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
1
0
0
P
F
9-
2
4
0
1
0
8
8
7
1
8
7
9
9/
3
0
1
0.
1
oi:
d
g |
or
c.
s
s.r
b
u
p
p://
htt
n
o
7
1
0
2
pril
A
3
1
n
o
d
e
h
s
bli
u
P
View Online
Polymer Chemistry Series
Editor-in-chief:
Ben Zhong Tang, The Hong Kong University of Science and Technology,
Hong Kong, China
1
0
0
P
F Series editors:
9-
2 Alaa S. Abd-El-Aziz, University of Prince Edward Island, Canada
4
0
1 Stephen L. Craig, Duke University, USA
0
8
8 Jianhua Dong, National Natural Science Foundation of China, China
7
1
8 Toshio Masuda, Shanghai University, China
7
9
9/ Christoph Weder, University of Fribourg, Switzerland
3
0
1
0.
1 Titles in the series:
oi:
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
u
p
p:// 4: Fundamentals of Controlled/Living Radical Polymerization
htt 5: Healable Polymer Systems
on 6: Thiol-X Chemistries in Polymer and Materials Science
7
1 7: Natural Rubber Materials: Volume 1: Blends and IPNs
0
2
pril 8: Natural Rubber Materials: Volume 2: Composites and
A Nanocomposites
3
1 9: Conjugated Polymers: A Practical Guide to Synthesis
n
d o 10: Polymeric Materials with Antimicrobial Activity: From Synthesis to
e
h Applications
s
bli 11: Phosphorus-Based Polymers: From Synthesis to Applications
u
P
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
View Online
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
1
0
0
P
F
9-
2
4
0
1
0
8
8
7
1
8
7
9
9/
3
0
1
0.
1
oi:
d
g |
or
c.
s
s.r
b
u
p
p://
htt
n
o
7
1
0
2
pril
A
3
1
n
o
d
e
h
s
bli
u
P
How to obtain future titles on publication:
A standing order plan is available for this series. A standing order will
bring delivery of each new volume immediately on publication.
For further information please contact:
Book Sales Department, Royal Society of Chemistry, Thomas Graham House,
Science Park, Milton Road, Cambridge, CB4 0WF, UK
Telephone: [phone], Fax: [phone]
Email: [e-mail]
Visit our website at www.rsc.org/books
View Online
1
0
0
P
F
9-
2
4
0
1
0
8
8
7
1
8
7
9/9
3
0
1
0.
1
oi:
d
g |
or
c.
s
s.r
b
u
p
p://
htt
n
o
7
1
0
2
pril
A
3
1
n
o
d
e
h
s
bli
u
P
View Online
Miktoarm Star Polymers
From Basics of Branched Architecture to
Synthesis, Self-assembly and Applications
1
0
0
P
F
9-
2
4
0
1
0
8
8
7
1 Edited by
8
7
9
9/
03 Ashok Kakkar
1
10. McGill University, Montreal, Canada
oi: Email: [e-mail]
d
g |
or
c.
s
s.r
b
u
p
p://
htt
n
o
7
1
0
2
pril
A
3
1
n
o
d
e
h
s
bli
u
P
View Online
1
0
0
P
F
9-
2
4
0
1
0
8
8
7
81 Polymer Chemistry Series No. 25
7
9
9/
3 Print ISBN: 978-1-78262-575-9
0
1
0. PDF eISBN: 978-1-78801-042-9
1
oi: EPUB eISBN: 978-1-78801-125-9
g | d ISSN: 2044-0790
or
sc. A catalogue record for this book is available from the British Library
s.r
b
pu © The Royal Society of Chemistry 2017
p://
htt All rights reserved
n
o
7
1 Apart from fair dealing for the purposes of research for non-commercial purposes or for
0
pril 2 pArcitv 1a9te8 8st aunddy, tchreit Cicoispmyr oigrh rte avinedw R, aelsa pteedrm Riitgthedts uRnedgeurl athtieo nCso 2p0yr0i3g,h tth, iDse psuigbnlisc aatnidon P mataeny ts
A
3 not be reproduced, stored or transmitted, in any form or by any means, without the prior
1
n permission in writing of The Royal Society of Chemistry, or in the case of reproduction in
o
ed accordance with the terms of licences issued by the Copyright Licensing Agency in the UK,
h
blis or in accordance with the terms of the licences issued by the appropriate Reproduction
u Rights Organization outside the UK. Enquiries concerning reproduction outside the terms
P
stated here should be sent to The Royal Society of Chemistry at the address printed on
this page.
Whilst this material has been produced with all due care, The Royal Society of Chemistry
cannot be held responsible or liable for its accuracy and completeness, nor for any
consequences arising from any errors or the use of the information contained in this
publication. The publication of advertisements does not constitute any endorsement by The
Royal Society of Chemistry or Authors of any products advertised. The views and opinions
advanced by contributors do not necessarily reflect those of The Royal Society of Chemistry
which shall not be liable for any resulting loss or damage arising as a result of reliance
upon this material.
The Royal Society of Chemistry is a charity, registered in England and Wales, Number
207890, and a company incorporated in England by Royal Charter (Registered No.
RC000524), registered office: Burlington House, Piccadilly, London W1J 0BA, UK,
Telephone: [phone].
For further information see our web site at www.rsc.org
Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon, CR0 4YY, UK
7
0
0
P
F
9- Preface
2
4
0
1
0
8
8
7
1
8
7
9
9/
3
0
1 Miktoarm polymers constitute an intriguing and important class of macro-
0.
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
s.r
b insight into structure–property relationships toward the design of macro-
u
p
p:// molecules with pre-determined properties. It is also of significance in the
htt tailored and unique self-assembly behavior of these macromolecules in
n
o different media, which is of particular interest in constructing nanocarriers
7
01 for biological applications.
2
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
3
1 developing and simplifying the synthetic methodologies, as well as exploring
n
d o their self-assembly aspects, and exploiting their unique properties for a vari-
e
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
P
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
7
0 this concept is applied to miktoarm star polymers in terms of their self-
0
P
F assembly aspects.
9-
2 Miktoarm polymers continue to be a topical area of research. This class of
4
0
1 macromolecules is still relatively young, but some success has been achieved
0
8
8 and demonstrated in terms of their synthesis, self-assembly, and applica-
7
1
8 tions in biology in particular. This book brings forward the versatility and
7
9
9/ uniqueness of these branched architectures, and will be of great benefit to
3
10 young budding chemists, as well as researchers exploring this vibrant class of
0.
1 macromolecules. It is hoped that this book will give the reader a foundation
oi:
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.
s
s.r Ashok Kakkar
b
u
p
p://
htt
n
o
7
1
0
2
pril
A
3
1
n
o
d
e
h
s
bli
u
P
9
0
0
P
F
9- Contents
2
4
0
1
0
8
8
7
1
8
7
9
9/ Chapter 1 Miktoarm Star (µ-Star) Polymers: A Successful Story 1
3
0
1 Hermis Iatrou, Apostolos Avgeropoulos, Georgios Sakellariou,
0.
oi:1 Marinos Pitsikalis and Nikos Hadjichristidis
d
g |
or 1.1 The Genesis of Miktoarm (µ-Star) Star Polymers 1
c.
s 1.2 Synthesis of Miktoarm Star (µ-Star) Polymers 6
s.r
b 1.2.1 Divinylbenzene (Homopolymerizable Linking
u
p
p:// Agent) 6
htt 1.2.2 Double Diphenylethylenes
n
o (Non-Homopolymerizable Linking Agents) 7
7
01 1.2.3 Chlorosilanes 8
2
pril 1.3 Miktoarm-Based Polymers with Complex
A Architectures 13
3
1 1.4 Model Polyethylenes 15
n
d o 1.5 Individual Methods for the Synthesis of Miktoarm
e
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
n
1.5.3 µ-Star Copolymers of the A B Type 16
n m
1.5.4 µ-Star Terpolymers of the ABC Type 18
1.5.5 6µ-Star Copolymers of the A B Type 20
2 4
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
View Online
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
9
0
0
P
F 2.1 Introduction 32
9-
2 2.2 Synthesis of Multi-Arm and Multi-Component
4
0
1 Miktoarm Star Polymers by the Iterative Methodology
0
8
8 Using a Difunctional Compound X-F 34
7
1
8 2.2.1 Iterative Methodology Using
7
9
9/ 1-(4-(3-Bromopropyl)phenyl)-1-phenylethylene 34
3
10 2.2.2 Iterative Methodology Using 3 and Either
0.
1 1,3-Bis(1-phenylethenyl)benzene or
oi:
d 1,1-Bis(3-(1-phenylethenyl)phenyl)ethylene 35
org | 2.2.3 Iterative Methodology Using
sc. 3,5-Bis(3-(4-(1-phenylethenyl)phenyl)propoxy)
bs.r benzyl Bromide 37
u
p://p 2.2.4 Synthesis of Miktoarm Star Polymers Using
htt Intermediate Polymer Anions Prepared by the
on Iterative Methodology 41
7
1 2.2.5 Iterative Methodology Using 6-Bromo-3-
0
2
April 2.3 Secondm-Getehnyeleranteio-1n-h Ietexreanteiv e Methodology 4453
13 2.3.1 Second-Generation Iterative Methodology
n
o Using a Difunctional DPE Anion Bearing
d
he Trimethylsilyl and Tert-Butyldimethylsilyl
s
bli Ethers 47
u
P
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