Functionalized Polymers: Synthesis, Characterization and Applications

305 Pages·2021·23.651 MB·English

by  Narendra Pal Singh Chauhan

Functionalized Polymers
Synthesis, Characterization and Applications
Edited by
Narendra Pal Singh Chauhan
Department of Chemistry
Bhupal Nobles’ University, Udaipur
Rajasthan, India
p,
A SCIENCE PUBLISHERS BOOK
Cover credit: Image reproduced by kind courtesy of Prof. Sharon Gerecht, Johns Hopkins University.
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Library of Congress Cataloging-in-Publication Data
Names: Chauhan, Narendra Pal Singh, editor.
Title: Functionalized polymers: synthesis, characterization and
applications / edited by Narendra Pal Singh Chauhan, Department of
Chemistry, Bhupal Nobles University, Udaipur Rajasthan, India.
Description: Boca Raton: CRC Press, [202111 Includes bibliographical
references and index.
Identifiers: LCCN 2020043459 1 ISBN 9780367420611 (hardcover)
Subjects: LCSH: Polymers. 1 Polymerization.
Classification: LCC QD381 .F865 20211 DDC 547/.7--dc23
LC record available at https:lIlccn.loc.gov/2020043459
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Preface
The field of functional polymer research comprises the synthesis of functional
polymer materials and the study and tuning of their properties. On the one
hand, polymers with specific functions are exciting in their underlying
principles of physics and chemistry, which result in outstanding tunability
of the resulting properties. Functional polymers are and will continue to be
in demand as they expand the property and range of application of their
non-functional counterparts.
On the other hand, functional polymers govern our lives in a variety of
applications, ranging from surface-specific coatings to polymer foams that
are indispensable in modern construction and building.
There are very few books in the market today that deal with practical
polymers. The existing books focus primarily on functional polymers for
versatile applications. In recent years, however, significant progress has been
made in the synthesis of functional polymers, and a number of national and
international academic conferences were held to address these developments.
This book consists of fourteen chapters. The first provides an introduction
as well as a view of future prospects. The subsequent chapters explain
conjugated polymers, amphiphilic hyperbranched polymers, biodegradable
polymers, pseudo-proteins, functionalized cellulose, 3D-printed polymers,
poly(vinylcarbazole), functional plastics and rubbers, polyurethane,
biopolymeric sensors, stimuli-responsive polymers and polysiloxane and
polycarbosilanes.
I sincerely hope that this book will be of interest to polymer scientists and
to all those who deal with the interdisciplinary branches of related subjects.
I believe this book offers a balanced, informative and innovative perspective
that is applicable to academics and industries.
I wish to thank all of the authors for their contributions and their sincere
efforts, without which the book would not be in its present form. Suggestions
from critics are always welcome. I am extremely thankful to Prof. Sharon
Gerecht, Johns Hopkins University for her valuable suggestions and also for
her kind consent of cover image.
Dr. Narendra Pal Singh Chauhan

Contents
Preface iii
1. Introduction and Future Prospects 1
Narendra Pal Singh Chauhan
2. Conjugated Polymers 10
Ebad Asadi and Noushin Ezzati
3. Amphiphilic Hyperbranched Polymers 33
Srijoni Sengupta, Prashant Gupta, Priyanka Sengupta and Ayan Dey
4. Biodegradable Polymers 64
Sayan Deb Dutta and Ki-Taek Lim
5. Functional Pseudo-Proteins 78
N. Zavradashvili, S. Kobauri, J. Puiggali and R. Katsarava
6. Functional Proteins 122
Keya Ganguly and Ki-Taek Lim
7. Functionalization of Cellulose—Chemical Approach 139
Merin Sara Thomas, Prasanth K.S. Pillai, Sabu Thomas
and Laly A. Pothen
8. Functionalized Polymers Processed by 3D Printing 153
Narendra Pal Singh Chauhan, Mahrou Sadri, Behnaz Sadat Eftekhari,
Farzin Sahebjam and Mazaher Gholipourmalekabadi
9. Polyvinylcarbazole Composite Membranes 169
Gaurav Sharma and Balasubramanian Kandasubramanian
10. Elastomeric and Plastomeric Materials 193
Mohsen Khodadadi Yazdi, Payam Zarrintaj, Saeed Manouchehri, Joshua
D. Ramsey, Mohammad Reza Ganjali and Mohammad Reza Saeb
1 1. Polyurethane 208
Noushin Ezzati, Ebad Asadi, Majid Abdouss and Elaheh Kowsari
1 2. Biopolymeric Sensors 235
Payam Zarrintaj, Saeed Manouchehri, Mohammad Davachi, Mohsen
Khodadadi Yazdi, Joshua D. Ramsey, Mohammad Reza Saeb
and Mohammad Reza Ganjali
vi Contents
13. Stimuli-Responsive Polymers and Their Biomedical Applications 250
Dinesh K. Patel and Ki-Taek Lim
14. Poly(siloxane)s, Poly(silazane)s and Poly(carbosiloxane)s 265
Claire E. Martin, Giovanni Fardella, Ricardo Perez
and Joseph W. Krumpfer
Index 297
CHAPTER
1
Introduction and Future Prospects
Narendra Pal Singh Chauhan
Department of Chemistry, Faculty of Science, Bhupal Nobles’ University,
Udaipur 313001, Rajasthan, India
1. Introduction
Polymers with atomic groups with higher polarity or reactivity than
traditional hydrocarbon chains are functional polymers (Chauhan 2019a).
Such materials display improved properties in contrast to their non-
functional counterparts in terms of stronger contact, separation or reactivity.
Living anion polymerization is a versatile and popular method to change
well-designed polymers with an in-chain or chain-end structure group or
classes (Vana and Yagci 2013). Such functional groups may be controlled by
reversible ionic activity, chain extension, branching or cross-linking reactions.
In some oligomeric or polymeric chains, these functional macromolecular
materials can often be combined with reactive copolymers (Chauhan et al.
2015). Polymerization or copolymerization of other monomers of sufficient
functional polymerization groups is also feasible.
The processing of bulk polymers results in chemical heterogeneity,
resulting in various advantages, such as improved reactivity, phase isolation,
and improved compatibility or association. The ability to construct self-
assemblies and supramolecular structures of functionalized polymers with
other architectures is another advantage (Chauhan 2019a). The creation or
dissociation of self-assembled materials can lead to “smart” materials in
response to chemical or physical stimuli. Many of the functional polymers
are used in single linear backbones, including block, grafted, chain-end
and in-chain polymer (Vana and Yagci 2013). For technical applications
such as optics, electronics or catalysis, functional polymers are essential.
These materials are often widely used for the synthesis of solid-phase
oligonucleotides and membranes (e.g., column chromatography). In rapidly
evolving medical environments, specially formulated functional polymer
products are essential, including suture protection issues, dental fillings,
Email: [email protected]
2 Functionalized Polymers
wound dressings, bone cement and hollow fiber dialysis (Chauhan 2019a).
Hydrogels and inhibitors that are the basis of ophthalmic surgery are usually
among these products.
Polymer functionalization is defined by a functional polymer synthesis
process consisting of three main categories: direct-functional polymer
synthesis (in situ), post-functionalization (post-polymer modification), and
functional group transformation.
2. Direct polymerization
2.1. End-functionalized polymerization
End-functional polymers are most often anionically generated using the post-
polymerization reactions of anionic living polymers with the appropriate
electrophiles to create the desired (possibly masked) functionality
(Konkolewicz et al. 2009). End-functional polymers have been produced
with carboxylic acid, hydroxyl, amine, thiol, aldehyde, acetyl, ring opening
of epoxy group and vinyl moieties having functionalized pendant groups
(Coessens et al. 2001).
Many variables, including chain-end structure, solvent, temperature,
concentration, stoichiometry, and the order and nature of the addition
of reagents (such as polar additives), have a dramatic effect on yield and
functionality. Side reactions can be minimized by optimizing the termination
procedure. Many of the functional groups can be utilized in the termination
reactions without protection, as the reactions with living chain polymers are
much quicker with haloalkyl moieties than in functional groups.
2.2. In-chain functionalized polymerization
Since most functional groups are deleterious for living anionic polymerization,
the use of protective groups in the production of polymeric materials
has become increasingly important. Monomers can provide protected
functionality that can be translated into reactive or associative pendant
groups. The anionic preparation of poly(methacrylic acid) is an important
example (Donini et al. 2002). The carboxylic acid groups in the backbone
are usually masked as tert-butyl esters and carboxylic acid is formed during
polymerization hydrolysis, a substance that cannot be produced by direct
anionic polymerization of the corresponding monomer (acrylic acid) (Morton
and Fetters 1975).
Similarly, a broad variety of designed polymers and copolymers can
be synthesized by sulfonation of homopolymers or styrene copolymers
(Yang and Mays 2002). A different route is used by a different protection
system. 1-Alkoxyethyl methacrylate is anionically polymerized to produce
a well-being substance and polyacids are formed by acetal group hydrolysis
(Zhang and Ruckenstein 1998). In particular, protective groups are needed
for functional groups with active hydrogen-containing organic compounds
such as alcohol, and primary and secondary amines.
Introduction and Future Prospects 3
Dimethyl-tert-butylsilyl will also protect alcohols (ROHs), with primary
and secondary amines (RNH and R NH) typically protected by trimethylsilyl
2 2
groups. Reactive polymer sites such as halogen may be used as sites for
attaching preformed side chains or sites for initiation. Various functionalized
monomers based on methacrylates, styrene and conjugated dienes with
different pendant groups have been made of smart functionalized polymers
for various applications from electronics to biomedical applications.
3. Post-polymerization
Sometimes it is difficult to polymerize directly, since certain functional
groups may interfere with polymerization; it is preferable to polymerize
by post-polymerization or post-modification (Theato and Klok 2013), a
technique that has been extensively used for many years (Gauthier et al. 2009).
Thiol-ene click reaction, sulphonylation, chloromethylation, carboxylation,
formylation, esterification, alkylation, acylation or amine functionality may
be incorporated into the polymer to achieve the desired functionalized
polymer.
4. Transformation of functional group
Functional group transformation can be used if functionalization of polymer
is difficult using direct and post-polymerization technique. In this method,
the synthesis of the undesired functional polymer is performed by direct or
post-functionalization and subsequent modification to the desired functional
polymer using a functional group transformation such as oxidation or
reduction.
5. Future prospects
The development of functional polymers has remained an area of considerable
interest and importance in electronics, industrial applications and rapidly
expanding biomedical subfields such as tissue engineering, drug delivery,
and gene delivery (Fig. 1).
Conducting polymers (CPs) such as polyacetylene, polyaniline,
polypyrrole and polythiophene provide semiconductive molecular
architectures and interesting sensing and biomedical properties (Chauhan
2019b). They have brought about significant progress in the field of sensing
and biomedical applications.
Unfortunately, the most important requirements for sensors, such as
analytical selectivity and detection of a particular analysis in a complex
environment, are not easily achieved by pristine CPs. Such shortcomings
in pristine CPs and processability necessitate the creation of functional
CPs by means of intelligent structural changes to pristine CPs or the
modification of CPs by incorporating functionalized moieties. The features