Miktoarm star polymers : from basics of branched architecture to synthesis, self-assembly and applications

240 Pages·2017·19.215 MB·English

by  Ashok Kakkar (ed.)

Miktoarm Star Polymers
From Basics of Branched Architecture to Synthesis, Self-assembly and
Applications
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Polymer Chemistry Series
Editor-in-chief:
Ben Zhong Tang, The Hong Kong University of Science and Technology,
Hong Kong, China
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F Series editors:
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2 Alaa S. Abd-El-Aziz, University of Prince Edward Island, Canada
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1 Stephen L. Craig, Duke University, USA
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8 Jianhua Dong, National Natural Science Foundation of China, China
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8 Toshio Masuda, Shanghai University, China
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9/ Christoph Weder, University of Fribourg, Switzerland
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1 Titles in the series:
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d 1: Renewable Resources for Functional Polymers and Biomaterials
org | 2: Molecular Design and Applications of Photofunctional Polymers and
sc. Materials
bs.r 3: Functional Polymers for Nanomedicine
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p:// 4: Fundamentals of Controlled/Living Radical Polymerization
htt 5: Healable Polymer Systems
on 6: Thiol-X Chemistries in Polymer and Materials Science
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1 7: Natural Rubber Materials: Volume 1: Blends and IPNs
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pril 8: Natural Rubber Materials: Volume 2: Composites and
A Nanocomposites
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1 9: Conjugated Polymers: A Practical Guide to Synthesis
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h Applications
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12: Poly(lactic acid) Science and Technology: Processing, Properties,
Additives and Applications
13: Cationic Polymers in Regenerative Medicine
14: Electrospinning: Principles, Practice and Possibilities
15: Glycopolymer Code: Synthesis of Glycopolymers and their
Applications
16: Hyperbranched Polymers: Macromolecules in-between Deterministic
Linear Chains and Dendrimer Structures
17: Polymer Photovoltaics: Materials, Physics, and Device Engineering
18: Electrical Memory Materials and Devices
19: Nitroxide Mediated Polymerization: From Fundamentals to Applications
in Materials Science
20: Polymers for Personal Care Products and Cosmetics
21: Semiconducting Polymers: Controlled Synthesis and Microstructure
22: Bio-inspired Polymers
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23: Fluorinated Polymers: Volume 1: Synthesis, Properties, Processing and
Simulation
24: Fluorinated Polymers: Volume 2: Applications
25: Miktoarm Star Polymers: From Basics of Branched Architecture to
Synthesis, Self-assembly and Applications
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Miktoarm Star Polymers
From Basics of Branched Architecture to
Synthesis, Self-assembly and Applications
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1 Edited by
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03 Ashok Kakkar
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81 Polymer Chemistry Series No. 25
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3 Print ISBN: 978-1-78262-575-9
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oi: EPUB eISBN: 978-1-78801-125-9
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9- Preface
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1 Miktoarm polymers constitute an intriguing and important class of macro-
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oi:1 molecules, in which the diversity in the key elements of the polymeric archi-
g | d tecture i.e., overall shape, well-defined molecular weight, and composition,
or offers a platform to develop materials for a wide variety of applications. Our
c.
s ability to fine-tune the branched and multifunctional structure can provide
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htt tailored and unique self-assembly behavior of these macromolecules in
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01 for biological applications.
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pril Since the inception of the term ‘miktoarm’ in the early 1990s for asymmet-
A ric branched macromolecules, there has been a tremendous effort devoted to
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1 developing and simplifying the synthetic methodologies, as well as exploring
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sh ety of applications. This book brings together some of the eminent players
ubli in the field, and makes an attempt to provide a coherent and collective look
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at the state-of-the-art in miktoarm polymer research. Chapter 1 gives a his-
torical perspective first, and then walks the reader through the synthetic
developments in miktoarm polymers and miktoarm polymer-based complex
architectures. Chapter 2 introduces the reader to a new iterative methodology
using living anionic polymerization to synthesize multi-component miktoarm
star polymers, including the evolution of the methodology into its second
generation using the diphenylethylene anion. Chapter 3 explores the syn-
thesis of multicomponent star copolymers using controlled polymerization
and ‘click chemistry’ methods. The adoption of ‘click chemistry’ in the syn-
thesis of miktoarm star polymers is then detailed in Chapter 4. In Chapter 5,
the self-assembly behavior of miktoarm star polymers is compared to that
Polymer Chemistry Series No. 25
Miktoarm Star Polymers: From Basics of Branched Architecture to Synthesis,
Self-assembly and Applications
Edited by Ashok Kakkar
© The Royal Society of Chemistry 2017
Published by the Royal Society of Chemistry, www.rsc.org
vii
View Online
viii Preface
of block-copolymers with particular emphasis on micellar and emulsion-
assisted drug delivery. Chapter 6 provides a look at how the construction of
miktoarm polymers can be tailored for applications in biology, especially
for drug delivery. Finally, in Chapter 7, the reader is introduced to the con-
cept of supramolecular chemistry; it then provides a detailed look at how
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0 this concept is applied to miktoarm star polymers in terms of their self-
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2 Miktoarm polymers continue to be a topical area of research. This class of
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1 macromolecules is still relatively young, but some success has been achieved
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8 and demonstrated in terms of their synthesis, self-assembly, and applica-
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8 tions in biology in particular. This book brings forward the versatility and
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9/ uniqueness of these branched architectures, and will be of great benefit to
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10 young budding chemists, as well as researchers exploring this vibrant class of
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1 macromolecules. It is hoped that this book will give the reader a foundation
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d to work upon and, in addition, stimulate them to seek unexpected and not
org | yet explored domains in their synthesis, self-assembly, and applications.
c.
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s.r Ashok Kakkar
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9- Contents
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9/ Chapter 1 Miktoarm Star (µ-Star) Polymers: A Successful Story 1
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1 Hermis Iatrou, Apostolos Avgeropoulos, Georgios Sakellariou,
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oi:1 Marinos Pitsikalis and Nikos Hadjichristidis
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or 1.1 The Genesis of Miktoarm (µ-Star) Star Polymers 1
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s 1.2 Synthesis of Miktoarm Star (µ-Star) Polymers 6
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b 1.2.1 Divinylbenzene (Homopolymerizable Linking
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htt 1.2.2 Double Diphenylethylenes
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o (Non-Homopolymerizable Linking Agents) 7
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01 1.2.3 Chlorosilanes 8
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A Architectures 13
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1 1.4 Model Polyethylenes 15
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sh Stars 15
Publi 1.5.1 3µ-Star Copolymers of the A2B Type 15
1.5.2 µ-Stars of the A B Type 16
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1.5.3 µ-Star Copolymers of the A B Type 16
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1.5.4 µ-Star Terpolymers of the ABC Type 18
1.5.5 6µ-Star Copolymers of the A B Type 20
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1.5.6 Miktoarm Macromolecular Chimeras 21
1.6 Microphase Separation of Miktoarm Stars 21
1.7 Concluding Remarks 25
Acknowledgements 26
References 26
Polymer Chemistry Series No. 25
Miktoarm Star Polymers: From Basics of Branched Architecture to Synthesis,
Self-assembly and Applications
Edited by Ashok Kakkar
© The Royal Society of Chemistry 2017
Published by the Royal Society of Chemistry, www.rsc.org
ix
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x Contents
Chapter 2 Precise Synthesis of Multi-Component Miktoarm Star
Polymers by a New Conceptual Iterative Methodology
Using Living Anionic Polymerization 31
Shotaro Ito, Tomoya Higashihara, Takashi Ishizone and
Akira Hirao
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F 2.1 Introduction 32
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8 Using a Difunctional Compound X-F 34
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8 2.2.1 Iterative Methodology Using
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1 1,3-Bis(1-phenylethenyl)benzene or
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org | 2.2.3 Iterative Methodology Using
sc. 3,5-Bis(3-(4-(1-phenylethenyl)phenyl)propoxy)
bs.r benzyl Bromide 37
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htt Intermediate Polymer Anions Prepared by the
on Iterative Methodology 41
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1 2.2.5 Iterative Methodology Using 6-Bromo-3-
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April 2.3 Secondm-Getehnyeleranteio-1n-h Ietexreanteiv e Methodology 4453
13 2.3.1 Second-Generation Iterative Methodology
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o Using a Difunctional DPE Anion Bearing
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he Trimethylsilyl and Tert-Butyldimethylsilyl
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bli Ethers 47
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2.3.2 Second-Generation Iterative Methodology
Using a Trifunctional DPE Anion Bearing
Trimethylsilyl, Tert-Butyldimethylsilyl, and
2-Tetrahydropyranyl Ethers 49
2.3.3 Second-Generation Iterative Methodology
Using a DPE Anion Bearing a 1,3-Dioxolane
Group 50
2.3.4 Second-Generation Iterative Methodology
Using 9 and In-Chain Block Copolymer Anions 51
2.4 Conclusions 53
References 54
Chapter 3 Facile Synthesis of Multicomponent Star Copolymers via
Controlled Polymerization and Click Chemistry 56
Youliang Zhao
3.1 Introduction 56
3.2 Miktoarm Stars Synthesized by Living/Controlled
Polymerization 59
3.2.1 ‘Core First’ Approach 59