotherharmfulgreenhousegasses,disposalinlandfillorworse,littering
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P ourenvironment.Furthermore,theleachingofpotentiallyharmfulpolymer
additives such as plasticisers, residual monomers or catalysts all have
potentially negative effects on the environment and ultimately people.
Theenvironmentalissues,aswellasconcernsoverthedepletionoffossil
fuelresourcesfromwhichmanypolymersaremade,haveledtoasignificant
and growing interest in ‘green’ chemistries. This is a broadly defined topic
that, with relation to polymer science, is dedicated to increasing the sus-
tainability of polymer synthesis and the connected process technologies,
withastrongfocusonimprovingthesustainabilityofallaspectsofplastics
technology from removal of harmful solvents to using more sustainably
sourcedprecursorstoalleviateenvironmentalconcerns,healthhazardsand
resourceefficiency.As oneof theguiding principlesof green chemistry, the
PolymerChemistrySeriesNo.31
OrganicCatalysisforPolymerisation
EditedbyAndrewDove,HaritzSardonandStefanNaumann
rTheRoyalSocietyofChemistry2019
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
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viii Preface
application of catalysis is a critical piece of the puzzle. Of all the tools in
the chemists’ arsenal, catalysis is probably the one able to contribute the
mosttothesegoals.Inpolymersynthesis,catalysisplaysanessentialrolein
increasing the rate of reactions and reducing side reactions that occur to
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00 improve selectivity thus leading to more predictable outcomes and less
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8-F waste. Given the excellent performance and vast array of opportunities that
73 metallo-organic chemistry offers through the almost infinite ligand/metal
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01 combinations,itisnotsurprisingthattransitionmetalsandorganometallic
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78 catalysts have dominated the field of polymerisation catalysis. However,
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78 in part due to concerns over the availability of some widely used metals
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9/ such as zinc or silver, which risk complete disappearance in the next
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1 100 years, or ruthenium, lithium or copper, which will be seriously threa-
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oi:1 tened in the future if their consumption continues to increase, the use of
g | d organic compounds to catalyse polymerisation reactions is gaining in-
or creasing interest. In the past two decades, the remarkable ability of small
c.
s organic molecules to mediate a variety of polymerisation processes has
s.r
b brought about the rapid evolution of metal-free, organocatalytic polymer-
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s:// isation techniques.
http Whiletheinterestinorganiccatalysishadbeengrowingformediatingan
n array of organic transformations, its initial translation into the world of
o
18 polymer synthesis was in the ring-opening transesterification polymer-
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er 2 isation of lactide in order to produce ‘soft-etch’ polymers for potential
mb microelectronics applications that were readily degradable in mild acidic
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v etching conditions and would not leave any metal residues. While the
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n in the biomedical field where metal-based impurities can be prohibitively
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d expensive to remove, organocatalysed polymerisation has now progressed
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blis far beyond the fact of merely being ‘metal-free’, presenting ways to lower
Pu toxic byproducts in polymers and to address resource efficiency concerns
associated with metals. Inspired by nature with the use of enzymes to
catalyse biochemical reactions, metal-free polymerisations offer unique
polymerisation pathways, access to various macromolecular architectures
and novel selectivities, quite often in combination with excellent control
over important polymer parameters such as molecular weights, poly-
dispersity, end groups and copolymer constitution. Indeed, the field has
progressed to the point that organic catalysts now provide many potential
advantages to their metallo-organic counterparts that mean that in many
cases they are now preferred (at least in the academic world) for polymer-
isation. Many organocatalytic species are inexpensive, commercially avail-
able molecules that either can be used as received or can be made and
purified through a limited number of steps. Indeed, a wide range of
the most commonly used species, although not all, are stable to both water
and oxygen, which beyond providing an advantage in handling also results
inlongershelfliveswithouttheneedforstorageininertatmospheres.While
some applications may still require removal of air/moisture (i.e. ring-
opening transesterification polymerisation), this is a process that is only
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Preface ix
undertakentoensurehighendgroupfidelityandagoodmatchofmolecular
parameters to those predicted/desired rather than any need for the organic
catalysttowork.Manyofthemostcommonlyusedorganiccatalystsarealso
stable to a large array of reaction conditions, solvents, and monomers,
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00 making them highly versatile. Finally, the acidic, basic or ionic nature of a
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73 by low cost methodologies such as washing or trapping in resin beads.
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01 The field of organic catalysis for ring opening polymerisation has grown
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78 significantly in the past 15 years to the point that the advantages of the
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78 approaches are being recognised and organocatalytic approaches are being
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9/ sought in preference to metal-based catalysts. A much broader range
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1 of monomers can now be polymerised, being extended far beyond its ori-
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oi:1 ginal scope to include not only lactones and carbonates, but also epoxides,
g | d anhydrides, siloxanes, lactams, acrylic monomers and many others.
or Alongside the development of innovative catalyst families that are able to
c.
s be highly selective towards one functionality over another, the field is
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b blossoming. While there are some reviews and viewpoints in the journal
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s:// literature, the many facets of organopolymerisation and an ever increasing
http numberofpublicationshasraisedthedemandforacomprehensivereview,
n especially since no comparable collection of information is currently
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18 available. As such, the presented edited book on Organic Catalysis for
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er 2 Polymerisationisthefirstofitskindonthisresearchtopic.Eminentexperts
mb intheirrespectivefieldshavetakenadetailedlookatallrelevantaspectsof
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v metal-free polymerisation approaches. The close interconnections between
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n are mirrored in the organization of the chapters, where two different
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d viewpoints are taken. The first part of the book presents the fundamental,
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blis metal-free catalyst polymerisation principles (nucleophilic, acid- and base-
Pu catalysed as well as dual or supramolecular catalysis, Chapters 1–4). Here
all relevant types of organocatalysts are detailed, with an emphasis on
polymerisation mechanisms and on elucidating the impact of structural
changesinthecatalystontheresultingpolymers.Together,thisdeliversan
informative profile on the evolution of the field and describes how the
different catalyst families are able to polymerise the various monomer
classes,highlightingthecrucialdifferencesbetweenthemtopresentclearly
the opportunities that remain in those areas. In the second part of the
book, the focus is turned onto the different classes of monomer, detailing
the existing metal-free polymerisation strategies for a given class of com-
pounds (lactones, lactides, carbonates, epoxides, other cyclic and acrylic
monomers, Chapters 5–11) to provide a one-stop guide to select the most
appropriate catalyst for any given process, as well as inspiration for where
the future challenges lie. These chapters will not only provide a com-
prehensive overview for the polymerisation of conventional monomers
suchaslactide,epoxides ortrimethylenecarbonatebutalsosummarizethe
most relevant results about the use of organocatalysis for the ring opening
polymerisation of aziridines or phosphester monomers amongst many
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x Preface
others. Taken together, this will facilitate access to this research field both
for readers interested in catalyst design and development as well as those
focusingonthe best methodologies tosynthesise aspecifictype of polymer
using organocatalytic routes. Finally, the focus is shifted to the more
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00 nascent, yet highly important areas of organocatalysed step-growth re-
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73 In this third part, the potential of organocatalysis for step-growth poly-
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01 merisation reaction and the preparation of industrially relevant polymers
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78 such as polyurethanes and in the emerging area of organocatalysed con-
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78 trolled polymerisation for the preparation of well-defined specific polymer
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9/ structures are described. Subsequently, Chapter 14 is focussed on the
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1 emerging subject of organocatalysis in polymer recycling/depolymerisation.
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oi:1 No doubt this area will grow significantly in importance over the coming
g | d years and, given the environmental credentials of organocatalysis, it could
or play an important role to facilitate the implementation of inexpensive and
c.
s sustainable chemical recycling processes. Finally, an outlook (Chapter 15)
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b provides a commentary of the most important developments in organic
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s:// catalysis for polymerisation to date and summarises some of the major
http challenges that face the field in the coming decade.
n We like to conclude with the grateful acknowledgement of all contribu-
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18 tors,whowiththeirexpertiseanddiligencewerecrucialtothesuccessofthis
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er 2 projectandwishthatreadersmayfindOrganicCatalysisforPolymerisationan
mb informative and thought-provoking inspiration.
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