Conversion of Living Anionic Polymerisation into Living ROMP

276 Pages·2014·9.98 MB·English

Durham E-Theses
Synthesis of block copolymers by the conversion of living
anionic polymerisation into living ROMP
Castle, Thomas Charles
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Castle, Thomas Charles (2004) Synthesis of block copolymers by the conversion of living anionic
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2
Synthesis of Block Copolymers by the
Conversion of Living Anionic Polymerisation
into Living ROMP
A thesis submitted for the degree of
Doctor of Philosophy
by
Thomas Charles Castle
A copyriglilt of this thesis rests
with tlb.e author. No quotation
from it should be published
without his prior written consent
and information derived from it
should! be acknowlledged.
Department of Chemistry
University of Durham
December 2004
Abstract
A methodology for the synthesis of well-defined block copolymers from living
anionic polymerisation and ring opening metathesis polymerisation (ROMP) using
well-defined ruthenium alkylidene initiators has been developed.
Polymers synthesised by anionic polymerisation were converted into
macromonomers, which were used as precursor polymers to well-defined ruthenium
macro initiators for ROMP. The macroinitiators were synthesised by an olefin
metathesis reaction, involving alkylidene exchange of RuCli =CHEt)(PCy with the
)
3 2
macromonomers. The ROMP of norbornene (NBE) derivatives using the
macroinitiators resulted in the synthesis of block copolymers. These copolymers
possessed low polydispersity indices (typically 1.2 or less) and contained small
quantities or none of the anionically polymerised homopolymer.
Poly(e thylene oxide) (PEO) macromonomers were synthesised by terminating
living PEO with 4-vinylbenzyl chloride. The PEO macromonomers were used to
synthesise block copolymers of ethylene oxide (EO) and NBE derivatives.
Polystyrene (PS) macromonomers were prepared by Williamson coupling of hydroxyl
functionalised PS and 4-VBC. The hydroxyl functionalised PS was synthesised by
end functionalising living PS with EO or by incorporating a hydroxy functionality
into the initiator in a protected form. Copolymers of styrene and NBE derivatives
were produced using the PS macromonomers. The applicability of this methodology
to other monomers that can be polymerised by an anionic mechanism was examined.
The ROMP monomers included NBE derivatives with imide, dicarboxylic
ester and chloromethyl groups, illustrating the range of functionalities that can be
incorporated into the ROMP block using this methodology.
I
Acknowlledgment§
I wish to thank my supervisor Dr Ezat Khosravi for his supervision and advice
throughout my PhD research and for sharing his knowledge of ROMP with me.
Similarly I wish to thank my collaborator and eo-supervisor Dr Lian Hutchings for his
help, not least for his insights into anionic polymerisation, and the use of his lab
equipment. I must thank Lian and Doug Carswell for the multitude of GPC
experiments they have performed for me. My great thanks must go to Dr Alan
Kenwright for his help in the interpretation of NMR spectra. I am also indebted to
Catherine Heffernan and Ian Mckeag for their help recording NMR spectra and
numerous other bits of help. Thanks go to Dr David Parker for recording the MALDI
spectra, often when he had very limited time in which to do so. I must thank Dr.
Michael Jones and Ms Lara. Turner for collecting data using the other mass spectral
techniques. I am grateful for the elemental analyses which were run by Mrs. Jarika
Dostal and for the highly skilled and timely work of the glassblowers, namely Mr.
Malcom Richardson and Mr. Peter Coyne. I am grateful for the help I have received
from the technicians elsewhere in the department, particularly those in stores, the
departmental information technology service, and the electrical and mechanical
workshops.
Thanks must go to all of the members of the IRC, both past and present who
helped me in any way, great or small. There are some individuals whom I feel I must
acknowledge specially, for various reasons. These include Craig Mason for helping
me when I started out in the lab, and for access to his reservoir of monomers. I have
enjoyed many mutually useful discussions on ROMP with Dave Haigh. Susan
Roberts-Bleming has been a source of helpful advice related to coupling reactions and
anionic polymerisations. I must also thank Oliver Henze for being a useful source of
critical advice when needed. I also wish to thank the denizens of CGl (particularly the
group of Dr Patrick Steele) for their help and advice on various matters.
Finally I must thank my parents and everybody else who has contributed to
getting me where I am now.
11
Dedauratiollll
The work reported in this thesis was carried out in the laboratories of the
Interdisciplinary Research Centre (IRC) in Polymer Science and Technology,
Department of Chemistry, University of Durham, between October 2001 and
September 2004. This work has not been submitted for any other degree in Durham or
elsewhere and is the original work of the author except where acknowledged by
means of appropriate reference.
Statement of Copyright
The copyright of this thesis rests with the author. No quotation from it should
be published without their prior written consent and information derived from it
should be acknowledged.
Financial Support
I gratefully acknowledge the Engineering and Physical Sciences Research
Council (EPSRC) for their generous funding of this research. I must thank the Society
of Chemical Industry (SCI), Macro Group UK, Ustinov College (The Graduate
Society), the European Union (EU), and the North Atlantic Treaty Organisation
(NATO) for funding my attendance at conferences and meetings to present this
research.
Ill
Contents
Page
Abstract I
Acknowledgements 11
Memorandum Ill
Statement of Copyright Ill
Financial Support Ill
Contents IV
Abbreviations VII
Chapter 1 - Overview and Introduction
1.1 Aims, Objectives and Overview 2
1.2 Synthesis and Applications of Block Copolymers 2
1.3 Anionic Polymerisation 4
1.3.1 The Living Anionic Polymerisation of Styrene 4
1.3.2 Initiators for Living Anionic Polymerisation 5
1.3.3 The Effect of Solvents, Salts and Additives on Anionic
Polymerisation 10
1.3.4 Functionalisation of Polymers Synthesised using Living
Anionic Polymerisation 12
1.3.5 Vinyl Monomers Polymerisable by Anionic Polymerisation 16
1.3.6 Anionic Ring Opening Polymerisation 23
1.4 Olefin Metathesis 29
1.4.1 The Mechanism of Olefin Metathesis 30
1.4.2 The Microstructure of Polymers Synthesised by ROMP 31
1.4.3 An Overview of the Development of Initiators for Olefin
Metathesis 32
1.4.4 Living ROMP Initiated using RuCh(=CHPh)(PCy3)2 44
1.5 Synthesis of Block Copolymers using Two Different
Polymerisation Techniques 48
1.5.1 Active Site Transformation 49
1.5.2 Use of Macroterminators to Synthesise Block Copolymers 52
1.6 References 53
IV
Chapter 2 -Block Copolymers of Ethylene Oxide and Norbornene Derivatives
2.1 Introduction 62
2.2 Results and Discussion 63
2.2.1 The Anionic Polymerisation of Ethylene Oxide 63
2.2.2 The Synthesis and Characterisation of Methyl
Iodide Terminated Poly(Ethylene Oxide) 66
2.2.3 The Synthesis and Characterisation of Poly(Ethylene Oxide)
Macromonomers 72
2.2.4 Synthesis and Characterisation of Ruthenium Propylidene
Complex RuCh(=CHEt)(PCy3)z 77
2.2.5 Synthesis and Properties of PEO Ruthenium Macroinitiators 80
2.2.6 Synthesis of an Exo Dicarboxyimide Norbornene Monomer 84
2.2.7 Synthesis and Characterisation of PNB Homopolymers 87
2.2.8 Synthesis and Characterisation of PEO-PNB Block Copolymers 100
2.3 Conclusions and Summary 106
2.4 Experimental 107
2.4.1 General 107
2.4.2 Synthesis of Poly(Ethylene Oxide) Homopolymers 109
2.4.3 Synthesis of Propylidene Initiator RuCh( =CHEt)(PCy3)2 112
2.4.4 Synthesis of a Ruthenium PEO Macroinitiator 113
2.4.5 Synthesis of ROMP Monomers 114
2.4.6 ROMP Homopolymerisations 116
2.4.7 Synthesis of PEO-PNB Block Copolymers 120
2.5 References 124
Chapter 3 -Block Copolymers of Styrene and Norbornene Derivatives
3.1 Introduction 128
3.2 Results and Discussion 129
3.2.1 Synthesis and Characterisation of PS Macromonomers from PSLi 129
3.2.2 Synthesis and Properties of PS Macroinitiators 144
3.2.3 Synthesis and Properties of PS-PNB Block Copolymers 147
3.3 Conclusions and Summary 159
3.4 Experimental 159
V
3.4.1 General 159
3.4.2 Synthesis of Polystyrene Homopolymers 162
3.4.3 Synthesis of the PS Ruthenium Macroinitiator 166
3.4.4 Synthesis of PS-PNB Block Copolymers 167
3.5 References 172
Chapter 4 ~ Macromonomers from Hydroxyl Groups Introduced by Anionic
Polymerisation using Protected initiators
4.1 Introduction 176
4.2 Results and Discussion 177
4.2.1 Polystyrene Macromonomers from a Protected Initiator 177
4.2.2 Attempted Synthesis of Poly(Methyl Methacrylate)
Macromonomer 186
4.2.3 Attempted Synthesis of Poly(Propylene Sulfide) Macromonomers 200
4.2.4 Applicability of this Methodology to the Synthesis of other Block
Copolymers 211
4.3 Conclusions and Summary 212
4.4 Experimental 213
4.4.1 General 213
4.4.2 Synthesis of Polystyrene Homopolymers using a Protected
Initiator 215
4.4.3 Synthesis of Poly(Methyl Methacrylate) Homopolymers using
a Protected Initiator 218
4.4.4 Synthesis ofPoly(Propylene Sulfide) by Anionic Polymerisation 221
4.5 References 223
Chapter 5 - Conclusions and Future Work
5.1 Conclusions 227
5.2 Future Work 228
Appendix 1 Publication and Conference Record
a
Appendix 2 -Appendices for Chapter 2
Appendix 3 ~ Appendices for Chapter 3
Appendix 4 -Appendices for Chapter 4
VI
Abbreviations
ACS American Chemical Society
AD MET Acyclic diene metathesis
AROP Anionic ring opening polymerisation
ATRP Atom Transfer Radical Polymerisation
BO 1-Butene oxide
b.p. Boiling point
Bu Butyl
CK Cumyl potassium
CM Cross metathesis
COD 1,5-Cyclooctadiene
cone. Concentrated
COSY Correlation Spectroscopy
Cy Cyclohexyl
d Doublet
DCPD Dicyclopentadiene
DPE 1,1-Diphenylethylene
DPMK Diphenylmethyl potassium
DMAP N,N-Dime thy laminopyridine
DMF Dimethyl formamide
DMSO Dimethyl sulfoxide
DP Degree of polymerisation
El-MS Electron impact mass spectroscopy
EO Ethylene oxide
Et Ethyl
Formula weight
g Gram(s)
GC-MS Gas chromatography mass spectroscopy
GPC Gel permeation chromatography (Size exclusion chromatography)
GPR General purpose reagent
h Hour(s)
H Head
HSQC Heteronuclear single quantum correlation
VII