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Progress in Fluorine Science Series

OPPORTUNITIES FOR
FLUOROPOLYMERS
Synthesis, Characterization,
Processing, Simulation and
Recycling

Edited by

BRUNO AMEDURI
Institut Charles Gerhardt; University Montpellier,
CNRS, ENSCM, Montpellier, France

SERGEY FOMIN
Institute of Chemistry and Ecology, Vyatka State
University, Kirov, Russian Federation

Series Editors

Bruno Ameduri and Olga Boltalina

Elsevier
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The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States

Copyright © 2020 Elsevier Inc. All rights reserved.

No part of this publication may be reproduced or transmitted in any form or by any means, electronic
or mechanical, including photocopying, recording, or any information storage and retrieval system,
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mation about the Publisher’s permissions policies and our arrangements with organizations such as
the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website:
www.elsevier.com/permissions.

This book and the individual contributions contained in it are protected under copyright by the Pub-
lisher (other than as may be noted herein).

Notices
Knowledge and best practice in this field are constantly changing. As new research and experience
broaden our understanding, changes in research methods, professional practices, or medical treat-
ment may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating
and using any information, methods, compounds, or experiments described herein. In using such
information or methods they should be mindful of their own safety and the safety of others, includ-
ing parties for whom they have a professional responsibility.

To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, as-
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Contributors

Gozde Aktas Eken

Macromolecular Engineering Research Group (MERG), Chemistry Department, Istanbul
Technical University, Istanbul, Turkey
Alexandru D. Asandei
Institute of Materials Science, Polymer Program and Department of Chemistry, University
of Connecticut, CT, United States
Sabine Beuermann
Clausthal University of Technology, Institute of Technical Chemistry, Clausthal-Zellerfeld,
Germany
Roberta Bongiovanni
Politecnico di Torino, Department of Applied Science and Technology, Torino, Italy
Florian Brandl
Clausthal University of Technology, Institute of Technical Chemistry, Clausthal-Zellerfeld,
Germany
Vyacheslav M. Buznik
Russian Academy of Sciences, Federal State Unitary Enterprise All-Russian Scientific
Research Institute of Aviation Materials State Research Center of the Russian Federation,
Moscow, Russian Federation
Marco Drache
Clausthal University of Technology, Institute of Technical Chemistry, Clausthal-Zellerfeld,
Germany
Abhirup Dutta
Institute of Materials Science, Polymer Program and Department of Chemistry, University
of Connecticut, CT, United States
Mariya Edeleva
N. N.Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Novosibirsk,
Russian Federation; National Research University – Novosibirsk State University,
Novosibirsk, Russian Federation
Behzad Farajidizaji
Department of Chemistry and the Marvin B. Dow Advanced Composites Institute,
Starkville, MS, United States
Karen K. Gleason
Department of Chemical Engineering, MIT, Cambridge, MA, United States
Metin Hayri Acar
Macromolecular Engineering Research Group (MERG), Chemistry Department, Istanbul
Technical University, Istanbul, Turkey

xi
xii Contributors

Ryo Honma
Department of Chemistry, Faculty of Science, Kanagawa University, Hiratsuka, Japan
Hisao Hori
Department of Chemistry, Faculty of Science, Kanagawa University, Hiratsuka, Japan
Polina Kaletina
N. N.Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Novosibirsk,
Russian Federation; National Research University – Novosibirsk State University,
Novosibirsk, Russian Federation
Sergey A. Khatipov
Leading Researcher, Doctor of Physical and Mathematical Sciences, Federal State
Budgetary Educational Institution of Higher Education “Vyatka State University”,
Kirov, Russian Federation
Joon-Sung Kim
Institute of Materials Science, Polymer Program and Department of Chemistry, University
of Connecticut,CT, United States
Jena M. McCollum
Department of Mechanical and Aerospace Engineering, University of Colorado Colorado
Springs, CO, United States
Ganesh Narayanan
Department of Chemistry and the Marvin B. Dow Advanced Composites Institute,
Starkville, MS, United States
Emanuele Nettis
Politecnico di Torino, Department of Applied Science and Technology, Torino, Italy
Hideo Sawada
Department of Frontier Materials Chemistry, Graduate School of Science and Technology,
Hirosaki University, Hirosaki, Japan
Jan Schwaderer
Clausthal University of Technology, Institute of Technical Chemistry, Clausthal-Zellerfeld,
Germany
Sergey A. Serov
Senior Researcher, Limited Liability Company “Research and production enterprise
“Arflon”, Moscow, Russian Federation
Irene Serrano Delgado
Department of Mechanical and Aerospace Engineering, University of Colorado Colorado
Springs, CO, United States
Dennis W. Smith
Department of Chemistry and the Marvin B. Dow Advanced Composites Institute,
Starkville, MS, United States
 Contributors xiii

Armand Soldera
Laboratory of Physical-Chemistry of Matter, Department of chemistry, Faculty of science,
Université de Sherbrooke, Sherbooke, QC, Canada
Vignesh Vasu
Institute of Materials Science, Polymer Program and Department of Chemistry, University
of Connecticut, CT, United States
Alessandra Vitale
Politecnico di Torino, Department of Applied Science and Technology, Corso Duca degli
Abruzzi, Torino, Italy
About the editors

Dr. Bruno Ameduri (DR CNRS Senior Researcher) leads the “Fluorine”
Group at the “Engineering and Macromolecular Architectures” Team of Institute
Charles Gerhardt in Montpellier, France. His main interests focus on the
synthesis and the characterization of fluorinated monomers (including cure
site monomers, telechelics, and polyfunctional ones), telomers, and copoly-
mers for various applications such as F-surfactants, F-elastomers, F-coatings,
and F-polymers related to energy (fuel cell membranes-protonic, alka-
line and quasianhydrous ones-, polymer gel electrolytes and separators for
Li-ions batteries, piezo-, ferro- or electroactive films), and nanocomposites.
Coauthor of three books, ca. 50 reviews or book chapters, >370 peer
review publications and coinventor of more than 80 patents, he is also a
member of the American and French Chemical Societies and is a member
of the Editorial Boards of the Journal of Fluorine Chemistry, European Polymer
Journal, Polymer Bulletin. Outside of research, Bruno enjoys cycling, soccer,
tennis, and jogging and is also an active member of the “Rire” Association
and visits, dressed as a clown, sick children in hospitals of Montpellier.

Sergey Fomin is the Director of the Institute of Chemistry and Ecology

of Vyatka State University (Russian Federation, Kirov). His main research
interests are in the field of adhesion of polymer materials, development
of new ingredients for polymer compositions, modeling, and calculations
of polymer products. The main research objects are elastomers of various
purposes, including fluoro-rubber, but also a great deal of attention is paid
to thermoplastic fluoropolymer materials. He led more than ten research
and design projects for industry (including for improving the frost resis-
tance of rubber, the development of production technology of self-healing
pneumatic tires, the development of methods for assessing the content of
polyaromatic hydrocarbons in rubber, the creation of a new production
of polymer monofilament, the creation of a new production of polymer
materials resistant to aggressive media, etc.). He has co-authored more than
30 articles in peer-reviewed publications, 4 patents in 2019. He was the
co-organizer of the the First Internation Conference on Fluoropolymers
in Russsia with Dr. Ameduri. He is also a member of the Nanotechnology
Society of Russia. Personal interests include music, playing electric guitar,
snowboarding, and running.
xv
Preface

New technologies are changing our daily lives. New green energy, means
of communication, computers, modern medicine and prosthetics, automo-
tive, and aerospace industries—all have been invented and created by man
to ensure that as our lives undergo changes, we experience better outcomes.
But, new products for a better life require novel materials in addition to
further needing new design and technology solutions. The importance of
the fact that materials fundamentally change the life of mankind is reflected
in the names of the eras. After all, anyone remembers that the Stone Age,
Bronze Age, Iron Age and so on, have been distinguished periods in history.
What age is it now? Without doubt, we are ready to answer that now
there is an era of polymers. It is difficult to imagine a modern world with-
out plastics, rubber, and composites. After all, these materials have been used
to make almost everything surrounding us.
Among many classes of macromolecules, fluoropolymers play a particular
and essential role. Such a class of specialty polymers is endowed with remark-
able properties, such as a wide temperature range of service, biological and
chemical inertnesses, excellent mechanical and optical properties, good ionic
or proton conductivity, piezoelectric characteristics, and shape memory ef-
fect. All this leads to the fact that fluoropolymers are indeed indispensable in
many high-tech areas. They are used to make parts for aerospace and auto-
motive industries, as well as membranes for fuel cells. They are involved in
gas separation, water filtration, actuators and sensor devices, components of
lithium-ion batteries, coatings for optical fibers, surfaces of household appli-
ances and cookware, as well as clothing and fabrics, building structures, and
many more applications.
Years have long passed when only polytetrafluoroethylene, PTFE, has
encompassed fluoropolymers. Now, in these polymer material classes, tens of
species and thousands of brands of materials with their own specificity have
been available. But at the same time, they all have a common feature—the
presence of fluorine atoms in the molecule. These atoms and their strong
and short covalent bonds to carbon have supplied these materials with all
their unique characteristics.
Two books from the “Fluoropolymers” series are offered to you:
BOOK 1: Opportunities of Fluoropolymers: Synthesis, Characteriza-
tions, Processing, Simulation, and Recycling
BOOK 2: Fascinating Fluoropolymers and their Applications
xvii
xviii Preface

The first book is devoted to processes and key strategies to obtain and
study various characteristics of fluoropolymers and simulation, as well as
highlighting their processing and recycling.
The chapters of this book deal with the synthesis and determination
of properties of various classes of fluoropolymers, such as PTFE, fluori-
nated aromatic perfluorocyclobutanes, polyvinylidene fluoride, and others,
including composites. Tackling the kinetics of radical polymerization and
controlling the molar masses and dispersities of synthesized polymers are
also considered. A chapter reports the success of the use of fluoro-substituted
compounds as initiators and controlling agents in various types of con-
trolled radical polymerization (RDRP). In addition, other chapters inform
about special polymerization processes such as a photoinitiated one and
chemical vapor deposition polymerization in a vacuum chamber. Attention
is paid to the modification of fluoropolymers (especially PTFE) by radiation
whereas the use of fluoroalkanoyl peroxides to control the structure of ter-
minal groups is also considered to induce lipophilic and superhydrophobic
properties of fluoropolymers. The production and processes of fluoropoly-
mers for membrane separation of water/oil suspensions and fluoropolymers
with shape memory, as well as the modeling of the molecular structure of
fluoropolymers (especially PVDF) for efficient production of their char-
acteristics, are also discussed. One of the chapters is devoted to a detailed
overview of technological approaches for processing fluoropolymers into
specific items by various methods which are also industrially developped.
The crucial issues of depolymerization and mineralization of different fluo-
ropolymers as well as their recycling, which can be used to reduce negative
impact on the environment, are also considered.
The second book focuses on the most important and advanced appli-
cations of these remarkable materials. Much attention is paid to the elec-
troactive (relaxor, multiferroic ferro- and piezoelectric) characteristics of
polymers, which allow them to be used as sensors and actuators. Several
sections are also devoted to membrane applications, either for ionic and
proton conductions for fuel cells or for purification or separation of various
substances. Another section reviews the optical properties of fluoropoly-
mers and methods to improve optical fibers and waveguides. In addition, a
chapter deals with the medical use of fluoropolymers, particularly in artifi-
cial blood circulation systems while two other ones report the development
of new organic electronics using fluoropolymers and their redox properties.
The use of fluoropolymer-based textiles in architecture is also discussed
 Preface xix

whereas a chapter summarizes the production of frost-resistant rubber con-

taining fine particles of PTFE.
These two books were initiated from the First International Con-
ference on Fluoropolymers in Kirov (Russia) in October 2019, entitled
“Fluoropolymers: Research, Production Problems, New Applications” and we would
like to thank all contributors who kindly extended their talks into such
book chapters, as well as authors who could not attend that meeting but
accepted to contribute in such books.
We are confident that these two books, written by internationally rec-
ognized scientists involved in cutting-edge research projects, will be highly
informative for researchers, engineers, and practitioners from industry or
academia working in materials science, chemistry, polymer physics, engi-
neering and energy, developing or facing synthesis or applications of fluo-
ropolymers in various aspects. They will also serve as excellent reference
sources of information for graduate students and scientists at all levels.

Bruno Ameduri
Sergey Fomin
CHAPTER 1

Semi-fluorinated aromatic
ether polymers via step-growth
polymerization of fluoroalkenes
Ganesh Narayanan, Behzad Farajidizaji, Dennis W. Smith, Jr.
Department of Chemistry and the Marvin B. Dow Advanced Composites Institute, Starkville, MS,
United States

1 Introduction
Ever since its discovery by Plunkett et al. [1], at the Dupont de Nemours
and company, Teflon has found niche applications where properties such as
thermal, chemical, and solvent resistance are required along with outstand-
ing electrical resistance. Impeccable success with Teflon led to the invention
of various fluorine containing homo-, co-, and terpolymers such as poly-
vinylidene fluoride (PVDF), P(VDF-hexafluoropropylene) (PVDF-HFP),
P(VDF-co-tetrafluoroethylene) (PVDF-TFE), and P(VDF-TFE-chlorotri-
fluoroethylene) (PVDF-TFE-CTFE) [2,3]. Two common features among
all the commodity fluoropolymers include the free-radical polymerization
of fluoro-olefins [4] along with higher crystallinity leading to higher melt
processing cost, and poor solution processing capability [5].
To overcome drawbacks associated with traditional commodity fluo-
ropolymers, various amorphous fluoropolymers containing fluoroalkene
groups have been reported in the past 30 years. Among these, the most
extensively studied fluoroalkene-containing polymer is perfluorocyclobutyl
(PFCB) aromatic ether polymer, which is obtained by the radical mediated,
[2 + 2] cyclodimerization of trifluorovinyl ether (TFVE)-bearing mono-
mers (Scheme 1.1A). Originally conceptualized by Babb et al., at The Dow
Chemical Company, who demonstrated the feasibility of 1,2- bisaryloxy-
substituted perfluorocyclobutane containing polymers for high perfor-
mance aerospace and electronics applications, has now been studied for
optical, opto-electronic, gas separation, and proton-exchange membranes.
In addition to PFCB aromatic ether polymers, two additional, comple-
mentary classes of fluoroalkene-containing polymers, namely: perfluorocy-
cloalkenes (PFCA) (Scheme 1.1B) and fluorinated arylene vinylene ether

Opportunities for Fluoropolymers Copyright © 2020 Elsevier Inc.

http://dx.doi.org/10.1016/B978-0-12-821873-0.00001-1 All rights reserved. 1
2 Opportunities for Fluoropolymers

Scheme 1.1 Three semi-fluorinated aromatic ether polymers discussed in this review.
(A) PFCB, (B) PFCA, (C) FAVE.

(FAVE) (Scheme 1.1C) have been reported in the past decade. The aim of
this chapter is to review the synthesis, characterization, and various applica-
tions of these three fluoroalkene-containing polymers, and to further pres-
ent recent advancements reported in the literature.

2 Synthesis of perfluorocyclobutyl (pfcb) aromatic ether

polymers from trifluorovinyl ether-bearing monomers
2.1 Synthesis of trifluorovinyl aromatic ethers (TFVE)
First report of synthesizing TFVE aromatic ether from the reaction of al-
kali metal phenoxide with tetrafluoroethylene was reported by Wall et al.
[6]. Even though aromatic trifluorovinyl ether was obtained albeit at lower
yields, two additional bi-products, namely, tetrafluoroethylphenyl ether and
1,2- diphenoxy-1,2-difluoroethylene, were also present preventing isolation
of highly pure TFVE monomers [6]. Furthermore, TFVE monomers did
not undergo radical mediated polymerization under light or heat but did
undergo polymerization under gamma radiation [6].
 Semi-fluorinated aromatic ether polymers via step-growth polymerization of fluoroalkenes 3

2.2 Synthesis of multifunctional trifluorovinyl ether

(TFVE)-bearing monomers
To overcome the drawbacks associated with the use of this technique for
preparing TFVE-monomers, various alternatives were proposed. The most
common and popular route for preparing TFVE monomers is via two-
step process starting with fluoroalkylation of phenolic derivatives by di-
bromotetrafluoroethane, followed by metal (mostly Zn or Mg) mediated
dehalogenation resulting in TFVE-bearing monomers (Scheme 1.2) [7].To
date, TFVE-bearing monomers have been synthesized from bis-, tris-, and
tetra functional phenolic derivatives (Scheme 1.3). Some of the prominent
phenols that have been converted this route into its corresponding TFVE
include: 4,4′-dihydroxybiphenyl (1), 4,4’-(9H-fluorene-9,9-diyl)diphenol
(2) 4,4′-(hexafluoroisopropylidene) diphenol (3), 4,4’-(prop-1-ene-1,2-
diyl)diphenol (4), 2,2-bis(4-hydroxyphenyl)propane, naphthalene-1,5-diol
(5), hydroquinone (6).
In addition to these well known, industrial bisphenols, more recently, our
group has utilized lesser known bisphenols from polycyclic aromatic hydro-
carbons such as acenaphthenequinone and phenanthrenequinone toward the
synthesis of TFVE monomers. In addition to bis functional phenolic deriva-
tives listed in Scheme 1.3, both tri-, and tetrafunctional monomers such
as 4,4’,4”,4’”-methanetetrayltetraphenol (7) and (R)-3,3,3’,3’-tetramethyl-
2,2’,3,3’-tetrahydro-1,1’-spirobi[indene]-5,5’,6,6’-tetraol (8). Unlike the
bis functional TFVE monomers which afford thermoplastic PFCB poly-
mers, tri- and tetra functional TFVE affords thermally cross-linkable PFCB
polymers. For example, spirophenol 9 upon treatment with fluoroalkylation
agent (1-(bromomethyl)-4-(bromotrifluoroethyloxy)benzene) and sub-
sequent zinc-mediated dehalogenation led to tetra TFVE monomer [8].
Cross-linked polymer was then obtained by thermal polymerization of tetra-
TFVE monomer transforming the monomer into a cross-linked network,
which was insoluble in common solvents such as THF, DMF, chloroform,
common solvents for solubilizing linear, thermoplastic PFCB polymers [8].
Although fluoroalkylation/dehalogenation still remains the choice of
method for obtaining TFVE monomers from phenolic derivatives, the yield

Scheme 1.2 A commonly used two-step process for preparing TFVE monomers from
phenolic derivatives.
4 Opportunities for Fluoropolymers

Scheme 1.3 Di-, tri-, and tetra functional trifluorovinyl aromatic ether monomers ob-
tained from phenolic precursors. Monomers 8 and 9 adapted with permission from Ref.
[2]. Published by The Royal Society of Chemistry.

is abysmal in starting materials containing electron withdrawing groups.

Additionally, fluoroalkylation and subsequent Br−F elimination is cum-
bersome in some phenolic precursors [9] and coupled this with the lack of
abundant phenolic precursors [7] and the occurrence of the impurity, tet-
rafluorovinyl ether, resulting in the low molecular weight of the polymers,
necessitating investigation of other strategies for preparing TFVE monomers.
 Semi-fluorinated aromatic ether polymers via step-growth polymerization of fluoroalkenes 5

Alternatively by using intermediate TFVE-bearing monomer,

p-bromo(trifluorovinyloxy)benzene, first reported by Smith et al. [10],
closely followed by organometallic (aryl lithium) reagents obtained via
metal-halogen exchange reactions affording novel functional fluoro-mono-
mers containing silicon, phosphorous, or other monomers with intact tri-
fluorovinyl ethers [11]. Subsequently, remarkable tolerance of the aromatic
TFVE group to functional group transformation at p-substitution was uti-
lized to create diversified portfolio of TFVE-monomers bearing, for exam-
ple, aldehyde, hydroxymethyl, carboxylic acid, and hydroxymethyl groups
(Scheme 1.4) [12]. Moreover, p-substitution by various functional groups
had an impact on the cyclodimerization rate, with general trend being the

Scheme 1.4 Representative TFVE-bearing monomers 11-16 obtained from p-trans-

formation of bromotrifluorovinyloxy benzene 10. Adapted and redrawn with permission
from Ref. [1]. Copyright John Wiley and Sons 2014.
6 Opportunities for Fluoropolymers

higher the electronegativity in the substituent group resulting in higher

activation energy [13]. Despite the obvious differences in the dimerization
activation energies attributed to the substituent types, two types of diaste-
reomers of the PFCB were formed and that too at almost equal amounts,
resulting in amorphous PFCB polymers [12].
Scheme 1.4 illustrates some of the derivatives obtained from the p-bro-
motrifluorovinyloxy benzene resulting in useful TFVE-bearing mono-
mers for accessing various functional monomers. For example, presence of
boronic acid in 11 affords the possibility of preparing various TFVE mono-
mers via Suzuki coupling [14]. Likewise, dimethyl(4-((1,2,2-trifluorovinyl)
oxy)phenyl)(vinyl)silane (14) and 1-allyl-4-((1,2,2-trifluorovinyl)oxy)ben-
zene (15) facilitated hydrosilation reaction and incorporation of siloxanes
in the fluoropolymer chemistry. Scheme 1.5 illustrates double nucleophilic
addition of Grignard reagent, p-MgBr-C6H4-OCF = CF2, to acenapthen-
equinone resulting in a diol (17), which was subsequently converted to
a ring-retained acenaphthene (18) and ring-cleaved (19) trifluorovinyl
ether (TFVE) monomers by treating with TiCl4 [15]. This one-pot, seem-
ingly facile procedure afforded two unique TFVE monomers, 18 and 19,

Scheme 1.5 Synthetic procedure for deriving ring-fused (18) and ring-open (19) ace-
naphthylene bearing-TFVE monomers from acenapthenequinone. Adapted with permis-
sion from Ref. [9]. Copyright John Wiley & Sons 2019.
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