İSTANBUL TECHNICAL UNIVERSITY  INSTITUTE OF SCIENCE AND TECHNOLOGY

THE SURFACE MODIFICATION OF SILICA

NANOPARTICLES VIA ABC TYPE MIKTOARM STAR POLYMER

M.Sc. Thesis by
Başak BULBA

Department : Chemistry

Programme : Chemistry

JANUARY 2010
İSTANBUL TECHNICAL UNIVERSITY  INSTITUTE OF SCIENCE AND TECHNOLOGY

THE SURFACE MODIFICATION OF SILICA

NANOPARTICLES VIA ABC TYPE MIKTOARM STAR POLYMER

M.Sc. Thesis by
Başak BULBA
(509081206)

Date of submission : 25 December 2009

Date of defence examination: 25 January 2010

Supervisor (Chairman) : Prof. Dr. Gürkan HIZAL (ITU)

Members of the Examining Committee : Prof. Dr. Ümit TUNCA (ITU)
Prof. Dr. Nergis ARSU (YTU)

JANUARY 2010
İSTANBUL TEKNİK ÜNİVERSİTESİ  FEN BİLİMLERİ ENSTİTÜSÜ

ABC TİPİ FARKLI KOLLU YILDIZ POLİMER İLE

SİLİKA NANOPARTİKÜLLERİNİN YÜZEY MODİFİKASYONU

YÜKSEK LİSANS TEZİ

Başak BULBA
(509081206)

Tezin Enstitüye Verildiği Tarih : 25 Aralık 2009

Tezin Savunulduğu Tarih : 25 Ocak 2010

Tez Danışmanı : Prof. Dr. Gürkan HIZAL (İTÜ)

Diğer Jüri Üyeleri : Prof. Dr. Ümit TUNCA (İTÜ)
Prof. Dr. Nergis ARSU (YTÜ)

OCAK 2010
FOREWORD

This master study has been achieved at Istanbul Technical University, Chemistry
Department.
I would like to express my deep appreciation and thanks for my thesis supervisor,
Prof. Dr. Gürkan HIZAL and co-supervisor Prof. Dr. Ümit TUNCA for offering
inestimably help in all possible ways, permanent encouragement and helpful critics
during this research.
I wish to express my special thanks to Hakan DURMAZ for his leading during my
research. Also, I would like to express my appreciation to him for his helpful and
understanding attitudes throughout my laboratory and thesis study. It has been a
pleasure to work with him.
I would like to also extend my sincere gratitude to my friend Aydan DAĞ for her
friendly and helpful attitudes and unbelievable sensibility during my laboratory
works. In addition, I would like to thank my group member Eda GÜNGÖR for her
support and sincerity during my laboratory study.
I would like to offer the most gratitude to my family Orhan BULBA, Kezban
BULBA, Berrin BULBA and Okan Anıl BULBA, and my friends Ġpek ÖSKEN,
Sevcan AYAKSIZ, Duygu GÜRSOY, Volkan KIRMIZI, Çiğdem BĠLĠR, Elif
ERDOĞAN, Ceyda Önen YALÇIN, and Dila KILIÇLIOĞLU for their patience,
understanding and moral support during all stages involved in the preparation of this
research.

December 2009 Başak BULBA

Chemist, M. Sc.

v
vi
TABLE OF CONTENTS

Page

FOREWORD .............................................................................................................. v
TABLE OF CONTENTS ......................................................................................... vii
ABBREVIATIONS ................................................................................................... ix
LIST OF FIGURES .................................................................................................. xi
SUMMARY ............................................................................................................. xiii
ÖZET......................................................................................................................... xv
1. INTRODUCTION .................................................................................................. 1
1.1 Purpose of the Thesis ......................................................................................... 3
2. THEORETICAL PART ....................................................................................... 5
2.1 Conventional Free Radical Polymerization ........................................................ 5
2.2 Conventional Living Polymerizations ................................................................ 6
2.3 Controlled/ „„Living” Free Radical Polymerizations ......................................... 8
2.3.1 Nitroxide-Mediated Living Free Radical (NMP)........................................ 9
2.3.2 Atom Transfer Radical Polymerization (ATRP) ...................................... 10
2.3.2.1 Monomers........................................................................................... 12
2.3.2.2 Initiators ............................................................................................. 12
2.3.2.3 Catalysts ............................................................................................. 13
2.3.2.4 Ligands ............................................................................................... 14
2.3.2.5 Solvents .............................................................................................. 15
2.3.2.6 Temperature and Reaction Time ........................................................ 15
2.3.2.7 Molecular weight and molecular weight distribution......................... 15
2.3.3 Reversible-Addition Fragmentation Chain Transfer (RAFT) ................... 16
2.4 Star Polymers ................................................................................................... 18
2.4.1 Stars by the Arm-First Method ................................................................. 18
2.4.2 Stars by the Core-First Method ................................................................. 20
2.5 ABC Terpolymers ............................................................................................ 21
2.6 Click Chemistry................................................................................................ 24
2.7 Surface-immobilized macromolecules ............................................................. 30
2.7.1 Synthesis of surface-immobilized macromolecules (polymer brushes) ... 30
2.7.2 “Grafting to” approach to fabricate polymer brushes ............................... 31
2.7.3 “Grafting from” approach to synthesize polymer brushes ........................ 32
2.7.3.1 Synthesis of tethered polymer brushes by conventional radical
polymerizations .................................................................................. 32
2.7.3.2 Synthesis of tethered polymer brushes by controlled radical
polymerization .................................................................................... 34
3. EXPERIMENTAL WORK ................................................................................. 37
3.1 Materials ........................................................................................................... 37
3.2 Instrumentation................................................................................................. 37
3.3 Synthesis of Initiator ........................................................................................ 38
3.3.1 Synthesis of 2,2,5-trimethyl-[1,3]dioxane-5-carboxylic acid ................... 38
3.3.2 Synthesis of prop-2-ynyl 2,2,5-trimethyl-1,3-dioxane-5-carboxylate ...... 38

vii
 3.3.3 Synthesis of prop-2-ynyl 3-hydroxy-2-(hydroxymethyl)-2-
methylpropanoate ...................................................................................... 39
3.3.4 Synthesis of prop-2-ynyl 3-(2-bromo-2-methylpropanoyloxy)-2-
(hydroxymethyl)-2-methylpropanoate ....................................................... 39
3.3.5 Synthesis of monocarboxylic acid terminated PEG (PEG-COOH) .......... 40
3.3.6 Synthesis of PEG-macroinitiator............................................................... 40
3.4 Synthesis of PEG-PMMA Copolymer with Alkyne at the Junction Point via
ATRP of Methyl Methacrylate (Alkyne-PEG-PMMA) ................................... 40
3.5 Synthesis of 3-(trimethylsilyl)prop-2-ynyl 2-bromo-2-methylpropanoate ...... 41
3.6 Synthesis Bromo End-functionalized Sillyl Protected PS via ATRP of
Styrene .............................................................................................................. 41
3.7 Synthesis of azide end – functionalized PS ...................................................... 42
3.8 Click reaction between Alkyne-PEG-PMMA and Sillyl protected PS-N3
(ABC Type Miktoarm Star Polymer) ............................................................... 42
3.9 Deprotection reaction of ABC Type Miktoarm Star Polymer (Hydrolysis
Reaction ............................................................................................................ 43
3.10 Synthesis of Azide Functionalized Silica Nanoparticles ................................ 43
3.10.1 Synthesis of azido ethanol ....................................................................... 43
3.10.2 Synthesis of teos azide ............................................................................ 43
3.10.3 The reaction between silica and TEOS azide (Si-N3) ............................. 44
3.11 Click Reaction Between Silica Azide and Alkyne PS-PEG-PMMA ............. 44
4. RESULTS AND DISCUSSION........................................................................... 45
4.1 Synthesis of Initiator......................................................................................... 45
4.2 Synthesis of PEG-PMMA Copolymer with Alkyne at the Junction Point via
ATRP of Methyl Methacrylate (Alkyne-PEG-PMMA ..................................... 50
4.3 Synthesis of Azide End–Functionalized PS ..................................................... 52
4.4 Synthesis of ABC Type Miktoarm Star Polymer ............................................. 55
4.5 Silica Modification of PS-PEG-PMMA via Click Reaction ............................ 58
5. CONCLUSION ..................................................................................................... 65
REFERENCES ......................................................................................................... 65
CURRICULUM VITAE .......................................................................................... 73

viii
ABBREVIATIONS

ATRP : Atom: Atom

Transfer RadicalRadical
Transfer Polymerization
Polymerization
NMP : Nitroxide Mediated
: Stable Polymerization
Free Radical Polymerization
CRP : Controlled/Living
: Styrene Radical Polymerization
St : Styrene
: Styrene
MMA : Methyl methacrylate
: Methyl methacrylate
PS : Polystyrene
PMMA : Poly(methyl metacrylate)
PEG : Poly(ethyleneglycol)
LFRP : Living Free Radical Polymerization
TEMPO : 2, 2', 6, 6'- Tetramethylpiperidinyloxy
PDI : Polydispersity Index
PRE : Persistent Radical Effect
Mtn : Transition metal
L : Ligand
Mn : Number Average Molecular Weight
Mw : Weight Average Molecular Weight
Mw/Mn : The Molecular Weight Distribution
ka : Rate constant of activation
kd : Rate constant of deactivation
kp : Rate constant of propagation
THF : Tetrahydrofuran
: Tetrahydrofuran
DMAP : 4-dimethylaminopyridine
PMDETA : N,N,N’,N’’,N’’- pentamethyldiethylenetriamine
GPC : Gel Permeation Chromotography
NMR : Nuclear Magnetic Resonance Spectroscopy

ix
x
LIST OF FIGURES

Page

Figure 2.1 : General free radical polymerization mechanism .................................... 6

Figure 2.2 : The general outline of the free-radical mechanism .............................. 10
Figure 2.3 : General scheme of transition-metal-catalyzed ATRP .......................... 12
Figure 2.4 : Derivatives of 2,2-bipyridine and nitrogen based ligands .................... 14
Figure 2.5 : Mechanism of RAFT polymerization ................................................... 17
Figure 2.6 : Scheme of star formation by the “arm-first method” ........................... 19
Figure 2.7 : Schematic presentation of all possible arrangements for an ABC
terpolymer ............................................................................................. 23
Figure 2.8 : Regioselectivity mechanism of triazole forming cycloaddition. .......... 27
Figure 2.9 : Proposed catalytic cycle for the Cu(I)-catalyzed ligation .................... 28
Figure 2.10: Preparation of polymer brushes by “physisorption”, “grafting to” and
“grafting from” ..................................................................................... 31
Figure 2.11: Schematic description of the concept for the preparation of cleavable
polymer brushes by “grafting from” approach ..................................... 33
Figure 4.1 : The 1H NMR spectrum of 2,2,5-trimethyl-[1,3]dioxane-5-carboxylic
acid in CDCl3 ........................................................................................ 45
Figure 4.2 : The 1H NMR spectrum of prop-2-ynyl 2,2,5-trimethyl-1,3-dioxane-5-
carboxylate in CDCl3 ............................................................................ 46
Figure 4.3 : The 1H NMR spectrum of prop-2-ynyl 3-hydroxy-2-(hydroxymethyl)-
2-methylpropanoate in CDCl3 .............................................................. 47
Figure 4.4 : The 1H NMR spectrum of prop-2-ynyl 3-(2-bromo-2
methylpropanoylo- xy)-2-(hydroxymethyl)-2-methylpropanoate in
CDCl3 .................................................................................................... 48
Figure 4.5 : The 1H NMR spectrum of PEG-COOH in CDCl3 ............................... 49
Figure 4.6 : The 1H NMR spectrum PEG-macroinitiator in CDCl3......................... 50
Figure 4.7 : The 1H NMR spectrum (Alkyne-PEG-PMMA) in CDCl3 ................... 52
Figure 4.8 : The 1H NMR spectrum of 3-(trimethylsilyl)prop-2-ynyl 2-bromo-2-
methylpropanoate in CDCl3 .................................................................. 53
Figure 4.9 : The 1H NMR spectrum of bromo end-functionalized sillyl protected
PS in CDCl3 .......................................................................................... 54
Figure 4.10: The 1H NMR spectrum of azide end-functionalized sillyl protected
PS in CDCl3 .......................................................................................... 54
Figure 4.11: The 1H NMR spectrum of ABC type miktoarm star polymer in
CDCl3 .................................................................................................. 56
Figure 4.12: The 1H NMR spectrum of alkyne functionalized ABC type miktoarm
star polymer in CDCl3........................................................................... 57
Figure 4.13: GPC chromatogram of the alkyne-PEG-PMMA, Si-p-PS-N3 and
ABC type miktoarm star polymer ......................................................... 57
Figure 4.14: The 1H NMR spectrum of 2-azido ethanol in CDCl3 .......................... 58
Figure 4.15: The 1H NMR spectrum of prop-2-ynyl 3- (triethoxysilyl)
propylcarbamate in CDCl3 .................................................................... 59

xi
Figure 4.16: TGA of Silica, Silica-azide, Alkyne-PS-PEG-PMMA and Silica-
Alkyne-PS-PEG-PMMA....................................................................... 62
Figure 4.17: The 1H NMR spectrum of silica-PS-PEG-PMMA in CDCl3 ............... 62

xii
THE SURFACE MODIFICATION OF SILICA NANOPARTICLES VIA ABC
TYPE MICTOARM STAR POLYMER

SUMMARY

In recent years surface modification of silica nanoparticles has attracted considerable

attention. Silica nanoparticles could be used for a diversity of applications depending
on their porosity and hardness. Mechanical, structural and thermal properties of
particle and the polymer could be altered via chemical modification of a silica
nanoparticle surface. Moreover, surface modification improves the stability of the
compound.
Star polymers have attracted much attention in research over the years due to their
unique-three dimensional shape and highly branched structure. There are two general
strategies used to produce star polymers: the arm-first and core-first techniques. In
the arm-first strategy, a polymer with a proper end-group functionality is reacted
with an appropriate multifunctional core to give a star polymer. In the second
strategy (core-first), the polymer chain is simultaneously grown from a
multifunctional initiator. In recent years, the use of controlled/living radical
polymerization techniques in the synthesis of star polymers has quickly increased
because of the variety of applicable monomers and greater tolerance to experimental
conditions in comparison with living ionic polymerization routes.
The development of controlled free radical polymerization is among the most
important advances in polymer chemistry. Living polymerization techniques afford
control over molecular weight distribution, architecture and functionalities of the
resulting polymer. Among the CRP processes, atom transfer radical polymerization
(ATRP), nitroxide mediated polymerization (NMP) and reversible addition
fragmentation techniques (RAFT), are the most efficient methods for the synthesis of
special polymers with complex architectures. Sharpless et al. Popularized the 1,3-
dipolar cycloaddition of azides and terminal alkynes, catalyzed by copper(I), in
organic synthesis. These reactions have a very high thermodynamic driving force
which makes them one of the efficient reactions available. Such reactions were
proven to be very practical because they can be performed in high yield, in multiple
solvents (including water), and in the presence of many other functional groups.
Both, ATRP and NMP methods based on the fast equilibrium between active and
dormant chains, actually it is the main effect to obtain controlled structure. One of
the advantageous of controlled radical polymerization techniques such as ATRP and
NMP is that the molecular weight and the chain end functionality can be controlled.
The wide range of functionality can be introduce into the polymer chain and this
leads to the synthesis of well-defined copolymers by a sequential two-step or one pot
method without any transformation or protection of initiating sites.
Recently, Huisgen type 1,3-dipolar cycloaddition reactions between azide and alkyne
functionalities yielding 1,2,3-triazole derivatives which are conducted at elevated
temperatures is an alternative route to carbon-carbon bond. In 2001, Sharpless and

xiii
coworkers reported that the reaction between azide and alkyne functionalities in the
presence of Cu(I)/Ligand as catalyst leaded 1,2,3-triazole derivatives with high yield
and high regioselectivity. Because of their efficiency and simplicity, these
cycloadditions were calssified as “click” reactions. Later, click chemistry strategy
was successfully applied to macromolecular chemistry, affording polymeric
materials varying from block copolymers to complex macromolecular structures.
The surface modification of silica nanoparticles via click chemistry has acquired
much attention in last years. There are several methods have been suggested to
surface modification of silica nanoparticles in literature but none of them includes
miktoarm star polymer. From this point of view, in this study was aimed to surface
modification of silica nanoparticles via ABC type miktoarm star polymer.
In this work, first of all well-defined azide end functionalized poly(styrene) and
alkyne functionalized poly(ethyleneglycol)-poly(methylmethacrylate) were obtained.
Then, ABC type miktoarm star polymer synthesized via click chemistry. Finally,
azide functionalized silica nanoparticles reacted with alkyne functionalized miktoarm
star polymers by using click chemistry. The obtained products were characterized by
Gel Permeation Chromatography (GPC), Nuclear Magnetic Resonance Spectroscopy
(NMR) and Thermal Gravimetric Analysis (TGA).

xiv
ABC TİPİ FARKLI KOLLU YILDIZ POLİMER İLE SİLİKA
NANOPARTİKÜLLERİNİN YÜZEY MODİFİKASYONU

ÖZET

Son yıllarda, nanopartiküllerin yüzey modifikasyonu önemli derecede ilgi

çekmektedir. Silika nanopartiküller, gözenek yapılarına ve sertliklerine göre değişik
uygulamalarda kullanılabilmektedirler. Silika nonopartiküllerin modifikasyonu ile
polimerin mekanik, yapısal ve termal özellikleri değiştirilebilmektedir. Bunun
yanında, yüzey modifikasyonu bileşiğin kararlılığını da arttırmaktadır.
Yıldız polimerler araştırmalarda üç boyutlu ve çok dallanmış yapılarından dolayı
yıllardır ilgi çekmektedirler. Yıldız polimerlerin elde edilmesinde kullanılan iki genel
yöntem vardır: kol öncelikli ve çekirdek öncelikli yöntemleri. Kol öncelikli
yönteminde, uygun uç grup fonksiyonalitesine sahip polimer ona uygun çok
fonksiyonlu bir çekirdekle yıldız polimer elde etmek için reaksiyona sokulur. Ġkinci
yöntemde (çekirdek öncelikli ) ise, polimer zinciri çok fonksiyonlu bir başlatıcıdan
eşzamanlı bir şekilde büyümektedir.Son yıllarda, yaşayan iyonik polimerizasyon
yöntemine kıyasla uygulanabilir monomerlerin çeşitliliğinin ve deneysel koşullardaki
toleransın daha fazla olması gibi sebeplerden dolayı, yıldız polimerlerin sentezinde
kontrollü/yaşayan polimerizasyon yönteminin kullanımı hızla artmaktadır.
Kontrollü serbest radikal polimerizasyonunun gelişimi polimer kimyasındaki en
önemli ilerlemeler arasındadır. Yaşayan polimerizasyon teknikleri, polimerin
moleküler kütle dağılımı, geometrik yapısı ve fonksiyonelliğini kontrol edebilmemizi
sağlamaktadır. CRP işlemi sırasında, atom transfer radikal polimerizasyonu (ATRP),
Nitroksit Ortamlı Radikal Polimerizasyonu (NMP) ve tersinir eklenme-parçalanma
zincir transferi (RAFT) teknikleri kompleks geometrik yapıya sahip özel polimerleri
sentezlemek için kullanılabilecek en etkili yöntemlerdir. Sharpless ve arkadaşları,
azid ve uç gruptaki alkinlerin bakır(I) katalizli 1,3-dipolar siklokatılma
reaksiyonlarını organik sentezlerde tercih edilir hale getirmişlerdir. Bu reaksiyonlar
sahip oldukları yüksek termodinamik itme gücü sayesinde mümkün olan en etkili
yöntemler olarak görülmektedir. Click reaksiyonları, yüksek verim ile, su dahil
olmak üzere farklı çözücü kullanılabilmesine olanak tanıyarak ve birçok fonksiyonel
yapının varlığında uygulanabilir olduğu için son derece pratik oldukları
kanıtlanmıştır. ATRP ve NMP yöntemleri, aktif ve durağan zincirlerin üzerindeki
hızlı dengeye dayanmaktadır, esasında bu kontrollü bir yapı elde etmenin temelidir.
ATRP, NMP gibi kontrollü radikal polimerizasyonu tekniklerinin avantajlarından
biri moleküler ağırlığın ve zincirin uç fonksiyonelliğinin kotrol edilebilir olmasıdır.
Bu teknikler sayesinde polimer uç gruplarına çok çeşitli fonksiyonellikler
kazandırılabilir bu da herhangi bir transformasyon reaksiyonu gerektirmeden iyi
tanımlı polimerlerin eldesine izin verir.
Son dönemlerde, 1,2,3-triazole türevlerini veren azid ve alkin fonksiyonaliteleri
arasındaki Huisgen tipi 1,3-dipolar siklokatılma reaksiyonları , yüksek sıcaklıklarda
karbon-karbon bağının oluşması için alternatif bir yöntemdir. 2001 yılında, Sharpless

xv
ve arkadaşları azid ve alkin fonksiyonalitelerinin Cu(I)/Ligand katalizör varlığındaki
reaksiyonunun yüksek verim ve alan-seçiciliği ile 1,2,3-triazole türevlerine
yönlendiğini bildirmişlerdir. Verimliliğinden ve basitliğinden dolayı, bu siklo
katılma reaksiyonları “click” reaksiyonları olarak sınıflandırılmışlardır. Daha sonra,
click kimyası yöntemi blok copolimerlerden kompleks makromoleküler yapılara
kadar değişen makromoleküler kimyaya başarılı bir şekilde uygulanmıştır.
Click kimyası ile yüzeye silika nanopartiküllerinin modifiye edilmesi son yıllarda
oldukça dikkat çekmiştir. Yüzeye silika nanopartiküllerinin modifiyesi için birçok
yöntem önerilse de, bu yöntemlerden hiçbiri farklı kollu yıldız polimeri
içermemektedir. Bu bakış açısı ile, bu çalışma silika nanopartikül yüzeyinin ABC tipi
farklı kollu yıldız polimer ile modifiye edilmesini amaçlamıştır.
Bu çalışmada, ilk olarak iyi tanımlanmış azid uç grup fonksiyonlu poli(stiren) ve
alkin fonksiyonlu poli(etilenglikol)-poli(metilmetakrilat) elde edilmiştir. Daha sonra,
click kimyası kullanılarak ABC tipi farklı kollu yıldız yıldız polimer sentezlenmiştir.
Son olarak, azid fonksiyonlu silika nanopartiküller click kimyası reaksiyonu ile alkin
fonksiyonlu farklı kollu yıldız yıldız polimerleri ile modifiye edilmiştir. Elde edilen
ürünler, Jel Geçirkenlik Kromatografisi (GPC), Nükleer Manyetik Rezonans
Spektroskopisi (NMR) ve Termal Gravimetrik Analiz (TGA) ile karakterize
edilmişlerdir.

xvi
1. INTRODUCTION

Silica nanoparticles are used for a variety of applications depending on their porosity
and hardness. However, the main challenge is to control the interparticle aggregation.
Aggregation can be controlled by covalently grafting polymer chains onto the
particle. The chemical modification of a silica nanoparticle surface with a polymer
not only improves the stability but can also alter the mechanical, structural, and
thermal properties of particle and the polymer [1]. Such hybrid organic–inorganic
materials find a number of applications in optics and electronics [2]. Both „„grafting-
to‟‟ and „„grafting-from‟‟ methods have been explored for the synthesis of hybrid
nanomaterials from preformed silica nanoparticles. The grafting-to technique
involves the chemical reaction of a reactive polymer end group to the surface [3].

A star structure is defined as a nonlinear polymer that consists of multiple backbone

chains existing from junction points [4]. Star polymers show different crystalline,
mechanical, and viscoelastic properties in comparison with their corresponding linear
analogues. Interest in star polymers arises from their compact structure and globular
shape, which predetermines their low viscosity when compared to linear analogues
and makes them suitable materials for several applications.

Much of the academic and industrial research on living polymerization has focused
on anionic, cationic, coordination, and ring-opening polymerizations. The
development of controlled/living radical polymerization (CRP) methods has been a
long-standing goal in polymer chemistry, as a radical process is more tolerant of
functional groups and impurities and is the leading industrial method to produce
polymers [5]. Synthesis of star polymers, which began in the 1950s with living
anionic polymerization, has recently received increased attention due to the
development of controlled/living radical polymerization (CRP) [6,7].

Typically, star polymers are synthesized via CRP by one of two strategies: core-first
and arm-first. The arm-first strategy can be further subcategorized according to the
procedure employed for star formation. One method is chain extension of a linear

1
arm precursor with a multivinyl crosslinking agent, and the other is coupling linear
polymer chains with a multifunctional linking agent or “grafting-onto” a
multifunctional core. Although both methods were successfully used for star
synthesis in anionic polymerization, to date only the former procedure, using a
multivinyl cross-linking agent, has been applied in CRP for synthesis of star
polymers containing multiple arms and/or functionalities [8,9].

Atom transfer radical polymerization (ATRP) is a particularly attractive CRP process

for synthesis of chain-endfunctionalized polymers [10,11]. The polymers produced
by ATRP preserve terminal halogen atom(s) that can be successfully converted into
various desired functional chain-end groups through appropriate transformations,
especially nucleophilic substitutions. The modified chain-end group, such as a
hydroxyl group or an amino group, cannot react with itself but can react with an
appropriate functional group on the multifunctional coupling agent, such as a
carboxylic acid group by esterification, to form a star polymer. However, a
commonly encountered drawback, when using such a method, is a low yield of star
products due to the slow and inefficient reactions between the modified polymer
chain ends and multifunctional linking agents. In other words, highly efficient site-
specific organic reactions are required in order for star synthesis to be highly
successful [9].

In the past few years, “click reactions”, as termed by Sharpless et al. (2004), have
gained a great deal of attention due to their high specificity, quantitative yields, and
near-perfect fidelity in the presence of most functional groups. The most popular
click chemistry reaction is the copper-catalyzed Huisgen dipolar cycloaddition
reaction between an azide and an alkyne leading to 1,2,3-triazole [12-15].

Lutz et al. (2005) used click chemistry to prepare an end-functionalized ATRP

polymer [16]. The bromine chain ends of the polymer were first transformed into an
azide end group and subsequently reacted with terminal alkynes to create different
functional end groups. van Hest et al. prepared terminal azide and alkyne
functionalized ATRP polymers to modularly synthesize block copolymers [17].
Matyjaszewski et al. (2005) synthesized an alkyneterminated ATRP initiator to
polymerize well-defined α-alkyne-ω-bromo-terminated polystyrene (PS). These
polymers prepared by ATRP were coupled via a step growth mechanism using click
coupling to yield PS containing triazole linkages in the repeat units [18].

2
Matyjaszewski et al. also synthesized α,ω-dihydroxypolystyrene and star polymers
via ATRP and click chemistry. Macrocyclic polymer, neoglycopolymer, and first-
generation dendritic copolymers have also been synthesized by combination of
ATRP and click chemistry [1, 19-20].

There are a number of reports on the synthesis of hybrid silica nanoparticles both by
grafting-to and grafting-from techniques. Procedures for the grafting-from technique
commonly involve covalent attachment of a suitable atom transfer radical
polymerization (ATRP) initiator or reversible addition fragmentation transfer
(RAFT) agent to silica. The grafting-to technique involves the chemical reaction of a
reactive polymer end group to the surface [3]. However the grafting density, which
controls the final properties of the hybrid nanomaterial, is low due to steric
hindrance. This drawback is overcome by using a grafting-from technique, in which
the polymer chain is grown from the surface through a covalently linked monomer
[21] or an initiator [22].

1.1 Purpose of the Thesis

The target of the present work was to modify the silica nanoparticles‟ surface by the
combination of ATRP and click reactions based on the arm-first method. For this
purpose, at first PEG-macroinitiator, (6), was obtained. On the other hand, well
defined azide-end-functionalized PS, (10), was synthesis and click reaction strategy
was followed between (6) and (10). Consequently, ABC type miktoarm star polymer
poly(styrene)-poly(ethylene glycol)-poly(methylmethacrylate), (12), in which alkyne
functionality at the junction point was obtained. Then, azide functionality on the
silica surface was obtained via simple sol-gel process. Finally, click reaction was
performed between ABC miktoarm star polymers and azide containing silica
nanoparticles in the presence of copper catalyst. Then, target compound was obtained
successfully. The characterization and efficiency of all reactions has been
investigated by Gel Permeation Chromatography (GPC), Nuclear Magnetic
Resonance Spectroscopy (NMR) and Thermal Gravimetric Analysis (TGA)
measurements.

3
4
2. THEORETICAL PART

2.1 Conventional Free Radical Polymerization

Free radical polymerization has been an important technological area for seventy
years. As a synthetic process it has enabled the production of materials that have
enriched the lives of millions of people on a daily basis. Free radical polymerization
was driven by technological progress, and its commercialization often preceded
scientific understanding. Free radical polymerization is (relatively) easy to introduce
on an industrial plant, it is compatible with water, and it could accommodate a wide
variety of functional monomers [6].

As chain reactions, free radical polymerizations proceed via four distinct processes:

Initiation: The first step in producing polymers by free radical

polymerization is initiation. This step begins when an initiator decomposes
into free radicals in the presence of monomers. The initiator-derived free
radicals that initiate polymerization are generated by thermal or
photochemical homolytic cleavage of covalent bonds, or by a redox process.
In this first step, a reactive site is formed, thereby “initiating” the
polymerization.

Propagation: Primary radicals generated by the decomposition of initiator

add to monomer to yield primary propagating radicals. This is followed by a
succession of rapid propagation steps that proceed with high regioselectivity
to form radical centers bearing a substituent. The reactive site is regenerated
after each addition of monomer.

Transfer: Transfer occurs when an active site is transferred to an

independent molecule such as monomer, initiator, polymer and solvent or
transfer agent. This process results in both a terminated molecule (see step
four) and a new active site that is capable of undergoing propagation.

5
 Termination: In this final step, eradication of active sites leads to
“terminated,” or inert, macromolecules. Termination refers to the bimolecular
reaction of propagating radicals by combination or disproportionation that
leads to the deactivation of propagating radical chain ends.

The free radical chain process is demonstrated schematically below at figure 2.1: R·
represents a free radical capable of initiating propagation; M denotes a molecule of
monomer; Rm and Rn refer to propagating radical chains with degrees of
polymerization of m and n, respectively; AB is a chain transfer agent; and Pn + Pm
represent terminated macromolecules.

Figure 2.1 : General free radical polymerization mechanism.

Free-radical polymerization proceeds via a chain mechanism, which basically

consists of four different types of reactions involving free radicals: (1) radical
generation from nonradical species (initiation), (2) radical addition to a substituted
alkene (propagation), (3) atom transfer and atom abstraction reactions (chain transfer
and termination by disproportionation), and (4) radical–radical recombination
reactions (termination by combination). It is clear that a good process and product
control (design) requires a thorough knowledge of the respective rates of these
reactions and preferably, knowledge about the physics governing these rates [23].

2.2. Conventional Living Polymerizations

Living polymerization was first defined by Szwarc (1956) as a chain growth process
without chain breaking reactions (transfer and termination) [24]. Such a
polymerization provides end-group control and enables the synthesis of block

6
copolymers by sequential monomer addition. However, it does not necessarily
provide polymers with molecular weight (MW) control and narrow molecular weight
distribution (MWD). Additional prerequisites to achieve these goals include that the
initiator should be consumed at early stages of polymerization and that the exchange
between species of various reactivities should be at least as fast as propagation [25-
27]. It has been suggested to use a term controlled polymerization if these additional
criteria are met [28]. This term was proposed for systems, which provide control of
MW and MWD but in which chain breaking reactions continue to occur as in RP.
However, the term controlled does not specify which features are controlled and
which are not controlled. Another option would be to use the term „„living‟‟
polymerization (with quotation marks) or „„apparently living,‟‟ which could indicate
a process of preparing well-defined polymers under conditions in which chain
breaking reactions undoubtedly occur, as in radical polymerization.

LRP requires all chains to begin growing (reversibly via exchange processes) at
essentially the same time and retain functionalities until the very end of the reaction.
This is in contrast to RP, where all chains terminate and initiation is never completed,
even when all monomer is consumed. Therefore, the three basic prerequisites for
LRP are

Initiation should be completed at low monomer conversions.

Relatively low MW (DP < 1000) should be targeted to avoid transfer effects.
This requires high concentration of growing chains, (e.g., > 10-2M for bulk
polymerization).

Concentration of propagating radicals ([Po] < 10-7 M) should be sufficiently

low to enable growth of chains to sufficiently high MW, before they
terminate.

In addition, there is not a general mechanism of polymerization on which to base

one‟s experiment: initiation may occur in some systems before complete dissociation
of initiator. Knowledge of the initiating mechanism must be determined a priori to
ensure a successful reaction. Despite the advantage of molecular control of living
systems, the experimental rigor involved in ionic polymerization is often too costly
for industrial use and free radical routes are preferred.

7
2.3. Controlled/ ‘‘Living” Free Radical Polymerizations

A special feature of LRP, and many other new living polymerization systems, such
as carbocationic, ring opening, group transfer, and ligated anionic polymerization of
acrylates, is the existence of equilibrium between active and dormant species [29].
The exchange between the active and dormant species allows slow but simultaneous
growth of all chains while keeping the concentration of radicals low enough to
minimize termination. This exchange also enables quantitative initiation necessary
for building polymers with special architectures and functionalities, presently
accessible in classic living polymerizations. The term controlled/living could also
describe the essence of these systems [28].

Ideally, living systems lead to polymers with degrees of polymerization

predetermined by the ratio of concentrations of consumed monomer to the introduced
initiator DPn=Δ[M]/[I]0, with polydispersities close to Poisson distribution (DPw/DPn
≈ 1 + 1/DPn), and with complete end functionalization. Experimentally, the best way
to evaluate such systems is to follow the kinetics of polymerization and the evolution
of molecular weights, polydispersities, and functionalities with conversion.

Free radical processes have been recently developed which allow for both control
over molar masses and for complex architectures. Such processes combine both
radical techniques with living supports, permitting reversible termination of
propagating radicals. In particular, three controlled free radical polymerizations have
been well investigated. Each of these techniques is briefly presented below and all
are based upon early work involving the use of initiator-transfer-agent-terminators to
control irreversible chain termination of classical free radical process.

Living polymerization is defined as a polymerization that undergoes neither

termination nor transfer. Polymer chains all grow at the same rate, decreasing the
polydispersity. The propagating center at 100 % conversion still exists and can be
further reacted, which can allow novel block, graft, star, or hyperbranched
copolymers to be synthesized. Living polymerizations have been realized in anionic
processes where transfer and termination are easy to suppress. Due to the favorable
coupling of two radical propagating centers and various radical chain transfer
reactions, the design and control of living radical processes is inherently a much
more challenging task. The living process of radical polymerization involves the

8
equilibration of growing free radicals and various types of dormant species. By tying
up a great deal of the reactive centers as dormant species, the concentration of free
radicals decreases substantially and therefore suppresses the transfer and termination
steps. These reactions are also denoted as controlled /living polymerizations rather
than as true living polymerizations because transfer and termination are decreased
but not eliminated. The methods at the forefront fall into one of three categories:
nitroxide mediated polymerization (NMP), atom transfer radical polymerization
(ATRP), and reversible addition fragmentation chain transfer (RAFT) [30].

2.3.1. Nitroxide-Mediated Living Free Radical (NMP)

Nitroxide–mediated living free radical polymerization (NMP) belongs to a much

larger family of processes called stable free radical polymerizations. This pioneering
work was one of the seminal contributions that provided the basis for the
development of living free radical polymerization (LFRP), and it is interesting to
note the similarity between the iniferter mechanism and the general outline of a
living free-radical mechanism (Figure 2.2). In this general mechanism, the reversible
termination of the growing polymeric chain is the key step for reducing the overall
concentration of the propagating radical chain end. In the absence of other reactions
leading to initiation of new polymer chains (i.e., no reaction of the mediating radical
with the vinylic monomer), the concentration of reactive chain ends is extremely
low, minimizing irreversible termination reactions, such as combination or
disproportionation. All chains would be initiated only from the desired initiating
species and growth should occur in a pseudoliving fashion, allowing a high degree of
control over the entire polymerization process with well-defined polymers being
obtained.

The identity of the mediating radical, X., is critical to the success of living free
radical procedures and a variety of different persistent, or stabilized radicals have
been employed [1,16,18,31]. However the most widely studied and certainly most
successful class of compounds are the nitroxides and their associated alkylated
derivatives, alkoxyamines. Interestingly, the development of nitroxides as mediators
for radical polymerization stems from pioneering work by Solomon, Rizzardo, and
Moad into the nature of standard free-radical initiation mechanisms and the desire to
efficiently trap carbon-centered free radicals [32].

9
 Figure 2.2 : The general outline of the free-radical mechanism

A NMP run can be done in two ways. In one way, polymerization is initiated with a
model alkoxyamine like S-TEMPO and BS-TEMPO, which is prepared and purified
independently. In the other way, the initiating alkoxyamine is prepared in situ [33].
Specifically, a conventional initiator such as benzoyl peroxide (BPO) is mixed with a
nitroxyl like TEMPO in monomer in a suitable ratio, for instance,
[TEMPO]/[BPO]=1.2, and the mixture is heated at a high temperature so that all
BPO molecules decompose in a short time to produce adducts of the type B-Mn-
TEMPO, where B and M denote the BPO fragment and the monomer moiety with
n=1 or 2 in most cases, [the adduct B-TEMPO (n=0) is unlikely to be formed]. These
adducts will work as an initiating alkoxyamine. For kinetic studies, the use of a
purified model alkoxyamine is obviously preferable to avoid unnecessary
complexities.

2.3.2. Atom Transfer Radical Polymerization (ATRP)

The name atom transfer radical polymerization (ATRP) comes from the atom
transfer step, which is the key elementary reaction responsible for the uniform
growth of the polymeric chains. ATRP originates in atom transfer radical addition
(ATRA) reactions, which target the formation of 1 : 1 adducts of alkyl halides and
alkenes, which are also catalyzed by transition metal complexes [34]. ATRA is a
modification of the Kharasch addition reaction, which usually occurs in the presence

10
of light or conventional radical initiators [35]. Because of the involvement of
transition metals in the activation and deactivation steps, chemo-, regio-, and
stereoselectivities in ATRA and the Kharasch addition may be different.

ATRP has some links to transition-metal-catalyzed telomerization reactions [36].

These reactions, however, do not proceed with efficient exchange, which results in a
nonlinear evolution of the molecular weights with conversions and polymers with
high polydispersities. ATRP is also related to transition metal initiated redox
processes and inhibition with transition metal compounds [37,38]. These two
techniques allow for either an activation or deactivation process, however, without
efficient reversibility.

ATRP was developed by designing a proper catalyst (transition metal compound and
ligands), using an initiator with an appropriate structure, and adjusting the
polymerization conditions, such that the molecular weights increased linearly with
conversion and the polydispersities were typical of a living process [39-41]. This
allowed for an unprecedented control over the chain topology (stars, combs,
branched), the composition (block, gradient, alternating, statistical), and the end
functionality for a large range of radically polymerizable monomers [41-46].

A general mechanism for ATRP is given below (Figure 2.3). The radicals, i.e., the
propagating species Pn*, are generated through a reversible redox process catalyzed
by a transition metal complex (activator, Mnt –Y=ligand, where Y may be another
ligand or a counterion) which undergoes a one-electron oxidation with concomitant
abstraction of a (pseudo)halogen atom, X, from a dormant species, Pn–X. Radicals
react reversibly with the oxidized metal complexes, X–Mtn+1/ligand, the deactivator,
to reform the dormant species and the activator. This process occurs with a rate
constant of activation, ka, and deactivation kda, respectively. Polymer chains grow by
the addition of the free radicals to monomers in a manner similar to a conventional
radical polymerization, with the rate constant of propagation, kp. Termination
reactions (kt) also occur in ATRP, mainly through radical coupling and
disproportionation; however, in a well-controlled ATRP, no more than a few percent
of the polymer chains undergo termination. Other side reactions may additionally
limit the achievable molecular weights. Typically, no more than 5% of the total
growing polymer chains terminate during the initial, short, nonstationary stage of the
polymerization. This process generates oxidized metal complexes, the deactivators,

11
which behave as persistent radicals to reduce the stationary concentration of growing
radicals and thereby minimize the contribution of termination at later stages [47]. A
successful ATRP will have not only small contribution of terminated chains but also
uniform growth of all the chains; this is accomplished through fast initiation and
rapid reversible deactivation.

Figure 2.3 : General scheme of transition-metal-catalyzed ATRP.

As a multicomponent system, ATRP includes the monomer, an initiator with a

transferable (pseudo)halogen, and a catalyst (composed of a transition metal species
with any suitable ligand). Both activating and deactivating components of the
catalytic system must be simultaneously present. Sometimes an additive is used. For
a successful ATRP, other factors, such as solvent, temperature, concentrations and
solubility of all components, and sometimes the order of their addition must be also
taken into consideration.

2.3.2.1. Monomers

A variety of monomers have been successfully polymerized using ATRP. The most
common monomers are methacrylates, acrylonitriles, styrenes, acrylates and
(meth)acrylamides, which contain substituents that can stabilize the propagating
radicals. Even under the same conditions using the same catalyst, each monomer has
its own unique atom transfer equilibrium constant for its active and dormant species.
In the absence of any side reactions other than radical termination by coupling or
disproportionation, the magnitude of the equilibrium constant (Keq=kact/kdeact)
determines the polymerization rate.

2.3.2.2. Initiators

The main role of the initiator is to determine the number of growing polymer chains.
Two parameters are important for a successful ATRP initiating system. First,
initiation should be fast in comparison with propagation. Second, the probability of
the side reactions should be minimized. In ATRP, alkyl halides (RX) are typically

12
used as initiators. To obtain well-defined polymers with narrow molecular weight
distributions, the halide group, X, should rapidly and selectively migrate between the
growing chain and the transition metal complex. Thus far, when X is either bromine
or chlorine, the molecular weight control is best. Iodine works well for acrylate
polymerizations in copper-mediated ATRP [48] and has been found to lead to
controlled polymerization of styrene in ruthenium and rhenium-based ATRP [49,50].
Some pseudohalogens, specifically thiocyanates and thiocarbamates, have been used
successfully in the polymerization of acrylates and styrenes [48,51-52].

Initiation should be fast and quantitative with a good initiator and proper selection of
group R. Any alkyl halide with activating substituents on the a-carbon, such as aryl,
carbonyl, or allyl groups, can potentially be used as ATRP initiators,
polyhalogenated compounds (e.g., CCl4 and CHCl3), and compounds with a weak
R–X bond, such as N–X, S–X, and O–X, can also be used as ATRP initiators. When
the initiating moiety is attached to a macromolecule, macroinitiators are formed, and
can be used to synthesize block or graft copolymers [41]. However, the efficiency of
block/graft copolymerization may be low if the apparent rate constant of cross-
propagation is smaller than that of the subsequent homopolymerization.

Many different types of halogenated compounds are potential initiators and their
different structures. For examples; halogenated alkanes, benzylic halides, α-
haloesters, α-haloketones, α-halonitriles and sulfonyl halides are uses as initiators.

2.3.2.3. Catalysts

Perhaps the most important component of ATRP is the catalyst. It is the key to
ATRP since it determines the position of the atom transfer equilibrium and the
dynamics of exchange between the dormant and active species. There are several
prerequisites for an efficient transition metal catalyst.

The metal center must have at least two readily accessible oxidation states
separated by one electron.

The metal center should have reasonable affinity toward a halogen.

The coordination sphere around the metal should be expandable on oxidation

to selectively accommodate a (pseudo)halogen.

The ligand should complex the metal relatively strongly.

13
 The position and dynamics of the ATRP equilibrium should be appropriate
for the particular system.

The most important catalysts used in ATRP are; Cu(I)Cl, Cu(I)Br, NiBr2(PPh3)2,
FeCl2(PPh3)2, RuCl2(PPh3)3/ Al(OR)3.

2.3.2.4. Ligands

The main roles of the ligand in ATRP is to solubilize the transition metal salt in the
organic media and to adjust the redox potential and halogenophilicity of the metal
center forming a complex with an appropriate reactivity and dynamics for the atom
transfer [53,54]. The ligand should complex strongly with the transition metal. It
should also allow expansion of the coordination sphere and should allow selective
atom transfer without promoting other reactions.

The most widely used ligands for ATRP systems are the derivatives of 2,2
bipyridine and nitrogen based ligands such as N,N,N’,N’’,N’’-
pentamethyldiethylenetriamine (PMDETA), tetramethylethylenediamine (TMEDA),
1,14,7,10,10-hexamethyltriethylenetetraamine (HMTETA), tris[2-(dimethylamino)
ethyl]amine (Me6-TREN) and alkylpyridylmethanimines.

Figure 2.4 : Derivatives of 2,2-bipyridine and nitrogen based ligands

14
2.3.2.5. Solvents

ATRP can be carried out either in bulk, in solution, or in a heterogeneous system

(e.g., emulsion, suspension). Various solvents, such as benzene, toluene, anisole,
diphenyl ether, ethyl acetate, acetone, dimethyl formamide (DMF), ethylene
carbonate, alcohol, water, carbon dioxide, and many others, have been used in the
polymerization of different monomers. A solvent is sometimes necessary, especially
when the polymer is insoluble in its monomer (e.g., polyacrylonitrile). ATRP has
been also successfully carried under heterogeneous conditions in (mini)emulsion,
suspension, or dispersion. Several factors affect the solvent choice. Chain transfer to
solvent should be minimal. In addition, potential interactions between solvent and the
catalytic system should be considered. Catalyst poisoning by the solvent (e.g.,
carboxylic acids or phosphine in copper-based ATRP) and solvent-assisted side
reactions, such as elimination of HX from polystyryl halides, which is more
pronounced in a polar solvent, should be minimized [55,56].

2.3.2.6. Temperature and Reaction time

The rate of polymerization in ATRP increases with increasing temperature due to the
increase of both the radical propagation rate constant and the atom transfer
equilibrium constant. As a result of the higher activation energy for the radical
propagation than for the radical termination, higher kp/kt ratios and better control
(„„livingness‟‟) may be observed at higher temperatures. However, chain transfer and
other side reactions become more pronounced at elevated temperatures [56,57]. In
general, the solubility of the catalyst increases at higher temperatures; however,
catalyst decomposition may also occur with an increase in temperature [58,59]. The
optimal temperature depends mostly on the monomer, the catalyst, and the targeted
molecular weight.

2.3.2.7. Molecular weight and molecular weight distribution

The average molecular weight of the polymer can be determined by the ratio of
consumed monomer and the initiator as in a typical living polymerization
(DPn=∆[M]/[I]o , DP=degree of polymerization) while there is a narrow molecular
weight distribution (1.0 < Mw/Mn < 1.5).

15
The molecular weight distribution or polydispersity Mw / Mn is the index of the
polymer chain distribution. In a well-controlled polymerization, Mw / Mn is usually
less than 1.1.

Polydispersity defined as;

Mw / Mn = 1 + [[RX]o kp / kd [D]] . [(2/p) – 1] (2.1)

Where, D: Deactivator, kp: Propagation rate constant, kd: Deactivation rate constant,
p: Monomer conversion

When a hundred percent of conversion is reached, in other words p=1, it can be

concluded that;

Polydispersities (molecular weight distributions) decrease, if the catalyst

deactivates the chains faster (smaller kp / kd )

For the smaller polymer chains, higher polydispersities are expected to obtain
because the smaller chains include little activation-deactivation steps
resulting in little control of the polymerization.

Polydispersities decrease as the concentration of the deactivator decreases.

(For example, the addition of a small amount of Cu(II) halides in copper-
based ATRP decreases the reaction rate thus leads to better controlled
polymerizations)

2.3.3. Reversible-Addition Fragmentation Chain Transfer (RAFT)

RAFT polymerization has received increasing attention in recent years. Among

available controlled free radical polymerization techniques, RAFT has arguably the
most important commercial significance because it works with the greatest range of
vinyl monomers and under a wide variety of experimental conditions [60].

The RAFT process is a versatile method for conferring living characteristics on

radical polymerizations which provides unprecedented control over molecular
weight, molecular weight distribution, composition and architecture [60-64]. It is
suitable for most monomers polymerizable by radical polymerization and is robust
under a wide range of reaction conditions. RAFT polymerizations of styrene were
described in the first communication of RAFT polymerization in 1998 [65] and have
been the subject of many subsequent papers. The mechanism of the RAFT process is

16
shown in Figure 2.6. Ideally, since radicals are neither formed nor destroyed as a
consequence of the RAFT equilibria, they should not directly affect the rate of
polymerization. RAFT agents can behave as ideal chain transfer agents [66-68].

Figure 2.5 : Mechanism of RAFT polymerization.

Reversible addition-fragmentation chain transfer (RAFT) is achieved by performing

a free radical polymerization in the presence of dithio compounds, which act as
efficient reversible addition-fragmentation chain transfer agents. Much like the first
two routes, the rapid switching mechanism between dormant and active chain ends
affords living polymerization character [69].

RAFT incorporates compounds, usually dithio derivatives, within the living

polymerization that react with the propagating center to form a dormant intermediate.
The dithio compound can release the alkyl group attached to the opposite sulfur atom
which can then propagate with the monomer. The greatest advantage to RAFT is the
incredible range of polymerizable monomers. As long as the monomer can undergo
radical polymerization, the process will most likey be compatible with RAFT.
However, there are many major drawbacks that arise when using this process. The
dithio end groups left on the polymer give rise to toxicity, color, and odor and their
removal or displacement requires radical chemistry. Also, the RAFT agents are

17
expensive and not commercially available. Another drawback is that the process
requires an initiator, which can cause undesired end groups and produce too many
new chains which can lead to increased termination rates [30].

2.4. Star Polymers

A star structure is defined as a nonlinear polymer, which consists of multiple arms

existing from junction points [70]. Star polymers show different properties from the
point of view: crystalline, mechanical, and viscoelastic properties compared to their
linear counterparts. Miktoarm star polymers constitute at least one arm that is
chemically different than others [71]. The miktoarm star polymers have been
obtained from living ionic polymerization methods, mainly anionic polymerization
until recently [72-74]. The types of miktoarm star polymers, A2B, A3B, A2B2, AnBn,
ABC are the most common examples found in the literature. Other less common
structures like AB5, AB2C2, and ABCD are now also available. However, more
recently different methods have been reported for the preparation of miktoarm star
polymers, ranging from the combinations of the controlled/living radical
polymerization systems (atom transfer radical polymerization (ATRP), nitroxide-
mediated radical polymerization (NMP), and reversible addition fragmentation chain
transfer (RAFT) polymerization), to the combinations of them with the other living
polymerization method (ring opening polymerization (ROP)) [75-84]. Therefore,
these methods gave rise to a variety of miktoarm stars like AB2, A3B3, A(BC)2, and
ABC. Star polymers have found applications in various areas like rheology modifiers,
pressure sensitive adhesives, etc.

2.4.1. Stars by the Arm-First Method

This technique involves the synthesis of preformed arms, usually through living
polymerization followed by reaction with a multifunctional linking agent [85-86].
Schematic representation of star formation by the “arm-first method” is shown in
Figure 2.7.

18
 X linear polymer chains
where;

Y Y
multifunctional linking agent

Figure 2.6 : Scheme of star formation by the “arm-first method”.

Star formation by using the arm first technique also involves the use of
divinylcoupling reagents such as divinylbenzene (DVB) as a multifunctional linking
agent. Initially, a few units of the divinyl coupling reagents are added to the
macroinitiator chain ends to form short block copolymers.

The block copolymers containing the divinyl units then start to react with each other
to form cross-linked cores, and this leads to the formation of star polymers. Finally
star-star coupling can occur, leading to the formation of higher molecular weight
stars.

Coupling of monofunctional living chains with a difunctional reagent was first

applied to living anionic polymerization. A similar approach has also been succesful
with ATRP. There are several parameters in an ATRP that should be controlled
carefully in order to maximize the yield of stars and prevent star-star coupling
reactions. Some detailed studies have been carried out on the coupling of
monofunctional polystyrenes and polyacrylates with (DVB) and di(meth)acrylates to
prepare star polymers and the following guidelines have been developed:

 The ratio of difunctional reagent to growing chains seems to be optimal in the

range of 10-20

19
  Monomer conversion (or reaction time) has to be carefully controlled and
stopped before star-star coupling occurs.

 Higher yields of stars are observed for polyacrylates than for polystyrenes.
This may be attributed to a higher proportion of terminated chains in styrene
polymerization.

 The choice of the difunctional reagent is important and reactivity should be

similar to, or lower than that of the arm-building monomers.

 Halogen exchange slightly improves efficiency of star formation.

 Solvent, temperature, catalyst concentration should be also optimized.

Some of the recent studies on star synthesis by the arm-first method are described
below: An original study based on the arm-first approach was reported by Fraser et
al., who synthesized 2,2-bipyridyl- carrying PS and PMMA chains by ATRP, which
they managed to chelate onto a hexadendate Fe(II)- based complex to form
corresponding star-like polymers, thus containing a metallic core.

To derive their PS stars, Matyjaszewski et al. used a preformed PS macroinitiator

obtained by ATRP that was allowed to react with various divinylic monomers, in the
presence of Cu/Br dipyridyl in anisole at 110oC. A ratio of 5:15 between
divinylbenzene and PS macroinitiator was found to be optimal for the star formation.
Other experimental parameters such as the choice of solvent, the addition of Cu(II),
and the reaction time were found to be crucial for the formation efficient star
formation.

2.4.2. Stars by the Core-First Method

The core-first approach has come to maturity after it was shown in the1990s that
stars of precise functionality could be obtained from multiionic initiators.

The core-first method involves the use of a multifunctional initiator, and the number
of arms in the star polymer can be determined by the number of initiating sites on the
initiator. In this technique multifunctional initiators are used to grow chains from a
central core resulting in macromolecules with well-defined structures in terms of
both arm number and length. Furthermore the reaction consists solely of stars in the
absence of linear polymers.Most of the star polymers were prepared by this
technique.

20
The first report of the core-first technique described the hexakis (bromomethyl)
benzene-initiated ATRP of styrene, methyl acrylate, and methylmethacrylate [44],
but its use was rather limited due to poor solubility in the reaction media.

2.5. ABC terpolymers

In recent years ternary triblock terpolymers have attracted increasing interest owing
to their rich variety of bulk morphologies [87].

Emerging technologies in medicine, microelectronics and optics require the

availability of novel polymeric materials with ever more sophisticated properties and
performances. Living and controlled/living polymerization methods have allowed for
the synthesis of tailor-made macromolecules of varying chemical structure,
composition, molecular characteristics and architecture. Among the different
architectures, block extended is the work dedicated to the synthesis, solution and
bulk properties of triblock terpolymers of the ABC type [88].

Linear ABC triblock terpolymers represent a relatively new class of polymeric

materials with an increasing interest for their properties in the bulk and in solution.
The three chemically different components of these materials, each placed in a
separate block, can confer to the terpolymer three different functions. Another
similar, but more novel, and equally interesting class of polymeric materials is that of
ABC heteroarm or miktoarm star terpolymers, bearing three arms, each of which is a
different homopolymer [89].

The presence of three different monomers placed in different blocks confers to these
polymers, three rather than two functions [90]. It is well known that the addition of a
third block leads to a much richer variety of phases (over 30 phases have been
identified to date in bulk). These materials have the potential to generate a variety of
well controlled multiphase microdomain structures with nanosized structural units in
bulk and thin films and to provide supramolecular structures in solution with a
mesoscopic length scale. Therefore, numerous applications such as multifunctional
sensors, multiselective catalysts for sequential or simultaneous chemical reactions,
separation membranes, filters, etc., are possible [88].

The purpose of this investigation was to further extend the synthetic work on three-
component polymers and prepare a new structure of star terpolymers whose arms are

21
not different homopolymers but ABC triblock terpolymers. A combination of two
hydrophilic and one hydrophobic monomers was chosen, leading to water-soluble,
amphiphilic materials [89].

ABC triblock copolymers comprised mostly of diene-, styrene-, metacrylate-, or

pyridine-based monomers have been studied extensively. These well-defined
structures have elicited fascination not only for theoreticians modeling phase
behavior but also in the physical realm for studying morphological transitions. The
phase behavior of these systems is governed by the Flory interaction parameter
between two domains, , and is strongly influenced by the weight fraction of the
various blocks present in the copolymer. The morphological possibilities for these
copolymers can range from a basic lamellar structure to highly complex core-shell
gyroid morphology and even to a unique knitting pattern. Blending these types of
copolymers definitely play a central role in polymer science.

Following the intense interest in the study of diblock and ABA triblock copolymers,
the polymer community starts now to focus on a new type of block copolymers, that
of ABC triblock copolymers comprising three blocks, each made of a different
monomer repeat unit [90]. In bulk, four different ordered structures can be obtained
(alternating lamellae, cylinders, body-centered cubic arrays of spheres and gyroid)
depending on the copolymer composition and architecture. Considerably less

block copolymers with other copolymers enables additional manipulation of the

morphological patterns. Until now, however, the monomers comprising the ABC
triblock copolymers have been limited to those that can be polymerized either
anionically or by group transfer polymerization. Recently, examples of
inorganic/organic hybrid ABC triblock copolymers synthesized by combining living
anionic ring-opening polymerization with atom transfer radical polymerization
(ATRP) have been presented, in addition to ABC triblock copolymers synthesized
wholly by ATRP or through reversible addition fragmentation chain transfer (RAFT).
Kelly and Matyjaszewski demonstrated that ABC triblock copolymers of various
chain architectures and monomer combinations can be successfully prepared using
ATRP methods [91].

The key to the controlled synthesis of block copolymers in ATRP is to maintain high
chain end functionality, i.e., limit termination and side reactions, and to balance the

22
reactivity of the end group with that of the monomer, i.e., avoid slow initiation.
While the latter consideration is not as problematic as it is in anionic or carbocationic
polymerizations and can be overcome through a careful choice of the block order,
radical termination cannot be completely avoided due to the nature of the
polymerization process. It can be limited, however, through the careful choice of the
polymerization conditions and through adjustment of the equilibrium between the
active and dormant species, often by adding a "persistent radical" in the form of a
higher oxidation state metal. Kelly and Matyjaszewski‟s report focuses on the
preparation of copolymers using these approaches to obtain well-defined multiblock
copolymers. Several different catalyst systems, based predominantly on linear amine
ligands, as well as different synthetic methodologies (i.e., the halogen exchange
technique) were utilized to successfully prepare these copolymers [91].

Recently, the co-terpolymerization reactions, involving two or three monomers for

the synthesis of synthetic polymers, have been commonly used. The properties of
available polymers can also be changed by these reactions and novel polymers can be
obtained by co-terpolymerization reactions. Thus, several useful terpolymers have
been synthesized and used for various purposes [16].

Figure 2.7 : Schematic presentation of all possible arrangements for an ABC

terpolymer. (a–c) Linear triblock terpolymer, ABC, BAC, CBA,
respectively (d). Miktoarm star terpolymer (e), Cyclic terpolymer (f–
h). One of the chains is cyclic (starts and ends at the junction point)
and the other two linear (i-k). One chain is linear and the two are
cyclic (l). All chains are cyclic (o).

23
As an important illustration, interesting results have been recently obtained with
SBM Nanostrengthw block terpolymers produced on an industrial scale. These
triblocks copolymers combine polystyrene (PS), 1–4 polybutadiene (PBu) and
polymethylmetacrylate (PMMA) segments. These engineering polymers can, for
instance, be used as additives, allowing a much better solubility between
incompatible commodity or technical plastics and fine tuning between toughness and
stiffness of the host matrix. Detailed characterization of these new block copolymers
obtained both by controlled radical polymerization and anionic polymerization
represents a real challenge due to their increasing complexity [88].

2.6. Click Chemistry

The click chemistry as a modular approach was introduced by Sharpless, which has
important features including high yields, functional group tolerance, and selectivity
[92].

Although demand for new chemical materials and biologically active molecules
continues to grow, chemists have hardly begun to explore the vast pool of potentially
active compounds. The emerging field of “click chemistry,” a newly identified
classification for a set of powerful and selective reactions that form heteroatom links,
offers a unique approach to this problem [88]. “Click chemistry” is a term used to
describe several classes of chemical transformations that share a number of important
properties which include very high efficiency, in terms of both conversion and
selectivity under very mild reaction conditions, and a simple work up. It works well
in conjunction with structure based design and combinatorial chemistry techniques,
and, through the choice of appropriate building blocks, can provide derivatives or
mimics of „traditional‟ pharmacophores, drugs and natural products. However, the
real power of click chemistry lies in its ability to generate novel structures that might
not necessarily resemble known pharmacophores.

A concerted research effort in laboratories has yielded a set of extremely reliable

processes for the synthesis of building blocks and compound libraries:

• Cycloaddition reactions, especially from the 1,3-dipolar family, but also

hetero-Diels-Alder (DA) reactions.

24
 • Nucleophilic ring-opening reactions, especially of strained heterocyclic
electrophiles, such as epoxides, aziridines, cyclic sulfates, cyclic sulfamidates,
aziridinium ions and episulfonium ions.

• Carbonyl chemistry of the non-aldol type (e.g. the formation of oxime ethers,
hydrazones and aromatic heterocycles).

• Addition to carbon–carbon multiple bonds; particularly oxidation reactions,

such as epoxidation, dihydroxylation, aziridination, and nitrosyl and sulfenyl
halide additions, but also certain Michael addition reactions.

Huisgen‟s 1,3-dipolar cycloaddition of alkynes and azides yielding triazoles is,

undoubtedly, the premier example of a click reaction [89]. Recently, DA reaction
based on the macromolecular chemistry has attracted much attention, particularly for
providing new materials. As an alternative route, recently, 1,3-dipolar cycloadditions,
such as reactions between azides and alkynes or nitriles, have been applied to
macromolecular chemistry, offering molecules ranging from the block copolymers to
the complexed macromolecular structures [91].

Sharpless and co-workers have identified a number of reactions that meet the criteria
for click chemistry, arguably the most powerful of which discovered to date is the
Cu(I)-catalyzed variant of the Huisgen 1,3-dipolar cycloaddition of azides and
alkynes to afford 1,2,3-triazoles [90]. Because of Cu(I)-catalyzed variant of the
Huisgen 1,3-dipolar cycloaddition of azides and alkynes reactions‟ quantitative
yields, mild reaction condition, and tolerance of a wide range of functional groups, it
is very suitable for the synthesis of polymers with various topologies and for polymer
modification [16]. Because of these properties of Huisgen 1,3-dipolar cycloaddition,
reaction is very practical. Moreover, the formed 1,2,3-triazole is chemically very
stable [93].

In recent years, triazole forming reactions have received much attention and new
conditions were developed for the 1,3-dipolar cycloaddition reaction between
alkynes and azides [94]. 1,2,3-triazole formation is a highly efficient reaction without
any significant side products and is currently referred to as a click reaction [95].

Huisgen 1,3-dipolar cycloadditions are exergonic fusion processes that unite two
unsaturated reactants and provide fast access to an enormous variety of five-

25
membered heterocycles. The cycloaddition of azides and alkynes to give triazoles is
arguably the most useful member of this family [96].

The copper(I)-catalyzed 1,2,3-triazole formation from azides and terminal acetylenes

is a particularly powerful linking reaction, due to its high degree of dependability,
complete specificity, and the bio-compatibility of the reactants. With the ~106-fold
rate acceleration of the copper(I)-catalyzed variant of Huisgen‟s 1,3-dipolar
cycloaddition reaction, the generation of screening libraries has reached a new level
of simplicity. Two subunits are reliably joined together by formation of a 1,4-
disubstituted 1,2,3-triazole linkage. This ligation process works best in aqueous
media without requiring protecting groups for any of the most common functional
groups, enabling compound screening straight from the reaction mixtures (i.e.
without prior purification) [89].

Azides usually make fleeting appearances in organic synthesis: they serve as one of
the most reliable means to introduce a nitrogen substituent through the reaction
–R–X→[R–N3]→R–NH2. The azide intermediate is shown in brackets because it is
generally reduced straightaway to the amine. Despite this azidophobia, this have
been learned to work safely with azides because they are the most crucial functional
group for click chemistry endeavors. Ironically, what makes azides unique for click
chemistry purposes is their extraordinary stability toward H2O, O2, and the majority
of organic synthesis conditions. The spring-loaded nature of the azide group remains
invisible unless a good dipolarophile is favorably presented. However, even then the
desired triazole forming cycloaddition may require elevated temperatures and,
usually results in a mixture of the 1,4 and 1,5 regioisomers.

Since efforts to control this 1,4- versus 1,5-regioselectivity problem have so far met
with varying success, it was found that copper(I)-catalyzed reaction sequence which
regiospecifically unites azides and terminal acetylenes to give only 1,4-disubstituted
1,2,3-triazoles. The process is experimentally simple and appears to have enormous
scope [96].

26
 1,5 triazole
1:1

Figure 2.8 : Regioselectivity mechanism of triazole forming cycloaddition

Since the initial discovery of Cu(I)-catalyzed alkyne–azide coupling, numerous

successful examples have been recorded in the literature, but as of yet, no systematic
study of optimal conditions has been reported. Further, conditions have varied widely,
particularly with respect to generation of the active Cu(I) species. Sources of Cu(I)
include Cu(I) salts, most commonly copper iodide, in-situ reduction of Cu(II) salts,
particularly Cu(II) sulfate, and comproportionation of Cu(0) and Cu(II). Recent
reports suggest that nitrogen-based ligands can stabilize the Cu(I) oxidation state
under aerobic, aqueous conditions and promote the desired transformation. Steric
factors and electronic effects may also play a role in the success of this click
chemistry [90].

27
 1,4 triazole

Stepwise

Cu catalyzed

91%

Thermal

Figure 2.9 : Proposed catalytic cycle for the Cu(I)-catalyzed ligation

The process exhibits broad scope and provides 1,4-disubstituted 1,2,3-triazole

products in excellent yields and near perfect regioselectivity [96].

This ligation process has proven useful for the synthesis of novel polymers and
materials in many laboratories, and its unique characteristics make it an ideal
reaction for model network crosslinking. Johnson et al. (2005) therefore envisioned
an azide telechelic macromonomer and a multifunctional small molecule alkyne, the
former with a cleavable functionality at its center, as fulfilling the requirements for a
degradable model network. Organic azides are most often made from alkyl halides,
and several groups have reported the quantitative postpolymerization transformation
(PPT) of polymeric halides to azides for the copper(I)-catalyzed azide-alkyne

28
cycloaddition (CuAAC) reaction by treatment with sodium azide in DMF. Atom
transfer radical polymerization (ATRP) of various styrenic, acrylic, and methacrylic
monomers from halide initiators is well-known to provide polymers of low
polydispersity possessing alkyl halide end groups. Therefore, by a sequence of ATRP
from a degradable halide-containing initiator, PPT, and CuAAC, one can
conveniently prepare model networks of different macromonomer structure (e.g., star
polymers, block copolymers) and incorporate a wide variety of functional groups
[97].

Some click reactions have already been successfully used in polymer and materials
chemistry. The efficient preparation of well-defined polymeric tetrazoles, or
dendrimers, amphiphilic block copolymers, cross-linked block copolymer vesicles,
and adhesives with triazole units has been reported. Click reactions were also used in
the synthesis of functionalized poly(oxynorbornenes) and block copolymers and are
a convenient alternative to other coupling reactions applied to polymers prepared by
ATRP (such as atom transfer radical coupling or reversible thiol oxidative coupling)
for the preparation of high molecular weight polymeric materials [98].

The halogen end group can be converted to other functional groups using standard
organic procedures. However, the transformation is preferably carried out under
mild conditions, as the substitution must be as free of side reactions as possible and
the yield of the transformation reaction must be quantitative. With ATRP, the alkyl
group of the alkyl halide initiator remains at one end of the produced polymer chain,
a halogen atom is quantitatively transferred to the other end of the chain. By
replacement of the halogen end group, several functional groups can be introduced at
the polymer chain end [100]. The functionalized polymers can find many
applications, for example as macromonomers, telechelics or other specialty polymers
[101]. An interesting functional group transformation is the one to azide end groups.
Azide groups can produce nitrenes on thermolysis or photolysis, or can be converted
to other functionalities such as amines, nitriles, isocyanates, etc.

In addition, click strategies have been used as an approach to synthetic cyclodextrins

and the decoration of cyclic peptides by glycosylation. Synthetic glycochemicals
have attracted increasing interest as carbohydrates are involved in a number of
important biological processes involving highly specific events in cell-cell
recognition, cell-protein interactions, and the targeting of hormones, antibodies, and

29
toxins. Sugars are information-rich molecules, and an increasingly large number of
known lectins are able to recognize subtle variations of oligosaccharide structure and
act as decoders for this carbohydrate-encoded information. Gaining insight into the
factors that control these phenomena may open the way for the development of new
antiinfective, anti-inflammatory, and anticancer therapeutics and agents [88].

Due to their biological activity of click reactions as anti-HIV and antimicrobial

agents, as well as selective β3 adrenergic receptor agonist, new methods for the regio-
and/or stereoselective synthesis of both 1,2,3 triazoles and 1,2,3,4-tetrazoles should
be highly valuable [101].

2.7 Surface-immobilized macromolecules

2.7.1. Synthesis of surface-immobilized macromolecules (polymer brushes)

This section describes the preparation of polymer brushes on solid substrate surfaces
(impenetrable interfaces). Generally, there are two ways to fabricate polymer
brushes: physisorption and covalent attachment (see Figure 2.15). For polymer
physisorption, block copolymers adsorb onto a suitable substrate with one block
interacting strongly with the surface and the other block interacting weakly with the
substrate. Covalent attachment can be accomplished by either “grafting to” or
“grafting from” approaches. In a “grafting to” approach, preformed end-
functionalized polymer molecules react with an appropriate substrate to form
polymer brushes. The “grafting from” approach is a more promising method in the
synthesis of polymer brushes with a high grafting density. However “grafting from”
well-defined self-assembled monolayers (SAMs) is more attractive due to a high
density of initiators on the surface and a well-defined initiation mechanism. Also
progress in polymer synthesis techniques makes it possible to produce polymer
chains with controllable lengths. Polymerization methods that have been used to
synthesize polymer brushes include cationic, anionic, TEMPO-mediated radical,
atom transfer radical polymerization (ATRP) and ring opening polymerization. In the
following section, the emphasis will be put on the synthesis of polymer brushes from
SAMs.

30
Figure 2.10 : Preparation of polymer brushes by “physisorption”, “grafting to” and
“grafting from”.

2.7.2. “Grafting to” approach to fabricate polymer brushes

“Grafting to” approach refers to preformed, end-functionalized polymers reacting

with a suitable substrate surface under appropriate conditions to form a tethered
polymer brush. The covalent bond formed between surface and polymer chain makes
the polymer brushes robust and resistant to common chemical environmental
conditions. This method has been used often in the preparation of polymer brushes.
End-functionalized polymers with a narrow molecular weight distribution can be
synthesized by living anionic, cationic, radical, group transfer and ring opening
metathesis polymerizations. The substrate surface also can be modified to introduce
suitable functional groups by coupling agents or SAMs.

In general, only a small amount of polymer can be immobilized onto the surface by
“grafting to” approach. Macromolecular chains must diffuse through the existing
polymer film to reach the reactive sites on the surface. This barrier becomes more
pronounced as the tethered polymer film thickness increases. Thus the polymer brush

31
obtained has a low grafting density and low film thickness. To circumvent this
problem, investigators have used the “grafting from” approach, which has become
more attractive in preparing thick, covalently tethered polymer brushes with a high
grafting density.

2.7.3.“Grafting from” approach to synthesize polymer brushes

The “grafting from” approach has attracted considerable attention in recent years in
the preparation of tethered polymers on a solid substrate surface. The initiators are
immobilized onto the surface followed by in situ surface initiated polymerization to
generate tethered polymers.

2.7.3.1. Synthesis of tethered polymer brushes by conventional radical

polymerizations

In many reported systems which used the “grafting from” method via a radical
polymerization mechanism, the immobilization of radical initiators usually involved
a series of steps. An anchor molecule was immobilized on the solid substrate surface
and then the initiating species was linked to the anchor molecules in one or more
additional steps. For example, Boven et al. (1991) treated glass beads with 3-
aminopropyltriethoxysilane (g-APS) to obtain amino functional groups on the
surface. The azo initiators were then immobilized onto the surface through the
formation of amide bonds between the g-APS modified surface and an acid chloride
functionalized azo initiator. Subsequent surface initiated radical polymerization
produced tethered PMMA chains[102].

Sugawara and Matsuda (1973) used a similar strategy to graft PS on poly(vinyl

alcohol) film and poly(- acrylamide) on poly(ethylene terephthalate) (PET)film. First
they coated the substratewith poly(allylamine) which had been partially derivatized
with photoreactive phenylazido [103]. Theaminated polymerwas chemically fixed on
the surface the reactive phenylnitrene generated from UV irradiation. Carboxylated
azo initiators were then immobilized onto the surface through a condensation
reaction with immobilized aminated polymer. Radical polymerization under suitable
conditions yielded tethered polymers.

Although these studies successfully prepared polymer brushes, there are several
disadvantages. Immobilization of initiator on the surface involved several steps,
which may lead to low graft densities of initiators and tethered polymers if the

32
reactions are not quantitative. Secondly, side reactions which possibly exist in the
initiator immobilization reaction may introduce some undesired structures on the
surface. Accurate characterization of the initiator layer is nontrivial. This lack of
knowledge about the exact composition of the initiator layer makes the
understanding of polymerization mechanism difficult in some cases. It has been
shown that the g-APS layer is a very complex structure, sometimes multilayer
structures may result. To circumvent this problem, Ru¨he and coworkers reported a
strategy in which the complete initiator was attached to the substrate‟s surface in one
step by SAM techniques. Polymerization experiments indicated this strategy had
achieved great success. The kinetics of polymerization initiated from the surface
bound initiator was studied by dilatometry. After polymerization the polymer was
cleaved off and the molecular weight was determined.

Using the same strategy, they also synthesized PS brushes and PMMA brushes on
planar silicate substrates. These polymer brushes have been characterized by various
surface characterization techniques including IR spectroscopy, surface plasmon
resonance measurement, ellipsometry, X-ray reflectometry, AFM and neutron
reflectometry.

Figure 2.11 : Schematic description of the concept for the preparation of cleavable
polymer brushes by “grafting from” approach.

33
2.7.3.2. Synthesis of tethered polymer brushes by controlled radical
polymerization

In order to achieve a better control of molecular weight and molecular weight

distribution and synthesize novel polymer brushes like block copolymer brushes,
controlled radical polymerizations including ATRP, reverse ATRP, TEMPO-
mediated and iniferter radical polymerizations have been used to synthesize tethered
polymer brushes on solid substrate surfaces [104-109].

In the 1990s, Otsu et al. (1998) reported that the polymerization of styrene and MMA
in solution was living-like by using dithiocarbamate derivatives as initiators which
were described as iniferters [110-111] Iniferters means that they act as initiator,
transfer agent and terminator. It was also reported that photolysis of the iniferter N,N-
diethyldithiocarbamate by UV irradiation yielded a reactive radical and nonreactive
radical which exclusively led to termination reaction through recombination with a
growing polymer chain. By use of this method, they successfully grafted PS and
PMMA onto crosslinked polystyrene containing dithiocarbamate groups [107]. On
the basis of Otsu‟s work, Nakayama and Matsuda (1998) immobilized N,N-
diethyldithiocarbamate groups on a cross-linked chloromethylated PS [104] .
Irradiation of this initiator-immobilized surface in the presence of a vinyl monomer
such as N,Ndimethylacrylamide, N-[3-(dimethylamino)- propyl]acrylamide,
methacrylic acid or styrene at room temperature produced tethered polymers. Since
polymerization proceeded only during photoirradiation and at irradiated areas, a
precise spatial control could be achieved. Recently, de Prucker et al. (1998) prepared
polymer brushes using surface-grafted iniferter monolayers [109].

ATRP is a newly developed controlled radical polymerization. It has attracted

considerable attention due to its control of molecular weight, molecular weight
distribution and synthesis of block copolymers [112]. Surface initiated
polymerization from the immobilized initiators in the presence of MMA under
suitable conditions produced PMMA brushes with high grafting density. The
molecular weight and molecular weight distribution were controlled by addition of a
predetermined amount of free initiator in the polymerization systems. The a-
bromoester is a good initiator for ATRP. They have successfully synthesized PMMA
brushes by the polymerization of MMA initiated from the SAMs. It has also been

34
reported that tethered polyacrylamide has been obtained from surface initiated ATRP
of acrylamide on a porous silica gel surface.

35
36
3. EXPERIMENTAL WORK

3.1 Materials

Styrene (St, 99%, Merck) and methyl methacrylate (MMA, 99%, Aldrich) were
passed through basic alumina column to remove inhibitor and then distilled over
CaH2 in vacuo prior to use. N, N, N’, N’’, N’’-pentamethyldiethylenetriamine
(PMDETA, Aldrich) was distilled over NaOH prior to use. Poly(ethylene glycol)
monomethylether (M-PEG) (Mn = 2000, Fluka) was dried over anhydrous toluene by
azeotropic distillation. Tetrahydrofuran (THF, 99.8%, J.T. Baker) was dried and
distilled over benzophenone-Na. Dichloromethane was purchased from Aldrich and
used after distillation over P2O5.Other solvents were purified by conventional
procedures. All other reagents were purchased from Aldrich and used as received.

3.2 Instrumentation

1
H NMR spectra was recorded on a Bruker NMR Spectrometer (250 MHz) in CDCl3.
Gel permeation chromatography measurements were obtained from an Agilent
instrument (Model 1100) consisting of a pump, a refractive index (RI) detector, and
four Waters Styragel columns (HR 5E, HR 4E, HR 3, and HR 2). THF was used as
eluent at a flow rate of 0.3 mL/min at 30 oC. Toluene was as an internal standard. To
measure the absolute molecular weights the second GPC system with an Agilent
model isocratic pump, four Waters Styragel columns (HR 5E, HR 4, HR 3, and HR
2), and a Viscotek TDA 302 triple detector (RI, dual laser light scattering (LS) (λ =
670 nm, 90° and 7°) and a differential pressure viscometer) was conducted in THF
with a flow rate of 0.5 mL/min at 35 °C. All three detectors were calibrated with a
PS standard having narrow molecular weight distribution (Mn = 115,000 g/mol,
Mw/Mn = 1.02, [η] = 0.519 dL/g at 35 °C in THF, dn/dc = 0.185 mL/g) provided by
Viscotek company. Data analyses were performed with PL Caliber Software. The
molecular weight of the polymers was calculated on the basis of linear polystyrene
standards (Polymer Laboratories). Fourier transform infrared (FTIR) analysis was
carried out with a Perkin Elmer Spectrum One FTIR spectrometer. Thermal

37
gravimetric analyses (TGA) were performed on Perkin–Elmer Diamond TA/TGA in
the temperature range of 30–1000 °C, working at 10 °C min-1 under nitrogen flow.

3.3 Synthesis of Initiator

3.3.1 Synthesis of 2,2,5-trimethyl-[1,3]dioxane-5-carboxylic acid (1)

The 2,2-bis(hydroxymethyl)propanoic acid (16 g, 119.36 mmol) along with p-TSA

(0.448 g, 2.32 mmol), and 2,2-dimethoxypropane (22.4mL, 179.2 mmol) dissolved in
80 mL of dry acetone, and stirred 2h at room temperature. In the vicinity of 2 h,
while stirring continued the reaction mixture was neutralized with 12 mL of totally
NH4OH (25 %), and absolute ethanol (1:1), filtered off by-products and subsequent
dilution with dichloromethane (200 mL) , and once extracted with distilled water (80
mL). The organic phase dried with Na2SO4, concentrated to give as white solid after
evaporation of the solvent (Yield =15.8 g, 76 %).

3.3.2 Synthesis of prop-2-ynyl 2,2,5-trimethyl-1,3-dioxane-5-carboxylate (2)

Propargyl alcohol (4 mL, 69 mmol) was dissolved in 50 mL of CH2Cl2 and 2,2,5-

trimethyl-[1,3]dioxane-5-carboxylic acid (8 g, 46 mmol), and DMAP (2.81 g, 23
mmol) were added to the reaction mixture in that order. After stirring 5 minutes at
room temperature, DCC (10.44 g, 50.6 mmol) dissolved in 30 mL of CH2Cl2 was
added. Reaction mixture was stirred overnight at room temperature and urea
byproduct was filtered. Then reaction mixture was extracted with water/CH2Cl2 (1:4)
two times and combined organic phase was dried with Na2SO4. Solvent was
evaporated and the remaining product was purified by column chromatography over
silica gel eluting with hexane/ethyl acetate (9:1) to give pale yellow oil (Yield = 7.5
g; 77 %). 1H NMR (CDCl3, δ) 4.72 (d, J = 2.4 Hz, 2H, CH CCH2O), 4.18 (d, J =
11.6 Hz, 2H, CCH2O), 3.63 (d, J = 11.6 Hz, 2H, CCH2O), 2.45(t, J = 2.4 Hz, 1H,
CH CCH2O), 1.40 (s, 3H, CCH3) 1.36 (s, 3H, CCH3), 1.18 (s, 3H,
13
C=OC(CH2O)2CH3). C NMR (CDCl3, δ) 173.47 (C=O), 98.11 (CCH3)2, 76.58
(CH CCH2O), 73.03 (CH CCH2O), 65.84 (CH2O), 52.35 (CH CCH2O), 49.96
(CCH3), 25.68 (CCH3), 23.66 (CCH3), 17.37 (C=OC(CH2O)2CH3).

38
3.3.3 Synthesis of prop-2-ynyl 3-hydroxy-2-(hydroxymethyl)-2-
methylpropanoate (3)

Propargyl 2,2,5-trimethyl-1,3-dioxane-5-carboxylate (7.4 g, 35 mmol) was dissolved

in a mixture of 30 mL of THF and 30 mL of 1 M HCl. The reaction mixture was
stirred for 2 h at room temperature. The precipitated product was filtered off and
reaction mixture was concentrated and extracted with 200 mL of CH2Cl2 and 50 mL
of water. The combined organic phase was dried with Na2SO4 and concentrated.
Hexane was added to the reaction mixture and it was kept in deep freeze overnight to
give white solid, Mp = 50 C (Yield = 5 g, 83 %). 1H NMR (CDCl3, δ) 4.72 (d, J =
2.4 Hz, 2H, CH CCH2O), 3.88 (d, J = 11.3 Hz, 2H, CH2OH), 3.69 (d, J = 11.3 Hz,
2H, CH2OH), 2.93 (br, 2H, OH), 2.48 (s, 1H, CH CCH2O), 1.07 (s, 3H, CCH3).
13
C NMR (CDCl3,δ) 175.08 (C=O), 76.56 (CH CCH2O), 73.28 (CH CCH2O), 67.70
(CH2OH), 52.52 (CCH3), 50.04 (CH CCH2O), 18.05 (CCH3).

3.3.4 Synthesis of prop-2-ynyl 3-(2-bromo-2-methylpropanoyloxy)-2-

(hydroxymethyl)-2-methylpropanoate (4)

Propargyl 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate (6.42 g, 37.3 mmol)

was dissolved in 50 mL of CH2Cl2 and triethylamine (Et3N) (11.4 mL, 82.06 mmol)
was added to the mixture and cooled to 0 oC. 2-Bromo isobutrylbromide (4.61 mL,
37.3 mmol) in 15 mL of CH2Cl2 was added dropwise within 30 minutes. The
reaction mixture was stirred overnight at room temperature. After filtration the
mixture was extracted with CH2Cl2 and saturated aq. NaHCO3. The aqueous phase
was again extracted with CH2Cl2 and combined organic phase was dried with
Na2SO4. The solution was concentrated and the crude product was purified by
column chromatography over silica gel eluting with hexane/ethyl acetate (9:1) to
give pale yellow oil (Yield = 7.9 g, 66 %). 1H NMR (CDCl3, δ) 4.72 (d, J = 2.4 Hz,
2H, CH CCH2O), 4.43 and 4.30 (dd, J = 11.2 Hz, 2H, CH2OC=O), 3.75 (d, J = 6.3
Hz, 2H, CH2OH), 2.47 (t, J = 2.4 Hz, 1H, CH CCH2O), 2.33 (br, 1H, OH), 1.91 (6H,
CBr(CH3)2), 1.27 (s, 3H, (s, 3H, CCH3). 13C NMR (CDCl3,δ) 173.28 (C=O),171.50
(C=O), ,76.53 (CH CCH2O), 75.29 (CH CCH2O), 66.93 (CH2OC=O), 64.93
(CH2OH), 55.42 (CBr(CH3)2), 52.54 (CCH3), 48.54 (CH CCH2O), 30.66
(CBr(CH3)2), 17.26 (CCH3).

39
3.3.5 Synthesis of monocarboxylic acid terminated PEG (PEG-COOH) (5)

M-PEG (10 g, 5 mmol) was dissolved in 200 mL of CH2Cl2 and succinic anhydride
(3 g, 30 mmol) was added. To the reaction mixture were added Et3N (4.17 mL, 30
mmol) and DMAP (0.92 g, 7.5 mmol). The reaction solution was poured into ice-
cold water (200 mL) and extracted with CH2Cl2. The organic phase again extracted
with 1M HCl (200 mL).Water phases extracted with CH2Cl2 and combined organic
phase was dried with anhydrous Na2SO4, and the solvent was removed in vacuo. The
polymer was dissolved in CH2Cl2 and precipitated into diethyl ether for two times.
The product, PEG-COOH having terminal monocarboxylic acid group was dried for
24 h in a vacuum oven at 40 oC (Yield = 9 g, 86%). Mn,theo = 2100; Mn,NMR = 2050;
Mn,GPC = 1520; Mw/Mn = 1.19. 1H NMR (CDCl3, δ) 2.62 (s, 4H, O=CCH2CH2C=O),
3.36 (s, 3H, OCH3), 3.53-3.90 (m, 4H, OCH2CH2O backbone), 4.24 (d, 4H,
C=OOCH2).

3.3.6 Synthesis of PEG-macroinitiator (6)

PEG-COOH (7.0 g, 3.3 mmol) was dissolved in 150 mL of dry CH2Cl2. prop-2-ynyl
3-(2-bromo-2-methylpropanoyloxy)-2-(hydroxymethyl)-2-methylpropanoate (7.41 g,
23.1 mmol) and DMAP (0.81 g, 6.6 mmol) were added to the reaction mixture in that
order. After stirring for 5 min at room temperature, DCC (4.77 g, 23.1 mmol)
dissolved in 50 mL of CH2Cl2 was added. Reaction mixture was stirred 48 h at room
temperature. After purification with silica gel column, the solution was concentrated
and precipitated in cold diethyl ether and this procedure was repeated two times.
(Yield = 6.4 g, 80%). Mn,theo = 2420; Mn,NMR = 2700; Mn,GPC =2050; Mw/Mn = 1.13
(Relative to linear PS). 1H NMR (CDCl3, d): 4.7 (s, 2H, HC CCH2O), 4.4–4.2 (m,
6H, CH2OC=O), 3.9 (t, 2H, C=OOCH2CH2-PEG), 3.8–3.5 (m, 4H, CH2CH2O of
PEG), 3.4 (s, 3H, CH2OCH3), 2.6 (s, 4H, C=O(CH2)2C=O), 2.5 (s, 1H, HC CCH2),
1.9 (s, 6H, C(Br)(CH3)2), 1.3 (s, 3H, C=OCCH3)

3.4 Synthesis of PEG-PMMA Copolymer with Alkyne at the Junction Point via
ATRP of Methyl Methacrylate (Alkyne-PEG-PMMA) (7)

Alkyne-PEG-PMMA copolymer was prepared by the ATRP of PMMA using PEG

macroinitiator. To a 50 mL Schlenk tube, methyl methacrylate (10 mL, 93.5 mmol),
PMDETA (0.097 mL, 0.46 mmol), CuCl (0.046 g, 0.46 mmol), PEG-macroinitiator

40
(1.12 g, 0.46 mmol) were added and solved in 10 mL toluene. After that, reaction
mixture was degassed by three freeze-pump-thaw cycles and left in vacuo. The tube
was then placed in a thermostated oil bath at 90 °C for 10 min. The polymerization
mixture was diluted with THF, passed through an alumina column to remove the
catalyst, and precipitated into methanol. The polymer was dried in a vacuum oven at
40 °C. ( [M]0/[I]0 = 200; [I]0:[CuCl]0:[PMDETA]0=1:1:1; conversion = 30 %; Mn,theo
= 8400; Mn,NMR = 8050; Mn,GPC = 9050; Mw/Mn= 1.12). 1H NMR (CDCl3, δ) 4.71 (s,
2H, CH CCH2O), 4.22 (m, 6H, PEG-OCH2CH2OC=O and CH2OC=O ), 3.89 (t, 2H,
PEG-OCH2CH2OC=O), 3.67-3.62 (br, 4H, OCH2CH2- of PEG), 3.60-3.50 (br,
OCH3 of PMMA), 3.36 (s, OCH3 end group of PEG), 2.62 (s, 4H,
C=OCH2CH2C=O), 2.52 (s, 1H, CH CCH2O), 2.0-0.6 (aliphatic protons).

3.5 Synthesis of 3-(trimethylsilyl)prop-2-ynyl 2-bromo-2-methylpropanoate (8)

3-(trimethylsilyl)prop-2-yn-1-ol (1.14 mL, 7.8 mmol) and DMAP (0.48 g, 3.9 mmol)
was dissolved in 30 mL of CH2Cl2, Et3N (1.62 mL, 11.7 mmol) was added to the
mixture and cooled to 0 oC. 2-Bromo isobutrylbromide (1.15 mL, 9.35 mmol) in 15
mL of CH2Cl2 was added dropwise within 30 minutes. The reaction mixture was
stirred overnight at room temperature. After filtration the mixture was extracted with
CH2Cl2 and saturated aq. NaHCO3. The aqueous phase was again extracted with
CH2Cl2 and combined organic phase was dried with Na2SO4. The solution was
concentrated and the crude product was purified by column chromatography over
silica gel eluting with hexane/ethyl acetate (4:1) to give yellow viscose liquid (Yield
= 1.72 g, 80 %). 1H NMR (CDCl3, δ) 4.75 (s, 2H, C CCH2-O), 1.91 (s, 6H,
CBr(CH3)2), 0.17 (s, 6H, (CH3)3Si-)

3.6 Synthesis Bromo End-functionalized Sillyl Protected PS via ATRP of

Styrene (9)

To a 50 mL Schlenk tube, styrene (20 mL, 174.5 mmol), PMDETA (0.18 mL, 0.87
mmol), CuBr (0.125 g, 0.87 mmol), 3-(trimethylsilyl)prop-2-ynyl 2-bromo-2-
methylpropanoate (0.24 g, 0.87 mmol) were added and the reaction mixture was
degassed by three freeze-pump-thaw cycles and left in vacuo. The tube was then
placed in a thermostated oil bath at 110 °C for 40 min. The polymerization mixture
was diluted with THF, passed through an alumina column to remove the catalyst, and

41
precipitated into methanol. The polymer was dried in a vacuum oven at 40 °C.
( [M]0/[I]0 = 200; [I]0:[CuBr]0:[PMDETA]0=1:1:1; conversion = 21%; Mn,theo = 4750;
Mn,NMR = 4900; Mn,GPC = 4850; Mw/Mn= 1.06). 1H NMR (CDCl3, δ) 7.4-6.2 (br, 5H,
aromatic protons of PS), 4.4 (br, 1H, CH-Br end group of PS), 4.11 (m, 2H,
CH CCH2O), 2.5-1 (br, 3H aliphatic protons of PS), 0.15 (s, 9H, (CH3)3Si-).

3.7 Synthesis of azide end – functionalized PS (10)

Previously obtained bromo end-functionalized PS (3.5 g, 0.71 mmol) was dissolved

in DMF (15 mL), and sodium azide (0.93 g, 14.2 mmol) was added. The reaction
mixture was stirred overnight at room temperature. The reaction mixture was
precipitated into methanol (this procedure was repeated two times), filtered, and
dried in vacuum oven at 40 °C, yielding a white solid (3.42 g, 95 %). Mn,GPC = 5000;
Mw/Mn= 1.08 1H NMR (CDCl3, δ) 7.4-6.2 (br, 5H, aromatic protons of PS), 4.11 (m
1H, CH-N3 end group of PS and 2H, CH CCH2O), 2.5-1 (br, 3H aliphatic protons of
PS), 0.15 (s, 9H, (CH3)3Si-).

3.8 Click reaction between Alkyne-PEG-PMMA and Sillyl protected PS-N3

(ABC Type Miktoarm Star Polymer) (11)

Alkyne-PEG-PMMA copolymer (1.5 g, 0.18 mmol) and PS-N3 (1.5 g, 0.3 mmol)
were dissolved in DMF (15mL) in a schlenk tube equipped with magnetic stirring bar.
CuBr (0.077 g, 0.54 mmol) and PMDETA (0.113 mL, 0.54 mmol) were added and
the reaction mixture was degassed by three freeze-pump-thaw cycles and left in
vacuum and stirred at room temperature for three days. The polymerization mixture
was diluted with THF, passed through a neutral alumina column to remove the
catalyst, and precipitated into diethyl ether. Then ABC type polymer was dried in a
vacuum oven at 40 °C. Mn,theo = 12950; Mn,NMR = 14750; Mn,GPC = 14650; Mw/Mn=
1.18). 1H NMR (CDCl3, δ) 7.38 (s, 1H, CH of triazole), 7.3-6.2 (br, 5H, aromatic
protons of PS), 5.06 (s, 3H, CH-triazole end group of PS and triazole-CH2-CO), 4.16
(m, 8H, CH CCH2O and PEG-OCH2CH2OC=O, C-CH2-O-C=O and CH2OC=O ),
3.63-3.61 (br, 4H, OCH2CH2- of PEG), 3.60-3.50 (br, OCH3 of PMMA), 3.36 (s,
OCH3 end group of PEG), 2.46 (s, 4H, C=OCH2CH2C=O), 2.5-1 (br, 3H aliphatic
protons of PS), 0.15 (s, 9H, (CH3)3Si-).

42
3.9 Deprotection reaction of ABC Type Miktoarm Star Polymer (Hydrolysis
Reaction) (12)

ABC type star polymer (1.8 g, 0.12 mmol) was dissolved in 10 mL of THF. The
reaction mixture was stirred for 2 h at room temperature. The reaction mixture
precipitated into methanol. Mn,NMR = 14750; Mn,GPC = 15550; Mw/Mn= 1.19). 1H NMR
(CDCl3, δ) 7.38 (s, 1H, CH of triazole), 7.3-6.2 (br, 5H, aromatic protons of PS),
5.06 (s, 3H, CH-triazole end group of PS and triazole-CH2-CO), 4.16 (m, 8H,
CH CCH2O and PEG-OCH2CH2OC=O, C-CH2-O-C=O and CH2OC=O ), 3.63-
3.61 (br, 4H, OCH2CH2- of PEG), 3.60-3.50 (br, OCH3 of PMMA), 3.36 (s, OCH3
end group of PEG), 2.46 (s, 4H, C=OCH2CH2C=O), 2.45 (s, 1H, CH CCH2O), 2.5-1
(br, 3H aliphatic protons of PS).

3.10 Synthesis of Azide Functionalized Silica Nanoparticles

3.10.1 Synthesis of azido ethanol (13)

Bromo ethanol (3.5 g, 0.028 mol) was dissolved in in a mixture of 30 mL of acetone

and 30 mL of water, and sodium azide (0.93 g, 14.3 mmol) was added. The reaction
mixture was stirred for overnight at reflux temperature. It was evaporated to remove
acetone. CH2Cl2 (100 mL) was than added, and the reaction mixture extracted two
times with distilled water. The organic layer was dried with anhydrous Na2SO4, and
the solvent was removed in vacuo to give the compound as a colorless liquid.
(Yield=2.4 g, 98 %). 1H NMR (CDCl3, δ) 3.71 (t, 2H, CH2-CH2-OH), 3.36 (t, 2H,
N3-CH2-CH2) and 3.17 (s, 1H, CH2CH2-OH).

3.10.2 Synthesis of teos azide (14)

3-(Isocyanatopropyl)triethoxysilane (4.74 mL, 19.1 mmol) was dissolved in 50 mL

THF. Azidoethanol (1 g, 11.5 mmol) and dibuthyltindilaurate (2 droplet) was added
to the reaction mixture. Reaction mixture was stirred for overnight at reflux
temperature. It was evaporated to remove THF. CH2Cl2 (100 mL) was than added,
and the reaction mixture extracted two times with distilled water. The organic layer
was dried with anhydrous Na2SO4, and the solvent was removed in vacuo. The
compound was obtained as a pale yellow oil. Yield 88 %). 1H NMR (CDCl3, δ) 5.05
(s, 1H, -CH2-NH-COO), 4.2 (t, 2H, O=CO-CH2-CH2), 3.83-3.67 (m, 6H, (CH3CH2-

43
O)3-Si-), 3.4 (d, 2H, SiCH2CH2-CH2-NH), 3.15 (q, 2H, 0-CH2-CH2-N3), 1.67-1.58 (q,
2H, SiCH2CH2-CH2-NH), 1.2 (t, 9H, (CH3CH2-O)3-Si-) and 0.61 (t, 2H, SiCH2CH2-
CH2-NH).

3.10.3 The reaction between silica and TEOS azide (Si-N3) (15)

Silica (2 g) was dissolved in toluene (50 mL), and previously obtained (14) was
added. The reaction mixture was stirred overnight at 80 oC in a thermostated oil bath.
The reaction mixture was centrifuged two times with toluene, three times with THF,
and once with acetone. The obtained product, silica azide, was dried for 24 hours in
vacuum oven at 40 oC.

3.11 Click Reaction Between Silica Azide and Alkyne PS-PEG-PMMA

Azide end-functionalized silica (0.02 g, 0.023 mmol) and alkyne PS-PEG-PMMA

(0.50 g, 0.034 mmol) were dissolved in DMF (10mL) in a schlenk tube equipped
with magnetic stirring bar. CuBr (0.05 g, 0.34 mmol) and PMDETA (0.07 mL, 0.34
mmol) were added and the reaction mixture was degassed by three freeze-pump-thaw
cycles and left in vacuum and stirred at room temperature for three days. After that
time the mixture was subjected to centrifugation, the solid part redispersed in THF
and centrifugated again.This procedure was repeated five times. Finally the obtained
product dried in vacuum oven at 40 oC for overnight.

44
4. RESULTS AND DISCUSSION

4.1 Synthesis of Initiator

The initiator synthesis was obtained by the following routes; first of all 2,2,5-
trimethyl-[1,3]dioxane-5-carboxylic acid (1) was synthesized by this way; 2, 2-bis
(hydroxymethyl)-propanoic acid was reacted with excess amount of dry acetone
using p-toluene sulfonic acid as catalyst. Additionally, 2,2-dimethoxy-propane was
deliberately used to provide acetone during the reaction (4.1).

(4.2)

The structure of compound (1) was confirmed by 1H NMR and spectrum is shown in
Figure 4.1.

Figure 4.1 : The 1H NMR spectrum of 2,2,5-trimethyl-[1,3]dioxane-5-carboxylic

acid in CDCl3.

45
Subsequent esterification reaction between propargyl alcohol and (1) was carried out
using DCC as a coupling agent and catalytic amount of DMAP as catalyst and to
give prop-2-ynyl 2,2,5-trimethyl-1,3-dioxane-5-carboxylate (2).

(4.2)

The 1H NMR spectrum of the compound (2) is shown in Figure 4.2. From the NMR
spectrum the new signals appeared at δ 2.45 ppm of CH CCH2O– (alkyne) and
CH2O next to the carbonyl at δ 4.72 ppm indicates that the esterification reaction was
performed successfully.

Figure 4.2 : The 1H NMR spectrum of prop-2-ynyl 2,2,5-trimethyl-1,3-dioxane-5-

carboxylate in CDCl3.

Then, hydrolysis of compound (2) was taken placed in THF using dilute HCl to
produce prop-2-ynyl 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate (3).
Procedure of the reaction is given schematically in (4.3).

46
 (4.3)

The structure of the compound (3) was confirmed by 1H NMR as seen in Figure 4.3.
In the 1H NMR spectrum of (3), –CH3 protons from the compound (2) at δ 1.36 and
1.40 ppm were completely disappeared after the hydrolysis reaction and the new
protons belong to hydroxyl groups revealed at δ 2.93 ppm as a broad signal.

Figure 4.3 : The 1H NMR spectrum of prop-2-ynyl 3-hydroxy-2-(hydroxymethyl)-2-

methylpropanoate in CDCl3.

Then, prop-2-ynyl 3-(2-bromo-2-methylpropanoyloxy)-2-(hydroxymethyl)-2-

methylpropanoate (4) was synthesized via an esterification reaction between (3) and
2-bromoisobutryl bromide, in this step one point has to be stressed that the reaction
must take place at zero temperature with drop by drop addition of 2-bromoisobutryl
bromide. Reaction is defined with molecular structure of the compounds in (4.4).

47
 (4.4)

The 1H NMR spectrum of the compound (4) given in Figure 4.4. From the NMR
spectrum, it was evident that CH2 protons next to carbonyl group appeared at δ 4.3
ppm and methyl protons next to bromine atom at δ 1.91 ppm clearly indicates the
ester formation.

Figure 4.4 : The 1H NMR spectrum of prop-2-ynyl 3-(2-bromo-2 methylpropanoylo-

xy)-2-(hydroxymethyl)-2-methylpropanoate in CDCl3.

Before the synthesis of PEG-macroinitiator, monocarboxylic acid terminated PEG

(PEG-COOH) (5) was achieved from commercially available M-PEG (2000) using
succinic anhydride in the presence of Et3N and DMAP as catalyst.

(4.5)

The 1H NMR spectrum of the compound (5) is given in Figure 4.5. From the NMR
spectrum, the characteristic peak of the backbone at δ 3.62 ppm, CH2OC=O next to

48
carbonyl at δ 4.23, and C=OCH2CH2C=O at δ2.65 ppm suggests that PEG-COOH
was obtained successfully.

Figure 4.5 : The 1H NMR spectrum of PEG-COOH in CDCl3.

Finally, PEG-macroinitiator (6) which has both alkyne and bromine functionalities,
was prepared via esterification reaction between PEG-COOH and 4 in the presence
of DMAP/DCC in CH2Cl2 at room temperature. Later has an initiation capability for
ATRP. Scheme 4.6 shows procedure of the reaction.

(4.6)

49
 1
The structure of compound (6) was confirmed by H NMR spectroscopic
measurements (Fig 4.6). 1H NMR measurement displayed new multiplet signal
arising from CH2OC=O at 4.4–4.2 ppm together with typical CH2CH2O of PEG.
Mn,NMR of PEG-macroinitiator [Mn,NMR =(55 x 44) + 320 (MW of (4)) = 2700] was
calculated from a ratio of peak areas of CH2CH2O repeating unit of PEG at 3.8–3.5
and CH2 adjacent to alkyne at 4.7 ppm. A GPC trace of PEG-macroinitiator showed
a tail at higher molecular weight region because of the condensation reaction taking
place between PEG-COOH and residual M-PEG. Nevertheless, the theoretical
molecular weight (Mn,theo = 2420) and Mn,NMR values are in good agreement.

Figure 4.6 : The 1H NMR spectrum PEG-macroinitiator in CDCl3.

4.2 Synthesis of PEG-PMMA Copolymer with Alkyne at the Junction Point via
ATRP of Methyl Methacrylate (Alkyne-PEG-PMMA)

For this purpose, PEG-b-PMMA-alkyne (7) was prepared by ATRP of degassed

MMA by using 6 and CuCl/PMDETA as a catalyst and toluen was added as solvent.
Then, tube was placed in a thermostated oil bath at 90°C for 10 min. Procedure of
this reaction is given schematically in (4.7). 1H NMR analysis clearly revealed an
incorporation of MMA segment into the PEG block (Figure 4.7).

50
 (4.7)

Notably, CH and CH2 protons of alkyne group were identified as signals at 4.7 and
2.6 ppm, respectively. Mn,theo of (7) precursor was calculated by using the following
equation: Mn,theo = (([M]o/[I]o) x conversion x 100.1) + Mn,NMR of (6) =8400. Mn,NMR
of (7) precursor [Mn,NMR = (48 (DPn of PMMA) x 100.1) + (40 (DPn of PEG) x 44) +
320 = 8050] was calculated by adding Mn,NMR of PMMA and PEG blocks which were
obtained by comparing the integral of the alkyne CH2O signal a 4.7 ppm to those of
OCH3 repeating unit of PMMA at 3.60-3.50 ppm and OCH2CH2 repeating unit of
PEG at 3.67-3.62 ppm, respectively. The GPC trace of the block copolymer was
monomodal, having low polydispersity index (1.06), and furthermore clearly shifted
to a higher region relative to that of PEG-macroinitiator, displaying that both chain
end functionality of macroinitiator and the blocking efficiency were rather high.

51
 Figure 4.7 : The 1H NMR spectrum (Alkyne-PEG-PMMA) in CDCl3.

4.3 Synthesis of Azide End–Functionalized PS

Firstly, the synthesis of initiator was done. For this purpose, 3-(trimethylsilyl)prop-2-
yn-1-ol was reacted with 2-bromo-2-methylpropanoyl bromine in the presence of the
DMAP, Et3N and as a solvent CH2Cl2 for overnight. In this step one point has to be
stressed that the reaction must take place at zero temperature with drop by drop
addition of 2-bromoisobutryl bromide. Consequently, 3-(trimethylsilyl)prop-2-ynyl
2-bromo-2-methylpropanoate (8) was successfully synthesized.

(4.8)

The 1H NMR spectrum of the compound (8) is shown at Figure 4.8. From the NMR
spectrum, it is evident that CH2 protons next to carbonyl group appeared at δ 4.75
ppm and methyl protons next to bromine atom at δ 1.91 ppm clearly indicates the
ester formation.

52
Figure 4.8 : The 1H NMR spectrum of 3-(trimethylsilyl)prop-2-ynyl 2-bromo-2-
methylpropanoate in CDCl3.

After the synthesis of initiator, sillyl protected PS (9) synthesized via ATRP of
styrene. Therefore, compound (8) was used as initiator and CuBr, PMDETA was
used as the catalyst of the ATRP at 110 oC. And the resulted polymer chains carried
α-sillyl protected alkyne- functionality. Reaction process is seen schematically in
(4.9).

(4.9)

The 1H NMR Spectrum of compound (9) shows aliphatic and aromatic protons of PS
clearly. As seen at the spectrum, aromatic protons appear at δ 7.4-6.2 ppm and
aliphatic protons appear at δ 2.5-1 ppm as a broad signal. Also, protons of Si(CH3)3
at δ 0.17 ppm as a sharp peak (Figure 4.9).

53
Figure 4.9 : The 1H NMR spectrum of bromo end-functionalized sillyl protected PS
in CDCl3.

Previously obtained (9) was dissolved in DMF and sodium azide was added at room
temperature for overnight. After which time, the azide end – functionalized PS (10)
was obtained with high yield (%95) as seen in (4.10).

(4.10)

The 1H NMR spectrum of (10) is shown at Figure 4.10. As seen at the spectrum,
proton next to bromine atom of PS end group is shifted to 3.9 ppm that is the
evidence of bromine functionality was turned to azide functionality successfully.

Figure 4.10 : The 1H NMR spectrum of azide end-functionalized sillyl protected PS

in CDCl3.

54
4.4 Synthesis of ABC Type Miktoarm Star Polymer

After the preparation of the (10), PS-PEG-PMMA miktoarm star polymer (11) was
prepared. For the synthesis of (11) Alkyne-PEG-PMMA copolymer and PS-N3
reacted via click reaction. For this purpose CuBr/PMDETA was used as catalyst in
the present of DMF, at room temperature for three days. The reaction procedure is
clearly seen in scheme (4.11).

(4.11)

From 1H NMR spectrum, the backbone protons of PS at δ 7.5-6.3 ppm, δ 3.55 ppm
for PMMA and δ 3.65 ppm for PEG clearly seen. 1H NMR spectrum of ABC Type
Si-p-PS-PEG-PMMA miktoarm star polymer is given in Figure 4.11.

55
Figure 4.11 : The 1H NMR spectrum of ABC type miktoarm star polymer in CDCl3.

After the synthesis of Si-p-PS-PEG-PMMA, sillyl protection was removed. This

protection provides that click reaction between Si-PS and PEG-PMMA is performed
with any side reactions. However, for silica modification via click chemistry ABC
type miktoarm star polymer must include alkyne functionality at the junction point.
For this aim, (11) was reacted with TBAF in THF. As seen in schematically in (4.12),
alkyne-PS-PEG-PMMA (12) was synthesized.

(4.12)

56
1
H NMR spectrum is obviously indicated that protons of tri methyl sillyl at δ 0.16-
0.18 ppm disappeared totally. Moreover, ≡CH peak is seen clearly at δ 2.45 ppm. As
monitored by the Figure 4.12, deprotection reaction was achieved and compound
(12) was synthesized.

Figure 4.12 : The 1H NMR spectrum of alkyne functionalized ABC type miktoarm
star polymer in CDCl3.

Furthermore, GPC chromatogram (Figure 4.13) showed ABC type miktoarm star
polymer was synthesized successfully. Molecular weight of (7) and (10) are 9050
and 5000. As expected, compound (11) had higher molecular weight which is close
to sum of the molecular weight of the precursor polymers.

Figure 4.13 : GPC chromatogram of the alkyne-PEG-PMMA, Si-p-PS-N3 and ABC

type miktoarm star polymer.

57
4.5 Silica Modification of PS-PEG-PMMA via Click Reaction

In this ultimate part of the synthesis, silica solid particle must be azide functionalized
to give click reaction between (12). In this case, three steps of reactions were
performed. Then, alkyne functionalized PS-PEG-PMMA was modified to silica
nanoparticles.

Firstly, 2-azido ethanol (13) was synthesized by the reaction of the bromo ethanol
with sodium azide as seen below.

(4.13)

1
H NMR spectrum of (13) is shown in Figure 4.13. As seen at the spectrum, CH2CH2
protons of the molecule gave signal at δ 3.71 ppm and 3.36 ppm. Also, hydroxyl
proton gave signal at δ 3.17 ppm.

Figure 4.14 : The 1H NMR spectrum of 2-azido ethanol in CDCl3.

Secondly, [(3-Triethoxysilanyl-propyl)]-carbamic acid 2-azido-ethyl ester (14) was

prepared. For this purpose, 3-(Isocyanatopropyl)triethoxysilane was dissolved in
THF. Then, compound (13) and dibuthyltindilaurate (2 droplets) was added to the
reaction mixture. Reaction mixture was stirred for overnight at reflux temperature
(4.14).

58
 (4.14)

From 1H NMR spectrum of compound (14) is given below (Figure 4.15). It is seen
clearly that ester proton (C=OOCH2) at δ 4.65 ppm and NH proton at 5.05 ppm
suggests that the compound (14) was obtained successfully.

Figure 4.15 : The 1H NMR spectrum of prop-2-ynyl 3- (triethoxysilyl)

propylcarbamate in CDCl3.

Finally, silica nanoparticles were obtained azide end functionality via the reaction of
SiO2 with (14) in the presence of toluene (4.15). In this step, the unbound azide on
silica surface was removed after several centrifugation-dispersion process.

59
 (4.15)

Then, TGA measurement was done to evaluate the amount of the organic part of
compound (15). So, amount of the azide which was grafted on silica nanoparticles
calculated as 1.17 mmol/g. From the TGA measurement (Figure 4.15) weight loss of
organic part is seen as 22 %, this show that synthesis of azide functionalized silica is
achieved. The grafting density was also calculated according to the equation shown
in (4.16). The grafting density was calculated as 5.72 azide/nm2.

(4.16)

MA= 171 g/mol

NA= 6.02x1023 mol-1

Ssp= 160 m2/g

Finally, the synthesis of silica modification of ABC type star polymer was achieved.
Well-defined PS-PEG-PMMA, with alkyne-end-functional groups was reacted with
Si-N3 to give the corresponding ABC type miktoarm star polymer modified
nanoparticles (16) via click chemistry. Click reaction was performed in DMF with
CuBr/PMDETA complex for three days at room temperature (4.16). This click

60
reaction was done in presence of excess polymer. After the click reaction silica
particles could be easily collected by centrifugation.

(4.16)

Moreover, the presence of the star polymer on silica nanoparticles was proved by
TGA and 1H NMR. From TGA measurement the difference between the weight loss
of polymer modified and azide modified silica nanoparticles was calculated as 40 %.
This difference suggests that surface modification was successfully performed. Also,
grafting density of the ABC type miktoarm star polymer on silica nanoparticles was
calculated using equation shown in (4.17). Using this equation the grafting density
was calculated to be 0.31 polymer/nm2.

(4.17)

Mn SEC = 14650 g/mol

NA= 6.02x1023 mol-1

Ssp= 160 m2/g

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Figure 4.16 : TGA of Silica, Silica-azide, Alkyne-PS-PEG-PMMA and Silica-
Alkyne-PS-PEG-PMMA

Figure 4.17 : The 1H NMR spectrum of silica-PS-PEG-PMMA in CDCl3.

62
Although compound (16) was not fully dissolved in CDCl3, an attempt was made to
take its 1H NMR spectrum. From 1H NMR spectrum (Figure 4.17), the backbone
aromatic protons of PS can be seen in δ 7.6-6.2 ppm, PEG and PMMA backbone
protons at δ 4-3 ppm suggest that the modification was performed efficiently.

63
64
5. CONCLUSION

As a conclusion, surface modification of silica nanoparticles via ABC type miktoarm

star polymer was achieved which permitted the combination of ATRP and click
chemistry. For this purpose, PEG-macroinitiator, (6), which has both alkyne and
bromine functionalities, was obtained via esterification reaction between PEG-
COOH and prop-2-ynyl 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate in the
presence of DMAP/DCC. And so, alkyne-PEG-PMMA, (7), was obtained via ATRP
and (6) was used as initiator. Then, ATRP was performed to synthesize sillyl
protected PS and bromine end group of the polymer was converted to azide using
NaN3 in order to give well defined azide end-functionalized polymer. ABC type
miktoarm star polymer was obtained by using of click reaction between Si-p-PS and
PEG-PMMA and later, sillyl protection was removed with TBAF to synthesized
alkyne terminated star polymer, (12). Finally, azide functionalized silica (15) was
synthesized via simple sol-gel process. The click reactions were performed between
miktoarm star polymers and azide containing silica nanoparticles. The grafting
density of the polymers on silica nanoparticles were determined by TGA and
calculated as 0.31 polymer/nm2. These results suggest that surface modification via
miktoarm star polymers were performed succesfully.

In all required steps the structures of well defined polymers and their molecular
weights are proved by GPC and NMR. To follow the surface modification of silica
TGA was used. By the collapse of the peaks the efficiency of the reaction is
documented.

65
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CURRICULUM VITAE

Candidate’s full name: Başak BULBA

Place and date of birth: Burdur/22.08.1984

Permanent Address: Kemal Pasa Mah. Erkin S. No:22/3 K.Cekmece/İST

Universities and
Colleges attended: Fahrettin Kerim Gokay Anatolian High School
(1998-2002).
Istanbul Technical University – Faculty of Science and
Letters – Chemistry (2002 – 2008).
Istanbul Technical University – Institute of Science and
Technology – Chemistry MSc. (2008 - 2010).

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