Synthesis and Self-Assembly of Novel ABC Miktoarm Star Terpolymers

192 Pages·2013·18.27 MB·English

Synthesis and Self-Assembly of
Novel ABC Miktoarm Star
Terpolymers

DISSERTATION

zur Erlangung des akademisches Grades eines
Doktors der Naturwissenschaften (Dr. rer. nat.)
im Fach Chemie
an der Bayreuther Graduiertenschule
für Mathematik und Naturwissenschaften
der Universität Bayreuth

vorgelegt von
Andreas Hanisch
Geboren in Kulmbach

Bayreuth, 2013

Die vorliegende Arbeit wurde in der Zeit von Juli 2008 bis Januar 2013 in Bayreuth am
Lehrstuhl Makromolekulare Chemie II unter Betreuung von Herrn Prof. Dr. Axel H. E.
Müller angefertigt.
Vollständiger Abdruck der von der Bayreuther Graduiertenschule für Mathematik und
Naturwissenschaften der Universität Bayreuth genehmigten Dissertation zur Erlangung
des akademischen Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.).

Dissertation eingereicht am: 25.01.2013
Zulassung durch die Promotionskomission: 13.02.2013
Wissenschaftliches Kolloquium: 26.04.2013

Amtierender Dekan: Prof. Dr. Beate Lohnert

Prüfungsausschuss:
Prof. Dr. Axel H. E. Müller (Erstgutachter)
Prof. Dr. Stephan Förster (Zweitgutachter)
Prof. Dr. Matthias Karg (Vorsitz)
Prof. Dr. Karlheinz Seifert

“
Life is like riding a bicycle.
”
To keep your balance you must keep moving.
Albert Einstein

Meiner Familie
Greta und Oskar

Table of Contents
Table of Contents
Summary 1
Zusammenfassung 3
Glossary 7
1 – Introduction 9
1.1 Solution Based Self-Assembly in Polymer Systems 9
1.1.1 General Aspects of Self-Assembly 9
1.1.2 Multicompartment Structures from Ternary Systems 10
1.1.2.1 Linear Triblock Terpolymers and Directed Self-Assembly 12
1.1.2.2 Miktoarm Star Terpolymers 16
1.2 Miktoarm Star Polymers 19
1.2.1 Synthesis 19
1.2.1.1 ABC Miktoarm Star Terpolymers as Model Systems 19
1.2.1.2 Other Miktoarm Star Polymer Systems 26
1.2.2 Self-Assembly in Bulk 27
1.2.3 Application of ABC Miktoarm Star Terpolymers for Functional
Materials 29
1.3 Synthetic Strategies in Polymer Science 31
1.3.1 DPE Chemistry in Anionic Polymerization 31
1.3.2 Click Chemistry 32
1.4 Aim of this Thesis 34
1.5 References 35
2 – Overview of the thesis 41
2.1 Modular Synthesis of Miktoarm Star Terpolymers 42
2.2 Counterion-Mediated Hierarchical Self-Assembly of an ABC Miktoarm
Star Terpolymer Containing a Poly(N-methyl-2-vinylpyridinium
iodide) Segment 45
2.3 Application of the Triiodide-Directed Self-Assembly to other ABC
and ABA’ Miktoarm Star Polymers with a Poly(N-methyl-2-vinyl-
pyridinium iodide) Segment 47
2.4 Individual Contributions to Joint Publications 51
3 – A Modular Route for the Synthesis of ABC Miktoarm Star
Terpolymers via a New Alkyne-Substituted Diphenylethylene
Derivative 53
3.1 Introduction 54
3.2 Experimental Section 57
3.3 Results and Discussion 60
3.3.1 Synthesis of 1-[(4-(tert-Butyldimethylsilyl)ethynyl)-phenyl]-1-phenyl-
ethylene (click-DPE) 60
3.3.2 Synthesis of Alkyne Mid-Functionalized Diblock Copolymers 61
3.3.3 Hydrolysis of the Alkyne Mid-Functionalized Diblock Copolymers 64
3.3.4 Synthesis of ω-Azido Homopolymers 66
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Table of Contents

3.3.5 Synthesis of Miktoarm Star Terpolymers via Click Chemistry 67
3.4 Conclusions 74
3.5 References 76
3.6 Supporting Information 78
3.6.1 Additional Experimental Section 78
3.6.2 Additional Figures 82
3.6.3 Test Polymerization with P2VP and Click-DPE 86
3.6.4 Characterization of ω-Azido Homopolymers 88
3.6.5 Click Reaction with ω-Azido-Functionalized Poly(tert-butyl
methacrylate) 91
3.6.6 References 92
4 – Counterion-Mediated Hierarchical Self-Assembly of an ABC
Miktoarm Star Terpolymer 93
4.1 Introduction 94
4.2 Results and Discussion 97
4.2.1 Synthesis and Characterization of the PB-P2VP-PtBMA
Miktoarm Star Terpolymer 97
4.2.2 Self-Assembly Behavior of µ-BVqT 98
4.2.2.1 Hierarchical Superstructure Formation 100
4.2.2.2 Importance of the Nature of the Counterion 102
4.2.3 Structural Characterization of “Woodlouse” Aggregates 105
4.3 Conclusions 109
4.4 Experimental Section 111
4.5 References 116
4.6 Supporting Information 119
4.6.1 Additional Experimental Section 119
4.6.2 Synthesis and Characterization of PB-arm-P2VP-arm-PtBMA Miktoarm
Star Terpolymer 121
4.6.3 Self-Assembly of µ-BVqT 123
4.6.3.1 Intermediate Structures of “Woodlouse” Aggregates 124
4.6.3.2 Importance of the Nature of the Counterion 127
4.6.3.3 Structural Characterization of “Woodlouse” Aggregates 129
4.6.4 References 131
5 – Hierarchical Self-Assembly of Miktoarm Star Polymer
Systems Containing a Polycationic Segment: A General Concept 133
5.1 Introduction 135
5.2 Experimental Part 138
5.3 Results and Discussion 142
5.3.1 Miktoarm Star Ter- and Copolymer Synthesis 142
5.3.2 Hierarchical Self-Assembly of Miktoarm Star Polymers of Different
Composition and Chemistry 144
5.3.2.1 Hydrophilic/Hydrophobic Balance 144
5.3.2.2 Effect of a High-T Core-Forming Block 150
g
5.4 Conclusions 158
5.5 References 160
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