ebook download Opportunities for Fluoropolymers: Synthesis, Characterization, Processing, Simulation and Recycling (Progress in Fluorine Science) 1st Edition Bruno Ameduri (Editor) - eBook PDF all chapter

Opportunities for Fluoropolymers:
Synthesis, Characterization,
Processing, Simulation and Recycling
(Progress in Fluorine Science) 1st
Edition Bruno Ameduri (Editor) - eBook
PDF
Go to download the full and correct content document:
https://ebooksecure.com/download/opportunities-for-fluoropolymers-synthesis-charact
erization-processing-simulation-and-recycling-progress-in-fluorine-science-ebook-pdf/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...
Fascinating Fluoropolymers and Their Applications 1st

Edition Ameduri Bruno. (Ed.) - eBook PDF
https://ebooksecure.com/download/fascinating-fluoropolymers-and-
their-applications-ebook-pdf/
Progress in Heterocyclic Chemistry Volume 29 1st

Edition - eBook PDF
https://ebooksecure.com/download/progress-in-heterocyclic-
chemistry-ebook-pdf/
(eBook PDF) Translational Medicine in CNS Drug

Development, Volume 29
http://ebooksecure.com/product/ebook-pdf-translational-medicine-
in-cns-drug-development-volume-29/
Fluorine: A Paradoxical Element Volume 5 (Progress in

Fluorine Science) 1st edition - eBook PDF
https://ebooksecure.com/download/fluorine-a-paradoxical-element-
volume-5-progress-in-fluorine-science-ebook-pdf/
Synthesis, Characterization, and Applications of
Graphitic Carbon Nitride 1st Edition - eBook PDF
https://ebooksecure.com/download/synthesis-characterization-and-
applications-of-graphitic-carbon-nitride-ebook-pdf/
Recycling and Reusing of Engineering Materials:

Recycling for Sustainable Developments 1st edition-
eBook PDF
https://ebooksecure.com/download/recycling-and-reusing-of-
engineering-materials-recycling-for-sustainable-developments-
ebook-pdf/
Cardiology-An Integrated Approach (Human Organ Systems)

(Dec 29, 2017)_(007179154X)_(McGraw-Hill) 1st Edition
Elmoselhi - eBook PDF
https://ebooksecure.com/download/cardiology-an-integrated-
approach-human-organ-systems-dec-29-2017_007179154x_mcgraw-hill-
ebook-pdf/
(eBook PDF) Science of Synthesis: Flow Chemistry in

Organic Synthesis
http://ebooksecure.com/product/ebook-pdf-science-of-synthesis-
flow-chemistry-in-organic-synthesis/
Nanomaterial and Polymer Membranes. Synthesis,

Characterization, and Applications 1st Edition Tawfik
Abdo Saleh - eBook PDF
https://ebooksecure.com/download/nanomaterial-and-polymer-
membranes-synthesis-characterization-and-applications-ebook-pdf/
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
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
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,
without permission in writing from the publisher. Details on how to seek permission, further infor-
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-
sume any liability for any injury and/or damage to persons or property as a matter of products liabil-
ity, negligence or otherwise, or from any use or operation of any methods, products, instructions, or
ideas contained in the material herein.
Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress
British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library
ISBN: 978-0-12-821966-9
For information on all Elsevier publications

visit our website at https://www.elsevier.com/books-and-journals
Publisher: Susan Dennis

Acquisitions Editor: Emily M. McCloskey
Editorial Project Manager: Lindsay Lawrence
Production Project Manager: R.Vijay Bharath
Designer: Mark Rodgers
Typeset by Thomson Digital

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
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
Germany
Abhirup Dutta
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
of Connecticut,CT, United States
Jena M. McCollum
Department of Mechanical and Aerospace Engineering, University of Colorado Colorado
Springs, CO, United States
Ganesh Narayanan
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
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
Contributors xiii
Armand Soldera
Laboratory of Physical-Chemistry of Matter, Department of chemistry, Faculty of science,
Université de Sherbrooke, Sherbooke, QC, Canada
Vignesh Vasu
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.
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.
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.
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.
demonstrating the feasibility of accessing polycyclic aromatic hydrocarbon

cores resulting in PFCB aryl ether polymers [15]. Not only were the poly-
cyclic aromatic hydrocarbon (PAH) cores accessible to TFVE moieties, the
resulting PFCB polymers formed stable, mechanically strong, creasable films
and also showed high glass transition temperatures (>200 °C) and thermal
stabilities under N2 and air environments (Td 5% >500 °C) [15].
Prior to this work, very few PAH cores, for example, hexa-peri-hexa-
benzocoronene (HBC) [16] and rylene diimide [17], have been successfully
made into processable TFVE-bearing monomers, which were subse-
quently converted into PFCB polymers. Two different hexaphenylbenzene
compounds were synthesized from p-bromotrifluorovinyloxy benzene (10)
first by Sonagashira coupling, and then by cobalt-catalyzed cyclotrimer-
ization of diphenylacetylenes affording compound 20 (Scheme 1.6 left)
[12]. Hexakis intermediate 20 underwent FeCl3-mediated oxidative ring
fusion affording 21 (Scheme 1.6 right). Both 20 and 21 showed propensity
towards thermal cyclodimerization to form PFCB networks, with polymer
from 20 demonstrating excellent solubility in common organic solvents
[12]. Although solubility is still a concern with these aromatic systems, 20
and 21 underwent thermal copolymerization with commercial TFVE-
monomers 42 and, copolymer of 3 and 20 showed HBC luminescence, in
addition to the emission (360 nm) attributed to the homopolymer poly20,
providing access to potentially processable optical materials from HBC [12].
Scheme 1.6 TFVE-bearing hexaphenylbenzene 20 and preparation of fused ring hexa-

peri-hexabenzocoronene 21. Monomers 20 and 21 adapted with permission from Ref.
[10]. Copyright American Chemical Society 2004.
Like HBC, a new structural fluoropolymer, polynaphthalene-contain-

ing fluoropolymer (PFN) (23) was obtained via oxidative coupling of cor-
responding monomer (22) in tetrachloroethane using FeCl3 as oxidative
coupling agent (Scheme 1.7) [18]. The monomer 22, 1,2-Bis(1-naphthoxy)
hexafluorocyclobutane was obtained by heating 1-(1,2,2-trifluorovinyloxy)
naphthalene at 180 °C for 36 h under in argon atmosphere (Scheme 1.7)
and subsequent recrystallization from methanol and ethanol (1:1 V/V)
[18]. More interestingly, PFN polymers showed extremely low dielectric
constant of 2.33 with very low dielectric loss (<1.2 × 10−3 at 30 MHz)
along with superior mechanical properties (Young’s modulus and bonding
strength between the thin film and a silicon wafer of 17.13 and 13.46 GPa,
respectively). In addition, PFN films also showed high hydrophobicity (con-
tact angle of 101 °) and low surface roughness implying possible applica-
tions in electronics industry [18].
Another way for preparing PAH-enchainment in PFCB technology is
to couple tetrabromide containing PAH moieties via a modified Suzuki–
Miyaura cross-coupling reaction with anhydrous potassium phosphate (24,
Scheme 1.8) [17]. Similarly, tetraaryloxy monomer can also be synthesized by
a nucleophilic substitution reaction between tetrabromide containing PAH
moieties with TFVE-bearing hydroxyl group 25 as shown in Scheme 1.8.
Swager research group synthesized compounds 24 and 25 from tetrabromide
containing-terrylene diimides using established procedures [17]. Although,
24 and 25 did not elicit optical properties that were drastically different
Scheme 1.7 Chemical structure and schematic representation of PFN 23 synthesis via
oxidative coupling, beginning with the fluoroalkylation of 1-naphthol, followed by Zn-
mediated dehalogenation, and thermal mediated cyclodimerization of 1,2-bis(1-naph-
thoxy)hexafluorocyclobutane 22. Adapted with permission from Ref. [12]. Copyright John
Wiley & Sons 2013.
Scheme 1.8 Synthesis of representative terrylene dyes-bearing TFVE moieties 24 and

25 and thermal polymerization into PFCB polymers.Monomers 24 and 25 adapted and
reprinted with permission from Ref. [11]. Copyright American Chemical Society 2011.
from parent dye (terrylene diimide), both showed unique photophysical

properties compared to linear TFVE-bearing monomers obtained from
dibromo-containing terrylene diimides (not shown) [17]. For example, not
only the fluorescent quantum yields were significantly lower (0.08 and 0.17
for 24 and 25, respectively compared to other diimide-bearing monomers
which ranged from 0.61 to 0.88, but the excited state lifetimes were con-
siderably shorter (5.7 and 2.4 ns for 24 and 25, respectively versus 8.7 and
9.8 ns for two other diimide monomers), illustrating possible mechanisms to
modulate the photophysical properties of the PFCB-polymers [17]. More
interestingly, 24 and 25 were synthesized into chromophore nanoparticles
and subsequently polymerized/crosslinked into PFCB polymers.
An identical method was more recently reported by Fang’s research
group, who first synthesized bromine-containing bisphenols from fluorene
(4,4’-(2-bromo-9H-fluorene-9,9-diyl)diphenol) (26) [19]. Subsequently,
using standard fluoroalkylation and dehalogenation techniques (dibromo-
tetrafluoroethane and Zn), bisphenol was converted into trifluorovinyloxy
groups with intact Br in the fluorene skeleton, which was subsequently
eliminated by Suzuki coupling affording tetrafunctional TFVE-bearing
monomer 28 [19]. Polymer 29 was then obtained by thermal cyclodi-
merization of 28 affording crosslinked polymer that was insoluble in most
organic solvents (THF, chloroform, chlorobenzene, etc) (Scheme 1.9).
Scheme 1.9 Synthesis and transformation of fluorene-based bisphenols into PFCB-

based molecular glass. Monomers 26-28 and polymer 29 adapted and reprinted with per-
mission from Ref. [19]. Copyright Royal Society of Chemistry 2016.
While the photophysical properties were not extensively studied like

those studies from Swager [17] or from our group [16], dielectric and
mechanical properties showed low dielectric constant (<2.5) and dissipa-
tion factor (2.0 × 10–2) between the frequencies 0 to 30 MHz [19]. These
values are significantly lower than commercial low k materials such as, for
example, polyimides, polysiloxanes, and poly(aryl ether). Not only did these
fluorine-based PFCB polymers show low k values, they also demonstrated
extremely low surface roughness, high hydrophobicity, and mechanical
properties (strength and Young’s modulus), making them suitable for appli-
cations in electronics/optical industry [19].
As can be seen from limited examples of PAH-enchainment in PFCB
technology, combination of semi-fluorination with PAH moieties lead to
improvements in optical, thermal, surface, and mechanical properties, while
also addressing processing issues (poor solubility in solvents) in commonly
plaguing PAH chemistries. However, PFCB aryl ether technology needs
to be evaluated in higher aromatic systems like corannulene, buckybowl,
buckminister fullerene-like molecular structures for their influence on the
photophysical, mechanical, and thermal properties of PFCB polymers.
2.3 PFCB containing monomers for classical polymerization

Despite broad spectrum of possible PFCB polymers, TFVE monomers are
susceptible to nucleophilic fluoride addition in the presence of stronger
base resulting in (-O-CHF-CF3) side products, which inhibit increase in the
molecular weight [17]. Also, in some cases, functional groups present in the
aryl monomers are less tolerant of the polymerization processes, necessitat-
ing alternative strategies for expanding the pool of PFCB aryl ether poly-
mers [20]. One way is to utilize preformed PFCB oligomer or monomer
(from TFVE) and subsequently polymerize the end groups via coupling
chemistry, which have shown excellent selectivity, reactivity, and reliability
[21,22]. Qing’s research group at Donghua University reported the first
click chemistry (copper (I) catalyzed Huisgen’s 1,3-dipolar [3 + 2] cycload-
dition) reaction between compounds containing polyethylene glycol-bear-
ing diazides and PFCB-bearing dialkynes, leading to the formation of series
of aromatic ether polymers containing PFCB and triazole units [23].
In subsequent study, the same group studied Huisgen’s 1,3-dipolar
[3 + 2] cycloaddition reaction between 1,2-bis(4-azidomethylphenoxy)
perfluorocyclobutane (30) and PFCB-bearing bisethynyl compounds (31)
(Scheme 1.10) [24]. Both 30 and 31 were obtained in three straightforward
steps from phenolic precursors, beginning with fluoroalkylation/dehaloge-
nation of monofunctional phenols by BrCF2CF2Br / Zn, respectively [24].
Scheme 1.10 A schematic illustrating the synthesis of aromatic ether polymers con-
taining perfluorocyclobutyl and triazole units via click chemistry. Monomers 30-31 and
polymer 32 adapted and reprinted with permission from Ref. [18]. Copyright Elsevier Ltd
2008.
Further, PFCB monomer was obtained by cyclodimerization and subse-

quently brominated via NBS (N-bromosuccinimide) under IR lights.
Finally, azidization of bromophenoxy PFCB compound was achieved by
sodium azide, affording compound 30 [24]. Upon polymerization via click
chemistry, polymers (32) showed Mn values ranging from 30 to 70, 000 and
Mw values ranging from 36 to 86,000, making the PDI values significantly
low (1.19–1.24) [24]. Despite high molecular weights obtained in this study,
Tg and Td (5% decomposition) values ranged from 90 to 150 °C and from
330 to 370 °C [24]. More interestingly, first 1,3 cycloaddition study which
investigated the click chemistry between polyethylene glycol-bearing dia-
zides and PFCB-bearing dialkynes reported low Mn and Mw values that
ranged from 7 to 20,000 and 10 to 25,000 (PDI from 1.2 to 1.7), but
reported higher Td values (>420 °C) [24].
Recently, bisethynyl compounds from biphenol, bisphenol-A, 4,4’-sul-
fonyldiphenol (bisphenol-S) without PFCB linkage have been reported for
step-growth polymerization with bisazide-bearing PFCB monomer [25].
Surprisingly, both the Mn (>50,000 in 3 of 4 polymers) and Mw (>65,000
in 3 of 4 polymers) were higher compared to the previous studies [23,24]
which first reported the click chemistry for synthesizing aryl ether poly-
mers bearing PFCB and triazole units. While the Tg and Td values were
largely dependent on the starting material and were in general low
(Td ranged from 106 to 156 °C and Td 5% ranged from 330 to 370 °C), all
the polymers showed very low surface energy (14.11–14.38 mJ/m2) [25].
Scheme 1.11 Synthesis of triazine and benzocyclobutene containing PFCB linkage by

the step-growth polymerization of dichloro-s-triazine-bearing benzocyclobutene (33)
and bisphenols-bearing PFCB monomer 34. Monomers 33-34 and polymer adapted and
reprinted with permission from Ref. [20]. Copyright Royal Society of Chemistry 2017.
More recently, step-growth polymerization was carried out between

dichloro-s-triazine-bearing benzocyclobutene (33) and bisphenol-contain-
ing PFCB units (34) (Scheme 1.11) in the presence of phase transfer catalyst
(PTC) [26]. Presence of PTC and the PTC type played a key role in the
molecular weight and distribution, and total yield, although no particu-
lar relationship was established between the PTC and the polymer char-
acteristics [26]. Having benzocyclobutene in the reactive monomer 33 is
well known to produce a reactive intermediate o-quinodimethane, which
is also known to participate as a diene in the Diels–Alder reaction, provid-
ing thermocrosslinkable sites [26]. Using identical approach, triazine-based
polymers have been derived from triazine-modified anethole containing
thermocrosslinkable benzocyclobutene and bisphenols-bearing PFCB
monomers [27]. In addition to step-growth polymerization, presence of
benzocyclobutene was found to initiate the Diels–Alder polyaddition reac-
tion resulting in thermoset PFCB-bearing triazine polymers [27]. Unlike
the previous studies that utilized azide-based click chemistry [23,24], all the
triazine-based polymers showed much improved thermal stability (Td 5%
>430 °C compared to <350 °C for aryl ether polymers-bearing triazole
units), thermomechanical stability (stable storage modulus >6 GPa even at
300 °C), and extremely low dielectric constants (as low as 1.5 DK at up to
30 MHz) [27].
Another advantage with the presence of PFCB monomer units in

either the main or in the side chain is the possibility of radical-mediated
polymerization leading to the formation of well controlled copolymers-
bearing PFCB units. Huang’s group demonstrated the first atom transfer
radical polymerization (ATRP) of PFCB-containing methacrylate-based
monomer, 4-(4′-p-tolyloxyperfluorocyclobutoxy)benzyl methacrylate (35)
initiated by methyl 2-bromopropionate, and copolymer of 35 with poly-
ethylene glycol (PEG) segments (also synthesized by ATRP) acting as mac-
roinitiators [28]. 1H-, 13C-, 19F-NMR experiments on homopolymer from
35 clearly showed disappearance of double bonds attributed to the meth-
acrylates, presence of PFCB units between 105.0 and 115.2 ppm, further
corroborated by peaks between −127 and 132 ppm, respectively. Addition
of PFCB-units further increased the Tg and thermal stability of the methac-
rylate homopolymer while retaining the optical clarity.
The same group pursued a different approach for synthesizing poly-
methacrylate-bearing PFCB units in the main chain via free radical polym-
erization using 2,2′-azobis(isobutyronitrile) (AIBN) or benzoyl peroxide
(BPO) as radical initiators [29]. Key differences between the studies include
using simple and directly relevant starting materials such as p-substituted
phenol, tetrafluoroethylene and methacryloyl chloride (precursor for meth-
acrylate) for synthesizing PFCB-containing methacrylate monomers [29].
Substituting groups in the phenols had a significant influence in the Tg
values of the polymer. For example, methyl substitution resulted in a very
low Tg of 160 °C; whereas, cumyl substitution resulted in a Tg of 213 °C.
Succeeding these studies, various homo-, and copolymers (including tri-
block) such as polyacrylic acid (PAA) [30], PEG and poly(methacrylic
acid) (PMAA) [31], polyisobutylene (PIB) [32], poly(2-(diethylamino)ethyl
methacrylate) (PDEAEMA) [33], polymethoxylmethyl acrylate (PMOMA)
[34]- bearing PFCB units in the polymer main or side chain via ATRP or
reversible addition–fragmentation chain-transfer (RAFT) techniques. One
general advantage of combining PFCB units with other monomers is the
formation of polymers bearing hydrophobic and hydrophilic moieties capa-
ble of self-assembly, resulting in the formation of micelles, which can have
profound effects in various applications [28-34].
Instead of PFCB-bearing monomer units, PFCB polymers can be
directly accessed for developing perfluorocyclobutyl aromatic ether-based
copolymers. For example, an ABA-type (A: polystyrene block; B: PFCB
block) have been reported via ATRP polymerization technique using
2-bromo-1-(p-trifluorovinyloxy)phenylpropan-1-one as an ATRP initiator
Scheme 1.12 Representative examples of PFCB-based radical monomer, 4-(4′-p-tol-

yloxyperfluorocyclobutoxy)benzyl methacrylate 35 and TFVE-based ATRP initiator,
2-bromo-1-(p-trifluorovinyloxy)phenylpropan-1-one 36. Monomers 35 and 36 adapt-
ed and reprinted with permission from Ref. [22] and [29]. Copyright Elsevier Ltd 2008 and
American Chemical Society 2005.
36 (Scheme 1.12) [35]. At all studied mole ratios (monomer: initiator) and
reaction times, the PDI was low (<1.3). Furthermore, with reaction times,
an increase in the molecular weight was observed. Since the TFVE do
not undergo radical polymerization and exclusively polymerizes via [2 + 2]
mechanism, using a transformational strategy such as forming PFCB
monomer or polymeric units would therefore facilitate conventional radi-
cal polymerization techniques with other monomers that undergo radical
polymerization [35].
2.4 Postpolymerization modification on PFCB aryl ether

polymers
An advantage of PFCB polymer over TFVE monomer is their capabil-
ity to undergo postpolymerization reactions such as sulfonation shown in
Scheme 1.13. Taking cues from studies that investigated fluorene-based
polymer blends [36], PFCB-based blends were selectively sulfonated for
Scheme 1.13 Synthesis of PFCB from biphenol and sulfone-based TFVE and sulfona-
tion of the PFCB homopolymers/blends. Scheme adapted and reprinted with permission
from Ref. [31]. Copyright Elsevier Ltd 2013.
imparting hydrophilic properties and nanophase-separated morphologies

for improving proton conductivity and performance [37].
While it would be more attractive to polymerize functionalized mono-
mer, that is, sulfonated TFVE, dehalogenation step using Zn/CuCl2 resulted
in an abysmal 5% yield, with the major products being organo-zinc salts and
hydrogenated species [37]. Therefore, postpolymerization route of first syn-
thesizing PFCB polymers and subsequent sulfonation is a preferred route
as fewer steps are required to achieve target product and at higher yields
(>65%) [37]. Another added advantage of polymer blending (BP-PFCB
with SO2-PFCB) is greater control in ion exchange capacity (1.36 and 1.37
for sBP/BP-PFCB and sBP/SO2-PFCB vs 0.82 mmol/g for Nafion®)
and proton conductivity at all studied temperatures (25, 50, and 80 °C)
[37]. This result suggests postpolymerization route to be yet another route
for effectively using PFCB-based polymers as high performance materials
(additional references 50 and 51 in Table 1.1).
2.5 Characterization of TFVE monomers and PFCB aromatic

ether polymers
The aromatic TFVE monomer and polymeric PFCBs are best charac-
terized by Fourier transform infrared (FT-IR) and Raman spectroscopy,
thermal analysis (in particular, differential scanning calorimetry) and NMR
spectroscopic (13C-, and 19F-NMR) techniques.
2.5.1 Infrared and Raman spectroscopy of TFVE monomers and PFCB

aromatic ether polymers
As a preliminary characterization technique, FT-IR of TFVE exhibits a
characteristic, but faint band at ∼1830 cm–1, which vanishes and a new
sharp band in the IR near 960 cm–1emerges, which is diagnostic band for
the presence of the hexafluorocyclobutane group [10] (Fig. 1.1). As most
characteristic functional groups do not elicit any response in these ranges
of IR spectrum (1830 or 960 cm–1), these easily resolvable absorption bands
have proven to be a useful analytic tool for TFVE monomers and PFCB
linkage [10].
While a weak signal is observed for TFVE group in FT-IR as seen in
Fig. 1.1 [10], Raman spectroscopy provides enhanced signal intensity for
these fluoro-olefins [38]. Due to enhanced sensitivity, quantification of the
signal intensity provides accurate cure kinetic information, which is not
feasible with FT-IR [38]. As an example, Raman spectroscopy of conversion
of tris(trfluorovinyloxyphenyl)ethane monomer 39 into cross-linked PFCB
Table 1.1 Selected physical, thermal, mechanical, dielectric, and optical properties
of PFCB-based polymers reported in the past 10 Years. Chemical structures for the
compounds are listed in Scheme 1.14.
Refer-
Entry Salient features ences
43 Tg = −11 °C (homopolymer) (DSC) [44]

Td (5%) = 476 °C (in N2) (TGA)
Storage modulus =103 and 101 MPa at 20 and 120 °C) (DMA)
Loss modulus =100.5 at 20 and 120 °C and 101 MPa at 105 °C)
(DMA)
Transmittance: 91% in wavelengths from 1100 to 420 nm
(UV-vis-NIR)
Surface roughness = 0.4 nm and peak to valley roughness of
8 nm) (AFM)
Dk and Df = 2.58 and 1.8 x 10–3 at 1 MHz; and 4.0 and 1.8 x 10–3
at 30 MHz
44 Tg = 316 °C (DSC) [8]
Td (5%) = 417 °C (in N2) (TGA)
Young’s modulus = 14.82 GPa (nanoindentation)
Bonding strength to silicon wafer = 0.23 GPa (nanoindentation)
Average coefficient of thermal expansion = 59.5 ppm °C–1 (TMA)
Average surface roughness = 0.34 nm (AFM)
Dk and Df =< 2.58 and 0.01 between 1 and 30 MHz
Water contact angle = 98.6 degree
Water absorption = 0.45 % (after in boiling water for 72 h)
45 Tg not observed (highly crosslinked (DSC) [45]
Td (5%) = 492 °C (in N2) (TGA)
Storage modulus = 103.75 and 103.6 MPa between 20 and 400 °C
(DMA)
Tan δ = between 0.01 and 0.03 (20 and 400 °C (DMA)
Transmittance: >93% in wavelengths from 1100 to 420 nm
(UV-vis-NIR)
Average coefficient of thermal expansion = 51.1 ppm °C–1 (TMA)
Water absorption = 0.08 % (after in boiling water for 72 h)
Dk and Df = 2.27 and 2.0 x 10–3 between 40 Hz and 30 MHz
46 Td (5%) = 436 °C (in N2) (TGA) [46]
Surface roughness (0.49 nm and peak to valley roughness of
6.2 nm) (AFM)
Transmittance: >92% in wavelengths from 1100 to 420 nm (UV-
vis-NIR)
Water absorption = 0.07 and 0.08 % (after in boiling water for 24
and 72 h)
Dk and Df= 2.56 and 3.1 x 10–3 between 40 Hz and 30 MHz
Water contact angle = between 105.98 and 98.6 degree after im-
mersion in boiling water.
Young’s modulus = 4.64 GPa (nanoindentation)
Hardness = 0.22 GPa (nanoindentation)
(Continued)
compounds are listed in Scheme 1.14. (Cont.)
Refer-
47 Tg = 135 °C (DSC) [47]
Td (5%) = 385 °C (in N2) (TGA)
Transmittance: = 93% (λ = 800 nm) and 75% (λ = 400 nm)
(UV-vis-NIR)
Water contact angle = 103 °C
Mass gain = 0.08% after immersion in 1 M HCl (7-days)
Dk = 2.68 between 0.1 and 30 MHz
Storage modulus = 400 MPa (DMA)
Elastic modulus and elongation at break (790 MPa and 1.7%)
(quasi-static mechanical testing).
48 Tg = 59 °C uncured homopolymer (DMA) [48]
Td (5%) = 412 °C (in N2) (TGA)
Average coefficient of thermal expansion = 90.9 ppm °C–1
(between 50 and 300 °C) (TMA)
Storage modulus = 103 and 102.5 MPa (30 and 350 °C (DMA)
Tan δ =< 0.01 (30 and 350 °C (DMA)
Surface roughness = between 1.44 and 2.35 nm depending on the
cure) (AFM)
Transmittance: = > 90% (λ = between 550 and 1100 nm)
(UV-vis-NIR)
Dk and Df= 2.65 and 4.3 x 10–3 between 40 Hz and 25 MHz
(fully crosslinked material)
Water contact angle and surface energy = 104 degree and 26.8 mJ
m–2 (fully crosslinked material).
49 Td (5%) = 460 °C (in N2) (TGA) [49]
Water absorption = 0.11 to 0.67 % depending on the cure and
monomer type (after immersion in boiling water for 96 h)
Dk and Df= 2.1 and 3.0 x 10–3 between 0.1 and 30 MHz
50 Mn and Mw = 123,500 and 149,500 (prior to sulfonation) (reac- [50]
tion time of 12 h at 200 °C)
Tg = 163 °C (Tg increased with increase in the degree of sulfo-
propylation) (DSC)
Td (5%) = 196 °C (in N2) (Td5% decreased with increase in the
degree of sulfopropylation) (TGA)
51 Td (5%) = 200 °C at 99% degree of sulfonation (in N2) (Td5% [51]
decreased with increase in the degree of sulfonation) (TGA)
Tg values of precursor gradually increased with the increasing
degrees of demethylation
Sulfonated polymers showed excellent solubility in DMSO, DMF,
DMAc and were partially soluble in methanol and acetone. And
completely insoluble in isopropanol and chloroform.
compounds are listed in Scheme 1.14. (Cont.)
Refer-
52 Tg >350 °C (not obviously observed (DSC) [52]
Td (5%) = 472 °C (in N2) (TGA)
Dk and Df= < 2.45 and 2.1 x 10–3 between 1 and 30 MHz (fully
crosslinked material)
Water contact angle = 105 dgree
Young’s modulus and hardness = 10.06 and 0.392 GPa (nanoin-
dentation)
Surface roughness = < 5.79 nm (on 1 sq. µm) (AFM)
DMA, dynamic mechanical analysis; AFM, atomic force microscopy; TMA, thermomechanical analysis;
Dk and Df, dielectric constant and dissipation factor; tan δ, loss factor.
Figure 1.1 FT-IR Spectra of TFVE-monomers and PFCB polymers. In this example, TFVE-
monomer (bottom spectra) shows a characteristic faint peak at 1836 cm−1 which van-
ishes upon conversion to PFCB-polymers and a new PFCB characteristic band emerges
at ∼960 cm−1. Unpublished work. Copyright Smith group 2019.
Scheme 1.14 Chemical structures of PFCB-based polymers discussed in Table 1.1.

43-52 adapted and reproduced with permission Refs. [2,38–46]. Copyright Royal Society
of Chemistry 2017, American Chemical Society 2017, American Chemical Society 2016,
American Chemical Society 2017, American Chemical Society 2019, John Wiley & Sons 2015,
Elsevier Ltd 2016, Springer Nature Ltd 2019, American Chemical Society 2014.
polymer is shown in Fig. 1.2 [39]. Between the Raman shifts 1850 and
1550 cm–1, three characteristic peaks at 1831, 1605, and 1554 cm–1 attrib-
uted to TFVE, phenyl rings, and residual mesitylene, were observed. With
increases in the curing at 150 °C, intensity increase and peak broadening for
phenyl rings (1605 cm–1) and decrease for TFVE groups (1831 cm–1) were
observed (Fig. 1.2) [39].
The normalized intensity of the 1831 cm–1 peak (with respect to
1605 cm–1) was used to calculate the extent of cure at various temperatures
(130, 150, 170, 190, and 210 °C). Based on the extent of cure at various cure
temperatures, depending on the study cure temperature, half-life for this
monomer was observed to vary from 450 min to less than 10 min, indicat-
ing the possibility of utilizing the Raman spectroscopy for optimizing the
curing process (Fig. 1.3) [39].
2.5.2 Carbon nuclear magnetic resonance (NMR) spectroscopy

13
C-NMR is yet another technique commonly utilized to interpret changes
in the vinylic carbons and emergence of multiplets ascribed to the PFCB
Another random document with
no related content on Scribd:
In his turn, Dr. Richardson, speaking of the Temple of Dendera,
says: “The female figures are so extremely well executed, that they
do all but speak; they have a mildness of feature and expression that
never was surpassed.”
Every one of these stones is covered with hieroglyphics, and the
more ancient they are, the more beautifully we find them chiselled.
Does not this furnish a new proof that history got its first glimpse of
the ancients when the arts were already fast degenerating among
them? The obelisks have their inscriptions cut two inches, and
sometimes more, in depth, and they are cut with the highest degree
of perfection. Some idea may be formed of their depth, from the fact
that the Arabs, for a small fee, will climb sometimes to the very top of
an obelisk, by inserting their toes and fingers in the excavations of
the hieroglyphics. That all of these works, in which solidity rivals the
beauty of their execution, were done before the days of the Exodus,
there remains no historical doubt whatever. (All the archæologists
now agree in saying that, the further back we go in history, the better
and finer become these arts.) These views clash again with the
individual opinion of Mr. Fiske, who would have us believe that “the
sculptures upon these monuments (of Egypt, Hindustan, and
Assyria), moreover, betoken a very undeveloped condition of the
artistic faculties.”[777] Nay, the learned gentleman goes farther.
Joining his voice in the opposition against the claims of learning—
which belongs by right to the sacerdotal castes of antiquity—to that
of Lewis, he contemptuously remarks that “the extravagant theory of
a profound science possessed by the Egyptian priesthood from a
remote antiquity, and imparted to itinerant Greek philosophers, has
been utterly destroyed (?) by Sir G. C. Lewis[778] ... while, with
regard to Egypt and Hindustan, as well as Assyria, it may be said
that the colossal monuments which have adorned these countries
since prehistoric times, bear witness to the former prevalence of a
barbaric despotism, totally incompatible with social nobility, and,
therefore, with well sustained progress.”[779]
A curious argument, indeed. If the size and grandeur of public
monuments are to serve to our posterity as a standard by which to
approximately estimate the “progress of civilization” attained by their
builders, it may be prudent, perhaps, for America, so proud of her
alleged progress and freedom, to dwarf her buildings at once to one
story. Otherwise, according to Professor Fiske’s theory, the
archæologists of A.D. 3877 will be applying to the “Ancient America”
of 1877, the rule of Lewis—and say the ancient United States “may
be considered as a great latifundium, or plantation, cultivated by the
entire population, as the king’s (president’s) slaves.” Is it because the
white-skinned Aryan races were never born “builders,” like the
Eastern Æthiopians, or dark-skinned Caucasians,[780] and,
therefore, never able to compete with the latter in such colossal
structures, that we must jump at the conclusion that these grandiose
temples and pyramids could only have been erected under the whip
of a merciless despot? Strange logic! It would really seem more
prudent to hold to the “rigorous canons of criticism” laid down by
Lewis and Grote, and honestly confess at once, that we really know
little about these ancient nations, and that, except so far as purely
hypothetical speculations go, unless we study in the same direction
as the ancient priests did, we have as little chance in the future. We
only know what they allowed the uninitiated to know, but the little we
do learn of them by deduction, ought to be sufficient to assure us
that, even in the nineteenth century, with all our claims to supremacy
in arts and sciences, we are totally unable, we will not say to build
anything like the monuments of Egypt, Hindustan, or Assyria, but
even to rediscover the least of the ancient “lost arts.” Besides, Sir
Gardner Wilkinson gives forcible expression to this view of the
exhumed treasures of old, by adding that, “he can trace no primitive
mode of life, no barbarous customs, but a sort of stationary
civilization from the most remote periods.” Thus far, archæology
disagrees with geology, which affirms that the further they trace the
remains of men, the more barbarous they find them. It is doubtful if
geology has even yet exhausted the field of research afforded her in
the caves, and the views of geologists, which are based upon
present experience, may be radically modified, when they come to
discover the remains of the ancestors of the people whom they now
style the cave-dwellers.
What better illustrates the theory of cycles than the following fact?
Nearly 700 years b.c., in the schools of Thales and Pythagoras was
taught the doctrine of the true motion of the earth, its form, and the
whole heliocentric system. And in 317 a.d., we find Lactantius, the
preceptor of Crispus Cæsar, son of Constantine the Great, teaching
his pupil that the earth was a plane surrounded by the sky, which is
composed of fire and water, and warning him against the heretical
doctrine of the earth’s globular form!
Whenever, in the pride of some new discovery, we throw a look
into the past, we find, to our dismay, certain vestiges which indicate
the possibility, if not certainty, that the alleged discovery was not
totally unknown to the ancients.
It is generally asserted that neither the early inhabitants of the
Mosaic times, nor even the more civilized nations of the Ptolemaic
period were acquainted with electricity. If we remain undisturbed in
this opinion, it is not for lack of proofs to the contrary. We may
disdain to search for a profounder meaning in some characteristic
sentences of Servius, and other writers; we cannot so obliterate
them but that, at some future day, that meaning will appear to us in
all its significant truths. “The first inhabitants of the earth,” says he,
“never carried fire to their altars, but by their prayers they brought
down the heavenly fire.”[781] “Prometheus discovered and revealed
to man the art of bringing down lightning; and by the method which
he taught to them, they brought down fire from the region above.”
If, after pondering these words, we are still willing to attribute them
to the phraseology of mythological fables, we may turn to the days of
Numa, the king-philosopher, so renowned for his esoteric learning,
and find ourselves more embarrassed to deal with his case. We can
neither accuse him of ignorance, superstition, nor credulity; for, if
history can be believed at all, he was intently bent on destroying
polytheism and idol-worship. He had so well dissuaded the Romans
from idolatry that for nearly two centuries neither statues nor images
appeared in their temples. On the other hand old historians tell us
that the knowledge which Numa possessed in natural physics was
remarkable. Tradition says that he was initiated by the priests of the
Etruscan divinities, and instructed by them in the secret of forcing
Jupiter, the Thunderer, to descend upon earth.[782] Ovid shows that
Jupiter Elicius began to be worshipped by the Romans from that
time. Salverte is of the opinion that before Franklin discovered his
refined electricity, Numa had experimented with it most successfully,
and that Tullus Hostilius was the first victim of the dangerous
“heavenly guest” recorded in history. Titus Livy and Pliny narrate that
this prince, having found in the Books of Numa, instructions on the
secret sacrifices offered to Jupiter Elicius, made a mistake, and, in
consequence of it, “he was struck by lightning and consumed in his
own palace.”[783]
Salverte remarks that Pliny, in the exposition of Numa’s scientific
secrets, “makes use of expressions which seem to indicate two
distinct processes;” the one obtained thunder (impetrare), the other
forced it to lightning (cogere).[784] “Guided by Numa’s book,” says
Lucius, quoted by Pliny, “Tullus undertook to invoke the aid of
Jupiter.... But having performed the rite imperfectly, he perished,
struck by thunder.”[785]
Tracing back the knowledge of thunder and lightning possessed
by the Etruscan priests, we find that Tarchon, the founder of the
theurgism of the former, desiring to preserve his house from
lightning, surrounded it by a hedge of the white bryony,[786] a
climbing plant which has the property of averting thunderbolts.
Tarchon the theurgist was much anterior to the siege of Troy. The
pointed metallic lightning-rod, for which we are seemingly indebted
to Franklin, is probably a re-discovery after all. There are many
medals which seem to strongly indicate that the principle was
anciently known. The temple of Juno had its roof covered with a
quantity of pointed blades of swords.[787]
If we possess but little proof of the ancients having had any clear
notions as to all the effects of electricity, there is very strong
evidence, at all events, of their having been perfectly acquainted with
electricity itself. “Ben David,” says the author of The Occult
Sciences, “has asserted that Moses possessed some knowledge of
the phenomena of electricity.” Professor Hirt, of Berlin, is of this
opinion. Michaelis, remarks—firstly: “that there is no indication that
lightning ever struck the temple of Jerusalem, during a thousand
years. Secondly, that according to Josephus,[788] a forest of points
... of gold, and very sharp, covered the roof of the temple. Thirdly,
that this roof communicated with the caverns in the hill upon which
the temple was situated, by means of pipes in connection with the
gilding which covered all the exterior of the building; in consequence
of which the points would act as conductors.”[789]
Ammianus Marcellinus, a famous historian of the fourth century, a
writer generally esteemed for the fairness and correctness of his
statements, tells that “The magii, preserved perpetually in their
furnaces fire that they miraculously got from heaven.”[790] There is a
sentence in the Hindu Oupnek-hat, which runs thus: “To know fire,
the sun, the moon, and lightning, is three-fourths of the science of
God.”[791]
Finally, Salverte shows that in the days of Ktesias, “India was
acquainted with the use of conductors of lightning.” This historian
plainly states that “iron placed at the bottom of a fountain ... and
made in the form of a sword, with the point upward, possessed, as
soon as it was thus fixed in the ground, the property of averting
storms and lightnings.”[792] What can be plainer?
Some modern writers deny the fact that a great mirror was placed
in the light-house of the Alexandrian port, for the purpose of
discovering vessels at a distance at sea. But the renowned Buffon
believed in it; for he honestly confesses that “If the mirror really
existed, as I firmly believe it did, to the ancients belong the honor of
the invention of the telescope.”[793]
Stevens, in his work on the East, asserts that he found railroads in
Upper Egypt whose grooves were coated with iron. Canova, Powers,
and other celebrated sculptors of our modern age deem it an honor
to be compared with Pheidias of old, and strict truth would, perhaps,
hesitate at such a flattery.
Professor Jowett discredits the story of the Atlantis, in the
Timæus; and the records of 8,000 and 9,000 years appear to him an
ancient swindle. But Bunsen remarks: “There is nothing improbable
in itself in reminiscences and records of great events in Egypt 9,000
years b. c., for ... the Origines of Egypt go back to the ninth
millennium before Christ.[794] Then how about the primitive
Cyclopean fortresses of ancient Greece? Can the walls of Tiryns,
about which, according to archæological accounts, “even among the
ancients it was reported to have been the work of the Cyclops,”[795]
be deemed posterior to the pyramids? Masses of rock, some equal
to a cube of six feet, and the smallest of which, Pausanias says,
could never be moved by a yoke of oxen, laid up in walls of solid
masonry twenty-five feet thick and over forty feet high, still believed
to be the work of men of the races known to our history!
Wilkinson’s researches have brought to light the fact that many
inventions of what we term modern, and upon which we plume
ourselves, were perfected by the ancient Egyptians. The newly-
discovered papyrus of Ebers, the German archæologist, proves that
neither our modern chignons, skin-beautifying pearl powders, nor
eaux dentifrices were secrets to them. More than one modern
physician—even among those who advertise themselves as having
“made a speciality of nervous disorders” may find his advantage in
consulting the Medical Books of Hermes, which contain prescriptions
of real therapeutic value.
The Egyptians, as we have seen, excelled in all arts. They made
paper so excellent in quality as to be timeproof. “They took out the
pith of the papyrus,” says our anonymous writer, previously
mentioned, “dissected and opened the fibre, and flattening it by a
process known to them, made it as thin as our foolscap paper, but
far more durable.... They sometimes cut it into strips and glued it
together; many of such written documents are yet in existence.” The
papyrus found in the tomb of the queen’s mummy, and another one
found in the sarcophagus of the “Chambre de la Reine,” at Ghizeh,
present the appearance of the finest glossy white muslin, while it
possesses the durability of the best calf-parchment. “For a long time
the savants believed the papyrus to have been introduced by
Alexander the Great—as they erroneously imagined a good many
more things—but Lepsius found rolls of papyri in tombs and
monuments of the twelfth dynasty; sculptured pictures of papyri were
found later, on monuments of the fourth dynasty, and now it is
proved that the art of writing was known and used as early as the
days of Menes, the protomonarch;” and thus it was finally discovered
that the art and their system of writing were perfect and complete
from the very first.
It is to Champollion that we owe the first interpretation of their
weird writing; and, but for his life-long labor, we would till now remain
uninformed as to the meaning of all these pictured letters, and the
ancients would still be considered ignorant by the moderns whom
they so greatly excelled in some arts and sciences. “He was the first
to find out what wondrous tale the Egyptians had to tell, for one who
could read their endless manuscripts and records. They left them on
every spot and object capable of receiving characters.... They
engraved, and chiselled, and sculptured them on monuments; they
traced them on furniture, rocks, stones, walls, coffins, and tombs, as
on the papyrus.... The pictures of their daily lives, in their smallest
details, are being now unravelled before our dazzled eyes in the
most wondrous way.... Nothing, of what we know, seems to have
been overlooked by the ancient Egyptians.... The history of
‘Sesostris’ shows us how well he and his people were versed in the
art and practice of war.... The pictures show how formidable they
were when encountered in battle. They constructed war-engines....
Homer says that through each of the 100 gates of Thebes issued
200 men with horses and chariots; the latter were magnificently
constructed, and very light in comparison with our modern heavy,
clumsy, and uncomfortable artillery wagons.” Kenrick describes them
in the following terms: “In short, as all the essential principles which
regulate the construction and draught of carriages are exemplified in
the war-chariots of the Pharaohs, so there is nothing which modern
taste and luxury have devised for their decoration to which we do not
find a prototype in the monuments of the eighteenth dynasty.”
Springs—metallic springs—have been found in them, and,
notwithstanding Wilkinson’s superficial investigation in that direction,
and description of these in his studies, we find proofs that such were
used to prevent the jolting in the chariots in their too rapid course.
The bas-reliefs show us certain melées and battles in which we can
find and trace their uses and customs to the smallest details. The
heavily-armed men fought in coats of mail, the infantry had quilted
tunics and felt helmets, with metallic coverings to protect them the
better. Muratori, the modern Italian inventor who, some ten years
ago, introduced his “impenetrable cuirasse,” has but followed in his
invention what he could make out of the ancient method which
suggested to him the idea. The process of rendering such objects as
card-board, felt, and other tissues, impenetrable to the cuts and
thrusts of any sharp weapon, is now numbered among the lost arts.
Muratori succeeded but imperfectly in preparing such felt cuirasses,
and, notwithstanding the boasted achievements of modern chemistry
he could derive from it no preparation adequate to effect his object,
and failed.
To what perfection chemistry had reached in ancient times, may
be inferred from a fact mentioned by Virey. In his dissertations, he
shows that Asclepiadotus, a general of Mithradates, reproduced
chemically the deleterious exhalations of the sacred grotto. These
vapors, like those of Cumæ, threw the Pythoness into the mantic
frenzy.
Egyptians used bows, double-edged swords and daggers,
javelins, spears, and pikes. The light troops were armed with darts
and slings; charioteers wielded maces and battle-axes; in siege-
operations they were perfect. “The assailants,” says the anonymous
writer, “advanced, forming a narrow and long line, the point being
protected by a triple-sided, impenetrable engine pushed before them
on a kind of roller, by an invisible squad of men. They had covered
underground passages with trap-doors, scaling ladders, and the art
of escalade and military strategy was carried by them to perfection....
The battering ram was familiar to them as other things; being such
experts in quarrying they knew how to set a mine to a wall and bring
it down.” The same writer remarks, that it is a great deal safer for us
to mention what the Egyptians did than what they did not know, for
every day brings some new discovery of their wonderful knowledge;
“and if,” he adds, “we were to find out that they used Armstrong
guns, this fact would not be much more astonishing than many of the
facts brought out to light already.”
The proof that they were proficient in mathematical sciences, lies
in the fact that those ancient mathematicians whom we honor as the
fathers of geometry went to Egypt to be instructed. Says Professor
Smyth, as quoted by Mr. Peebles, “the geometrical knowledge of the
pyramid-builders began where Euclid’s ended.” Before Greece came
into existence, the arts, with the Egyptians, were ripe and old. Land-
measuring, an art resting on geometry, the Egyptians certainly knew
well, as, according to the Bible, Joshua, after conquering the Holy
Land, had skill enough to divide it. And how could a people so skilled
in natural philosophy as the Egyptians were, not be proportionately
skilled in psychology and spiritual philosophy? The temple was the
nursery of the highest civilization, and it alone possessed that higher
knowledge of magic which was in itself the quintessence of natural
philosophy. The occult powers of nature were taught in the greatest
secresy and the most wonderful cures were performed during the
performing of the Mysteries. Herodotus acknowledges[796] that the
Greeks learned all they knew, including the sacred services of the
temple, from the Egyptians, and because of that, their principal
temples were consecrated to Egyptian divinities. Melampus, the
famous healer and soothsayer of Argos, had to use his medicines
“after the manner of the Egyptians,” from whom he had gained his
knowledge, whenever he desired his cure to be thoroughly effective.
He healed Iphiclus of his impotency and debility by the rust of iron,
according to the directions of Mantis, his magnetic sleeper, or oracle.
Sprengel gives many wonderful instances of such magical cures in
his History of Medicine (see p. 119).
Diodorus, in his work on the Egyptians (lib. i.), says that Isis has
deserved immortality, for all nations of the earth bear witness to the
power of this goddess to cure diseases by her influence. “This is
proved,” he says, “not by fable as among the Greeks, but by
authentic facts.” Galen records several remedial means which were
preserved in the healing wards of the temples. He mentions also a
universal medicine which in his time was called Isis.[797]
The doctrines of several Greek philosophers, who had been
instructed in Egypt, demonstrates their profound learning. Orpheus,
who, according to Artapanus, was a disciple of Moyses (Moses),[798]
Pythagoras, Herodotus, and Plato owe their philosophy to the same
temples in which the wise Solon was instructed by the priests.
“Antiklides relates,” says Pliny, “that the letters were invented in
Egypt by a person whose name was Menon, fifteen years before
Phoroneus the most ancient king of Greece.”[799] Jablonski proves
that the heliocentric system, as well as the earth’s sphericity, were
known by the priests of Egypt from immemorial ages. “This theory,”
he adds, “Pythagoras took from the Egyptians, who had it from the
Brachmans of India.”[800] Fénelon, the illustrious Archbishop of
Cambray, in his Lives of the Ancient Philosophers, credits
Pythagoras with this knowledge, and says that besides teaching his
disciples that as the earth was round there were antipodes, since it
was inhabited everywhere, the great mathematician was the first to
discover that the morning and evening star was the same. If we now
consider that Pythagoras lived in about the 16th Olympiad, over 700
years b.c., and taught this fact at such an early period, we must
believe that it was known by others before him. The works of
Aristotle, Laërtius, and several others in which Pythagoras is
mentioned, demonstrate that he had learned from the Egyptians
about the obliquity of the ecliptic, the starry composition of the milky
way, and the borrowed light of the moon.
Wilkinson, corroborated later by others, says that the Egyptians
divided time, knew the true length of the year, and the precession of
the equinoxes. By recording the rising and setting of the stars, they
understood the particular influences which proceed from the
positions and conjunctions of all heavenly bodies, and therefore their
priests, prophesying as accurately as our modern astronomers,
meteorological changes, could, en plus, astrologize through astral
motions. Though the sober and eloquent Cicero may be partially
right in his indignation against the exaggerations of the Babylonian
priests, who “assert that they have preserved upon monuments
observations extending back during an interval of 470,000
years,”[801] still, the period at which astronomy had arrived at its
perfection with the ancients is beyond the reach of modern
calculation.
A writer in one of our scientific journals observes “that every
science in its growth passes through three stages: First, we have the
stage of observation, when facts are collected and registered by
many minds in many places. Next, we have the stage of
generalization, when these carefully verified facts are arranged
methodically, generalized systematically, and classified logically, so
as to deduce and elucidate from them the laws that regulate their
rule and order. Lastly, we have the stage of prophecy, when these
laws are so applied that events can be predicted to occur with
unerring accuracy.” If several thousand years b.c., Chinese and
Chaldean astronomers predicted eclipses—the latter, whether by the
cycle of Saros, or other means, matters not—the fact remains the
same. They had reached the last and highest stage of astronomical
science—they prophesied. If they could, in the year 1722 b.c.,
delineate the zodiac with the exact positions of the planets at the
time of the autumnal equinox, and so unerringly as Professor
Mitchell, the astronomer, proved, then they knew the laws that
regulate “carefully-verified facts” to perfection, and applied them with
as much certainty as our modern astronomers. Moreover, astronomy
is said to be in our century “the only science which has thoroughly
reached the last stage ... other sciences are yet in various stages of
growth; electricity, in some branches, has reached the third stage,
but in many branches is still in its infantine period.”[802] This we
know, on the exasperating confessions of men of science
themselves, and we can entertain no doubt as to this sad reality in
the nineteenth century, as we belong ourselves to it. Not so in
relation to the men who lived in the days of the glory of Chaldæa,
Assyria, and Babylon. Of the stages they reached in other sciences
we know nothing, except that in astronomy they stood equal with us,
for they had also reached the third and last stage. In his lecture on
the Lost Arts, Wendell Phillips very artistically describes the
situation. “We seem to imagine,” says he, “that whether knowledge
will die with us or not, it certainly began with us.... We have a pitying
estimate, a tender pity for the narrowness, ignorance, and darkness
of the bygone ages.” To illustrate our own idea with the closing
sentence of the favorite lecturer, we may as well confess that we
undertook this chapter, which in one sense interrupts our narrative,
to inquire of our men of science, whether they are sure that they are
boasting “on the right line.”
Thus we read of a people, who, according to some learned
writers,[803] had just emerged from the bronze age into the
succeeding age of iron. “If Chaldea, Assyria, and Babylon presented
stupendous and venerable antiquities reaching far back into the night
of time, Persia was not without her wonders of a later date. The
pillared halls of Persepolis were filled with miracles of art—carvings,
sculptures, enamels, alabaster libraries, obelisks, sphinxes, colossal
bulls. Ecbatana, in Media, the cool summer retreat of the Persian
kings, was defended by seven encircling walls of hewn and polished
blocks, the interior ones in succession of increasing height, and of
different colors, in astrological accordance with the seven planets.
The palace was roofed with silver tiles; its beams were plated with
gold. At midnight, in its halls, the sun was rivalled by many a row of
naphtha cressets. A paradise, that luxury of the monarchs of the
East, was planted in the midst of the city. The Persian empire was
truly the garden of the world.... In Babylon there still remained its
walls, once more than sixty miles in compass and, after the ravages
of three centuries and three conquerors, still more than eighty feet in
height; there were still the ruins of the temple of the cloud-
encompassed Bel; on its top was planted the observatory wherein
the weird Chaldean astronomers had held nocturnal communion with
the stars; still there were vestiges of the two palaces with their
hanging gardens, in which were trees growing in mid-air, and the
wreck of the hydraulic machinery that had supplied them from the
river. Into the artificial lake, with its vast apparatus of aqueducts and
sluices, the melted snows of the Armenian mountains found their
way and were confined in their course through the city by the
embankments of the Euphrates. Most wonderful of all, perhaps, was
the tunnel under the river-bed.”[804] In his First Traces of Man in
Europe, Albrecht Müller proposes a name descriptive of the age in
which we live, and suggests that “the age of paper” is perhaps as
good as any that can be discussed. We do not agree with the
learned professor. Our firm opinion is, that succeeding generations
will term ours, at best, the age of brass; at worst, that of albata or of
oroide.
The thought of the present-day commentator and critic as to the
ancient learning, is limited to and runs round the exoterism of the
temples; his insight is either unwilling or unable to penetrate into the
solemn adyta of old, where the hierophant instructed the neophyte to
regard the public worship in its true light. No ancient sage would
have taught that man is the king of creation, and that the starry
heaven and our mother earth were created for his sake. He, who
doubts the assertion, may turn to the Magical and Philosophical
Precepts of Zoroaster, and find its corroboration in the following:[805]
“Direct not thy mind to the vast measures of the earth;

For the plant of truth is not upon ground.
Nor measure the measures of the sun, collecting rules,
For he is carried by the eternal will of the Father, not for your
sake,
Dismiss the impetuous course of the moon;
For she runs always by work of necessity.
The progression of the stars was not generated for your
sake.”
A rather strange teaching to come from those who are universally

believed to have worshipped the sun, and moon, and the starry host,
as gods. The sublime profundity of the Magian precepts being
beyond the reach of modern materialistic thought, the Chaldean
philosophers are accused, together with the ignorant masses, of
Sabianism and sun-worship.
There was a vast difference between the true worship taught to
those who showed themselves worthy, and the state religions. The
magians are accused of all kinds of superstition, but this is what a
Chaldean Oracle says:
“The wide aërial flight of birds is not true,

Nor the dissections of the entrails of victims; they are all mere
toys,
The basis of mercenary fraud; flee from these
If you would open the sacred paradise of piety
Where virtue, wisdom, and equity, are assembled.”[806]
Surely, it is not those who warn people against “mercenary fraud”

who can be accused of it; and if they accomplished acts which seem
miraculous, who can with fairness presume to deny that it was done
merely because they possessed a knowledge of natural philosophy
and psychological science to a degree unknown to our schools?
What did they not know? It is a well-demonstrated fact that the
true meridian was correctly ascertained before the first pyramid was
built. They had clocks and dials to measure time; their cubit was the
established unit of linear measure, being 1,707 feet of English
measure; according to Herodotus the unit of weight was also known;
as money, they had gold and silver rings valued by weight; they had
the decimal and duodecimal modes of calculation from the earliest
times, and were proficient in algebra. “How could they otherwise,”
says an unknown author, “bring into operation such immense
mechanical powers, if they had not thoroughly understood the
philosophy of what we term the mechanical powers?”
The art of making linen and fine fabrics is also proved to have
been one of their branches of knowledge, for the Bible speaks of it.
Joseph was presented by Pharaoh with a vesture of fine linen, a
golden chain, and many more things. The linen of Egypt was famous
throughout the world. The mummies are all wrapped in it and the
linen is beautifully preserved. Pliny speaks of a certain garment sent
600 years b. c., by King Amasis to Lindus, every single thread of
which was composed of 360 minor threads twisted together.
Herodotus gives us (book i.), in his account of Isis and the Mysteries
performed in her honor, an idea of the beauty and “admirable
softness of the linen worn by the priests.” The latter wore shoes
made of papyrus and garments of fine linen, because this goddess
first taught the use of it; and thus, besides being called Isiaci, or
priests of Isis, they were also known as Linigera, or the “linen-
wearing.” This linen was spun and dyed in those brilliant and
gorgeous colors, the secret of which is likewise now among the lost
arts. On the mummies we often find the most beautiful embroidery
and bead-work ornamenting their shirts; several of such can be seen
in the museum of Bulak (Cairo), and are unsurpassable in beauty;
the designs are exquisite, and the labor seems immense. The
elaborate and so much vaunted Gobelins tapestry, is but a gross
production when compared with some of the embroidery of the
ancient Egyptians. We have but to refer to Exodus to discover how
skilful was the workmanship of the Israelitish pupils of the Egyptians
upon their tabernacle and sacred ark. The sacerdotal vestments,
with their decorations of “pomegranates and golden bells,” and the
thummim, or jewelled breastplate of the high priest, are described by
Josephus as being of unparalleled beauty and of wonderful
workmanship; and yet we find beyond doubt that the Jews adopted
their rites and ceremonies, and even the special dress of their
Levites, from the Egyptians. Clemens Alexandrinus acknowledges it
very reluctantly, and so does Origen and other Fathers of the
Church, some of whom, as a matter of course, attribute the
coincidence to a clever trick of Satan in anticipation of events.
Proctor, the astronomer, says in one of his books, “The remarkable
breastplate worn by the Jewish high priest was derived directly from
the Egyptians.” The word thummim itself is evidently of Egyptian
origin, borrowed by Moses, like the rest; for further on the same
page, Mr. Proctor says that, “In the often-repeated picture of
judgment the deceased Egyptian is seen conducted by the god
Horus (?), while Anubis places on one of the balances a vase
supposed to contain his good actions, and in the other is the emblem
of truth, a representation of Thmèi, the goddess of truth, which was
also worn on the judicial breastplate.” Wilkinson, in his Manners and
Customs of the Ancient Egyptians, shows that the Hebrew thummim
is a plural form of the word Thmèi.[807]
All the ornamental arts seem to have been known to the
Egyptians. Their jewelry of gold, silver, and precious stones are
beautifully wrought; so was the cutting, polishing, and setting of them
executed by their lapidaries in the finest style. The finger-ring of an
Egyptian mummy—if we remember aright—was pronounced the
most artistic piece of jewelry in the London Exhibition of 1851. Their
imitation of precious stones in glass is far above anything done at
the present day; and the emerald may be said to have been imitated
to perfection.
In Pompeii, says Wendell Phillips, they discovered a room full of
glass; there was ground-glass, window-glass, cut-glass, and colored-
glass of every variety. Catholic priests who broke into China 200
years ago, were shown a glass, transparent and colorless, which
was filled with liquor made by the Chinese, and which appeared to
be colorless like water. “This liquor was poured into the glass, and
then looking through, it seemed to be filled with fishes. They turned it
out and repeated the experiment and again it was filled with fishes.”
In Rome they show a bit of glass, a transparent glass, which they
light up so as to show you that there is nothing concealed, but in the
centre of the glass is a drop of colored glass, perhaps as large as a
pea, mottled like a duck, and which even a miniature pencil could not
do more perfectly. “It is manifest that this drop of liquid glass must
have been poured, because there is no joint. This must have been
done by a greater heat than the annealing process, because that
process shows breaks.” In relation to their wonderful art of imitating
precious stones, the lecturer speaks of the “celebrated vase of the
Genoa Cathedral,” which was considered for long centuries “a solid
emerald.” “The Roman Catholic legend of it was that it was one of
the treasures that the Queen of Sheba gave to Solomon, and that it
was the identical cup out of which the Saviour drank at the Last
Supper.” Subsequently it was found not to be an emerald, but an
imitation; and when Napoleon brought it to Paris and gave it to the
Institute, the scientists were obliged to confess that it was not a
stone, and that they could not tell what it was.
Further, speaking of the skill of the ancients in metal works, the
same lecturer narrates that “when the English plundered the
Summer Palace of the Emperor of China, the European artists were
surprised at seeing the curiously-wrought metal vessels of every
kind, far exceeding all the boasted skill of the workmen of Europe.”
African tribes in the interior of the country gave travellers better
razors than they had. “George Thompson told me,” he adds, “he saw
a man in Calcutta throw a handful of floss silk into the air, and a
Hindu sever it into pieces with his sabre of native steel.” He
concludes by the apt remark that “the steel is the greatest triumph of
metallurgy, and metallurgy is the glory of chemistry.” So with the
ancient Egyptians and Semitic races. They dug gold and separated it
with the utmost skill. Copper, lead, and iron were found in
abundance near the Red Sea.
In a lecture delivered in 1873, on the Cave-Men of Devonshire, Mr.
W. Pengelly, F.R.S., stated on the authority of some Egyptologists
that the first iron used in Egypt was meteoric iron, as the earliest
mention of this metal is found in an Egyptian document, in which it is
called the “stone from heaven.” This would imply the idea that the
only iron which was in use in days of old was meteorite. This may
have been the case at the commencement of the period embraced in
our present geological explorations, but till we can compute with at
least approximate accuracy the age of our excavated relics, who can
tell but that we are making a blunder of possibly several hundred
thousand years? The injudiciousness of dogmatizing upon what the
ancient Chaldeans and Egyptians did not know about mining and
metallurgy is at least partially shown by the discoveries of Colonel
Howard Vyse. Moreover, many of such precious stones as are only
found at a great depth in mines are mentioned in Homer and the
Hebrew Scriptures. Have scientists ascertained the precise time
when mining-shafts were first sunk by mankind? According to Dr.
A. C. Hamlin, in India, the arts of the goldsmith and lapidary have
been practiced from an “unknown antiquity.” That the Egyptians
either knew from the remotest ages how to temper steel, or
possessed something still better and more perfect than the
implement necessary in our days for chiselling, is an alternative from
which the archæologists cannot escape. How else could they have
produced such artistic chiselling, or wrought such sculpture as they
did? The critics may take their choice of either; according to them,
steel tools of the most exquisite temper, or some other means of
cutting sienite, granite, and basalt; which, in the latter case, must be
added to the long catalogue of lost arts.
Professor Albrecht Müller says: “We may ascribe the introduction
of bronze manufacture into Europe to a great race immigrant from
Asia some 6,000 years ago, called Aryas or Aryans.... Civilization of
the East preceded that of the West by many centuries.... There are
many proofs that a considerable degree of culture existed at its very
beginning. Bronze was yet in use, but iron as well. Pottery was not
only shaped on the lathe, but burned a good red. Manufactures in
glass, gold, and silver, are found for the first time. In lonely mountain
places are yet found dross, and the remains of iron-furnaces.... To be
sure, this dross is sometimes ascribed to volcanic action, but it is
met with where volcanoes never could have existed.”
But it is in the process of preparing mummies that the skill of this
wonderful people is exemplified in the highest degree. None but
those who have made special study of the subject, can estimate the
amount of skill, patience, and knowledge exacted for the
accomplishment of this indestructible work, which occupied several
months. Both chemistry and surgery were called into requisition. The
mummies, if left in the dry climate of Egypt, seem to be practicably
imperishable; and even when removed after a repose of several
thousand years, show no signs of change. “The body,” says the
anonymous writer, “was filled with myrrh, cassia, and other gums,
and after that, saturated with natron.... Then followed the marvellous
swathing of the embalmed body, so artistically executed, that
professional modern bandagists are lost in admiration at its
excellency.” Says Dr. Grandville: “ ... there is not a single form of
bandage known to modern surgery, of which far better and cleverer
examples are not seen in the swathings of the Egyptian mummies.
The strips of linen are found without one single joint, extending to
1,000 yards in length.” Rossellini, in Kenrick’s Ancient Egypt, gives a
similar testimony to the wonderful variety and skill with which the
bandages have been applied and interlaced. There was not a
fracture in the human body that could not be repaired successfully by
the sacerdotal physician of those remote days.
Who but well remembers the excitement produced some twenty-
five years ago by the discovery of anæsthesia? The nitrous oxide
gas, sulphuric and chloric ether, chloroform, “laughing gas,” besides
various other combinations of these, were welcomed as so many
heavenly blessings to the suffering portion of humanity. Poor Dr.
Horace Wells, of Hartford, in 1844, was the discoverer, and Drs.
Morton and Jackson reaped the honors and benefits in 1846, as is
usual in such cases. The anæsthetics were proclaimed “the greatest
discovery ever made.” And, though the famous Letheon of Morton
and Jackson (a compound of sulphuric ether), the chloroform of Sir
James Y. Simpson, and the nitrous oxide gas, introduced by Colton,
in 1843, and by Dunham and Smith, were occasionally checked by
fatal cases, it still did not prevent these gentlemen from being
considered public benefactors. The patients successfully put to sleep
sometimes awoke no more; what matters that, so long as others
were relieved? Physicians assure us that accidents are now but
rarely apprehended. Perhaps it is because the beneficent anæsthetic
agents are so parsimoniously applied as to fail in their effects one-
half of the time, leaving the sufferer paralyzed for a few seconds in
his external movements, but feeling the pain as acutely as ever. On
the whole, however, chloroform and laughing gas are beneficent
discoveries. But, are they the first anæsthetics ever discovered,
strictly speaking? Dioscorides speaks of the stone of Memphis (lapis
Memphiticus), and describes it as a small pebble—round, polished,
and very sparkling. When ground into powder, and applied as an
ointment to that part of the body on which the surgeon was about to
operate, either with his scalpel or fire, it preserved that part, and only
that part from any pain of the operation. In the meantime, it was
perfectly harmless to the constitution of the patient, who retained his
consciousness throughout, in no way dangerous from its effects, and
acted so long as it was kept on the affected part. When taken in a
mixture of wine or water, all feeling of suffering was perfectly
deadened.[808] Pliny gives also a full description of it.[809]
From time immemorial, the Brahmans have had in their
possession secrets quite as valuable. The widow, bent on the self-
sacrifice of con-cremation, called Sahamaranya, has no dread of
suffering the least pain, for the fiercest flames will consume her,
without one pang of agony being experienced by her. The holy plants
which crown her brow, as she is conducted in ceremony to the
funeral pile; the sacred root culled at the midnight hour on the spot
where the Ganges and the Yumna mingle their waters; and the
process of anointing the body of the self-appointed victim with ghee
and sacred oils, after she has bathed in all her clothes and finery, are
so many magical anæsthetics. Supported by those she is going to
part with in body, she walks thrice around her fiery couch, and, after
bidding them farewell, is cast on the dead body of her husband, and
leaves this world without a single moment of suffering. “The semi-
fluid,” says a missionary writer, an eye-witness of several such
ceremonies—“the ghee, is poured upon the pile; it is instantly
inflamed, and the drugged widow dies quickly of suffocation before
the fire reaches her body.”[810]
No such thing, if the sacred ceremony is only conducted strictly
after the prescribed rites. The widows are never drugged in the
sense we are accustomed to understand the word. Only
precautionary measures are taken against a useless physical
martyrdom—the atrocious agony of burning. Her mind is as free and
clear as ever, and even more so. Firmly believing in the promises of
a future life, her whole mind is absorbed in the contemplation of the
approaching bliss—the beatitude of “freedom,” which she is about to
attain. She generally dies with the smile of heavenly rapture on her
countenance; and if some one is to suffer at the hour of retribution, it
is not the earnest devotee of her faith, but the crafty Brahmans who
know well enough that no such ferocious rite was ever
prescribed.[811] As to the victim, after having been consumed, she
becomes a sati—transcendent purity—and is canonized after death.
Egypt is the birthplace and the cradle of chemistry. Kenrick shows
the root of the word to be chemi or chem, which was the name of the
country (Psalms cv. 27). The chemistry of colors seems to have

ebook download Opportunities for Fluoropolymers: Synthesis, Characterization, Processing, Simulation and Recycling (Progress in Fluorine Science) 1st Edition Bruno Ameduri (Editor) - eBook PDF all chapter

Uploaded by

Copyright:

Available Formats

You might also like

ebook download Opportunities for Fluoropolymers: Synthesis, Characterization, Processing, Simulation and Recycling (Progress in Fluorine Science) 1st Edition Bruno Ameduri (Editor) - eBook PDF all chapter

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

ebook download Opportunities for Fluoropolymers: Synthesis, Characterization, Processing, Simulation and Recycling (Progress in Fluorine Science) 1st Edition Bruno Ameduri (Editor) - eBook PDF all chapter

Uploaded by

Copyright:

Available Formats

Opportunities for Fluoropolymers:

Fascinating Fluoropolymers and Their Applications 1st

Progress in Heterocyclic Chemistry Volume 29 1st

(eBook PDF) Translational Medicine in CNS Drug

Fluorine: A Paradoxical Element Volume 5 (Progress in

Recycling and Reusing of Engineering Materials:

Cardiology-An Integrated Approach (Human Organ Systems)

(eBook PDF) Science of Synthesis: Flow Chemistry in

Nanomaterial and Polymer Membranes. Synthesis,

Bruno Ameduri and Olga Boltalina

Copyright © 2020 Elsevier Inc. All rights reserved.

Library of Congress Cataloging-in-Publication Data

British Library Cataloguing-in-Publication Data

For information on all Elsevier publications

Publisher: Susan Dennis

Typeset by Thomson Digital

Gozde Aktas Eken

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

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

Opportunities for Fluoropolymers Copyright © 2020 Elsevier Inc.

2 Synthesis of perfluorocyclobutyl (pfcb) aromatic ether

2.2 Synthesis of multifunctional trifluorovinyl ether

is abysmal in starting materials containing electron withdrawing groups.

Alternatively by using intermediate TFVE-bearing monomer,

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

higher the electronegativity in the substituent group resulting in higher

demonstrating the feasibility of accessing polycyclic aromatic hydrocarbon

Scheme 1.6 TFVE-bearing hexaphenylbenzene 20 and preparation of fused ring hexa-

Like HBC, a new structural fluoropolymer, polynaphthalene-contain-

Scheme 1.8 Synthesis of representative terrylene dyes-bearing TFVE moieties 24 and

from parent dye (terrylene diimide), both showed unique photophysical

Scheme 1.9 Synthesis and transformation of fluorene-based bisphenols into PFCB-

While the photophysical properties were not extensively studied like

2.3 PFCB containing monomers for classical polymerization

Further, PFCB monomer was obtained by cyclodimerization and subse-

Scheme 1.11 Synthesis of triazine and benzocyclobutene containing PFCB linkage by

More recently, step-growth polymerization was carried out between

Another advantage with the presence of PFCB monomer units in

Scheme 1.12 Representative examples of PFCB-based radical monomer, 4-(4′-p-tol-

2.4 Postpolymerization modification on PFCB aryl ether

imparting hydrophilic properties and nanophase-separated morphologies

2.5 Characterization of TFVE monomers and PFCB aromatic

2.5.1 Infrared and Raman spectroscopy of TFVE monomers and PFCB

43 Tg = −11 °C (homopolymer) (DSC) [44]

Scheme 1.14 Chemical structures of PFCB-based polymers discussed in Table 1.1.

2.5.2 Carbon nuclear magnetic resonance (NMR) spectroscopy

“Direct not thy mind to the vast measures of the earth;

A rather strange teaching to come from those who are universally

“The wide aërial flight of birds is not true,

Surely, it is not those who warn people against “mercenary fraud”

You might also like