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Zheng, Yu (2010) Preparation of hyperbranched polymers by controlled/living polymerisations ... PDF

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Zheng, Yu (2010) Preparation of hyperbranched polymers by controlled/living polymerisations. PhD thesis, University of Nottingham. Access from the University of Nottingham repository: http://eprints.nottingham.ac.uk/14098/1/523224.pdf Copyright and reuse: The Nottingham ePrints service makes this work by researchers of the University of Nottingham available open access under the following conditions. This article is made available under the University of Nottingham End User licence and may be reused according to the conditions of the licence. For more details see: http://eprints.nottingham.ac.uk/end_user_agreement.pdf For more information, please contact Preparation of Hyperbranched Polymers by Controlled! Living Polymerisations The University of Nottingham Yu Zheng, M.Sc Thesis submitted to the University of Nottingham for the degree of Doctor of Philosophy April 2010 Declaration Except where specific reference has been made to other sources. the work presented in this thesis is the original work of the author. It has not been submitted, in whole, or in part, for any other degree or professional qualification. Signed ...~ .~ ...... . Date .0...t.t..o...r.. .(..1..0.1.<.). . Yu Zheng Acknowledgement Foremost I would like to express my sincere gratitude to my supervisor Prof. Steven. M. Howdle for his warm encouragement and thoughtful guidance during my Ph.D study and research. Without his guidance and inspiration, this work and thesis could not be successfully completed. I am grateful to Dr Wenxin Wang, Dr Derek Irvine and Dr Kristofer Thurecht for all their professional advice and support to my research. I would also like to thank Professor Martyn Poliakoff for his invaluable advice. Also, I'd also like to thank Helen Carson who does an amazing work for our group. I further express my thanks to all the staff and colleagues in the Clean Tech Group. Special thanks to Dr Jaouad El Harfi, Dr Jixin Yang, Dr Hongyun Tai, Dr Silvia Villarroya. Maria Gonzalez and Mark Guyler. Finally, my deepest appreciation goes to my family who give me much love and warmth. Thanks to Katie for accompanying me during the toughest time. Thanks to the 'Brothers' in my house, Wenbo, Zifeng and Hongge. Thank you all for so much support, love and understanding. Yu Zheng, April 2010 ii Abstract This thesis describes the development of a novel route for preparation of hyperbranched polymers. The aim is to produce hyperbranched polymers via enhanced deactivation ATRP without crosslinking even at high conversion. Our strategy will be to use excess Cu(I1) to control gelation, so called enhanced deactivation ATRP. Chapter I provides a general introduction to the basic concepts of living polymerisation and dendritic polymers. Chapter 2 covers the hyperbranched homopolymer prepared by enhanced deactivation ATRP. The hyperbranched poly(divinylbenzene) and poly(ethylene glycol dimethacrylate) are synthesised by enhanced deactivation ATRP in a concentrated system. Chapter 3 focuses on the synthesis of hyperbranched copolymer via the enhanced deactivation ATRP. Also. the interesting potential applications, for example dye encapsulation and viscosity control are explored in this chapter. Chapter 4 demonstrates two routes to prepare novel core-shell polymers. First, the hyperbranched polyDYB was used as a core to produce hyperbranched core-shell polymers. Second, a novel hyperbranched polymer which combines ring open polymerisation and RAFT technique was developed. Chapter 5 summarises all the research presented in this thesis. Moreover, some possible research routes for the investigation in the future are listed in this part. III Abbreviations VFRP Kinetics chain length in free radical polymerisation V;\TRP Kinetics chain length in atom transfer radical polymerisation t Life-time of radicals in free radical polymerisation t' Actual life-time of the radicals in atom transfer radical polymerisation tact Time span of activation in atom transfer radical polymerisation tdcaCI Time span of deactivation in atom transfer radical polymerisation ACP-RAFT 4A-Azobis( 4-cyanovaleric acid) RAFT AFM Atomic Force Microscopy AGET Activator Generated by Electron Transfer AIBN 2,2'-Azo-bis-isobutyronitrilc ARGET Activator Regenerated by Electron Transfer ATRA Atom Transfer Radical Addition ATRP Atom Transfer Radical Polymerisation BOD 4A-bioxepanyl-7,7-dione Bpy 2,2'-bipyridine CCTP Cobalt Catalytic Transfer Polymerisation CDCh Deuterated chloroform CHCh Chloroform Cload Encapsulation ability of dyes Conv. Monomer Conversion eR Congo Red CLRP Controlled/Living Free Radical Polymerisation Degrees Celsius DB Degree of Branching DE-ATRP Deactivation Enhanced ATRP DLS Dynamic Light Scattering DMAEMA 2-Dimethylaminoethyl Methacrylate iv DMF N,N-dimethylformamide dNbpy 4,4' -dinonyl-2.2' -bipyridi ne Degree of Polymerisation DSC Differential Scanning Calorimetry DVB Divinylbenzene EGDMA Ethylene glycol dimethacrylate EVB Ethylvinylbenzene FRP Free Radical Polymerisation GTP Group Transfer Polymerisation GPe Gel Permeation Chromatography HBP Hyperbranched Polymer HMTETA 1,1,4,7,10,10-Hexamethyltriethylenetetramine IFIRP Initiator-Fragment Incorporation Radical Polymerisation kac\ Activation rate in atom transfer radical polymerisation kdeac\ Deactivation rate in atom transfer radical polymerisation K ATRP Equilibrium constant for atom transfer radical polymerisation KBO Bond dissociation energy of the alkyl halide KEA Electron affinity of the halogen KET Equilibrium constants for electron transfer of metal complexes Kx Equilibrium constant for the heterolytic cleavage of the Cu"-X bond LRP Living Free Radical Polymerisation MALLS Multi-Angle Laser Light Scattering MBrAc Methyl bromoacetate MBriP Methyl 2-bromoisobutyrate MBrP Methyl 2-bromopropionate MCIP Methyl 2-chloropropionate MIP Methyl 2-iodopropionate Me4-cyclam 1,4,8, Il-tetramethyl-l ,4,8, Il-tetraazacyc1otetradecane Me6-TREN Tris[(2-dimethylamino )ethyl]amine v MeOH Methanol MMA Methyl Methacrylate Mn Number Average Molecular Weight MO Methyl Orange MW Molecular Weight Weight Average Molecular Weight NMP Nitroxide Mediated Polymerisation NMR Nuclear Magnetic Resonance PCL Poly( caprolactone) POI Polydispersity Index POMAEMA Poly(2-( diethy lamino )ethy I methacrylate) POMS Poly(dimethyl siloxane) POMS-ma Poly(dimethyl siloxane) monomethacrylate PE Polyethylene PEBr I-Phenylethyl bromide PMOETA N,N,N' ,N" ,N" -pentamethyldiethylenetriamine PMMA Poly(methyl methacrylate) PP Polypropylene PRE Persistent radical effect PS Polystyrene PSD Particle Size Distribution PYA Poly(vinyl alcohol) PVAc Poly(vinyl acetate) R Free Radical Leaving Group on RAFT Agent RAFT Reversible Addition Fragmentation Chain Transfer Rg Gyration Radius Rh Hydrodynamic Radius RI Refractive Index ROP Ring-Opening Polymerisation vi rpm Rotations Per Minute SCVP Self-Condensation Vinyl Polymerisation SEC Size Exclusion Chromatography SET Single Electron Transfer Sn(OCT)2 Tin (II) Ethyl Hexanoate/ Stannous octoate SR&NI Simultaneous Reverse and Normal Initiation Tg Glass Transition Temperature THF Tetrahydrofuran TMEDA N. N. N. N-tetramethylethylenediamine tNtpy 4,4'-trinonyl-2,2' -6',2" -terpyridine Tm Melting Temperature UV-vis Ultraviolet-visible wt% Weight % Z Stabilising Group on RAFT Agent E-CL e-capro lactone vii Table of Contents CHAPTER ONE: INTRODUCTION 1.1 Polymers and Polymerisation 1 1. 1.1 General 1 1.1.2 Free Radical Polymerisation 3 1.1.3 Controlled! Living Free Radical Polymerisation 6 1.2 Atom Transfer Radical Polymerisation (ATRP) 14 1.2.1 Mechanism of Atom Transfer Radical Polymerisation 14 1.2.2 Mechanism of Electron Transfer 19 1.2.3 Kinetics and Components 21 1.2.4 Different ATRP Procedures 24 1.2.5 Monomers 28 1.2.6 Initiators 29 1.2.7 Transition Metal Catalysts 32 1.2.8 Ligands 33 1.2.9 Materials Made by ATRP 35 1.2.10 Deactivation Enhanced ATRP (DE-ATRP) 41 1.3 Reversible Addition Fragmentation Chain Transfer Polymerisation (RAFT) 49 1.4 Hyperbranched Polymers 53 1.4.1 Dendritic Polymers 53 1.4.2 Dendrimers 54 1.4.3 Random Hyperbranched Polymers 57 1.4.4 Previous Synthesis of Hyperbranched Polymers 58 1.5 An Overview of This Thesis 65 1.6 References 67 viii

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