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

279 Pages·2016·38.95 MB·English

Zheng, Yu (2010) Preparation of hyperbranched
polymers by controlled/living polymerisations. PhD
thesis, University of Nottingham.
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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
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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
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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
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