3  Fluorinated Polyimides: Synthesis, Properties,
and Applications
Anindita Ghosh, Ershad Ali Mistri, and Susanta Banerjee
Materials Science Centre, Indian Institute of Technology, Kharagpur, West Bengal, India
O U T L I N E
3.1 Introduction 97
3.2 Synthesis, Characterization, and Properties
of Polymers 98
3.2.1 One-Step Polymerization 98
3.2.2 Two-Step Polymerization 98
3.2.2.1 Thermal Imidization of Poly
(Amic Acid) 99
3.2.2.2 Chemical Imidization of Poly
(Amic Acid) 100
3.2.3 Fluorinated Polyimides 106
3.2.4 Fluorinated Poly(Ether Imide)s 107
3.2.5 Polyimide Block Copolymer Aerogels 125
3.2.6 Fluorinated Poly(Imide Sulfone)s 125
3.3 Fluorinated Polyimides for Membrane-Based
Applications125
3.3.1 Fluorinated Polyimides in Gas Separation 127
3.3.1.1 Gas Transport Mechanisms through
Membranes128
3.3.1.2 Terminology in Gas Transport 129
3.1 Introduction
In 1908, aromatic polyimides were first reported
by Bogert and Renshaw [1]. Aromatic polyimides
became well-known in 1950, after successful devel-
opment of two-step polyimide synthesis by DuPont [2].
This class of polymers possesses a number of out-
standing properties such as excellent thermal
stability, mechanical strength, and electrical proper-
ties that have led to application in several fields from
engineering thermoplastics to the aerospace and
electronics industries, as well as for fibers and adhe-
sives and in matrices for composite materials [3–5].
In addition, polyimides have high thermo-oxidative
stability and chemical- and solvent-resistive proper-
ties, leading to many membrane-based applications
Handbook of Specialty Fluorinated Polymers. http://dx.doi.org/10.1016/B978-0-323-35792-0.00003-9
Copyright © 2015 Elsevier Inc. All rights reserved.
3.3.1.3 Physical and Gas Transport
Properties of Fluorinated
Polyimides130
3.3.2 Fluorinated Polyimides in Pervaporation146
3.3.2.1 Principles of Separation 147
3.3.2.2 Mass Transport in Pervaporation
Membranes148
3.3.2.3 Physical and Pervaporation
Properties of Fluorinated
Polyimides149
3.3.3 Fluorinated Sulfonated Polyimides
as PEMs 152
3.3.3.1 Proton Conduction Mechanisms
in PEMs 154
3.3.3.2 Physical and PEM Properties of
Fluorinated Sulfonated
Copolyimides155
3.4 Summary 172
References173
such as pervaporation, fuel cell application, and gas
separation [6,7].
However, this class of polymers has the problems
of a high softening temperature and poor solubility in
different organic solvents, which prevent both melt
processing and solution processing routes. Several
approaches have been taken to overcome the poor
processability of this class of polymers. One suc-
cessful approach was executed by General Electric
with the introduction of flexible ether linkage (–O–)
[8,9] and isopropylidene [–C(CH3)2–] moiety [10,11]
into the polymer backbone, resulting in Ultem® 1000
[12] based on BPADA (bisphenol-A[diphthalic anhy-
dride]) and MPD(m-phenylene diamine). Ultem®
1000 has high thermal stability and good mechani-
cal properties. Researchers have investigated several
97
98 Handbook of Specialty Fluorinated Polymers

approaches to improving the processing of poly- 3.2.1  One-Step Polymerization

imides, such as adding bulky side groups/units to
In one-step polymerization, completely cyclized
the polymer backbone [13,14] or noncoplanar [15]
polyimides are obtained directly from their corre-
or alicyclic monomers [16] to the main chain. Incor-
sponding equimolar mixture of tetracarboxylic acid
poration of hexafluoroisopropylidene (–C[CF3]2–)
dianhydride and diamine in the presence of a high-
or pendant trifluoromethyl (–CF3) groups is of great
boiling tertiary amine (e.g., isoquinoline). Several
interest and increases the free volume of the poly-
high-boiling solvents are used, such as p-chlorophe-
imides, thereby improving various properties such as
nol, α-chloronaphthalene, m-cresol, nitrobenzene,
solubility, chemical resistivity, and gas permeabili-
o-dichlorobenzene, and dipolar aprotic amide sol-
ties without reducing thermal stability [17–19]. The
vents and their mixtures for direct conversion [22–
presence of these groups helps decrease crystallin-
24]. During the process of polymerization, water
ity, color, and water absorption and increases opti-
generated as a byproduct is continually removed by
cal transparency, environmental stability, and flame
azeotropic distillation. This method of direct polym-
resistance [20,21].
erization is usually used when the final polyimide is
All of these approaches to making processable
soluble in the polymerizing solvent. However, this
polyimides reduce several types of polymer inter-
method has enormous drawbacks such as the use of
chain interactions, chain packing, and charge transfer
carcinogenic solvents and a low polymerization con-
electronic polarization interactions or charge transfer
centration (usually less than 10% w/v), which ham-
complex (CTC) formation. The current chapter pres-
pers direct processing of the polyimides into the final
ents a comprehensive review focusing on –C(CF3)2–
products (e.g., films and fibers) from their polymer-
and –CF3-based aromatic polyimides that have been
ization solutions, and longer reaction times (typically
developed between 2000 and 2010, such as low
more than 18 h).
dielectric constant polymers, and well as membrane-
based applications such as pervaporation, fuel cell,
and gas separation.
3.2.2  Two-Step Polymerization
In two-step polymerization, initially the polyamic
3.2  Synthesis, Characterization, acid is formed from an equimolar mixture of dian-
and Properties of Polymers hydride and diamine in a polar aprotic solvent such
as N,N-dimethylacetamide (DMAc) or N,N-dimeth-
Polyimides are class of polymers generally ylformamide (DMF). The reaction pathway for the
prepared from organic diamines and organic tet- formation of poly(amic acid) involving intermediates
racarboxylic acid dianhydrides by condensation is presented in Scheme 3.2. The reaction mechanism
polymerization. There are mainly two synthetic involves nucleophilic attack of the amino group to
routes for polyimides: one-step and two-step polym- the electrophilic carbonyl carbon of the anhydride
erization. Scheme 3.1 shows a generalized route of group. This opens the anhydride ring to form an amic
polyimide synthesis from an aromatic dianhydride acid group. Formation of the poly(amic acid) is an
and an aromatic diamine. equilibration reaction in which the forward reaction

O O O O

NH OH
n O Ar O + nHN 2 Ar' NH2
HO
Ar
NH Ar'

O O O O
n
Polyamic acid intermediate
O O

-H2O
N Ar N Ar'

O O n

Scheme 3.1  Synthesis of polyimide.

3: Fluorinated Polyimides
O O
O + H2N O
O NH2
O
O imidization). Advantages of this method over one-
O
OH O and direct processing of soluble polyamic acids to
NH NH2
O
O
Scheme 3.2 Reaction pathway in poly(amic acid)
synthesis.
is thought to start with the formation of a CTC
between the dianhydride and the diamine [25]. Sus-
ceptibility of the nucleophilic attack increases with
an increase in the electrophilicity of the dianhydride
group. Thus, the reactivity of the dianhydride mono-
mer has been correlated to its electron affinity; higher
values indicate greater reactivity of the dianhydride
[26]. Electron affinity values for some dianhydrides
are listed in Table 3.1. Strong electron withdrawing
groups activate the anhydride toward a nucleophilic
attack on the anhydride carbonyl. Table 3.1 shows
that PMDA has the highest value of electron affin-
ity (1.90 eV) and BPADA has the minimum value
of 1.12 eV. On the other hand, the reactivity of the
diamine is related to its basicity.
The rate constants for imidization increase as the
pKa of the protonated amine increases. Highly basic
amines (e.g., aliphatic amines) may form salts dur-
ing the initial stages of the reaction, upsetting the
stoichiometry and preventing the formation of high
molecular weight. Solvent also have an important
role in the reaction. Highly polar aprotic solvents
used for this type of polymerization form strong
hydrogen bonds with the carboxyl group that help
shift the equilibrium to the forward side, that is, to the
amic acid side. The reaction rate is generally faster in
more basic solvents. Several other minor important
side reactions concomitantly proceed with the main
reaction. These side reactions may become signifi-
cant under certain conditions, particularly when the
main reaction is slow because of low monomer con-
centration and low monomer reactivity. The presence
of water in the reaction system causes lower-molec-
ular-weight development of poly(amic acid) owing
to the hydrolysis of the dianhydride moiety [27].
99
During this step, self-catalyzed cyclization to form
polyimides cannot occur because of the strong inter-
action between the amic acid and the basic solvent or
the larger acylation equilibrium constant [3,6].
In the second step, polyamic acid is cyclo-dehy-
drated at elevated temperatures (thermal imidization)
or in the presence of a cyclizing agent (chemical
step polymerization are the use of less toxic solvents
form the final polyimide products in the form of films
or fibers by thermal imidization. However, the storage
instability of polyamic acid intermediates and the con-
trol of thermal imidization are still important issues
[28]. A detail description of the thermal and chemical
imidization of poly(amic acid) is given below.
3.2.2.1  Thermal Imidization
of Poly(Amic Acid)
In general, conversion of poly(amic acid) to a
polyimide occurs through a bulk (or melt) imidization
technique [29–31]. Therefore, thermal imidization
is generally used in an industry in which poly(amic
acid) is heated to about ~200–300 °C for a given
amount of time to form the imide ring by removing
the solvent and water. At a higher temperature, irre-
versible cyclodehydration occurs, which leads to the
formation of high-molecular-weight polyimide. In
this method, the films of poly(amic acid)s are often
cast from polar aprotic solvents, such as N,N-dimeth-
ylformamide, N,N-dimethylacetamide, etc., followed
by drying and imidization. This method is suitable
for fabricating polyimides in the form of films, coat-
ings, and powders to allow the diffusion of byprod-
ucts and solvent without the formation of voids in the
final polyimide products. The problem of film crack-
ing as a result of shrinkage can be avoided by care-
fully controlling the curing profile. A typical heating
schedule involves a stage below 150 °C, followed by
a relative rapid rise in temperature to a second stage
above the Tg of the resulting polyimides. The cast
films are dried and gradually heated to 250–350 °C,
depending on the stability and Tg of the polyimides.
The maximum amount of solvent is slowly driven off
in the first stage and imidization occurs in the sec-
ond stage, in which curing and shrinkage are reli-
able [32]. At the initial stage of imidization, a small
amount of the poly(amic acid) undergoes a revers-
ible reaction with the anhydride and amine instead
of forming the imide ring, resulting in lower-molec-
ular-weight development [33,34]. Two pathways for
100 Handbook of Specialty Fluorinated Polymers

Table 3.1  Electron Affinity Values for Different Anhydrides

Electron Affinity
Dianhydride Structure Name of Dianhydride Values (eV)
O O
O O
O O BPADA 1.12

O H3C CH3 O

O O

O O BPDA 1.38

O O

2 2 2

2 2 BTDA 1.55

2 2

O O O O
S
O O DSDA 1.57

O O

O O
O O
O O HQDA 1.19

O O

O O
O
O O ODPA 1.30

O O

O O

O O PMDA 1.90

O O

Data taken from Ref. [26].

imidization are possible during thermal imidization
and are shown in Scheme 3.3 [35].
3.2.2.2  Chemical Imidization
of Poly(Amic Acid)
Poly(amic acid)s can also be chemically imidized.
This is accomplished by using chemical dehydrat-
ing agents combined with basic catalysts [36].
Various reagents have been employed, including
acetic anhydride, propionic anhydride, and n-butyric
anhydride as dehydrating agents, and pyridine, tri-
ethylamine, and isoquinoline as basic catalysts. A
reaction pathway for chemical imidization is shown
in Scheme 3.4.
Polyimides bearing pendant (–CF3) groups are
greatly interesting to materials/polymer chemists
because the presence of a bulky –CF3 group in the poly-
imide structure causes remarkable improvements in
3: Fluorinated Polyimides 101

O
O HO
OH OH
OH
NH N
NH

O O O

Path one - H2O

O O O

OH -H O OH

NH NH N

O O O

O HO OH HO O
- H2O H
N N N

O O O

Path two

Scheme 3.3  Two possible pathways in thermal imidization.

various properties compared with their non-fluorinated
analogues [37]. The incorporation of fluorene affects
different properties of the polymers, such as an
increase in free volume, which decreases the dielec-
tric constant by reducing the number of polarizable
groups in a unit volume. The increase in free vol-
ume can be attributed to the larger size of fluorene
atoms relative to hydrogen atoms, which interferes
with efficient chain packing. In addition, the signifi-
cant mutual repulsion of fluorene atoms on different
chains may influence free volume. Furthermore, elec-
tronic polarization is always lowered with fluorene
substitution because of the smaller electronic polar-
izability of the C–F bond relative to C–H. In cases
where fluorene is positioned non-symmetrically, an
increase in the dipole moment is realized. This could
lead to a substantial increase in dipole orientation
polarizability at low frequencies, thereby increasing
the low-frequency dielectric constant [38].
The combination of electronic and steric effects
reduces interchain interactions; in particular, steric
congestion hinders the formation of CTCs [28]. The
C–F bond is a high-energy bond, so polyimides con-
taining fluorene are in general polymers with high Tg
and exhibits high thermo-oxidative stability. More-
over, greater fluorene content improves flame retar-
dant properties and increases the hydrophobicity of
the polymer. Low water uptake results in a decrease
in the bulk dielectric constant at higher frequencies.
Thus, fluorinated polyimides are an attractive class
of materials for various applications such as in high-
performance structural resins, coatings and films that
are thermally stable, gas separation membranes, opti-
cal waveguides, and other electronic and optoelec-
tronic applications [39–41].
Fluorinated polyimides are interesting for optical
applications because they have good optical transpar-
ency. The optical transparency of polyimide films is
significant in some applications such as liquid crys-
tal display devices and optical half-wave plates for
planar light wave circuits. However, most polyimides
have strong absorption between ultraviolet (UV) and
102
O O
H3C C O C CH3 + NR 3
O O
OH
NH + NR3
O O
O O
- CH3COOH
N
O
Scheme 3.4  Reaction pathway in chemical imidization.
the visible range, which renders their color close to
yellow or brown. The reduction of color from brown-
ish or yellowish to a light color with enhanced trans-
parency might be attributed to incorporation of the
–CF3 groups, which in turn decreases intermolecular
interactions and reduces chain packing.
The bulky and electron-withdrawing –CF3 group
in the diamine monomer is effective in decreasing
CTC formation between polymer chains through ste-
ric hindrance and the inductive effect (by decreasing
the electron-donating property of diamine moieties).
It reduces the intermolecular CTC between alternat-
ing electron donor (diamine) and electron acceptor
(dianhydride) moieties. In general, fluorinated poly-
imides exhibit lighter color and greater transparency
than non-fluorinated analogues [42].
All of the newly developed fluorinated diamines
and dianhydrides were targeted to prepare processable
aromatic polyimides possessing many useful proper-
ties, such as high Tg, excellent dimensional stability,
low dielectric constants, and outstanding thermal and
thermo-oxidative stabilities. The combination of these
properties leads the polyimides to be widely used as
interlayer dielectrics, flexible circuitry substrates,
Handbook of Specialty Fluorinated Polymers
O O
H3C C O + H3C C NR 3
O
O O
ONHR3 H3C C NR 3 O C CH3
NH NH
O
O
O C CH3 O
O
O C CH3
NH
O
O
NH
- CH3COOH
NH
stress buffers, and passivation layers. Between 2000
and 2010 there have been several research publications
on low dielectric constant materials [43]. Currently
there is enormous demand for new inter-metal dielec-
tric layers (IMD) with lower dielectric constants to
reduce signal delay and drive voltage and power con-
sumption for high-powered integrated circuits (ICs).
Silicon dioxide (SiO2), which is mostly used as an IMD
material, has a dielectric constant (ε) of about ~4.0. It
is expected that the new generation of insulating poly-
meric film materials should have dielectric constants
of about ~3, and it is expected that future devices may
require materials with even lower dielectric constants
approaching 2.0 or below. Until then, there are a lim-
ited number of materials with dielectric constants less
than 3.0. The limitation in materials arises owing to
the stringent IC processing conditions such as ther-
mal stability, chemical resistance, mechanical stabil-
ity, and ease of use for the ultimate construction of
novel molecular devices possessing extraordinary
low dielectric properties. Several high-performance
polymers, such as poly(arylene ether)s, polyimides,
aramids, and polyesters, have been exploited in vari-
ous electronic devices and components. Among these
3: Fluorinated Polyimides
polymers, polyimide seems to be superior as an ILD
material in electronic devices such as ICs because
of their high thermal stability, ease of processing,
low water uptake, low coefficient of thermal expan-
sion, low dielectric constant, high resistivity, and high
breakdown voltage [44]. In electronic packaging, low
dielectric materials reduce cross-talk and maximize
signal propagation speed in devices. Commercially
available polyimides such as Kapton, which is made
from pyromellitic dianhydride/oxydianiline (PMDA/
ODA), have a dielectric constant of 3.2 at 1 MHz.
Hence, research is focused on developing polyimides
with increasingly lower dielectric constants [45].
Accordingly, a number of fluorinated polyimides have
been synthesized and the structure–property relation-
ships of fluorene-containing polyimides have been
studied; the results have been reported in several pub-
lications and patents.
Among various strategies that have been used to
synthesize polyimides with lower dielectric con-
stants, the most common approach is to incorpo-
rate fluorene, in the form of trifluoromethyl groups,
into diamine and dianhydride units that minimize
polarizability and increase the free volume [46]. It
is well-known that fluorene atom has unique char-
acteristics such as high electronegativity and low
electric polarity. These properties give fluorinated
polymers (e.g., poly[tetrafluoroethylene]) attrac-
tive features such as low water uptake, water and
oil repellency, low permittivity, low refractive indi-
ces, resistance to wear and abrasion, and thermal
and chemical stability. Fluorination is also known
to enhance solubility and optical transparency and
to lower the moisture absorption of polyimides.
Therefore, it is expected that fluorinated poly-
imides will be widely applied in the electro-optical
and semiconductor industries. The polymer series
studied was essentially limited mainly to 6F dian-
hydride because it proved to be the only dianhy-
dride with which many of the fluorinated diamines
would form polymer films suitable for physical
characterization.
Studies [41,47] have demonstrated that poly-
imides derived from ether-bridged aromatic diamines
with –CF3 groups are soluble, high-temperature
polymer materials with low moisture absorption,
low dielectric constant, high optical transparency,
and low birefringence. The effect of fluorene sub-
stitution on the dielectric constant of polyimides has
been demonstrated for a broad spectrum of fluorene-
containing diamine structures (Table 3.2). The
103
presence of bulky –CF3 groups might be partly
responsible for reducing the dielectric constant,
which results in an increase in the free volume and
reduces interchain packing. In addition, the strong
electronegativity of fluorene results in low polariz-
ability of the C–F bonds, thus decreasing the dielec-
tric constant. The introduction of a –CF3 group leads
to a decrease in dielectric constant but the strong
electron-withdrawing ability of –CF3 could reduce
the reactivity of the monomer, leading to a low-
molar-mass polymer. The presence of a –CF3 group
located at the ortho-position of the amine group fur-
ther reduces the reactivity of the amines as a result
of steric hindrance. Dielectric constants are influ-
enced primarily by polarizability. The polarizability
of a polymer can be altered by the free volume and
fluorene content. An increase in free volume lowers
the polarization by decreasing the number of polariz-
able groups per unit volume. Fluorination increases
the free volume, lowers the electronic polarization,
and can either increase dipole polarization when the
fluorination is asymmetric or have no effect on dipole
polarization when the fluorination is symmetric.
Fluorine substitution generally substantially
reduced the dielectric constant in cases with sym-
metric substitution. It was estimated that around
50% of the observed decreasing trend in the dielec-
tric constant versus the percentage of fluorene can be
attributed to a reduction in absorbed moisture as the
result of an increase in hydrophobicity. The remain-
ing 50% can be apportioned, on average, between
the increased free volume (approximately 25%) and
reduced total polarizability (approximately 25%).
Little effect of fluorene substitution on dynamic ther-
mal or thermo-oxidative stability was observed for a
series of fluorinated polyimides [48]. Low dielectric
constant polyimides and low water absorption poly-
imides were reported by several researchers [49–51].
The correlation between a high free volume and
dielectric constant in polyimides has been previously
reported in the literature [52].
Free volume fractions were quantified by posi-
tron lifetime spectroscopy and group additive meth-
ods. The introduction of free volume to a polymer
decreases the number of polarizable groups per unit
volume, resulting in lower values for εatomic and
εdipolar. To reduce chain packing in polyimides, incor-
poration of pendant groups, flexible bridging units,
and bulky groups all have been used to increase the
free volume, and the effect of free volume on dielec-
tric constant has been examined as well. Fluorine
Table 3.2  Molecular Structures of Fluorinated Diamines
Serial No. Structure Reference
3-1 H2N CH2 CF2 CH2 NH2 [58]
n

3-2 CF3 [59]

H2N NH2
CF3

3-3 NH2 NH2 [60]

CF3

3-4 H2N NH2 [61]

C
O O(CH2)2C6F13

3-5 F [62]
H2N NH2

F CF3
F

3-6 F [63]
F
N

H2N NH2
F

3-7 H2N N NH2 [63]

F F
NH2

3-8 H2N N NH2 [63]

F F
Cl

3-9 H2N N NH2 [63]

F F
H

3-10 H3C CH3 [64]

CF3
H2N NH2

H3C CH3

F F
F
3: Fluorinated Polyimides
substitution is an important aspect in determining
an increase or decrease in dielectric constant value.
Symmetric substitution of fluorene does not increase
the dielectric constant because the net dipole moment
of the polymer does not increase. Symmetric fluo-
rene substitution leads to a lower dielectric constant,
which can be attributed to lower electronic polariz-
ability and larger free volume. In the literature, sym-
metric and non-symmetric fluorinated groups were
used to examine the influence of fluorene content on
dielectric constant [53,54].
Polymer optical waveguides are attractive as more
economical and practical optoelectronic devices and
as interconnections in optical communication sys-
tems. The polymers have been used to fabricate wave-
guides for light-wave circuits, including directional
couplers and thermo-optic switches. Several poly-
mers, such as deuterated and fluorinated poly(methyl
methacrylate), polystyrene, poly(organosiloxane),
polyimide, an acrylate photopolymerizable monomer
system, epoxy resin, cross-linked acrylate polymer,
and benzocyclobutene, have been used as waveguide
materials. One important factor for such waveguides
is that the material should be of high thermal stability
for compatibility with high-performance electronic
device fabrication processes; fluorinated polyimides
are a preferred candidate with high thermal stabil-
ity. Optical loss in polymers at near-infrared (IR)
wavelengths occurs as a result of adsorption from
vibrational overtones of the C–H bond, which can
be overcome by substituting hydrogen atoms with
chlorine or fluorene. The rigid structure of polyimide
films makes them frequently highly birefringent (the
difference in refractive index between in-plane and
out-of-plane). Different polarized lights would travel
at different speeds through these highly birefringent
materials. Thus, the signals become complicated
and cause polarization-dependent waveguide loss.
Accordingly, for waveguide applications, low bire-
fringence materials are essential. Refractive indices
or birefringence in polymers are affected by several
factors, including chain rigidity, linearity, geometry
of the repeat unit, polarizability, and orientation of
the bonds.
Electronic transition causes absorption in the UV
and visible regions. On the other hand, stretching
vibration of the chemical bonds causes absorption in
the near-IR region. C–H and O–H bond are strongly
affected by absorption in the near-IR region. Poly-
mer used in optical devices should have low absorp-
tion in optical communication wavelengths (1.3 and
105
1.55 μm). Absorption resulting from the C–H bond
can be diminished by replacing hydrogen with heavier
atoms such as fluorene [55]. Therefore, the higher the
number of C–F bond is, lower is the absorption in the
near-IR region. The hydrophobic nature of fluorene
helps to decrease water absorption in fluorinated poly-
mers. Low water absorption is an important criterion
for a low-loss optical waveguide. Absorbed water can
cause absorption loss at optical communication wave-
lengths owing to O–H absorption and can change
the refractive index. Kwansoo Han [56] reported
some fluorinated polyimides for optical waveguide
application. These polyimides were prepared by the
reaction of 2,2-bis(3,4-dicarboxyphenyl) hexafluoro-
propane dianhydride (6FDA) with 1,4-bis-(4-amino-2-
trifluoromethyl-phenoxy)tetrafluorobenzene (ATPT),
1,4-bis-(4-amino-2- trifluoromethyl-phenoxy)benzene
(ATPB), and 1,3–bis-(4-amino-2-trifluoromethyl-
phenoxy) 4,6-dichlorobenzene (ATPD), respectively
(Scheme 3.5). These polyimides had glass transition
temperatures in the range 260–280 °C, low water
absorption (<0.4%), low optical loss (>0.2 dB/cm)
at 1.3 and 1.55 μm, and birefringence values in the
range 0.0041–0.0066. He et al. [57] prepared fluori-
nated polyimides containing nonlinear optical (NLO)
chromophores in the side chain using the Mitsunobu
reaction (Scheme 3.6). A flexibilizing ether group
and –CF3 groups were introduced into the polyimide
backbone to increase the solubility and processabil-
ity of NLO polyimides with retention of high Tg and
thermal stability. Polyimides P1 and P2 containing
hetaryl azo chromophores with large hyperpolariz-
ability achieved a high electro-optic coefficient (as
high as 18 pm/V at 1.55 mm), which was larger than
that of polyimide P3 attached Disperse Red 1(DR1).
The polymers possessed high Tg (193–200 °C) with
thermal stability up to 290 °C, indicating the high
O F3C CF3 O F3C
N N O Ar O
n
O O CF3
F F
Ar =
F F Cl Cl
Scheme 3.5 Representative structures of fluori-
nated polyimides for optical waveguide application.
Taken from Ref. [56].
106 Handbook of Specialty Fluorinated Polymers

O O O O
CH3 CF3
CF3 CF3
O O
N N N N
CH3 CF3
CF3 CF3
O HO OH HO OH
O O
n
m

THF
NLO chromophore Ph3P
DEAD

O O O O
CH3 CF3
CF3 CF3
O O
N N N N
CH3 CF3
O CF3 O O CF3 O
O O O O

m n

Where m:n =1:1

NLO chromophore

N CH2CH3
N N N P1
O2N S
CH2CH2

O2N CH2CH3
S
N N N P2
N
CH2CH2

CH2CH3
O2N N N N P3
CH2CH2

Scheme 3.6 Fluorinated polyimides for optical waveguide application for electro-optical device fabrication.
Reproduced with permission from Ref. [57].

temporal stability of the NLO effect. Low optical loss
(1.8–2.1 dB/cm at 1.55 mm) was obtained for these
polymers.
3.2.3  Fluorinated Polyimides
Between 2000 and 2010 a library of diamine struc-
tures to prepared fluorinated polyimides has been
identified and prepared by several researchers. Some
of the structures [58–63] are listed in Table 3.2. Ishida
et al. prepared fluorinated diamine (3-1 in Table 3.2),
namely, [58] α,ω-dianiline-polyfluoroalkane in high
yield and in a lesser reaction time to be used as precur-
sors for highly fluorinated benzoxazines. Oishi et al.
prepared fluorene-containing alicyclic polyimides
from fluorene-containing alicyclic diamine (3-2 in
Table 3.2), namely, 4,4′-hexafluoroisopropylidene
bis(cyclohexylamine) [59] with a high Tg of 271 °C
and with a low refractive index of 1.50 with 6FDA
as a dianhydride in the polymer backbone. Yang
et al. [60] prepared pyridine containing fluorinated
diamine, namely, 4-(3′-trifluoromethylphenyl)-2,6-
3: Fluorinated Polyimides
bis(3′-aminophenyl)pyridine (3-3 in Table 3.2) and
studied the thermal, mechanical, and dielectric prop-
erties of the polyimides. Kim et al. [61] incorporated
fluorinated alkyl side groups in the diamine structure
(3-4) for the preparation of polyimides and studied
the gas permeation properties and compared the
results with polyimides without fluorinated alkyl
side groups. Incorporation of fluorinated side groups
into the polyimide membranes decreased their sur-
face free energies (Tgs) and solubility parameters
and increased the fractional free volume (FFV),
therefore enhancing permeability for CO2, O2,
N2, and CH4 gases but reducing the selectivity for
CO2–CH4, O2–N2, and CO2–N2 gas pairs depend-
ing on the structure of the dianhydride monomers
(6FDA, ODPA, BTDA, and PMDA) used for the
study. Malykhin et al. [62] developed highly fluo-
rinated aromatic polyimides based on hexafluoro-
2,4-toluenediamine (3-5 in Table 3.2) that had good
solubility in organic solvents, including in chloro-
form, with high Tgs (330–345 °C) and thermal and
thermo-oxidative stability (Td,5 >500 °C), which
they attributed to the presence of a –CF3 group and
fluorene atoms in the meta-linked phenylenedi-
amine fragment. Malykhin’s groups developed new
fluorinated pyridylenediamines (3-6 to 3-9 in Table
3.2) [63] with the aim of tuning polyimide proper-
ties. However, the Tg values and thermo-oxidative
stability were similar to the results reported in their
previous work. Zhao et al. [64] prepared fluorinated
polyimides containing both –CF3 and fluorene in
the diamine structure (3-10 in Table 3.2) with the
aim of imparting good optical and dielectric proper-
ties. The 6FDA containing polyimide had a Tg value
of 365 °C and a Td,5% of 484 °C in a nitrogen atmo-
sphere with birefringence as low as 0.0099 and a
dielectric constant value of 2.50.
Swager et al. [65] reported fluorinated polyimides
with triptycene moiety. The extremely low dielec-
tric constant of 1.42 at optical frequencies of the
fluorinated polyimide was attributed to the increase
in nanoporosity as a result of the larger triptycene
O O
CF3
N N
CF3
O O
n n
Scheme 3.7  Triptycene-based fluorinated polyimides.
107
moiety in combination with bulky bridged hexafluo-
roisopropylidene moieties in the main chain.
Furthermore, Swager et al. prepared triptycene
containing other fluorinated polyimides [66] with
a fused naphthale ring that had high solubility not
only in polar aprotic solvents but also in low-boiling
solvents such as THF, CHCl3, CH2Cl2, and acetone.
The Tg was higher than 450 °C and the Td,10% was
recorded at 540 °C in a nitrogen atmosphere. The
structures of triptycene-based fluorinated polyimides
are shown in Scheme 3.7.
3.2.4  Fluorinated Poly
(Ether Imide)s
The successful commercialization of Kapton®
by Du Pont was a breakthrough in the polyimide
world. The PMDA-ODA–based polyimide exhib-
ited a high glass transition temperature (Tg approx-
imately 390  °C) and high mechanical strength
(tensile strength [TS], 158 MPa; and tensile modu-
lus, 3.2 GPa), and accordingly found widespread
application as an electrical insulating material, for
example, interlayer dielectrics/intermetal dielec-
trics (ILD/IMD) [67]. However, in its fully imidized
form, the insolubility and infusibility of Kapton® led
to processing difficulties. In general, it is processed
by poly(amic acid) precursors and then converted to
polyimide via rigorous thermal treatment. However,
this method has several limitations, such as the poor
shelf life of poly(amic acid) and the emission of vola-
tile byproducts such as water during imidization.
Accordingly, several approaches have been under-
taken by different researchers to increase polyimide
processability. Incorporation of flexible linkages,
bulky side groups/units in the polymer backbone, and
noncoplanar or alicyclic monomers in the main chain
have been investigated. Hougham reported a number
of fluorinated diamines and dianhydrides in his review
in 1999 [37]. Polyimides containing flexible spacers
have gained significant importance in polyimide pro-
cessing. Some polyimides containing oligoethylene
O CF3 O
N N
CF3
O O
108
glycol moiety have been presented as processable
polyimides with potential application as thermally
stable adhesives and thermoplastics [68,69]. Other
examples of important bridging linkages are –O–,
C]O, –S–, –SO2–, –C(CH3)2–, –CH2–, –CHOH–,
and –C(CF3)2 [49–51,70,71]. The presence of fluo-
rene and/or –CF3 groups in polyimide considerably
improves solubility.
Banerjee’s group prepared unsymmetrical diamine
[11] (3-11 in Table 3.3) to improve the solubility of
polyimides by disrupting chain packing. In general,
polyimides synthesized using different commercial
dianhydrides had a high Tg in the range 252–283 °C
with thermal stability as high as 532 °C at Td,5%.
Banerjee et al. prepared several fluorinated diamines
of wholly aromatic structures [20,47] (3-12, 3-13,
and 3-14 in Table 3.3). Banerjee et al. [72] also
introduced heterocyclic moieties such as pyridine or
thiophene units in the main chain (3-15 and 3-16 in
Table 3.3) and studied the thermal, mechanical, and
dielectric properties of polyimides. Banerjee et al.
[73] designed three diamine monomers (3-17, 3-18,
and 3-19 in Table 3.3) by combining a flexible com-
ponent to allow better solubility and a rigid biphenyl
unit to obtain high Tg in the resulting polyimides. The
Tg of the polyimides was in the range 228–309 °C
and thermal stability was observed in the range 468–
516 °C in an air atmosphere at Td,5%.
Banerjee et al. also prepared several diamine
monomers [74–76] (3-20, 3-21, 3-22 in Table 3.3)
with high FFV that were used for gas separation, and
studied properties such as gas permeation and gas
selectivities for several gas pairs. Banerjee et al. pre-
pared high-Tg polymers by incorporating imido aryl
[77] moiety (3-23 in Table 3.3) and further studied
the gas separation properties. A fluorinated diamine
monomer with anthracene moiety [78] (3-24 in
Table 3.3) was also synthesized by Banerjee et al.;
the resulting polymers had high Tg values in the
range 256–330 °C.
Hsiao et al. [79] prepared an asymmetric diamine
monomer (3-25 in Table 3.3) containing flexible ether
linkages, bulky –CF3 substituents, and rigid naphtha-
lene units. The bulky, rigid units in the polymer main
chain had high Tg values in the range 236–268 °C and
improved solubility because of the decreased packing
density. Ma et al. [80] introduced a pyridine-based
fluorinated diamine monomer (3-26 in Table 3.3) to
improve solubility, which the authors attributed to the
bulky –CF3 groups and to the polarizability of nitrogen
atoms present in the pyridine moiety. Wang et al. [81]
Handbook of Specialty Fluorinated Polymers
introduced both –CF3 and methyl groups at the ortho-
position of the ether linkage leading to a kink conco-
planar structure (3-27 in Table 3.3) to impart several
desirable properties in the polyimides, such as good
solubility, high optical transparency, and low dielec-
tric constants. Liu et al. [82] prepared a diamine
monomer with three –CF3 groups (3-28 in Table 3.3).
The resulting polyimides contained a laterally
attached, noncoplanar unit of diamine that sterically
disrupted chain packing and inhibited significant
chain–chain interactions. The fluorinated polyimides
had a shorter cutoff wavelength and high optical
transparency of 85–95%. Yang et al. [83] synthesized
an unsymmetrical diamine monomer with an ether-
ketone group and –CF3 group to form a bent structure
(3-29 in Table 3.3) in the resulting polyimides. The
unsymmetrical diamine structure together with the –
CF3 group improved the solubility of the polyimides.
In addition, the presence of –CF3 groups inhibited
the absorption of moisture. The polyimides had low
moisture absorption in the range 0.41–0.67%. Jiang
et al. [84] prepared unsymmetrical and noncoplanar
diamine containing –CF3 and methyl groups at the
ortho-position of the flexible ether linkage (3-30 in
Table 3.3). The diamine monomer also contained an
additional ketone moiety in the structure. The authors
showed that the electron-withdrawing –CF3 group
and ketone moiety reduced CTC formation between
polymer chains by decreasing the electron-donating
behavior of the diamine monomer. The presence of
–CF3 and methyl groups at the ortho-position of the
ether linkage hindered C–O–C bond rotation, leading
to a noncoplanar conformation that lowered the cut-
off wavelength and enhanced optical transparency in
the resulting polyimides. The cutoff wavelength was
in the range 343–372 nm and optical transparency at
the wavelength of 450 nm was in the range 80–87%
in the polyimides.
Jang et al. [85] prepared a highly kinked diamine
(3-31 in Table 3.3), a fluorinated diamine (3-32 in
Table 3.3), and a biphenyl based-fluorinated diamine
(3-33 in Table 3.3) and studied the color intensity
and optical properties of the synthesized polyimides.
Introduction of kink structures disrupted effective
CTC formation, leading to colorless polyimide films
with high transmittance. Wang et al. [86] developed
meta-diamine, namely 4,4′-bis(3-amino-5-trifluoro-
methylphenoxy) biphenyl (3-34 in Table 3.3), with
the aim of improving the melt processability and sol-
ubility of the polyimides. Shao et al. [87] designed
a –CF3-substituted unsymmetrical diamine (3-35
3: Fluorinated Polyimides 109

Table 3.3  Chemical Structures of Fluorinated Diamines with Flexible Ether Linkages
Serial No. Structure Reference
3-11 [11]
H2N O NH2

CF3

3-12 CF3 [20]

H2N O O NH2

F3C

3-13 CF3 [20]

H2N O O NH2

F3C

3-14 CF3 [47]

H2N O O NH2

F3C

3-15 CF3 [72]

H2N O O NH2
N

F3C

3-16 CF3 [72]

H2N O O NH2
S
F3C

3-17 F3C [73]

CH3
H2N O C O NH2
CH3
CF3

3-18 F3C [73]

CF3
H2N O C O NH2
CF3
CF3

3-19 [73]

F3C

H2N O O NH2

CF3

3-20 O [74]

N
F3C

H2N O O NH2

CF3

Continued
110 Handbook of Specialty Fluorinated Polymers

Table 3.3  Chemical Structures of Fluorinated Diamines with Flexible Ether Linkages—cont’d

Serial No. Structure Reference

3-21 F3C [75]

CH3
H2N O O NH2

CF3 H3C CH3

3-22 H3C
CH3 [76]
F3C
H2N O
O NH2
CF3
H3C CH3

3-23 F3C
[77]

H2N O O NH2

CF3
O O
N

3-24 F3C
[78]

H2N O O NH2

CF3

3-25 CF3 F3C [79]

H2N O O NH2

3-26 CF3 F3C [80]

N
H2N O O NH2

3-27 CF3 H3C [81]

O
H2N O C NH2

H3C

3-28 CF3 F3C [82]

H2N O O NH2

CF3
3: Fluorinated Polyimides 111

Table 3.3  Chemical Structures of Fluorinated Diamines with Flexible Ether Linkages—cont’d

Serial No. Structure Reference

3-29 F3C [83]

O
C O NH2
H2N

3-30 CF3 [84]

O
H2N O C NH2

H3C

3-31 CF3 F3C [85]

H2N O O O NH2

3-32 CF3 F3C [85]

CF3
H2N O O NH2
CF3

3-33 CF3 F3C [85]

H2N O O NH2

3-34 [86]
H2N O O NH2

CF3 CF3

3-35 CF3 [87]

H2N O O NH2

3-36 F3C [88]

O NH2
H2N O

CF3

3-37 F3C [88]

O NH2
H2N O

CF3

3-38 F3C [89]

H2N O O NH2

CF3

Continued
112 Handbook of Specialty Fluorinated Polymers

Table 3.3  Chemical Structures of Fluorinated Diamines with Flexible Ether Linkages—cont’d

Serial No. Structure Reference

3-39 F3C [90]

H2N O O NH2

CF3

3-40 H3C CH3 F3C [91]

H2N O O NH2

CF3 H3C CH3

3-41 F3C [92]

H2N O O NH2

CF3
H3C CH3

3-42 F3C [93]

H2N O O NH2

CF3
F3C CF3

3-43 F3C [94]

H2N O O NH2

CF3

3-44 O [95]
H2N NH2

O O
CF3 CF3

3-45 H2N [96]

F3C N N CF3

NH2

3-46 H2N [97]

O CF3

F3C O

NH2
3: Fluorinated Polyimides 113

Table 3.3  Chemical Structures of Fluorinated Diamines with Flexible Ether Linkages—cont’d

Serial No. Structure Reference

3-47 CF3 F3C [98]

H2N O O NH2

N NH

3-48 O [99]
H2N O P O NH2

F3C CF3

3-49 CF3 [100]

H2N O O O NH2

F3C

3-50 F F [101]

H2N O NH2

F F

3-51 F3C [102]

H2N O O NH2

CF3

Continued
114
Table 3.3  Chemical Structures of Fluorinated Diamines with Flexible Ether Linkages—cont’d
Serial No. Structure
3-52
O
F3C NH2
in Table 3.3) to enhance solubility. The good solu-
bility of the polyimides was attributed to the more
bent structure of the polyimides owing to the bulky
–CF3 groups and unsymmetrical diamine structure.
Yang et al. [88] synthesized diamines with a twisted
2,2′-disubstituted binaphthyl unit (3-36 in Table 3.3)
and biphenyl unit (3-37 in Table 3.3), respectively,
and two bulky CF3 groups to disrupt chain packing
of the polyimides. Xie et al. and Chiang et al. [89,90]
introduced –CF3-substituted ether bridged diamine
(3-38 and 3-39 in Table 3.3) to improve solubility and
reduce moisture uptake in polyimides. Chen et al.
[91] prepared a fluorinated diamine monomer (3-40
in Table 3.3), with methyl substituents on a ring unit
at ortho-positions to the ether linkage with the aim
to enhance the solubility and to reduce the dielectric
constant because of the increased free volume caused
by the –CF3 groups and methyl substituents. Chen
et al. [92] further developed a fluorinated diamine
monomer (3-41 in Table 3.3), with isopropylidene
units to improve solubility and lower color inten-
sity, dielectric constant, and lower moisture absorp-
tion for the synthesized polyimides. Chen et al. [93]
also developed a highly fluorinated diamine mono-
mer with hexafluoroisopropylidene groups (3-42 in
Table 3.3) with the aim of preparing soluble and light-
colored polyimides by reduced CTC formation and
low dielectric constants. Chiang et al. [94] prepared a
diamine monomer with fluorine moiety and pendant
–CF3 groups (3-43 in Table 3.3) to prepare high-Tg
polyimides with improved thermal stability and solu-
bility. Bu et al. [95] prepared asymmetric diamine
monomer with a ketone group (3-44 in Table 3.3) to
synthesize asymmetric fluorinated polyimides. The
resulting fluorinated polyimides had good solubil-
ity owing to the presence of bulky –CF3 groups and
an unsymmetrical structure provided by the diamine
monomer. The introduction of kink structures into
polymer chains can prevent chain alignment and
Handbook of Specialty Fluorinated Polymers
Reference
H2N CF3 [103]
O
disrupt the formation of efficient CTCs. Damaceanu
et al. [96] introduced ortho-kink structures based
on –CF3-containing diamine, namely, 1,4-bis(2-
amino-4-[trifluoromethyl]phenyl)piperazine (3-45 in
Table 3.3). The polyimides were easily soluble at
room temperature in polar aprotic solvents and even
in less polar solvents such as THF and CHCl3. The
piperazine-based polymers had thermal stability, in
the range 345–360 °C and Tg in the range 211–266 °C.
Behniafar et al. [97] introduced indirect alignment in
the polymer chain to enhance asymmetry (3-46 in
Table 3.3) to endow the chains with a large amount
of polarity, thereby enhancing organo-solubility, par-
ticularly in polar solvents. Ghaemy et al. [98] synthe-
sized a diamine monomer with flexible ether linkages
and bulky carbazole and –CF3 groups (3-47 in
Table 3.3) in the polymer backbone, which decreased
interaction between polymer chains and packing effi-
ciency, resulting in an increase in free volume in the
polymers and easier diffusion of solvent molecules.
Qing et al. [99] prepared a new fluorinated diamine
containing phenylphosphine oxide moiety (3-48 in
Table 3.3); the resulting polyimides had good solu-
bility in common organic solvents. The good solu-
bility was attributed to the noncoplanar structure of
the phenylphosphine oxide group, the introduction
of flexible links (meta-ether linkage), and the –CF3
groups, which reduced CTCs, resulting in low color
in the polymer films. Zhang et al. [100] introduced
kinked spiro fluorine units and bulky –CF3 moieties
(3-49 in Table 3.3) in the diamine structure, which
increased disorder in the chains and hindered dense
chain packing, thus reducing interchain interac-
tions and affording good solubility to the resulting
polyimides.
Behniafar et al. [101] prepared a new fluorinated
diamine monomer (3-50 in Table 3.3) to improve the
solubility and processability of polyimides, which
they attributed to the high electronegativity of the
3: Fluorinated Polyimides
fluoro groups, resulting in higher polarity and hence
improving solubility in the resulting polyimides.
Sheng et al. [102] prepared a –CF3-based bis(ether
amine) monomer, 9,9-bis(4-[4-amino-2-trifluoro-
methylphenoxy]phenyl)xanthenes (BATFPX) (3-51
in Table 3.3), which gave room temperature solubility
of the polyimides even in low-boiling solvents such
as THF and chloroform. Behniafar’s group [103]
synthesized an ortho-aligned diamine, 2,2′-bis(2-
amino-4-trifluoromethylphenoxy)-1,1′-binaphthyl
(AFPBN) (3-52 in Table 3.3), endowing the poly-
mer chains with greater polarity and hence improved
organosolubility compared with the para-aligned
fluorinated analogue [104].
Hu et al. [105] prepared fluorinated semi-alicyclic
polyimides with the aim of preparing colorless, trans-
parent, and soluble polyimides that retained high ther-
mal stability. The highly fluorinated polyimide with
6FDA as a dianhydride had a transmittance of about
85% at 450 nm, indicating good optical transparency
at the visible light region, which the authors attrib-
uted to the reduction in intermolecular CTC between
alternating electron-donor (fluorinated diamine) and
electron-acceptor (1,2,3,4-cyclobutanetetracarboxylic
dianhydride) moieties. Liu et al. [106] also obtained
light-colored fluorinated polyimide film, is illus-
trated in Fig. 3.1. Table 3.3 represents a list of several
Figure 3.1  Photographs of a piece of the fluorinated polyimide film (89 μm thick) (a) and a piece of the Kapton
(pyromellitic dianhydride–oxydianiline-based polyimide) film (90 μm thick) (b). Reproduced with permission from
Ref. [106].
115
fluorinated diamines with flexible ether linkages (3-11
to 3-52) developed between 2000 and 2010.
In recent years a list of fluorinated dianhy-
drides (3-53 to 3-59) has been identified by sev-
eral researchers and is provided in Scheme 3.8.
Liu et al. [106] synthesized bis(ether dianhydride)
monomers, namely, 4,4′-(2-[3′-trifluoromethylphenyl]-
1,4-phenylenedioxy)-diphthalic anhydride (3-53 in
Scheme 3.8) and 4,4′-(2-[3′,5′-ditrifluoromethylphenyl]-
1,4-phenylenedioxy)-diphthalic anhydride (3-54 in
Scheme 3.8), which were further converted into
poly(ether imide)s by polycondensation with aromatic
diamines. Because of the presence of pendant groups
and aryl ether groups along the polymer backbone of
the repeat unit, the obtained poly(ether imide)s effec-
tively reduced overall CTC formation in both inter- and
intramolecular electronic interactions, leading to light-
colored films. The poly(ether imide)s had a shorter cut-
off wavelength than 380 nm and exhibited high optical
transparency of 87–89%.
A fluorinated aromatic dianhydride, 4,4′-(2,2,2-tri-
fluoro-1-[3,5-ditrifluoromethylphenyl]ethylidene)
diphthalic anhydride (9FDA) (3-55 in Scheme 3.8)
was synthesized by Li et al. [107] and the solubility,
thermal, and mechanical properties as well as electri-
cal and optical properties were systematically investi-
gated. Transmittance of the polyimide films at 450 nm
116 Handbook of Specialty Fluorinated Polymers

2
2
2 2
2 2 2 2 2
2 2 &)
2 2
2 2 2 2
2
2
2 2 2
)& &) )& &)
&)
>@
>@  >@
 

2 2 )& &) )& &)

&)

2 2 2 2 2 2

2 2 2 2 2 2
&)
>@ 2 2 2 2

>@

)& &)
2 2
2 2 >@

2 2

2 )& &) 2
>@


Scheme 3.8  Molecular structures of fluorinated dianhydrides.

was over 80%, which was attributed to the presence
of pendant –CF3 groups in the polymer structure. A
new fluorinated aromatic dianhydride, 4,4′-(2,2,2-tri-
fluoro-1-[3-trifluoromethyl-phenyl]ethylidene)diph-
thalic anhydride (TFDA) (3-56 in Scheme 3.8) was
synthesized by coupling of 3′-trifluoromethyl-2,2,2-
trifluoroacetophenone with o-xylene using trifluo-
romethanesulfonic acid as catalyst, followed by
oxidation of KMnO4 and dehydration. Thereafter,
Yang et al. [21] prepared a series of fluorinated aro-
matic polyimides from the fluorinated aromatic dian-
hydride TFDA with various aromatic diamines. The
polyimides had good electrical properties such as
dielectric constants of 2.75–3.02 at 1 MHz, a low dis-
sipation factor in the range 1.27–4.50 × 10−3, and low
moisture absorption <1.3%.
Myung et al. [108] prepared mono-substituted
asymmetric dianhydride monomer containing fluoro-
phenyl moiety, namely, 1-(3′,5′-bis[trifluoromethyl]-
phenyl) pyromellitic dianhydride (6FPPMDA) (3-57
in Scheme 3.8), via Suzuki cross-coupling reaction
followed by oxidation and cyclodehydration, in
an effort to prepare polyimides with high Tg, good
solubility, and good dielectric and optical properties.
The 6FPPMDA-based polyimides exhibited high Tg
(280–316 °C), good thermal stability (>520 °C in air),
low water absorption (1.46–2.16 wt.%), and excel-
lent solubility and were soluble even in acetone. The
6FPPMDA-based polyimides also had low dielectric
constants (2.73–3.10), low refractive indices, and
very low birefringence in the range 0.0052–0.0098.
Myung et al. [109] also prepared a fluorinated dian-
hydride monomer, 3,6-di(3′,5′-bis[trifluoromethyl]
phenyl)pyromelliticdianhydride (12FPMDA) (3-58
in Scheme 3.8). The polyimides derived from this
monomer had high Tgs (>311 °C) and good thermal
stability (>518 °C in air). They also demonstrated
low water absorption (1.26–1.35  wt.%) and low
dielectric constants in the range 2.49–2.52. Hsu et al.
[110] prepared a fluorinated dianhydride monomer,
2,2-bis(4-[3,4-dicarboxyphenoxyl]phenyl)hexafluo-
ropropane dianhydride (3-59 in Scheme 3.8) and
further prepared poly(ether imide)s that were light-
colored and exhibited good solubility, some of which
were even soluble in acetone and had higher optical
transparency. The lowest dielectric constant obtained
was 3.04, which was lower than that of Kapton poly-
imide film (ε = 3.2).
Generally, the presence of these kink link-
ages between aromatic rings or between phthalic
3: Fluorinated Polyimides
anhydride units disrupts the planarity of the polymer
repeat unit and increases torsional mobility. In addi-
tion, these bonds lead to an increment of the repeat-
ing unit chain length, which in turn separates the
imide rings, resulting in relatively lower density of
the imide moiety, which may be responsible for the
polymer tractability. The suppression of the copla-
narity of the structure is maximal when large groups
are introduced into the main chain, for instance, sul-
fonyl or hexafluoroisopropylidene groups, or when
the monomers are enlarged by more than one flexible
linkage. Hexafluoropropylidene, carbonyl, and sulfo-
nyl groups are the most advantageously incorporated
ones regarding processability.
A poly(ether imide) marketed under the trade
name Ultem® by General Electric, is an example of
an engineering thermoplastic. The polymer is soluble
in several organic solvents and has Tg values around
217 °C. This polymer possesses excellent melt flow
characteristics because of flexible ether linkages in
the main chain and serves as a true high-performance
engineering thermoplastic. Rusanov et al. prepared
several organo-soluble aromatic polyimides using
side phthalimide groups or by introducing pendant
imide groups [111,112]. The phenyl group contain-
ing cardo groups are the most promising among
various other groups. It does not decrease thermal
stability and provides a measure of molecular irregu-
larity and separation of chains beneficial in terms of
an increase in free volume and a decrease in cohesive
energy density [53,113–116]. On the other hand, the
presence of bulky side substituents in polyimides or
in any other linear polymer lowers the chain’s tor-
sional mobility and generally causes an increment
of Tg [117]. A thiazole-containing unsymmetrical
ortho-diamine monomer was synthesized by Zhao
et al. [118] that increased the degree of bending of
the polyimide main chain, improving solubility.
Banerjee et al. synthesized an unsymmetrical
diamine and prepared several poly(ether imide)s (3-
60 to 3-63 in Table 3.4 [11]) by varying dianhydrides.
The differential scanning calorimetry (DSC) showed
distinct transition temperatures ranging from 251 to
288 °C. The most rigid polymer (3-60 in Table 3.4),
with a PMDA unit in the main chain, had the highest
Tg of 288 °C. The higher Tg of polymer 3-62 (in Table
3.4) compared with 3-61 (in Table 3.4) was expected
because of the presence of a bulky 6F unit in the poly-
mer backbone. Polymer 3-63 (in Table 3.4) exhib-
ited the lowest Tg in the series, which was because
of the presence of additional flexible ether linkages
117
coming from the dianhydride unit. The polymers had
high thermal stability at Td,5% in air in the range 501–
532 °C. Thin films of these polymers had good TS in
the range 84–135 MPa and elongation at break (EB)
up to 25%. These values are comparable with com-
mercially available poly(ether imide)s such as Ultem®
1000, which has a TS of 105 MPa and EB of 60%;
and Ultem® 6000, with a TS of 103 MPa and EB of
30%. The dielectric constants obtained for the poly-
mers were lower than Kapton®. Banerjee et al. further
synthesized and studied the properties of fluorinated
polyimides (3-64 to 3-69 in Table 3.4 [20]) derived
from diamines, namely, 1,3-bis(3′-trifluoromethyl-
4′[4″-amino benzoxy] benzyl)benzene and 4,4-bis(3′-
trifluoromethyl-4′[4-amino benzoxy]benzyl)biphenyl.
Here, the polyimides with biphenyl moiety (3-67, 3-68,
and 3-69 in Table 3.4) in the main chain had higher Tg
and thermal decomposition temperatures because of the
greater rigidity compared with the meta phenyl moiety
(3-64 to 3-66 in Table 3.4) in the main chain. The Tg
values of these polymers are higher than commercial
Ultem 1000 (Tg = 217 °C) but lower than Kapton® film
(Tg = 390 °C). The Td,5% in air of these polymers was in
the range 491–516 °C for m-terphenyl moiety contain-
ing poly(ether imide)s and 519–531 °C for quadriphe-
nyl moiety containing polymers. The poly(ether imide)s
with quadriphenyl moiety in the main chain had greater
thermal stability than the poly(ether imide)s with an
m-terphenyl ring owing to the greater rigidity of the
quadriphenyl moiety. The TS of the poly(ether imide)
s with the quadriphenyl moiety was also higher (109–
148 MPa), with a higher EB in the range 19–31% com-
pared with the poly(ether imide)s with an m-terphenyl
ring, which had lower TS values in the range 87–98 MPa
with an EB in the range 9–11%. The authors attributed
the higher TS and EB to the extended geometry in the
case of a quadriphenyl unit containing poly(ether imide)
s. Here, too, the dielectric constants obtained for the
polymers were lower than Kapton® H (ε = 3:5 at 1 kHz),
Upilex R® (ε = 3:5 at 1 kHz), Upilex S® (ε = 3:5 at 1 kHz),
and Ultem® 1000(ε = 3:15 at 1 kHz).
Banerjee et al. [47] synthesized a diamine
monomer, namely, 4,4′-bis(aminophenoxy)-3,3′-
trifluoromethyl terphenyl, and furthermore prepared
fluorinated polyimides (3-70 to 3-72 in Table 3.4).
The Tg of the polyimides depended on the rigidity
of the dianhydride unit. The polyimide with PMDA
as dianhydride had the highest Tg of 294 °C in the
series, with a thermal stability as high as 532 °C in
an air atmosphere. The TS of the poly(ether imide)
s were in the range 96–112 MPa with an EB in the
Table 3.4  Fluorinated Polyimides and Their Repeat Unit Structures with the Respective Dielectric Constants Measured at 1 MHz
Dielectric
Constant
Serial Td,5% in air TS EB (ε) at
No. Polyimide Tg (°C) (°C) (MPa) (%) 1 MHz Reference

3-60 O O 283 516 98 5 3.12 [11]

O N N
n
CF3 O O

3-61 O O O 258 514 135 18 2.91 [11]

O N N
n
CF3 O O

3-62 O F3C CF3 O 280 501 84 4 2.82 [11]

O N N
n
CF3 O O

3-63 O O 252 532 125 25 2.81 [11]

O
O N N
n
CF3 O O

3-64 F3C O O 269 513 98 11 2.93 [20]

O O N N
n
CF3 O O

3-65 F3C O O O 234 491 87 9 2.97 [20]

O O N N
n
CF3 O O

3-66 F3C O F3C CF3 O 251 516 97 9 2.76 [20]

O O N N
n
CF3 O O
3-67 F3C O O 316 519 125 19 2.91 [20]

O O N N
n
CF3 O O

3-68 F3C O O O 262 531 148 31 2.98 [20]

O O N N
n
CF3 O O

3-69 F3C O F3C CF3 O 273 526 109 21 2.74 [20]

O O N N
n
CF3 O O

3-70 F3C O O 294 532 112 21 2.94 [47]

O O N N
n
CF3 O O

3-71 F3C O O O 272 525 100 17 2.98 [47]

O O N N
n
CF3 O O

3-72 F3C O F3C CF3 O 278 519 96 19 2.72 [47]

O O N N
n
CF3 O O

3-73 CF3 F3C O O 187 532 97 11 2.84 [80]

O
N
O O N N
n
O O

Continued
Table 3.4  Fluorinated Polyimides and Their Repeat Unit Structures with the Respective Dielectric Constants Measured at 1 MHz—cont’d
Dielectric
Constant
Serial Td,5% in air TS EB (ε) at
No. Polyimide Tg (°C) (°C) (MPa) (%) 1 MHz Reference

3-74 292 554 85 7 2.68 [94]

F3C O F3C CF3 O

O O N N
n
CF3 O O

3-75 CF3 O 290 523 103 9 2.85 [102]

F3C O

N
O O N CF3

O n
CF3 O

3-76 F3C O O 254 531 147 30 2.82 [119]

O
O O N N
n
CF3 O O

3-77 F3C O O 242 519 129 22 2.88 [119]

O
O O N N
n
CF3 O O

3-78 F3C O O 211 517 118 5 2.92 [119]

O
O O N N
n
CF3 O O

3-79 F3C O O 241 514 131 6 3.24 [119]

O
O O N N
N n
CF3 O O
3-80 F3C O O 234 486 116 15 3.19 [119]
O
O O N N
S n
CF3 O O

3-81 O O 217 545 78 25 2.78 [121]

CF3
O O (10%)
O O N N
CF3 n
O O

3-82 CF3 221 – 108 9 2.55 [122]

O F3C CF3 O

N N O O
n
O O

3-83 O F3C CF3 O CF3 F3C 264 574 107 11 2.47 [123]

N N O O
n
O O

3-84 O O CF3 271 565 117 10 2.48 [124]

F3C CF3
(10%)
N N O

O O O

F3C
n

3-85 O F3C CF3 O CF3 271 545 129 9 3.17 [125]

N N O

O O O

n
CF3

Continued
Table 3.4  Fluorinated Polyimides and Their Repeat Unit Structures with the Respective Dielectric Constants Measured at 1 MHz—cont’d
Dielectric
Constant
Serial Td,5% in air TS EB (ε) at
No. Polyimide Tg (°C) (°C) (MPa) (%) 1 MHz Reference

3-86 CF3 O 234 – 88 6 2.49 [126]

F3C O
CF3
N
O O N CF3

O n
CF3 O

F3C CF3

3-87 CF3 O 239 472 – – 2.65 [130]

F3C O

N
O O N CF3

O n
CF3 O

3-88 CF3 O 290 570 91 5 2.05 [131]

F3C O
(10%)
N
O O N CF3
n
O
CF3 O

3-89 CH2 217 514 94 15 2.60 [132]

CH
(271) (525) (96) (13)

CF3 O
O O CF3 O CF3
O O CF3
N
N N O O N CF3
CF3 CF3 7
3
O
O O F3C O
3: Fluorinated Polyimides
range 17–21%, which were lower compared with the
poly(ether imide)s with quadriphenyl moiety in the
polymer backbone [20]. The dielectric constants of
the polyimides were recorded in the range 2.72–2.98.
The lowest value was obtained for the polyimide
with 6FDA as the dianhydride unit, indicating that
dielectric constant decreased with an increase in fluo-
rene content.
Ma et al. [80] designed a pyridine-based diamine
monomer, namely, 4-phenyl-2,6-bis(3-[4′-amino-2′-
trifluoromethyl-phenoxy]phenyl)pyridine, to improve
the thermal and chemical stability of the polyimides
at high temperature. A representative structure of the
polyimide with ODPA as a dianhydride unit is shown
in 3-73 (in Table 3.4). The Tg of the polyimide was
reported to be 187 °C with a Td,5% as high as 532 °C in
air. The TS of the polyimide was recorded at 97 MPa
and the EB at 11%, indicating the strong and tough
nature of the polyimide.
Yang et al. [94] introduced bulky fluorine and –CF3
groups in the diamine monomer to increase molecular
asymmetry, which hindered dense chain packing and
improved the solubility of the polyimides. A represen-
tative structure of fluorinated polyimide with 6FDA as
a dianhydride unit is shown in 3-74 (in Table 3.4). In
general, the polyimide with bulky fluorene moiety had
high Tg and high thermal stability. The highly fluori-
nated polyimide containing 6FDA as a dianhydride
unit had a dielectric constant value as low as 2.68
in the polyimide series synthesized by Yang’s group
compared with the other synthesized polyimides con-
taining non-fluorinated dianhydride units.
Sheng et al. [102] introduced both xanthene and –
CF3 moieties in the main chain to improve solubility
by reducing interchain interactions. Different fluo-
rinated polyimides were synthesized using various
dianhydrides. A representative structure of a highly
fluorinated polyimide is shown in 3-75 (in Table 3.4).
The Tg of the polyimides depended on the rigidity
of the dianhydride unit, showing a value of 290 °C
with the 6FDA unit in the main chain. The highly
fluorinated polyimide had a high thermal stability
of 523 °C at Td,5%. The polyimide had good TS of
103 MPa but the EB was low. The dielectric constant
value of the highly fluorinated polyimide was as low
as 2.85 in the series.
It is worth noting the Tg values of fluorinated
polyimides (3-76 to 3-80 in Table 3.4) prepared
by Banerjee et al. using different fluorinated
diamines with ODPA as the dianhydride unit [119].
The following order of Tg is shown in Fig. 3.2:
123
Figure 3.2  Catenation angle of different arylene rings.
quadriphenyl > 1,4-diphenyl benzene > 2,6-diphenyl
pyridine > 2,5-diphenyl thiophene. This order may
be explained by considering three factors: rigidity,
the catenation angle of different groups, and the
polarity.
The poly(ether imide) derived from 4,4-bis(3′-
trifluoromethyl-4′[4-amino benzoxy]benzyl)biphenyl
(3-76 in Table 3.4) had considerably higher Tg values
than the poly(ether imide) (3-77 in Table 3.4) derived
from 4,4′-bis(aminophenoxy)-3,3′-trifluoromethyl ter-
phenyl. The poly(ether imide) (3-76 in Table 3.4) had
the highest Tg because of the presence of rigid moieties.
The poly(ether imide) (3-78 in Table 3.4) prepared
from diamine 1,3-bis(3′-trifluoromethyl-4′[4″-amino
benzoxy]benzyl)benzene had the lowest Tg compared
with the terphenyl and biphenyl unit. The catenation
angle of the 1,4-phenyl and biphenyl moieties is 180°
whereas that of the 1,3-phenyl moiety is 120°. There-
fore, polymers containing the 1,3-phenyl moiety were
less restricted in their mobility, which lowered Tg com-
pared with the Tg values of 3-76 and 3-77 in Table 3.4.
The Tg of the polyimides containing pyridine (3-79 in
Table 3.4) and thiophene units in the polymer backbone
(3-80 in Table 3.4) had different behavior. A decrease
in Tg was observed for the thiophene containing poly-
mers more than the pyridine containing polymers
although the catenation angle for thiophene moiety
was 148°, which was higher than the pyridine moi-
ety, 120°. This may be due to the polarity of the pyri-
dine ring. Pyridine has a less extended geometry than
thiophene; at the same time, pyridine has four times
more polarity than thiophene (μpyridine = 7.4 × 10−30 Cm;
μthiophene = 1.83 × 10−30 Cm) [120], which is the probable
reason for higher Tg for pyridine ring-containing poly-
mers. The polymers had high thermal stability above
480 °C at 5% weight loss temperature in air. The TS was
recorded in the range 116–147 MPa with EB values in
the range 5–30%; the highest value was recorded for the
quadriphenyl unit containing polyimide (3-76 in Table
3.4) because of the extended geometry discussed above.
Yang et al. [121] synthesized a series of color-
less poly(ether imide)s from BPADA and fluorinated
diamines and investigated the solubility, thermal,
mechanical, and optical properties. A representa-
tive structure of poly(ether imide) (3-81) is shown in
124
Table 3.4. The polymers had good solubility in com-
mon organic solvents and the films had a UV absorp-
tion cutoff wavelength below 390 nm. The Tg of the
poly(ether imide) was similar to commercially avail-
able Ultem 1000 and retained good mechanical prop-
erties. Zhou et al. [122] synthesized a diamine, namely,
1,4-(4′-aminophenoxy)-2-(3′-trifluoromethylphenyl)
benzene, and further prepared poly(ether imide)s by
reaction with commercially available aromatic dian-
hydrides. The representative structure of fluorinated
poly(ether imide) shown in 3-82 (in Table 3.4) was
soluble both in the strong dipolar solvents NMP or
DMAc and in common organic solvents such as THF,
CHCl3, and acetone, along with a Tg value of 221 °C
and Td,5% at 547 °C in nitrogen. The fluorinated
poly(ether imide) had a good TS of 108 MPa but a low
EB value of 9%. Several bis(ether amine) monomers,
namely, 2,7-bis(4-amino-2-trifluoromethylphenoxy)
naphthalene [123], 2,6-bis(4-amino-2-trifluorometh-
ylphenoxy)naphthalene [124], and 1,5-bis(4-amino-
2-trifluoromethylphenoxy)naphthalene [125], were
synthesized by Hsaio et al. and then converted to flu-
orinated poly(ether imide)s by thermal and chemical
imidization routes when reacted with various dian-
hydrides. The representative structures of fluorinated
poly(ether imide) are shown in 3-83, 3-84, and 3-85
(Table 3.4). The presence of bulky naphthalene moi-
ety in the poly(ether imide) backbones led to a high
Tg value in the range 264−271 °C with high thermal
stability. The polymers retained good mechanical
properties with TS of approximately 107–129 MPa
and EB of about 11% with dielectric constant values
as low as 2.47.
Tao et al. prepared fluorinated polyimide (3-86
in Table 3.4) [126], from multi-trifluoromethyl-
substituted diamine, which had a dielectric constant
as low as 2.49. The dielectric constants decreased
gradually with an increase in fluorene loading. The
dielectric constant value was not only much lower
than non-fluorinated polyimides such as PMDA-
ODA (3.16) [127], it was also lower than some of
the fluorinated polyimides such as those derived from
3,3′,5,5′-tetrafluoro-4,4′-diaminodiphenylmethane
(TFDAM) and dianhydrides (2.73–2.82) [128] and
from α,α-bis(4-amino-3,5-difluorophenyl)phenyl-
methane (4FMA) and dianhydrides (2.60–2.83)
[129]. Wang et al. [130] prepared fluorinated poly-
imides (3-87 in Table 3.4) by incorporating diiso-
propyl-substituted fluorene moieties, which led to
an improvement in solubility and dielectric prop-
erties. The dielectric constant obtained with the
Handbook of Specialty Fluorinated Polymers
6FDA-containing polyimide was 2.65, which the
authors attributed to the introduction of the bulky
pendant –CF3 groups, which increased the free vol-
ume and reduced polymer packing, leading to a low
dielectric constant value. Hsiao et al. [131] prepared
fluorinated triptycene-based polyimides (3-88 in
Table 3.4), which had a dielectric constant as low as
2.05. The rigid, three-dimensional triptycene units
helped reduce interchain interactions and hindered
close chain packing, thus improving solubility, and
decreasing color intensity without reducing the Tg
values of the polyimides. Yao et al. [132] prepared
fluorinated polyimides containing cross-linkable
styryl groups (3-89 in Table 3.4) in the polymer back-
bone; after thermal curing of the copolyimide, the Tg
increased from 217 to 271 °C and thermal stability
of the cured film (525 °C) was also higher than the
uncured film sample (514 °C). Mechanical proper-
ties such as the TS of the polyimides improved after
curing, showing marginal increments from 94 to
96 MPa. The dielectric constant was 2.60. The poly-
imides exhibited high optical transparency of about
90% at a wavelength of 550 nm. Several fluorinated
polyimides developed by different researchers are
listed in Table 3.4.
Incorporation of larger amounts of pendant per-
fluoroalkyl groups in the preparation of highly flu-
orinated polyimides can be difficult with respect to
synthetic approaches. Another approach to decreas-
ing a polymer’s bulk dielectric constant is to intro-
duce nanoscopic porosity into the polymer film.
Foamed films with pores in the 10-nm range have
been successfully demonstrated to exhibit low
dielectric constants. For use for interconnect fabri-
cation for circuits with minimum feature sizes, the
pores should not be much larger than 10 nm in diam-
eter. In addition, they should be regular with a narrow
size distribution and they must not be interconnected.
Carter et al. prepared low dielectric constant porous
polyimide films by a nanofoam approach in a two-
step process [133,134]. The nanoporous foams were
prepared from triblock copolymers with the major
phase composed of polyimide and the minor phase
composed of a thermally labile block followed by
selective removal of labile blocks by thermal treat-
ments, leaving pores of suitable size and shape in the
original copolymer morphology. The films were then
finally heated in a stepwise manner to 310 °C in an
argon atmosphere or under high vacuum to remove
the solvent and densify the copolymer. In the second
step, the thermolabile block poly(propylene oxide)
3: Fluorinated Polyimides
was removed by heating the copolymer in an oxygen
atmosphere at 250 °C for 10–12 h. Pore sizes ranged
in tens of nanometers in the copolymer. A similar
type approach was undertaken by several research-
ers to prepare this type of nanoporous polymer
[135–137]. A low dielectric constant of 1.43 was also
realized by us for electrospun polyimide nanofibers
compared with the neat fluorinated polyimide owing
to the large pores and high surface-to-volume ratio of
the polyimide mats [138].
3.2.5  Polyimide Block Copolymer
Aerogels
Miranda et al. [139] synthesized two different
anhydride-capped polyimide oligomers: one from
2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane
dianhydride (6FDA) and 4,4′-oxidianiline (ODA)
and the other from BPDA and ODA. The oligomers
were combined with 1,3,5-triaminophenoxybenzene
(TAB) to form a block copolymer networked struc-
ture that gelled in 1 h. The polyimide gels were super-
critically dried to give aerogels with relative dielectric
constants as low as 1.08. Increasing the amount of
6FDA blocks by up to 50% of the total dianhydride
decreased the density of the aerogels, presumably
by increasing the free volume and by decreasing the
amount of shrinkage seen upon processing, resulting
in a concomitant decrease in dielectric properties.
Scheme 3.9 shows the synthesis steps for the for-
mation of polyimide block copolymer aerogels with
TAB cross-links.
3.2.6  Fluorinated Poly(Imide
Sulfone)s
Bruma et al. prepared several poly(amide imide
sulfone)s [140] and investigated the thermal and
dielectric properties of the polymers. The fluorinated
polymer as shown in Scheme 3.10 had the lowest Tg,
279 °C, which resulted from the combined effects of
meta-structures with the highest amount of flexible
bridges, –SO2– and –O–, per repeat unit of the mac-
romolecule. The dielectric constants of polymer films
were in the range 3.49, close to the dielectric con-
stant (3.2) of Kapton. This shows that introduction of
hexafluoroisopropylidene units into the main chain
does not significantly affect the electrical properties;
probably both amide and sulfone groups, which are
polar, were also present in the macromolecule.
125
A new aromatic diamine monomer with four pen-
dant –CF3 groups was successfully synthesized by a
three-step reaction using bis(4-fluorophenyl)sulfone
and N-bromosuccinimide as starting materials. Then,
a series of fluorinated poly(ether sulfone imide)s was
conveniently prepared from the diamine and three
aromatic dianhydrides (BPDA, BTDA, and ODPA)
via one-step solution polycondensation.
Ren et al. [141] incorporated bulky multi-pendant
–CF3 groups and brought about improvement in solu-
bility, optical, and dielectric properties. A representa-
tive structure of fluorinated poly(ether sulfone imide)
is shown in Scheme 3.11. They were readily soluble
in NMP, DMAc, CHCl3, CH2Cl2, and THF at room
temperature, which could be attributed to the effect
of weakening of the intermolecular interactions
owing to the incorporation of multi-pendant –CF3
groups. The Tg values of poly(ether imide sulfone)
s were in the range 212–231 °C. The 5% weight loss
temperatures in nitrogen and in air atmosphere were
in the range 549–561 °C and 561–572 °C, respec-
tively, indicating its tolerance for withstanding a high
processing temperature required to fabricate micro-
electronics. The light-colored transparent films had
a cutoff wavelength in the range 321–337 nm, and
the transparency at 450 nm was higher than 80%
owing to reduction of the aromatic conjugation and
intermolecular CTC along the polymer backbone by
incorporating ether linkage and bulky –CF3 as pen-
dant groups. The dielectric constants of the fluori-
nated poly(ether imide sulfone)s were in the range
2.74–2.90 at 1 MHz, respectively, which were much
lower than that of commercial Kapton film (3.48 at
1 MHz) measured under the same testing conditions.
3.3  Fluorinated Polyimides for
Membrane-Based Applications
Membrane technologies have emerged as an
important category of separation processes compared
with other conventional separation processes [142–
144]. Membranes can be used to satisfy many separa-
tion requirements, including separation of molecular
and particulate mixtures, controlled release of active
agents, in membrane reactors and artificial organs,
and in energy storage (batteries) and conversion (fuel
cells) systems. Membrane technologies are classified
for use in several applications, such as microfiltra-
tion, ultrafiltration, nanofiltration, reverse osmosis,
pervaporation, gas separation, and proton exchange
126 Handbook of Specialty Fluorinated Polymers

Scheme 3.9  Synthesis of polyimide block copolymer aerogels with TAB cross-links. Reproduced with permis-
sion from Ref. [139].

2 &) 2

1+ $U ; $U 1+ & $U
1 1 $U
&
&)
2 2 Q
2 2
2
$U  2 ;  6 $U
 
2

Scheme 3.10  Representative structure of fluorinated poly(amide imide sulfone). Taken from Ref. [140].
3: Fluorinated Polyimides
&) )&
)&
2
2 6
2 Q
Scheme 3.11  Representative structure of fluorinated poly(ether sulfone imide). Taken from Ref. [141].
membrane (PEM) fuel cell (PEMFC). Membrane
separation technologies refer to any separation pro-
cess in which membranes function as both a bar-
rier and a sieve for separating feed species such as
liquid mixtures, gas mixtures, and colloidal particle
mixtures [145–148]. Some important advantages
include high efficiency, low energy consumption,
and versatile applicability [149]. In membrane-based
technology, polyimide (PI) membranes have been
widely used for several years in a wide variety of
applications [150]. Because PIs combine excellent
thermal stability with good chemical stability, film-
forming ability, and mechanical strength [145,151],
they are an ideal material for membrane applications.
Currently, PIs make up the largest group of organic
polymers used as membranes for gas separation and
solvent-resistant nanofiltration [150].
The incorporation of fluorene into a PI backbone
is a promising method for modifying the properties
of the PIs. This method was intensively explored
between 2000 and 2010 with the hope of fine-tuning
several properties of particular interest. Fluorine
incorporation can enhance the processability, opti-
cal transparency, thermal stability, Tg, mechani-
cal strength, and chemical/oxidative stability while
reducing the dielectric constant (k), refractive indi-
ces, and moisture/water absorption; it also exhibits
interesting surface properties [152–155]. In addition,
the 6F (1,3-ditrifluoromethyl-2-isopropyl) groups in
the polymer backbone enhance polymer solubility (a
characteristic known as the fluorene effect) without
reducing thermal stability. The bulky trifluoromethyl
group (–CF3) also serves to increase the free volume
of the polymer, thereby improving gas permeability
and electrical insulating properties [154,155]. The
combination of electronic and steric effects of CF3
group reduces the ability for interchain interactions,
and particularly hinders the formation of CTCs,
which is a major factor for molecular packing and
intractability in aromatic PIs. Furthermore, the high
strength of the C–F bond in fluorinated polyimides
127
&)
2
2
2 1
1
2
2
results in properties such as high Tg and excellent
thermal properties, comparable to those of the con-
ventional aromatic polyimides. This excellent set
of properties has made fluorinated PIs attractive for
thermally stable coatings and films, polymeric mem-
branes for gas separation and pervaporation, and
PEMs for fuel cell applications.
3.3.1  Fluorinated Polyimides
in Gas Separation
Membranes in a gas permeation process act as a
selective barrier, usually thin, interposed between
two phases, which obstruct gross mass movement
between the phases but permit the passage of cer-
tain species from one phase to the other with vari-
ous degrees of restriction [156]. Generally, the bulk
phases are gas mixtures and separation occurs because
each type of gases diffuses at a different rate through
the membranes. This definition encompasses diverse
driving forces. These driving forces arise from a gra-
dient of chemical potential as a result of the concen-
tration gradient, pressure gradient, or both. Currently,
a large-scale membrane gas separation system is
acceptable in many industrial sectors to replace tradi-
tional separation techniques, owing to its advantages:
simplicity of operation and installation, lower capital
outlay, large reduction in power, compact size and
modules, mild operation conditions, and easy com-
bination with other separation processes. Actually,
membranes had been known to have the potential to
separate important gas mixtures long before 1980,
but the technology to fabricate high-performance
membranes and modules economically was lacking
and the overall success of gas separation membranes
lagged behind people’s expectations.
Membrane-based selective gas transport prop-
erties were first observed in 1829, when Thomas
Graham made the first scientific discovery of gaseous
osmosis through a wet animal bladder for an air–car-
bon dioxide system [157]. In 1866, he also studied
128
the first quantitative measurement of the rate of gas
permeation into vacuum rather than air and proposed
the “solution–diffusion” mechanism for gas transport
in membranes [158]. S. Von Wroblewski quantified
Graham’s model in 1879 and defined the permeability
coefficient as the penetrant flux times the membrane
thickness, divided by the pressure difference across
the membrane [159]. He also characterized the per-
meability coefficient as a product of diffusivity and
solubility coefficients, which is widely accepted as
an important model in membrane research area even
today. Currently, gas separation by selective perme-
ation through a polymer membrane is considered as
one of the fastest-growing separation technologies in
science and engineering. Membrane-based separa-
tion processes offer a number of significant advan-
tages. Lower energy requirements and lower capital
investment than conventional separation processes
have made this process more attractive. This process
is also cost-effective even at a low gas volume. The
necessary process equipment is simple, compact,
and relatively easy to operate and control. Hence,
Figure 3.3  Schematic representation of membrane-
based gas separation.
Upstream Upstream
rp Downstream
Downstream
Knudsen diffusion Molecular sieving
Figure 3.4  Gas transport mechanisms for membrane-based gas permeation. Reproduced with permission from
Ref. [156].
Handbook of Specialty Fluorinated Polymers
membrane-based gas separation is a viable alterna-
tive to traditional methods of gas separation such as
cryogenic distillation and pressure swing adsorption
[160–162].
3.3.1.1  Gas Transport Mechanisms
through Membranes
In membrane-based gas separation, the movement
of penetrant gases is driven by the pressure gradi-
ent imposed between upstream and downstream. A
membrane will separate gases only if some compo-
nents pass through the membrane more rapidly than
others, as shown in Fig. 3.3. There are three general
transport mechanisms for membrane-based gas sepa-
ration: Knudsen diffusion, solution–diffusion, and
molecular sieving [156,163]. A schematic represen-
tation of the mechanisms of membrane-based gas
separations is shown in Fig. 3.4.
Knudsen diffusion and separation is based on the
large difference between the mean free paths of the
molecules and the membrane pore radius. The sepa-
ration factor from Knudsen diffusion is the inverse
square root ratio of two molecular weights, assum-
ing the gas mixture consists of only two types of
molecules. The process is limited to systems with
large values for the molecular weight ratio, such as
that found in H2 separation, and is commercially less
attractive because of low selectivity.
The molecular sieving mechanism involves
the separation of vapor compounds of different
molecular sizes through a porous membrane. In
this mechanism diffusion occurs under a sufficient
driving force and smaller molecules pass through
with higher diffusion rates. Therefore, a large dif-
ference between the upstream partial pressure of the
faster gas and downstream partial pressure has to be
Upstream
Transient gap
opening in
matrix
Downstream
Solution– diffusion
3: Fluorinated Polyimides 129

maintained. The main limitation in this mechanism thickness l, gas permeability coefficient PA is defined
is that condensable gases cause fouling and alter the as the trans-membrane pressure difference, P1−P2,
structure of the membrane. Therefore, this process and thickness normalized steady-state gas flux,
is feasible only for commercial robust systems, in NJ [167]:
which the membranes used for gas separation are
NJ NJ
based on ultra-microporous carbon or hollow fiber PA = = (3.1)
glass. (P1 − P2 ) /l ( Δ P/l)
Solution diffusion through polymer selective lay-
where NJ is the normalized flux, P1 and P2 are the
ers is used exclusively in current commercial devices.
upstream and downstream pressures, respectively,
High-performance polymeric membranes based on
and ΔP is P1 – P2. For binary gas mixture, P1 and
the solution–diffusion mechanism can achieve high
P2 refer to the partial pressures of penetrant A at the
permeation rates favoring a given component in a
upstream and downstream sides of the membrane,
feed gas mixture. Such membranes form the basis for
respectively. The permeability coefficient of dense
simple, convenient processes to separate a wide spec-
film materials is commonly expressed in Barrer
trum of gas pairs [164].
units:
In this particular mechanism, the material trans-
port occurs through the following steps: absorp- cm3 (STP) cm (3.2)
tion, diffusion, and release. First, the penetrant 1 Barrer = 1 × 10 − 10
cm2 s cm Hg
gas molecules dissolve in the upstream (or high-
pressure) face of the membrane; second, penetrants
diffuse through the membrane; and third, the pen- 3.3.1.2.2  Solubility and Diffusion
etrants are released at the downstream (or low- Coefficient
pressure) face of the membrane. The second step is
Using the solution–diffusion model, the gas per-
the rate-determining step, which consists of creat-
meability coefficient can also be written as the
ing gaps of large enough size in the polymer matrix
product of a gas solubility coefficient, SA, and a con-
to accommodate the penetrant molecules by ther-
centration-averaged, effective diffusion coefficient,
mally stimulated, random, local, segmental poly-
DA [167]:
mer dynamics [165]. Effective solution–diffusion
polymeric membranes have no continuous passages PA = DA × SA (3.3)
but rely on the thermally agitated motion of chain
segments comprising the polymer matrix to gen-
The diffusion coefficient, “DA,” is a kinetic term
erate penetrant-scale transient gaps in the matrix,
governed by the amount of energy necessary for
thereby allowing diffusion from the upstream to the
a particular penetrant to execute a diffusive jump
downstream face of the membrane [166]. The pen-
through the polymer and the intrinsic degree of seg-
etrants undergo random jumps, but because of the
mental packing in the polymer matrix. The solu-
higher concentration at the upstream face than the
bility coefficient, “SA,” is a thermodynamic term;
downstream face, diffusion flux occurs toward the
it depends on factors such as the condensability
downstream face. Variations in the chemical nature
of the penetrant, interactions between the polymer
of the polymer allow control of the relative extent
and penetrant, and the amount of penetrant-scale
of solution and the relative rates of diffusion of dif-
nonequilibrium excess volume in glassy polymers.
ferent gases.
The diffusion coefficient is commonly expressed
as cm2/s, and solubility is often expressed as cm3
3.3.1.2  Terminology in Gas Transport
(STP)/(cm3 polymer atm) or cm3(STP)/(cm3 poly-
3.3.1.2.1  Permeability Coefficient mer cm Hg).
A gas separation membrane functions as a selec- The solubility coefficient in Eqn (3.3) is defined as
tive barrier material. A feed gas mixture contacts the the ratio of the concentration of gas in a polymer, C,
upstream side of the membrane, resulting in a perme- to the pressure of gas, P, contiguous to the polymer
ate mixture on the downstream side of the membrane [168]:
with enrichment in one of the components. For a
pure gas permeating through a polymer membrane of SA = C/P (3.4)
130
3.3.1.2.3 Selectivity
Separation of a gas mixture is achieved by using a
membrane material that permits a faster permeation
rate for one component over that of another. The effi-
ciency of the membrane in enriching a component
over another component in the permeate stream can
be expressed as a quantity called the separation factor,
α(A/B). For a binary gas mixture permeating through a
polymer membrane, selectivity of the polymer mem-
brane toward gas “A” relative to another gas, “B,” is
commonly expressed in terms of the ideal selectiv-
ity or ideal permselectivity, α*(A/B). When the down-
stream pressure is negligible relative to the upstream
pressure, α*(A/B) can be written as the ratio of perme-
abilities of gas penetrants A and B:
α * (A/B) = PA /PB (3.5)
Under these conditions, α*(A/B) is also called the
ideal separation factor, which provides a fundamen-
tal measure of membranes performance.
Expanding the permeability into diffusivity and
solubility terms, ideal selectivity can be expressed
by:
α * (A/B) = (DA × SA ) / (DB × SB ) (3.6)
where DA/DB is the ratio of the concentration-aver-
aged diffusion coefficients of penetrants “A” and
“B” and is referred to as the membrane’s “diffusiv-
ity selectivity.” SA/SB is the ratio of solubility coef-
ficients of penetrants “A” and “B” and is called the
“solubility selectivity” [168]. In typical gas separa-
tion applications, the downstream pressure is not
negligible; however, α*(A/B) generally provides a
convenient measure to assess the relative ability of
various polymers to separate gas mixtures. High per-
meability and high selectivity are the main criteria in
evaluating a membrane.
3.3.1.3  Physical and Gas Transport
Properties of Fluorinated Polyimides
Polyimides are the most studied polymeric materi-
als for membrane-based gas separation application.
Although aromatic polyimides have received much
attention as gas separation membrane materials, the
polyimide family encompasses a large number of
structural variants, and many studies on polyimide
membranes indicate that separation properties can be
tailored by using different dianhydride and diamine
monomers. It was reported in the late 1980s that
Handbook of Specialty Fluorinated Polymers
restricting chain mobility and chain packing can
simultaneously increase permeability and selectiv-
ity in polyimides [169,170]. Fluorinated polyimides
have garnered much attention in this regard from
both academia and industry [39,171–173]. In par-
ticular, polyimides bearing pendant –CF3 groups are
of great interest in this field because their presence
causes significant improvements in polymer proper-
ties compared with corresponding non-fluorinated
polyimides. Polyimides containing trifluoromethyl
(–CF3) groups serve to manipulate many polymer
properties into the positive direction compared with
non-fluorinated ones [174,175]. A series of struc-
turally different fluorinated monomers, especially
diamine monomers, have been reported in the litera-
ture as suitable reactants for fluorinated polyimide
preparation. Some examples of such diamines are
listed in Tables 3.2 and 3.3. Also, the repeat unit
structure of many different fluorinated polyimide is
been listed in Table 3.4.
Many research groups have been systematically
studied the effect of the structure–property relation-
ship on gas transport properties of fluorinated poly-
imides. In this connection, Kim et al. investigated the
effect of incorporating fluorinated alkyl side groups
into polyimide membranes in terms of their physical
and gas permeation properties (Table 3.5) [61]. They
demonstrated four polyimides with fluorinated side
groups and another four without side groups by poly-
condensation of 2-(perfluorohexyl)ethyl-3,5-diamino
benzoate (PFDAB) and m-PDA with four aromatic
dianhydrides (6FDA, ODPA, BTDA, and PMDA),
respectively (Scheme 3.12).
The investigation revealed that the incorporation
of fluorinated side groups into polyimide membranes
decreased their surface free energies (Tgs), increased
solubility parameters and FFVs, and therefore sub-
stantially enhanced gas permeability for CO2, O2,
N2, and CH4 gases with reduced selectivity for CO2–
CH4, O2–N2, and CO2–N2 gas pairs depending on the
structure of the dianhydride monomers.
The gas permeation stability of an asymmetric
polyimide membrane with a thin and defect-free skin
layer was investigated by H. Kawakami and co-work-
ers [176,177]. They studied both the effect of molec-
ular weight and the structure of polyimide using a
common fluorinated dianhydride, 6FDA (Scheme
3.13). They observed that for 2,2′-bis(4-aminophenyl)
hexafluoropropane (6FDA-6FAP)-based polyimide,
despite of different molecular weights, the perme-
ability of N2, O2, and CH4 had almost constant val-
ues whereas the CO2 permeability of the asymmetric
3: Fluorinated Polyimides 131

Table 3.5  Comparative Gas Transport Properties of Fluorinated and Non-Fluorinated Polyimide Membranes at
25 °C and 5 atm Pressure
Pure Gas Permeabilities (Barrer) Ideal Selectivities (α*A/B)

P(CO2) P(O2) P( N2 ) P( CH4 ) P(CO2 ) /P(CH4 ) P(O2 ) /P(N2 ) P(CO2 ) /P(N2 )

Polymer
6FDA-PFDAB 17.77 4.74 0.74 0.44 40.4 6.4 24.0
6FDA-m-PDA 9.73 2.55 0.38 0.21 46.3 6.7 25.6
ODPA-PFDAB 11.03 2.61 0.56 0.36 30.6 4.9 19.7
ODPA-m-PDA 0.301 0.081 0.012 0.0064 47.3 6.8 25.1
BTDA-PFDAB 10.10 2.20 0.48 0.29 34.8 4.6 21.0
BTDA-m-PDA 0.428 0.112 0.016 0.0086 49.8 7.0 26.8

Data taken from Ref. [176].

+1 1+ +1 1+

&
2 2&+&+ P3'$
3)'$%
2 $U 30'$
2

& & 2
2 $U 2 &
%7'$
& &
2 2 2
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'LDQK\GULGH
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)'$

2 2 2
2
& & & &
1 $U 1 1 $U 1
& & & &
2 2 Q 2
& 2 Q
2 2&+&+

3RO\LPLGH

Scheme 3.12  Schematic representation of polyimides with or without fluorinated side groups [61].

membrane with a relatively lower molecular weight
(Mw = 2.0 × 105 g/mol) increased upon exposure to
a CO2 pressure of 760 cm Hg (Fig. 3.5). They also
noticed that the CO2 permeability of the asymmetric
polyimide membrane prepared from 4.3 × 105 g/mol
molecular weight was almost constant during 20
experiments at 760 cm Hg, which indicated that the
membrane was not plasticized. These results indi-
cated that the molecular weight value of the polymer
has a great influence on CO2 permeation stability and
may be an important factor determining plasticization
of the membrane.
132
1 1
Scheme 3.13  Chemical structure of 6FDA–6FAP and 6FDA-APPS-based polyimide [177].
5.9
QCO2×104 (cm3(STP)/cm2 sec cmHg)
5.7
5.5
5.3
5.1
4.9
0 5
The number of measurement
Figure 3.5 Carbon dioxode permeation stability of
asymmetric 6FDA–6FAP membranes at 35 °C and
760 cm Hg: (□) membrane prepared from 2.0 × 105
molecular weight; (▲) membrane prepared from
4.3 × 105 molecular weight. Reproduced with permis-
sion from Ref. [176].
The authors also reported that CO2 permeability
through the asymmetric 6FDA–APPS (bis[4-(4-ami-
nophenoxy)phenyl]sulfone)-based polyimide mem-
brane (Mw = 1.6 × 105) in which the aromatic diamine
had no –CF3 group was almost constant after 50
experiments run at 760 cm Hg, which indicated that
the membrane was not plasticized. These results
show that the chemical structure of the polyimide
has a significant influence on CO2 permeation stabil-
ity and may be an important factor determining the
plasticization of the membrane. They suggested that
plasticization of 6FDA–6FAP by CO2 facilitates the
motion of the bulky –CF3 side groups, which may
perturb local packing of the polyimide and provide a
kinetic opening of sufficient size to diffuse the CO2.
Handbook of Specialty Fluorinated Polymers
)& &) 2
2 )& &)
1 1
Q
2 2
)'$)$3
)& &) 2
2
2
2 6 2
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)'$$336
On the contrary, the asymmetric 6FDA–APPS mem-
QCO2×104 (cm3(STP)/cm2 sec cmHg)
5.2 brane, which did not have –CF3 groups in the diamine
structure, was not plasticized by the high CO2 pres-
sure because of the formation of the packed structure
5.0
induced by strong intramolecular interactions. From
this study, they postulated that the absence of bulky
4.8 –CF3 groups on aromatic diamine moiety suppresses
the segmental motion of 6FDA–APPS by CO2.
4.6 Okamoto et al. reported that aromatic polyimides
containing –C(CF3)2– groups in their dianhydride
4.4 moieties (e.g., 6FDA-based polyimides) are consid-
erably more gas selective than other glassy polymers
10 15 20 25
with comparable permeability [18]. Substitutions of
–C(CF3)2– groups in dianhydride moieties appear to
be somewhat more effective in enhancing selectivity
than substitutions in diamine moieties of polyimides. In
addition, they showed that aromatic polyimides contain-
ing –C(CF3)2– groups in both dianhydride moieties and
diamine moieties exhibit high selectivity as well as high
permeability [18,19]. Permeability of the –C(CF3)2-
containing polyimide increased as a result of the steric
effect of bulky –C(CF3)2, which inhibited close pack-
ing and served as “molecular spacers” in the polyimide
matrix. On the other hand, –C(CF3)2 groups helped to
increase polymer chain stiffness by inhibiting intra-seg-
mental mobility. The greater chain stiffness enabled the
polyimide matrix to discriminate better between perme-
ating molecules of different sizes and shapes, and hence
selectivity was simultaneously enhanced.
A series of 6FDA-based polyimides contain-
ing laterally attached p-terphenyls and biphenyls
moiety was synthesized by Chung and co-workers
[178] to investigate the effect of noncoplanar com-
ponents on gas permeability and selectivity. The
chemical structures of the polyimides are shown in
Scheme 3.14. They observed that only p-terphenyl
3: Fluorinated Polyimides 133

2 )& &) 2

2 2 1 1
Q
2 2

)'$WHUSKHQ\O

2 )& &) 2

2 2 1 1
Q
2 2

)'$ELSKHQ\O

2 )& &) 2

2 2 1 1
Q
2 2

)'$SKHQ\O

Scheme 3.14  Chemical structures of polyimides containing laterally attached phenyl moiety [178].

polyimide exhibits a substantial increase in perme-
ability owing to its rigid structure with a high aspect
ratio. The order of permeability increased from
6FDA-phenyl to 6FDA-terphenyl (Table 3.6), which
is consistent with the calculated FFV and measured
permittivity. They inferred that the permeability
gain for 6FDA-terphenyl polyimide arose from the
enhancement in the apparent diffusion coefficient,
whereas the permeability increase for 6FDA-biphe-
nyl was mainly due to the increase in solubility.
To check the effect of thermal annealing and cova-
lent cross-linking on CO2–CH4 mixed gas separation
with polyimide membranes, W. J. Koros et al. syn-
thesized two novel 6FDA-based fluorinated copoly-
imides containing diaminobenzoic acid (DABA) units
in their main chain [179]. The structures of the two
copolyimides, designated as 6FDA-DAM:DABA and
6FDA-6FpDA:DABA, are shown in Scheme 3.15.
They used various diol compounds (viz. ethylene
glycol, butylene glycol, cyclohexane dimethanol, and
1,4-benzene dimethanol) to cross-link the copoly-
imide chains through the carboxylic acid group of
DABA moiety. At first, mono esterification took
place between the –OH group of diol with a free –
COOH group in the presence of catalytic amounts
of p-toluene sulfonic acid. Thereafter, the monoester
membranes were annealed at elevated temperatures
under vacuum to activate a solid-state cross-linking
reaction (trans-esterification). A general reaction
scheme of the two-step cross-linking reaction is
shown in Scheme 3.16.
They studied the mixed gas separation by taking
50–50 CO2–CH4 mixtures and multicomponent syn-
thetic natural gas mixtures at 35 °C and feed pres-
sures up to 55 atm. They observed that cross-linking
at 295 °C with 1,4-butylene glycol and 1,4-cyclo-
hexane dimethanol increases CO2 permeability by
factors of 4.1 and 2.4, respectively, at 20 atm feed
pressure without a loss in selectivity, relative to
cross-linking at 220 °C. They concluded that cross-
linking of DABA-containing copolymers can pro-
duce membranes with tunable transport properties
that offer significantly higher performance with
better plasticization resistance, which is better than
134 Handbook of Specialty Fluorinated Polymers

Table 3.6  Comparison of Permeability and Selectivity of 6FDA-Polyimides Containing Laterally Attached
Phenyl Moiety at 35 °C and 10 atm
Pure Gas Permeabilities (Barrer) Ideal Selectivities (α*A/B)

P(CO2) P(O2) P( N2 ) P( CH4 ) P(CO2 ) /P(CH4 ) P(O2 ) /P(N2 ) P(CO2 ) /P(N2 )

Polymer
6FDA-terphenyl 21.48 5.26 1.02 0.747 28.76 5.16 21.06
6FDA-biphenyl 12.97 3.46 0.616 0.358 36.23 5.62 21.06
6FDA-phenyl 11.89 3.23 0.563 0.353 33.68 5.74 21.12
% Increase 80.6 62.8 81.2 112 – – –
(6FDA-terphenyl
vs 6FDA- phenyl)
% Increase 9.1 7.1 9.4 1.4 – – –
(6FDA- biphenyl
vs 6FDA-phenyl)

Reproduced from Ref. [178].

)& &) 2 2 )& &) 2

2
&)
1 1 1
1
&) P Q
2 2 2 2
&22+
)'$ )S'$ )'$ '$%$

)& &) 2 2 )& &) 2

2 &+

1 1 1
1

2 +& &+ 2 2
2
&22+
P Q

)'$ '$0 )'$ '$%$

Scheme 3.15  Structures of 6FDA-6FpDA:DABA and 6FDA-DAM:DABA [179].

that of a few reported commercial polymers such as
Matrimid® and cellulose acetate for CO2 removal
from natural gas mixtures. In addition, these materi-
als are significantly more stable than the commercial
membranes (viz. cellulose acetate and Matrimid®)
and have more attractive CO2–CH4 separation prop-
erties, as shown in Fig. 3.6, an adaptation of Robe-
son’s “upper bound” plot [180].
To investigate the effect of sulfonic acid groups on
gas transport properties, K. Tanaka et al. [181] pre-
pared a new sulfonated polyimide containing hexaflu-
oroisopropylidene linkage (>C[CF3]2) (Scheme 3.17).
They systematically measured the permeability and
selectivity of pure gas (viz. H2, CO2, O2, N2, and
CH4) as well as a mixture of CO2–N2 for the sul-
fonated homopolyimides in the triethylamine salt
form (–SO3NH[C2H5]3, designated BAPHFDS[A])
and acid form [–SO3H, designated BAPHFDS[H])
and the values were compared with those of the non-
sulfonated homopolyimide (BAPHF) with the same
polymer backbone. They reported the permeability
coefficient values in the following order: BAPHF >
BAPHFDS(A) > BAPHFDS(H) (Table 3.7). Introduc-
tion of sulfonic acid groups into BAPHF polyimide
3: Fluorinated Polyimides 135

,QVROXWLRQ >+@
 +2 &+ 5 &+ 2+  +2
H[FHVV

+2 2 +2 &+ 5 &+2 2

0RQRHVWHULILFDWLRQ
$QQHDOLQJRIILOP


 +2 &+ 5 &+ 2+

+2 &+ 5 &+2 2 2 &+ 5 &+2 2

7UDQVHVWHULILFDWLRQ
9DFXXP

Scheme 3.16  Two-step cross-linking scheme for DABA-containing copolyimides [179].

1000
Commercially
attractive
region

100 50/50 CO2/CH4

Selectivity CO2/CH4

35°C, 25 atm

Cellulose acetate Matrimid

10 (50/50 mixed gas
Lit. Data 25 atm)
pure gas, Robeson’s 1991
< 10 atm Upper Limit

1
0.1 1 10 100 1000
CO2 permeability (Barrers)

Figure 3.6 CO2–CH4 upper bound plot for DABA-containing polyimides cross-linked with various diols, com-
pared with the commercial gas separation polymers cellulose acetate and Matrimid®. Reproduced with
permission from Ref. [179].

decreased the permeability coefficient by a factor of
1.6 to 3 owing to a decrease in the diffusion coef-
ficient (D), which exceed an increase in the solu-
bility coefficient (S). Furthermore, the exchange of
proton for triethylammonium increased the perme-
ability coefficient for CO2, N2, and CH4 by a factor
of 1.1–2.5, which was attributed to an increase in D
that exceeded a decrease in S. For smaller molecules
such as H2 and O2, the increase in D did not exceed
the decrease in S. As a result, the permeability coef-
ficient for H2 and O2 decreased. In addition, intro-
duction of sulfonic acid groups gave a membrane
with high selectivity for H2–CH4 separation under
dry conditions. Under wet conditions, the sulfonated
polyimide membranes had relatively high selectivity
with high gas permeability for CO2–N2 separation.
A systematic study of the synthesis, characteriza-
tion, and gas transport properties of novel 6FDA-based
copolyimides was performed by Yuan and co-workers
[182]. They varied the diamine ratios, namely, 2,4,6-
trimethyl-1,3-phenylenediamine (TMPDA)/2,6-
diamino toluene (DAT), to synthesize copolyimides by
chemical imidization in a two-pot procedure (Scheme
3.18). The physical properties including FFV of the
6FDA-based copolyimides with various TMPDA/DAT
ratios, along with the homopolymers (6FDA-TMPDA
136 Handbook of Specialty Fluorinated Polymers

2 2

1 1 $U 17'$EDVHGSRO\LPLGHV

2 2
$U
&)
2 2 %$3+)
&)

+26 62+
&)
2 2 %$3+)'6+

&)
+&1+26 62+1&+
&)
2 2 %$3+)'6$
&)

Scheme 3.17  Chemical structure of polyimides.

Table 3.7  Comparison of Permeability and Selectivity of NTDA-Based Fluorinated Polyimides in Sulfonated
and Non-Sulfonated form at 35 °C and 1 atm
Pure Gas Permeabilities (Barrer) Ideal Selectivities (α*A/B)
NTDA-Based
P( H2 ) P(CO2) P(O2) P( N2 ) P( CH4 ) P(H2 ) /P(CH4 ) P(CO2 ) /P(N2 ) P(O2 ) /P(N2 )
Polyimide
NTDA-BAPHF 50 21 4.4 0.72 0.48 100 29 6.1
NTDA-BAPHFDS(H) 52 13 2.8 0.37 0.16 330 36 7.8

NTDA-BAPHFDS(A) 29 14 2.3 0.42 0.40 72 34 5.5

Reproduced from Ref. [181].

and 6FDA-DAT), were investigated, as summarized in
Table 3.8. The gas permeability coefficients and ideal
selectivity of 6FDA-TMPDA/DAT series polyimides
for different gases were carefully measured at 35 °C
and 0.2 MPa (Table 3.9). The authors observed that the
gas permeabilities and diffusion coefficients decreased
with increasing DAT content, whereas the permselec-
tivity of gas pairs such as H2–N2, O2–N2, CO2–CH4,
and CO2–N2 was enhanced by the incorporation of
DAT moiety. They also noticed that the diffusion coef-
ficients for all of the polyimides followed the trend: D
(O2) > D(CO2) > D(N2) > D(CH4), which was different
from that of the permeability coefficients, in that P(CO2 )
is much greater than P(O2 ) whereas D(CO2) is smaller
than D(O2). They explained it as specific interactions
between CO2 and the polar groups (e.g., –[CF3]2, CO2)
in the 6FDA-based polyimides, which may hinder the
mobility of CO2 molecules in the polyimide matrix.
Moreover, all of the reported copolyimides in that work
exhibited performance close to, at, or above the existing
“upper bound” tradeoff lines of that time (1991, Robe-
son upper bound [180]), as shown in Fig. 3.7(a) and (b)
for O2–N2 and CO2–CH4 gases respectively.
To investigate the additional effect of triphe-
nylamine (TPA) moieties on >C(CF3)2 containing
polyimides, Liou et al. [183] synthesized a series of
novel organo-soluble aromatic polyimides bearing
pendant methoxy-substituted TPA moieties. They
also prepared the same polyimide series without the
>C(CF3)2 group to compare their physical proper-
ties. A synthetic scheme of the TPA containing poly-
imide series is shown in Scheme 3.19. All of the
3: Fluorinated Polyimides 137

)& &) &+ &+

2 2
+1 1+ +1 1+

2 2  

&+ &+
2 2

)'$ '$7 703'$

103
:9
57

)& &) 2 )& &) 2

2 2
&+ 2+ &+
+2 2+ +2

1+  +1 1+
+1

2 2 2 2 &+ &+
Q
Q

$FHWLFDQK\GULGH
7ULHWK\ODPLQH
K

)& &) 2 2 )& &) 2

2 &+ &+

1 1  1 1

&+
2 2 2 2 &+
Q Q

Scheme 3.18  Reaction scheme of copolyimides [182].

Table 3.8  Physical Properties of 6FDA-TMPDA/DAT Copolyimides

PI Tg(°C) 5% wt loss (°C) Mn (×104) Mw (×104) ρ (g/cm−3) FFV
6FDA-TMPDA 380 517 6.94 11.49 1.352 0.182
6FDA-TMPDA/ 362 520 6.34 11.35 1.372 0.176
DAT(3:1)
6FDA-TMPDA/ 351 527 9.54 18.12 1.383 0.175
DAT(1:1)
6FDA-TMPDA/ 343 527 4.28 8.03 1.395 0.173
DAT(1:3)
6FDA-DAT 334 531 6.29 10.20 1.410 0.179

Reproduced from Ref. [183].

synthesized membranes exhibited good solubility in
common organic solvents with excellent thermal sta-
bility and their films were electroactive. Gas transport
properties of the >C(CF3)2-based polyimides with
structurally different TPA moieties were thoroughly
investigated; the results are summarized in Table
3.10. They observed that 4-methoxy-substituted TPA-
containing polyimides have a better permeation coef-
ficient than that of the polyimides without 4-methoxy
substitution with a similar structure. For example,
138 Handbook of Specialty Fluorinated Polymers

Table 3.9  Permeability Coefficients and Permselectivity of 6FDA-TMPDA/DAT Polyimides at 35 °C and
0.2 MPa
P (Barrer) α

PI H2 O2 N2 CO2 CH4 H2–N2 O2–N2 CO2–CH4 CO2–N2

6FDA-TMPDA 499.90 110.35 30.13 555.72 24.49 16.59 3.66 22.70 18.45
6FDA-TMPDA 516 109 31.6 431 26.0 16.3 3.5 16.6 13.6
6FDA-TMPDA/ 224.82 36.50 8.28 187.63 5.54 27.16 4.41 33.86 22.66
DAT (3:1)
6FDA-TMPDA/ 182.56 26.81 5.71 130.21 3.35 31.96 4.69 38.85 22.79
DAT (1:1)
6FDA-TMPDA/ 125.41 15.40 2.99 74.69 1.56 41.94 5.15 47.86 24.98
DAT (1:3)
6FDA-DAT 81.96 8.83 1.53 39.59 0.69 53.45 5.76 57.41 25.82
6FDA-DAT 102 10.3 1.83 34.0 – 59.7 5.64 – 18.6

1 Barrer = 10−10 cm3 (STP) cm cm−2 s−1 cm Hg−1.
Reproduced from Ref. [182].

D E

 
Ğ&2&+
D21

5REHVRQXSSHUERXQG  5REHVRQXSSHUERXQG
)'$703'$ )'$703'$
D D
)'$703'$'$7 )'$703'$'$7
D D
)'$703'$'$7 )'$703'$'$7
D D
)'$703'$'$7 )'$703'$'$7
)'$'$7 )'$'$7
 
       
32%DUUHU 3&2%DUUHU

Figure 3.7 Performance of 6FDA-TMPDA/2,6-DAT copolyimides compared with (a) O2–N2 tradeoff limit and
(b) CO2–CH4 tradeoff limit. Reproduced with permission from Ref. [182].

( )
the oxygen permeability coefficients P(O2 ) of IIb that hindered intra-segmental mobility, disrupted
with 4-methoxy-substituted TPA-containing poly- interchain packing, and stiffened the backbones. By
imides was reported combining the excellent physical properties and good
( as 4.28 Barrer,
) which was higher
than that of Ib P(O2 ) : 0.69 without 4-methoxy- gas transport properties, they concluded that such
substituted TPA-containing polyimides under simi- polymers can be explored as newly processable high-
lar experimental conditions. Similar trends were performance polymers with multiple functions.
observed with other polyimides of the same series; Between 2000 and 2010, Banerjee and co-workers
that is, polymer IVb was more permeable to gases extensively worked on developing novel polyimide
than polymer IIIb. In addition, polyimides Ib, IIb, membranes for selective gas separation, particularly
and IVb had higher selectivity for CO2–CH4 separa- O2–N2 and CO2–CH4 gas pairs (Tables 3.11 and
tion owing to the presence of bulky a –C(CF3)2 group 3.12) [76,77,184–188]. Schematic representations
 +1 1+ 2 2

1  2 $U 2

2 2

5 

±

2 2
5710 3 1+ & & 2+
$U
1
+2 & & 1+
2 2 Q

5
2 2

1 $U 1
+2

1 2 2

5
,±,9

1 1
5 + &+
+&2 2&+

, ,, ,,, ,9

2
)& &)
6
$U 
2

D E

Scheme 3.19  Synthetic scheme of polyimides containing TPA-moiety via chemical imidization [183].

Table 3.10  Permeability Coefficients and Ideal Separation Factors of 6FDA-Based Polyimides with different
TPA Moieties, Measured at 35 °C and 1 atm
Permeation Permeabilities (Barrer) Permselectivities (αA/B)

P(O2) P( N2 ) P(CO2) P( CH4 ) P(O2 ) /P(N2 ) P(CO2 ) /P(CH4 )

Index
Ib 0.69 0.08 4.73 0.08 8.63 59.13
IIb 4.28 0.89 16.82 0.50 4.81 33.64
IIIb 1.97 0.45 11.77 1.24 5.05 9.49
IVb 2.94 0.59 12.97 0.40 4.98 32.43

Data taken from Ref. [183].

 140
Table 3.11  Ideal Gas Separation Properties for O2–N2 Gas Pair

P(O2) P( N2 )
Polymer αp(O2–N2) D(O2) D(N2) αD(O2–N2) Reference
BAQP-6FDA (Ia) 17.08 3.11 5.5 6.02 1.87 3.2 [186]
BATP-6FDA (Ib) 15.17 2.87 5.3 6.19 2.12 2.9 [186]
BAPy-6FDA (Ic) 12.15 1.91 6.4 4.85 1.35 3.6 [186]
BATh-6FDA (Id) 11.65 1.78 6.6 5.57 1.43 3.9 [186]
BPI-BPADA (IIa) 10.95 2.08 5.26 7.94 5.86 1.35 [184]

Handbook of Specialty Fluorinated Polymers

BPI-6FDA (IIb) 14.98 2.44 6.14 11.97 7.54 1.59 [184]
BPI-BTDA (IIc) 7.98 1.32 6.05 5.23 3.67 1.43 [184]
BPI-ODPA (IId) 8.95 1.42 6.30 7.08 4.45 1.60 [184]
BPI-PMDA (IIe) 12.22 2.36 5.18 9.34 6.77 1.38 [184]
BAPA-BPADA (IIIa) 4.25 0.95 4.47 4.17 1.07 3.90 [185]
BAPA-6FDA (IIIb) 10.23 1.71 5.98 7.47 1.38 5.41 [185]
BAPA-BTDA (IIIc) 4.33 0.83 5.22 4.81 1.28 3.76 [185]
BAPA-ODPA (IIId) 4.22 0.96 4.40 5.28 1.22 4.33 [185]
BAPA-PMDA (IIIe) 7.62 1.20 6.35 6.20 1.88 3.30 [185]
FBP-BPADA (IVa) 7.01 1.19 5.89 6.99 3.34 2.09 [187]
FBP-6FDA (IVb) 13.46 2.06 6.53 13.11 4.98 2.63 [187]
FBP-BTDA (IVc) 6.24 0.95 6.57 8.22 4.11 2.00 [187]
 3: Fluorinated Polyimides
FBP-ODPA (IVd) 7.86 1.22 6.44 8.08 3.61 2.24 [187]
BIDA-BPADA (Va) 10.32 1.23 8.39 11.44 1.95 5.87 [77]
BIDA-6FDA (Vb) 25.37 4.22 6.01 14.00 3.32 4.22 [77]
BIDA-BTDA (Vc) 6.99 0.98 7.13 6.30 1.59 3.96 [77]
BIDA-ODPA (Vd) 7.74 1.45 5.34 5.87 1.93 3.04 [77]
SBPDA-BPADA (VIa) 9.92 1.02 9.73 9.01 1.96 4.60 [76]
SBPDA-6FDA (VIb) 36.08 3.35 10.77 22.72 4.90 4.64 [76]
SBPDA-ODPA (VIc) 13.07 1.12 11.67 11.41 2.90 3.93 [76]
HQ-BPADA (VIIa) 3.21 0.49 6.55 1.46 1.05 1.39 [188]
HQ-6FDA (VIIb) 11.8 1.25 9.44 4.78 1.41 3.39 [188]
HQ- BTDA (VIIc) 3.33 0.44 7.57 4.83 1.39 3.47 [188]
HQ-ODPA (VIId) 2.8 0.49 5.71 1.72 1.53 1.12 [188]
HQ-PMDA (VIIe) 3 0.32 9.38 1.36 0.60 2.27 [188]

141
 142
Table 3.12  Ideal Gas Separation Properties for CO2–CH4 Gas Pair

P(CO2) P( CH4 )
Polymer αp(CO2–CH4) D(CO2) D(CH4) αD(CO2–CH4) Reference
BAQP-6FDA (Ia) 36.61 1.51 24.3 4.68 0.51 9.2 [186]
BATP-6FDA (Ib) 33.12 1.19 28.2 3.47 0.64 5.4 [186]
BAPy-6FDA (Ic) 51.92 1.95 26.6 2.18 0.31 7.0 [186]
BATh-6FDA (Id) 45.31 1.68 27.0 2.31 0.26 0.89 [186]
BPI-BPADA (IIa) 39.45 1.38 28.59 4.56 0.58 7.86 [184]

Handbook of Specialty Fluorinated Polymers

BPI-6FDA (IIb) 57.45 1.62 35.46 5.70 0.68 8.38 [184]
BPI-BTDA (IIc) 34.20 0.88 38.86 3.39 0.40 8.48 [184]
BPI-ODPA (IId) 35.78 0.98 36.51 4.24 0.49 8.65 [184]
BPI-PMDA (IIe) 44.68 1.52 29.39 4.83 0.64 7.55 [184]
BAPA-BPADA (IIIa) 16.61 0.84 19.77 1.96 0.55 3.56 [185]
BAPA-6FDA (IIIb) 53.85 1.01 53.32 3.79 0.92 4.12 [185]
BAPA-BTDA (IIIc) 17.09 0.62 27.57 1.46 1.24 1.18 [185]
BAPA-ODPA (IIId) 14.59 0.84 17.37 1.86 1.04 1.79 [185]
BAPA-PMDA (IIIe) 39.57 0.79 50.09 1.74 1.65 1.06 [185]
FBP-BPADA (IVa) 22.52 1.01 22.30 3.79 0.95 3.99 [187]
FBP-6FDA (IVb) 53.09 1.34 39.62 4.83 1.24 3.90 [187]
FBP-BTDA (IVc) 36.07 0.94 38.37 4.02 1.04 3.87 [187]
 3: Fluorinated Polyimides
FBP-ODPA (IVd) 25.91 1.04 24.91 4.01 1.02 3.93 [187]
BIDA-BPADA (Va) 25.65 0.69 37.17 2.54 1.64 1.55 [77]
BIDA-6FDA (Vb) 71.32 1.99 35.84 3.28 1.48 2.22 [77]
BIDA-BTDA (Vc) 16.06 0.55 29.20 1.26 1.54 0.82 [77]
BIDA-ODPA (Vd) 16.99 0.67 25.36 1.85 1.63 1.14 [77]
SBPDA-BPADA (VIa) 23.87 0.35 68.2 3.01 1.83 1.65 [76]
SBPDA-6FDA (VIb) 52.98 1.21 43.79 6.25 3.79 1.65 [76]
SBPDA-ODPA (VIc) 22.24 0.41 55.22 3.85 2.28 1.69 [76]
HQ-BPADA (VIIa) 13 0.27 48.15 1.24 0.59 2.10 [188]
HQ-6FDA (VIIb) 55.4 1.22 45.41 3.82 1.25 3.06 [188]
HQ- BTDA (VIIc) 10.53 0.27 39.0 1.43 0.85 1.68 [188]
HQ-ODPA (VIId) 10.22 0.59 17.32 1.58 1.29 1.22 [188]
HQ-PMDA (VIIe) 11 0.31 35.48 1.28 0.59 2.17 [188]

143
144
of all of the synthesized polyimides examined for
gas transport properties are shown in Scheme 3.20
and Scheme 3.21, respectively. They systematically
studied the physical and gas transport properties of
all of the membranes toward four different gases (O2,
N2, CO2, and CH4) at three different temperatures
(35, 45, and 55 °C) under an applied upstream pres-
sure of 3.5 bar. First, a series of four fluorinated
poly(ether imide)s was prepared from four differ-
ent fluorinated diamines (4,4-bis[3′-trifluoromethyl-
4′(4″-aminobenzoxy)benzyl] biphenyl [BAQP],
1,4-bis[3 ′ -trifluromethyl-4 ′ (4 ″ -aminobenzoxy)
benzyl]benzene [BATP], 2,6- bis[3′-trifluromethyl-
4′(4″-aminobenzoxy)benzyl]pyridine [BAPy],
and 2,5-bis[3′- trifluromethyl-4′(4″-aminobenzoxy)
benzyl] thiophene [BATh], respectively) using a
2 $U
&)
$U
D
E
F
G
Scheme 3.20  Chemical structure of the synthesized poly(ether imide)s, series I.
&)
2 $U
1
1
$U
Handbook of Specialty Fluorinated Polymers
common fluorinated dianhydride, 4,4′-(hexafluoro-
isopropylidene)diphthalic anhydride (6-FDA), as
presented in Scheme 3.20.
In a different study, they synthesized another five
series of poly(ether imide)s based on five different
cardo moiety containing diamines, designated as
BPI, BAPA, FBP, BIDA, and SBPDA, as presented
in Scheme 3.21. Five different aromatic dianhydride,
4,4 ′ -(4,4 ′ -isopropylidenediphenoxy)bis(phthalic
anhydride) (BPADA), 4,4′-(hexafluoro-isopropyli-
dene) diphthalic anhydride (6-FDA), 3,3′4,4´-benzo-
phenone tetracarboxylic acid dianhydride (BTDA),
4,4″-oxydiphthalic anhydride (ODPA), and benzene-
1,2,4,5-tetracarboxylic dianhydride (PMDA), were
used to prepare each series of poly(ether imide)s.
The O2–N2 and CO2–CH4 separation properties for
&) 2 &) &) 2
2 1 1
2 2 Q
1 6
2 2
2 1 $U
Q
&) 2 2
2 2
1

%3,,, %$3$,,, )%3,9 %,'$9 6%3'$9, +49,,

2
&+  &) &)
2
2 2
$U

&+ 

%3$'$D )'$E %7'$F 30'$H

2'3$G

Scheme 3.21  Chemical structure of poly(ether imide) series II, III, IV, V, VI, and VII.
3: Fluorinated Polyimides
all of the synthesized polyimide membranes were
presented in Robeson’s upper bound plot (Figs 3.8
and 3.9) and values were compared (with respect
to Robeson’s latest upper boundary limit) with two
potentially used polyimide membranes, Matrimid
and Ultem. Upon analysis of the gas transport prop-
erties of series I (“Ia,” “Ib,” “Ic,” and “Id”) poly-
imide membranes, they reported that incorporation
of an angular structure into the polymer backbone
along with an increase in polarity makes the mem-
brane more permeable to CO2 (data presented in
Table 3.12). Hence, membranes with a high through-
put of CO2 were developed from series I polymer
membranes, but at the cost of permselectivity of
CO2 over CH4. Also, the ideal permselectivity of the
membranes was below that of Matrimid and Ultem.
Figure 3.8 Robeson plot for comparison of O2–N2
separation properties of investigated polymers with
Matrimid® and Ultem®.
Figure 3.9 Robeson plot for comparison of CO2–CH4 separation properties of investigated polymers with
Matrimid® and Ultem®.
145
To obtain better gas transport properties, a bis-
phenol indane-based new polyimide series (series
II) was synthesized containing a cardo group with a
reduced intersegmental length. Among the five poly-
imides of that series (series II), polymer IIb (BPI-6FDA)
had a higher flux of CO2 along with good selectiv-
ity that was comparable to Matrimid (Fig. 3.9). In
their next study, the authors manipulated the FFV by
using phenolphthalein anilide as another cardo group
to prepare the polyimide series (series III). The pla-
nar geometry of phenolphthalein anilide helped to
optimize the interchain distance by forming an effec-
tive CTC and the intersegmental length was reduced.
As a result, the series (series III) of membranes had
improved CO2 permeability (up to 53.85 Barrer for
IIIb) and much better permselectivity of CO2–CH4
(up to 53.32 for IIIb), superior to that of both Mat-
rimid and Ultem. Two more polyimide series (series
IV, FBP-based polyimide; and series V, BIDA-based
polyimide) were prepared to further optimize gas
transport properties. The CO2 permeability increased
up to 71.3 Barrer for “Vb” (BIDA-6FDA) and O2–
N2 permselectivity was enhanced up to 8.4 for “Va”
(BIDA-BPADA) but no better CO2–H4 permselec-
tivity could be achieved compared with polyimide
“IIIb.” Combining all of the results, with increasing
polarity of the polymer structure, CO2 permeabil-
ity substantially increased with a loss of CO2–CH4
selectivity that was controlled by the rigidity of the
polymer backbone. Taking an idea from all these
study, the authors suggested that a polymer with high
rigidity and lower or moderate polarity could result
in better permselectivity (CO2–CH4) along with high
permeability of CO2. Hence, they prepared another
146
series of polyimide (series VI) containing rigid
bis-spiro indane moiety in the backbone structure.
As expected, this series of polyimides had excel-
lent permselectivity for both CO2–CH4 (up to 68.2
for VIa) and O2–N2 (up to 11.7 for VIc) gas pairs.
However, in this case, CO2 permeability was slightly
reduced whereas O2 permeability was remarkably
enhanced (up to 36.1 Barrer for VIb).
In addition to the cardo moiety-based polyimide
series, the authors synthesized a new series (VII) of
polyimides based on a flexible fluorinated diamine,
1,4-bis-([2′-trifluromethyl-4′-(4″-aminophenyl)phe-
noxy])benzene (HQA) and different aromatic dian-
hydrides, namely, BPADA, 6FDA, ODPA, BPDA,
BTDA, and PMDA [188]. These series of polyimides
were highly processable with high thermal stability
(Td,10% up to 558 °C) and mechanical strength (TS up
to 107 MPa with 15% EB). Surprisingly, these series
of polyimides had almost similar permeability coeffi-
cients (see Tables 3.11 and 3.12) with different perm-
selectivity values except for “VIIb.” The researchers
reported that polyimide
( VIIb had )very high CO2
permeability P(CO2 ) = 55.4 Barrer ( and moder-)
ately high O2 permeability P(O2 ) = 11.8 Barrer
(with high permselectivity for different gas ) pairs
P(CO2 ) /P(CH4 ) = 45.41andP(O2 ) /P(N2 ) = 9.44 , which
surpassed the upper boundary limit drawn by Robe-
son for the O2–N2 gas pair.
3.3.2  Fluorinated Polyimides
in Pervaporation
Between 2000 and 2010, membrane pervapora-
tion has gained acceptance in the chemical industry
as an effective process tool for the separation and
recovery of liquid mixtures. It is currently best iden-
tified with dehydration of liquid hydrocarbon to yield
high-purity organics, most notably ethanol, isopropyl
alcohol, and ethylene glycol. Because of its favor-
able economics, efficiency, and simplicity, it can
easily be integrated into distillation and rectification,
and depending on the specific process, it can even
replace them. Currently, considerable data are avail-
able on industrial-scale processes using pervapora-
tion to evaluate its performance. Contamination of
ground water and soil by volatile organic compounds
(VOCs) is a social problem. Their toxicity has been
noted for several years. Several processes, that is, aer-
ation and adsorption on activated carbon, photolysis,
and ozonation, have been proposed to remove VOCs
from contaminated ground water and wastewater.
Handbook of Specialty Fluorinated Polymers
Pervaporation is attractive and cost-competitive com-
pared with these methods.
Pervaporation is a membrane separation process
for separating liquid mixtures, in which the liq-
uid mixture is in contact with the membrane on the
feed or upstream side at atmospheric pressure and
the downstream is kept in a vacuum state or applied
with sweeping gas [189,190]. In pervaporation, a
liquid stream containing two or more components is
placed in contact with the upstream side of a non-
porous polymeric membrane or molecularly porous
inorganic membrane, allowing sorption of the com-
ponents into or onto the membrane. The penetrants
diffuse through the membrane and evaporate because
of the chemical potential difference across the mem-
brane induced by vacuum or gas purge [191]. Separa-
tion of different components is achieved when some
of the components preferentially diffuse across the
membrane. Figure 3.10 represents a schematic dia-
gram of pervaporation.
Pervaporation offers several distinct advantages
over conventional separation methods (e.g., distil-
lation, adsorption). First, it has superior separation
efficiency, especially in separating azeotropic and
close-boiling liquid mixtures [189] because the prin-
ciple of pervaporation is based on the differential
transport of penetrants through the membrane instead
of the vapor–liquid equilibrium. Second, it is an envi-
ronmentally friendly green technology, particularly
for the energy-saving aspect and the reduction of
emissions from environmental pollutants [189,192].
In addition, flexibility and simplicity in system pro-
cess control and in module fabrication make this pro-
cess attractive [193]. Thus, commercial membrane
applications have successfully displaced some con-
ventional processes, and this technology has become
an essential component in many industrial fields.
Figure 3.10  Schematic diagram of pervaporation.
3: Fluorinated Polyimides
Pervaporation differs from other membrane sepa-
ration processes in that the membrane constitutes
a barrier between a liquid in the feed and vapor in
permeate. Here, phase change occurring as a result
of partial pressure of the permeating components is
lower than the corresponding saturation pressures.
Currently, it is an important technique for separat-
ing close-boiling mixtures [194], dehydrating organ-
ics [190,195], separating organics from water [196],
removing sulfur from gasoline [197], and recovering
volatile organic chemicals from liquid mixtures at
very low concentrations, and it has emerged as a good
alternative for separating heat-sensitive products.
The phenomenon of pervaporation was first dis-
covered in 1917 by Kober [198] at the New York
State Department of Health Research Laboratories.
Kober mentioned the phenomenon of pervapora-
tion in a publication describing experiments with
water-selective permeation from an albumin–tolu-
ene solution through “colloidion containers” (cellu-
lose nitrate). Later, Farber (1935) at the University
of Toronto presented the results of work using per-
vaporation for concentrating a protein solution but no
extensive research was carried out until the 1950s.
During that period, pervaporation was only consid-
ered a laboratory tool that could at best compete in a
few particular cases with other membrane processes,
such as ultrafiltration and reverse osmosis. The low
magnitude of permeation flow rates through homoge-
neous dense film seemed likely to prevent large-scale
industrial application of this technique. This situa-
tion changed in the 1960s after the development of
a phase inversion procedure by Loeb and Sourirajan
[199]. Attempts were then made in several different
countries to solve certain major industrial separation
problems by pervaporation.
Between 1958 and 1962, Binning and co-workers
from the American Oil Company, Texas, carried out
a series of investigations concerning the separation
of hydrocarbon mixtures by partial vaporization
through a nonporous film of polyethylene [200,201].
At the similar time, systematic studies on pervapora-
tion and vapor permeation were studied in France by
Neel et al. (1965) [202]. They carried out experiments
with homogeneous films prepared from various func-
tionalized polymers or copolymers obtained from
polar monomers containing N-substituted amide or
lactam side groups.
A breakthrough was achieved in 1980s, when
Gesellschaft für Trenntechnik (GFT) Co, (West Ger-
many) developed a composite membrane composed
147
of a thin layer of cross-linked poly(vinyl alcohol)
supported on a porous poly(acrylonitrile) substrate
[203]. In 1982, the first industrial application of the
pervaporation process was launched by GFT GmbH
of Germany (since acquired by Sulzer Chemtech) for
the dehydration of ethanol using PVA/PAN compos-
ite membranes [191]. The first industrial plant was
built in Brazil and then in the Philippines for pro-
cesses using continuous fermentation of sugarcane,
sweet sorghum containing 5–7% ethanol. Ethanol
was distilled first up to 80–85% and then concen-
trated to 96 wt.% with vacuum pervaporation. In the
following years, about 20 more plants with larger
productive capacities were installed by GFT in West-
ern Europe and the United States (US) [204]. Another
built by Lurgi GmbH [205] was used to complement
a predistillation step and extract pure ethanol from
a fermentation broth. In Japan, the development of
pervaporation began under the leadership of Mitsui
Engineering and Shipbuilding Co, Ltd. under the
GFT license. Thereafter, until 1996, more than 90
industrial pervaporation units were globally installed
[206]. During that period, around 200 European and
US patents were published on pervaporation. To date,
the choice of pervaporation-based hybrid systems
is absolutely necessary for industrial applications
[192,207,208].
3.3.2.1  Principles of Separation
In separation technologies, membranes are defined
as the semipermeable interphase media between two
bulk phases [161]. A membrane process allows selec-
tive and controlled transfer of species from one bulk
phase to the other. The permeability and selectivity
define the characteristics of separation membranes.
In general, components in a mixture are separated by
membranes based on principles as follows [191]:
1. 
Separation occurs because of size or steric
effects that are related to macroscopic pores
in porous membranes or molecular-level inter-
space between macromolecules in nonporous
membranes. The size difference of the two com-
ponents results in a difference in flow rates, with
components with large sizes diffusing with more
resistance than those with smaller steric factors.
Good selectivity can be achieved for mixtures
of components with unlike steric factors.
2. Separation properties are related to interactions
among membrane materials and the components
 148 Handbook of Specialty Fluorinated Polymers

to be separated. In the case of nonporous mem-

branes, these factors are often dominant in con-
trolling separation performance.

3.3.2.2  Mass Transport in Pervaporation 

Membranes
Proper understanding of the membrane separation
mechanism may provide direct information about
research and development for an appropriate mem-
brane. Because of complicated penetrant membrane
interactions, it is difficult to formulate a single expla-
nation for the complex transport process. There are
three principal approaches to describing mass trans-
port in pervaporation: Figure 3.11 Schematic of pervaporation transport
mechanism (solution–diffusion model).
1. Solution–diffusion model
2. Pore flow model
3. Carrier transport model

1. Solution–diffusion model: In the solution–

diffusion model, permeates dissolve in the
membrane material and then diffuse through
the membrane down a concentration gradient.
Separation is achieved between different per-
meates because of differences in the amount
of material that dissolves in the membrane and
the rate at which the material diffuses through
the membrane. The solution–diffusion model
is the most widely accepted transport mecha-
nism for many membrane processes [209,210].
Selectivity and permeability of a pervapora-
tion membrane mainly depend on the first two
steps, that is, the solubility and diffusivity of
the components in the membrane. According to
this model, mass transport can be divided into
the three steps; the mechanism is shown in Fig.
3.11:
a. Sorption of liquids into the mem-
brane at the feed side
b. Diffusion of the sorbed components
through the membrane
c. Desorption–evaporation of the sorbed
components at the permeate side
2. Pore-flow model: In pore-flow model, perme-
ates are separated by pressure-driven convec-
tive flow through tiny pores. Separation is
achieved between different permeates because
Figure 3.12 Schematic representation of pore-flow
model.
one of the permeates is excluded (filtered) from
some of the pores in the membrane through
which other permeates move. This model was
first proposed by Matsuura et al. [193,211]. In
this model, mass transport involves
a. liquid transport from the pore inlet
to the liquid–vapor phase boundary,
b. evaporation at the phase boundary,
and
c. vapor transport from the phase
boundary to the pore outlet.
The main difference between the solution–diffusion
model and the pore-flow model is the location of phase
change in the membrane. In the pore-flow model, as
shown in Fig. 3.12, the phase change occurs at a cer-
tain distance from the membrane surface in contact
with the liquid feed, and accordingly the transport
3: Fluorinated Polyimides
Figure 3.13  Schematic representation of a carrier transport model.
mechanism changes from liquid permeation to vapor
permeation at the liquid–vapor boundary [193].
3. Carrier transport model: The basic idea of the
carrier transport mechanism for pervaporation
comes from biological membranes consisting
of polypeptides, and is based on the similarity
of molecular interactions between the peptides
and the functional groups in synthetic polymers
[212]. Membranes with carriers are classified
into two categories: fixed carrier membranes
and non-fixed carrier membranes [213].
Figure 3.13 represents mass transport in both
fixed carrier membranes and non-fixed carrier mem-
branes. Transport energy in the fixed carrier mem-
branes is much higher than that in non-fixed carrier
membranes because adsorption and desorption are
repeated continuously when a permeating compo-
nent forms a complex with a carrier in the membrane.
Alternatively, once a component forms a complex
with a carrier in a non-fixed carrier membrane, the
other component can move only after one carrier is
released from the former complex formed previously,
for which high selectivity is achieved.
3.3.2.3  Physical and Pervaporation 
Properties of Fluorinated Polyimides
The polyimide family has become increasingly impor-
tant over past decades for various separation processes,
of which pervaporation is one. Aromatic polyimides
belong to the class of high-performance polymers that
are well-known for their excellent thermal, chemical,
and physical properties and have superior film-forming
ability. The molecular structure of polyimide contains
149
four polar carbonyl groups that are capable of forming
hydrogen bonding with polar-protic solvents; this is one
of the most important reasons why aromatic polyimides
have been developed as pervaporation dehydration
membranes [214,215]. Furthermore, the chain stiffness
and packing density of polyimides that arise as a result
of the strong affinity of polar imide groups toward the
π-electrons of aromatic rings influences the selectivity
and permeability of the membranes for pervaporation
[216]. Using aromatic dianhydrides containing –CF3
groups such as 6FDA to synthesize polyimides, chain
mobility and chain packing can be restricted, which in
turn results in improvement in selectivity. Permeability
is simultaneously enhanced owing to the high FFV pro-
duced by the bulky –CF3 groups.
To investigate the effect of fluorinated alkyl side
groups into polyimide membranes on their physi-
cal and pervaporation properties, Kim et al. [217]
synthesized a few polyimide membranes with and
without fluorinated alkyl side groups and compared
their separation performance. The results showed
that incorporation of fluorinated alkyl side groups
lowers the cohesive energy and surface free energy
of polyimide membranes, and enhances free volume
between the polyimide segments and chain flex-
ibility. The researchers used several dilute aqueous
organic solutions to study the pervaporation proper-
ties of the membranes. They observed that pervapora-
tion selectivity and the permeation rate of polyimide
membranes with fluorinated side groups had higher
values than those without the side groups toward the
feed solution with hydrophobic solvents. This can be
explained in terms of their enhanced sorption/sorp-
tion selectivity and concentration-average diffusion
coefficient/diffusivity selectivity toward organic sol-
vent over water owing to enhanced hydrophobicity
150 Handbook of Specialty Fluorinated Polymers

and increased FFV obtained by the introduction of
fluorinated side groups. The authors concluded that
incorporation of fluorinated alkyl side group into
polyimide membranes significantly improved their
pervaporation performance for the separation of
hydrophobic organic solvents from water.
Kang et al. carried out synthesis of a fluorinated poly-
imide (FPI) with grafted poly(N-isopropylacrylamide)
(NIPAAm) side chains as a temperature-sensitive
microfiltration membrane [218]. Molecular modifica-
tion of the FPI was performed via ozone pretreatment
followed by thermally induced graft copolymeriza-
tion, as shown in Scheme 3.22. They cast the result-
ing FPIs with grafted NIPAAm polymer side chains
(DMMDA), to synthesize the polyimides (Scheme
3.23). Asymmetric polyimide membranes were pre-
pared by phase inversion and the inner structure was
analyzed by scanning electron microscopy (SEM). As
shown in Fig. 3.14, the cross-sectional SEM image of
the 6FDA–MDA membrane consisted of an ultrathin
skin layer and a porous finger-like structure. The per-
vaporation properties of the prepared polyimides asym-
metric membranes for n-heptane/thiophene mixtures
were investigated at 40–77 °C. The permeation flux and
sulfur enrichment factor of the polyimide membranes
2 &) &) 2

(FPI-g-P[NIPAAm] copolymers) into microfiltration

&+ 1 1
membranes by phase inversion in water at temperatures
ranging from 4 to 55 °C. They observed that the flux 2 2 Q
of water and 2-propanol through the FPI-g-P(NIPAAm) )'$±0'$
copolymer membrane exhibited strong dependence on &+ 2 &) &) 2
the casting temperature of the membrane and the per-
meate temperature in the temperature range 4–55 °C. &+ 1 1
Another kind of 6FDA-based organo-soluble fluoro- Q
&+ 2 2
polyimide membranes with high thermal stability was
)'$±'00'$
synthesized by Li and co-workers [219]. They used
two types of diamines, 4,4′-methylene diamine (MDA) Scheme 3.23 Molecular structure of 6FDA-based
and 4,4′-diamino-3,3′-dimethyldiphenylmethane fluorinated polyimides [219].

Scheme 3.22  Processes of thermally induced graft copolymerization of NIPAAm with the ozone-preactivated
fluorinated polyimide and preparation of an FPI-g-P(NIPAAm) membrane by phase inversion. Reproduced with
permission from Ref. [218].
3: Fluorinated Polyimides
were reported in the range 0.56–1.68 kg/m2 h and 3.12–
2.24, respectively, which were found to increase with an
increase in the operation temperature.
A systematic study of the temperature-dependent
separation of naphthalene/n-decane mixtures using
fluorinated-copolyimide membranes was reported
by Staudt et al. [220]. They synthesized fluorinated
non-cross-linked and cross-linked 6FDA–4MPD/
DABA (m:n) copolyimides from 4,4′-hexafluoroiso-
propylidene diphthalic anhydride (6FDA), 2,3,5,6-
tetramethyl-1,4-phenylene diamine (4MPD), and
3,5-diamino benzoic acid (DABA) for pervapora-
tion experiments (Scheme 3.24). To investigate the
appropriate conditions for enhanced permeation
of naphthalene, they varied the feed temperature
between 60 and 150 °C and pretreated the membrane
500 X
Figure 3.14 Scanning electron microscopy cross-
sectional image of 6FDA–MDA polyimide membrane.
Reproduced with permission from Ref. [219].
2 &) &) 2 +&
1 1
2 2 +&
)'$03''$%$PQ
151
before pervaporation experiments. They also var-
ied the copolymer compositions and cross-linking
agents to further investigate the pervaporation prop-
erties. All of the membranes were examined in
temperature-dependent pervaporation experiments;
enrichment factors as well as the fluxes increased
with an increase in temperature. It was also observed
for almost all membranes, the enrichment factors
(β) rose to a plateau at about 100 °C and remained
constant at values between β = 1.8 and β = 2.5, up to
150 °C. Furthermore, it was noticed that for the pre-
treated membranes, variation in the chain length of
the cross-linking agent had almost no influence on
the enrichment factors, but the same led to a reduc-
tion in permeability with increased chain length. In
addition, they reported that a low m:n ratio and short
chain length of the cross-linking agent led to high
flux whereas selectivity was only slightly influenced
by these parameters.
Chung et al. synthesized a novel 6FDA-NDA/
DABA polyimide and modified its structure via var-
ious cross-linking modifications for pervaporation
dehydration of ethanol–water mixtures [221]. First,
the pristine polyimide, 6FDA-NDA/DABA, was
synthesized from 6FDA and two types of diamine,
1,5-naphthalene diamine (NDA) and DABA, as
shown in Scheme 3.25. Thereafter, three different
cross-linking methods (thermal, diamino, and diol
cross-linking) were adopted and their effects on
membrane morphology and separation performance
were thoroughly investigated. They observed that
thermal treatment at high temperature (425 °C)
facilitated decarboxylation-induced cross-linking
&+ 2 &) &) 2
1 1
&+ 2 2
P Q
+2 2
QRQFURVVOLQNHG

2 &) &) 2 +& &+ 2 &) &) 2

1 1 1 1

2 2 +& &+ 2 2
P Q
2
2 2
)'$03''$%$PQ 2
FURVVOLQNHG ZLWK EXWDQHGLRO 

Scheme 3.24  Structure of non-cross-linked and cross-linked 6FDA-based copolyimides [220].

152 Handbook of Specialty Fluorinated Polymers

2 2 1+
) & &)
+ 1 1+
QP 2 2  Q  P
2 2 1+ &22+
)'$ 1'$ '$%$

2 ) & &) 2

2+
+1 2 ) & &) 2
+2 1
+ +2 1
2 2
1 2+

Q 2 2 &22+
P
+2
2 ) & &) 2

1 1 2 ) & &) 2

2 2 1 1

Q
2 2
&22+
P

Scheme 3.25  Synthetic scheme of 6FDA-NDA/DABA polyimide [221].

2 2 2 2

2+  +2 +2 2 +HDWLQJ


Scheme 3.26 Thermal cross-linking mechanism of the 6FDA-NDA/DABA polyimide containing carboxylic
groups [221].
(Scheme 3.26), which restricted membrane swelling
with enhanced d-spacing among polymer chains and
contributed to high permeation fluxes and compa-
rable separation factors of the resultant membranes
for ethanol dehydration. Upon diamino cross-
linking, imide groups were converted into amide
groups in polyimide molecules, which partly pre-
vented swelling and stabilized performance, but the
separation factor of these membranes was still low.
However, post-thermal treatment converted amide
groups back into imide groups, which facilitated
the formation of CTCs and increased membrane
hydrophilicity, resulting in improved separation
performance of the membrane. Diol cross-linking
(Scheme 3.27) also constrained membrane swell-
ing and resulted in higher d-spacing by the cross-
linking spacer, which led to higher flux but a lower
separation factor than membranes modified by the
above two other methods.
&2  &2 &URVVOLQNLQJ
Ultimately, the researchers found the separation
factors of the cross-linked membranes to be in the
order: thermally treated diamine cross-linked mem-
brane > thermally cross-linked membrane > diol cross-
linked membrane; the fluxes were in the opposite
order. Thus, they concluded that compared with other
polymeric membranes, the membranes in that study
exhibited impressive fluxes and comparable separa-
tion factors, which contribute to the selection of suit-
able monomers for polyimide synthesis and effective
cross-linking modifications of the resultant polyimide.
3.3.3  Fluorinated Sulfonated
Polyimides as PEMs
The development of PEMFCs has been strongly
related to improvements in the performance of
PEMs. The use of an ion exchange membrane as an
electrolyte was first suggested by Grubb in 1957,
3: Fluorinated Polyimides 153

&22+ 2+
  +2
2+ 2 2

&22+ 2 2
+2
2+

&22+

+2 2 2
2+

2 2

Scheme 3.27  Diol cross-linking mechanism of the 6FDA-NDA/DABA polyimide with ethylene glycol [221].

and the first fuel cell system based on a sulfonated

polystyrene electrolyte was developed by General
&DWDO\VW &DWDO\VW 2
Electric in the 1960s for NASA for application as
2[\JHQ
an on-board power source in the Gemini space pro- & 2 IURPDLU
3URWRQH[FKDQJH
gram. Basically, a PEMFC converts hydrogen and $ PHPEUDQH $ 2
oxygen electrochemically into electrical power, + + 1 +  7
+
heat, and water. The electrochemical reaction takes +\GURJHQ 2 +
place in the membrane electrode assembly (MEA). IURPWDQN + +
' 2 ([KDXVW
It typically consists of an ion-conducting polymer
( '
membrane sandwiched between the anode and cath-
( + 2
ode, each containing a macro-porous diffusion back-
ing and an active catalyst layer. In fact, hydrogen is H± H± +2
split into protons and electrons at the anode (nega-
tive electrode). The PEM placed in the center allows
H± H±
protons to pass from the anode to the cathode (posi- (OHFWULFFXUUHQW
tive electrode), whereas the electrons induce a cur-
rent through an external circuit to the cathode. At the $QRGHHOHFWURGH+ +H௅
cathode, the electrons recombine with the protons 
&DWKRGHHOHFWURGH2+ H௅ +2
that have crossed the membrane and with oxygen 2YHUDOOFHOOUHDFWLRQ+2 +2
from air, as presented in Fig. 3.15.
The roles of a PEM are to provide ionic conductiv- Figure 3.15  Schematic representation of a fuel cell.
ity, prevent the flow of electrons, act as a barrier to
the reactants, and maintain chemical and mechanical high mechanical strength, good film-forming ability,
stability. In the operating fuel cell, any gas or fuel and low fuel gas (or liquid) crossover. Most of their
permeation through the membrane, often quoted as physicochemical properties are different from those
fuel cross-over, is equivalent to an internal current of Nafion® [222,223]: (1) they swell mainly along the
(short), reducing cell voltage. Reasonable mechani- membrane thickness owing to their structural anisot-
cal strength and moderate dimensional changes are ropy, (2) there is incomplete separation between their
required when the electrolyte membrane is used to hydrophobic and hydrophilic domains, (3) they have
make the MEA, incorporating the MEA into a stack an almost constant value of λ over a wide range of
and during fuel cell operation. ion content, and (4) they have a multi-scale foliated
Sulfonated polyimides (SPI), especially sulfo- structure packed along the membrane thickness. All
nated six-member ring (naphthalenic)polyimides, are of them yield performance comparable to that of
proposed as promising candidates for PEMs because Nafion for PEMFC and DMFC, but they also have
of their excellent chemical and thermal stability, low water stability because of the high sensitivity of
154
the imide rings to hydrolysis under moist conditions
and moderate temperatures (>70 °C).
Various approaches to enhance the hydrolytic sta-
bility of sulfonated polyimides have been developed,
including (1) using monomers with flexible link-
ages [224]; (2) using monomers without a sulfonic
acid group and an amine group, both in the same
ring [225]; (3) using diamine monomers with high
nucleophilicity [226]; (4) using aliphatic diamines
[227]; (5) using napthalenic dianhydrides [228]; (6)
using diamines with the sulfonic acid group in a side
chain [229]; (7) using trifunctionalized monomers
with cross-linkable groups to initiate cross-linking
[230,231]; (8) blending with aromatic engineering
plastics or inorganic particles [232–239]; (9) forming
semi-interpenetrating polymer networks with suitable
materials [240,241]; and (10) incorporating fluorene
atoms into the polymer backbone [153,242]. This sec-
tion discusses sulfonated polyimides containing fluo-
rinated atoms/groups for PEM-based applications.
Fluorinated polyimides have attracted considerable
interest as PEM in fuel cell applications. The small
size and the high electronegativity of the fluorene atom
confer a strong C–F bond and low polarizability. Such
polymers have low intramolecular and intermolecular
interactions, which leads to low cohesive energy and
thus to low surface energy. They also exhibit high ther-
mal stability and chemical inertness, low refractive index
and friction coefficient, good hydrophobicity and lipo-
phobicity, valuable electrical properties, and low relative
permittivity. In addition, they are non-sticky and resis-
tant to UV from aging and to concentrated mineral acids
and alkalies. Nafion® (DuPont), a perfluorosulfonic acid
polymer possessing good chemical resistance, oxidative
stability, and good proton conductivity, is commercially
Proton Hopping
SO3– SO3–
H+ SO3–
+ H3O+
H3O+ SO – H3O SO –
H3O+ 3 3
H3O+ H3O+
H H
O O
H+ H H
O O
H H
Figure 3.16  Schematic representation of Grotthus mechanism of proton transport. Reproduced with permission
from Ref. [245].
Handbook of Specialty Fluorinated Polymers
used as a PEM in commercial systems. However, it has
limitations such as a high cost, high gas permeability,
and deterioration of properties at high temperatures. All
of these demerits have motivated further research into
the development of new PEM materials with low cost
and improved material properties. Sulfonated aromatic
polyimides have attracted significant attention in this
regard, owing to their superior chemical resistance, with
excellent thermal stability and mechanical strength as
well as good film-forming ability.
3.3.3.1  Proton Conduction Mechanisms 
in PEMs
The main characteristic to consider for a PEM to
be used in potential fuel cell is proton conductivity.
To achieve good performance of a PEM fuel cell, high
proton conductivity is essential, especially at a high
current density. To understand proton transport at a
molecular level in hydrated polymeric membranes,
there are two principal proton transport mechanisms:
(1) the Grotthus mechanism or proton hopping mech-
anism, and (2) the vehicular mechanism or diffusion
mechanism [243–245].
In the Grotthus mechanism, protons hop from one
hydrolyzed ionic site (SO3–H3O+) to another through
the membrane [244]. Protons at the anode side
adhere to water molecules and produce hydronium
ions, and one different proton from the hydronium
ion hops onto the other water molecule. It involves
the conversion of H-bonds to covalent bonds between
water molecules, and vice versa, and the proton is
transported. A schematic representation of the hop-
ping mechanism is shown in Fig. 3.16 [245]. Accord-
ing to this mechanism, hydrophilic ionic clusters are
SO3–
SO3– SO3– SO3–
SO3–
H3O+ H3O+ H3O+
H3O+
H H H
O
H
3: Fluorinated Polyimides 155

swollen by absorbing water and consequently form copolyimides controlling the degree of fluorinated
the interconnected network for proton transfer. monomer unit (0–60  mol.% bis[trifluoromethyl]
On the other hand, the vehicular mechanism biphenylene) [247]. A schematic representation of
involves the movement of the hydrated proton aggre- the copolyimide, designated as FSPIH-X, is pre-
gate. Here, in response to the electrochemical dif- sented in Scheme 3.28. The copolymer membranes
ference, hydrated proton (H3O+) diffuses through were soluble in common organic solvents. The prepared
the aqueous medium [244,245]. A schematic repre- membranes were used to study the physical and PEM
sentation of the vehicular mechanism is presented in related properties such as water uptake, oxidative
Fig. 3.17. In the vehicular mechanism, hydrated pro- stability, and proton conductivity. Comparison of
tons carry one or more molecules of water (H+[H2O]x) the properties with the other series of SPIs showed
through the membrane and are transferred with them that the bis(trifluoromethyl)biphenylene groups with
as a result of electro-osmotic drag. The major condi- a molecular size of 6.1 Å provided the polyimides
tion for proton transport through the vehicular mech- with interchain spaces to confine water molecules.
anism is the existence of free volumes within the The copolymers showed that the initial water uptake
polymer matrix of a PEM, which allow the passage value decreased from 102% to 68% upon increas-
of hydrated protons through the membrane. ing the bis(trifluoromethyl) biphenylene content,
x = 0 (ion exchange capacity (IEC) = 3.47 mEq./g))
3.3.3.2  Physical and PEM Properties to x = 10 (IEC = 3.02 mEq./g). However, the water
of Fluorinated Sulfonated Copolyimides uptake value increased to 73% with a further increase
in the value of x (x = 20; IEC = 2.65 mEq./g). All
3.3.3.2.1  Fluorinated Sulfonated Random FSPIH-X membranes exhibited high thermal stabil-
Copolyimides ity (approximately 280 °C, cleavage of CAr–SO3H
To improve the oxidative stability and proton- bonds) with no Tg below the decomposition tempera-
conductive properties of sulfonated polyimides, ture (280 °C). Introduction of –CF3 substituents was
Watanabe et al. synthesized a series of sulfonated highly effective in improving the oxidative stability of

9HKLFXODUPHFKDQLVP
D

62– + 62– 62– 62–

+ + + ++ + + 62 –

+
++ 62–
+ + +
62–
+
+ + +
+ + +
++
62– + – ++ ++
62 62– + +62 – + ++
 +
62–

62– + – 62– 62– 62–

+
– ++ +
–
– 62– +
+ + 62–
– – +
+ 62–
+ + –
+
+
+ +
62– –
+ – +– +
+
62 62– + +
62– +
62– +
+

:DWHU
1DQRSDUWLFOH
+\GURQLXP

Figure 3.17  Schematic representation of the vehicular mechanism of proton transport. Reproduced with permis-
sion from Ref. [246].
156 Handbook of Specialty Fluorinated Polymers

2 2 +26 )&
+1 1+
2 2 +1 1+ +1 1+

2 2 62+ &)

7($ ž&K
3K&22+ ž&K
LQPFUHVRO

2 2 +26 2 2 )& 2 2

1 1 1 1 1 1

2 2 62+ ; 2 2 &) ; 2 2 

Scheme 3.28  Synthetic scheme of fluorinated SPI copolymers FSPIH-X [247].

62 +
62 +

2 &) &) &)

2 2 2
2
1 1 1

2 P Q
P Q 2 2

6HULHV , 6HULHV ,,
Scheme 3.29  Structure of the two fluorinated SPI series [248].

the sulfonated polyimides owing to the hydrophobic
nature of fluorene atoms. Proton conductivity of the
FSPIH-X membranes increased linearly with IEC up
to 80 °C, whereas above 100 °C conductivity started
falling rapidly possibly as a result of the evaporation
of water from the membranes. The FSPIH-30 mem-
brane had proton conductivity higher than 0.2 S/cm
at 30–140 °C and 100% RH. Furthermore, the meth-
anol cross-over through the FSPIH-30 membrane
was only 30% that of Nafion® 112. Hence, from that
study the authors concluded that the optimum com-
position of bis(trifluoromethyl)biphenylene groups
was 30 mol.% from the viewpoint of oxidative sta-
bility, proton conductivity, methanol cross-over, and
their good balanced combination.
Zhang et al. also studied the effect of hydropho-
bic –CF3 groups on the ortho-position of the imido
group and reported low water uptake and excel-
lent oxidative stability of the fluorinated sulfonated
copolymer membranes [248]. They synthesized
two series of fluorinated sulfonated copolymers
(Scheme 3.29) with high molecular weight and
different degrees of sulfonation by Ni(0)-cata-
lyzed coupling of the monomers. They showed
that the –CF3 groups protected the polymer main
chains from attack by water molecules containing
highly oxidized radical species. The synthesized
copolyimides with 1,8-napthalimide units, which
exhibited higher hydrolytic and oxidative stability
as well as higher proton conductivity than copoly-
imides containing 1,4,5,8-napthalimide units. This
was attributed to the structural difference of the
polymer chains with respect to the naphthalimide
units and the number of carbonyl groups, which in
turn determined the PEM-related properties. From
all of these observations, the researchers inferred
that copolymers of series I containing 50% sulfo-
nated monomer exhibited the best combination
of properties to be used as a PEM material, with
proton conductivity (2.6 × 10−1 S/cm at 80 °C)
even higher than Nafion® 117 (1.5 × 10−1 S/cm
at 80 °C). Thus, this kind of membrane material
could be used as a potential alternative to Nafion®
membranes.
3: Fluorinated Polyimides 157

62+

2 2 2

+ 1 1+  2 2  + 1 $U 1+

2 2 2

PFUHVRO 62+

+26 %HQ]RLFDFLG

2 2 2 2 2

1 1 $U 1 1

2 2 P 2 2 2
Q

&)
$U 2 +26

&)
2'$, %$3+),,

Scheme 3.30  Synthetic scheme of BTDA-based sulfonated copolyimides [249].

Table 3.13  Oxidative Stability and Proton Conductivity of BTDA-Based SPI Membranes
Oxidative Stabilitya Proton Conductivityd (S/cm)

Membranes IEC (mEq./g) τ1b(h) τ2c(h) 20 °C 80 °C

SPI(I)-70 1.74 35 41 0.073 0.147
SPI(I)-80 1.90 34 40 0.112 0.184
SPI(II)-70 1.66 48 52 0.065 0.139
SPI(II)-80 1.84 42 48 0.093 0.175

a30 °C in 30% H2O2 containing 30 - ppm FeSO4.

bThe time when the membrane broke into pieces after being shaken drastically.
cThe time when the membrane dissolved completely.
dUnder fully hydrated conditions.

Data taken from Ref. [249].

To improve hydrolytic-oxidative stability and
maintain other desirable properties, Zhang et al. also
developed novel fluorinated SPI membrane materi-
als based on 4,4′-binaphthyl-1,1′,8,8′-tetracarboxylic
dianhydride (BTDA) and wholly aromatic diamine,
2,2′-bis(3-sulfobenzoyl) benzidine (2,2′-BSBB)
[249]. To obtain SPI copolymers (Scheme 3.30) with
a controlled degree of sulfonation (DS), they used two
types of non-sulfonated diamine monomers, with or
without fluorinated groups, and analyzed their prop-
erties. All of the BTDA-based co-SPI membranes
exhibited excellent hydrolytic-oxidative stability and
mechanical properties owing to their fully aromatic
structure extending through the backbone and pen-
dant groups. In addition, the unique binaphthalimide
structure had a major role in improving the stability
of the co-SPI. Also, the oxidative stability of fluori-
nated co-SPI (SPI-II series) is reported to be higher
than that of non-fluorinated co-SPI (SPI-I series)
membranes while maintaining comparable proton
conductivity values with similar sulfonation degrees
(Table 3.13). It was also reported that the SPI-(II)-80
membrane with IEC 1.84 mEq./g displayed reason-
ably high proton conductivity (1.75 × 10−1 S/cm at
158 Handbook of Specialty Fluorinated Polymers

2 2 62+
&) 
[\ 2 2  [ +1 2 1+  \ +1 2 2 1+
&) 
2 2 +2 6 7($PFUHVRO
%HQ]RLFDFLG
R&K
R&K
 
2 2 62 1 +(W
1 1 2 1
[ &) 
 
2 2 (W+ 1 2 6
Scheme 3.31 Schematic representation of synthesis of bis(4-[4-aminophenoxy]phenylhexafluoropropane)-
based co-SPI [250].
80 °C), which is higher than that of Nafion® 117
(1.70 × 10−1 S/cm at 80 °C) under similar experimental
conditions.
To investigate the effect of the DS on PEM prop-
erties, Choudhary et al. synthesized a series of fluo-
rinated SPI from 1,4,5,8-naphthalene tetracarboxylic
dianhydride (NTDA), 4,4′-diaminodiphenylether-
2,2′-disulfonic acid (ODADS), and a fluorinated
non-sulfonated diamine, bis(4-[4-aminophenoxy]
phenylhexafluoropropane) (BDAF) [250]. Different
co-SPIs with a similar repeat unit structure (Scheme
3.31) were prepared by varying the molar ratio of
ODADS:BDAF as 0.5:1.50, 0.75:1.25, 1:1, and
1.50:0.5 in the initial feed; the samples were designated
SPF-25, SPF-37, SPF-50, and SPF-75, respectively.
The co-SPI membranes were mechanically strong
and had good hydrolytic stability, except for SPF-75,
which was reported to be brittle in nature. The PEM
properties of the co-SPI membranes depended on the
composition, and proton conductivity (in the range
0.137–3.94 mS/cm) increased with an increase in the
DS. Membranes obtained from SPF-50 displayed pro-
ton conductivity, 3.94 mS/cm at 90 °C in the direction
of thickness, which was comparable to Nafion® 117
(3.24 mS/cm), whereas the methanol permeability
of the SPF-50 membrane (4.1 × 10–7 cm2/s at 50 °C)
was lower than that of Nafion® 117 (1.1 × 10−6 cm2/s)
under similar experimental conditions.
Fan and co-workers carefully investigated the
physical and PEM properties of two series of –CF3-
containing co-SPIs, designated SPI-N and SPI-B
[242]. To prepare the co-SPIs, they first synthe-
sized a novel side chain-type fluorinated sulfonated
,4
R&K
2 2
&) 
1 2 2
\
2 2
aromatic diamine, 5-(1,1-bis[4-aminophenyl]-2,2,2-
trifluoroethyl)-2-(4-sulfophenoxy)benzenesulfonic
acid (BABSA). The sulfonated diamine was then
used in 3:1 M proportion with various non-sulfonated
aromatic diamines and six-member dianhydrides,
NTDA or 4,4′-binaphthyl-1,1′,8,8´-tetracarboxylic
dianhydride (BNTDA) to prepare the co-SPIs
(Scheme 3.32). All of the synthesized co-SPIs exhib-
ited good solubility in many common organic sol-
vents, even in proton form, owing to the synergetic
effects of the bulky aromatic pendant groups and the
fluorinated substituents in the polymer structure. The
resulting co-SPI membranes as cast from m-cresol
had good dimensional stability with isotropic swell-
ing of 7–22% and high thermal stability at a desulfo-
nation temperature of 283–330 °C. These membranes
also had excellent hydrolytic-oxidation stability,
which was improved by incorporating –CF3 groups
into the polymer backbone. It was also reported that
NTDA-based co-SPI membranes (SPI-N series) had
better oxidative stability than the corresponding
BNTDA-based membranes (SPI-B series), which
was attributed to the relatively higher content of the
hydrophobic fluorinated groups. Also, all of the co-
SPI membranes had better permselectivity (Φ) with
a ratio of proton conductivity (σ) to methanol perme-
ability (PM) nearly two to three times that of Nafion®
115. This could be interpreted as the much lower
methanol permeability of the co-SPIs (0.46 × 10−6
to 0.98 × 10−6 cm2/sat 30 °C with 50 wt.% of metha-
nol content) than Nafion 115 (1.91  × 10−6 cm2/s)
under similar conditions. That study also demon-
strated that the SPI-N membranes had high proton
3: Fluorinated Polyimides 159

2 2
&)
[\ 2 5 2  [ +1 1+  \ +1 5 1+
5
2 2
62 + PFUHVRO7($
EHQ]RLFDFLG 17'$ %17'$
2
R &)
 &K
R&K
5 2 2

62 + )%$% )&
2 2 2 2 )&
&)
1 5 1 1 5 1 5 2 2
[ \
2 2 2 2 &) )$3%
62 +
2 2 2

%$3%

62 +

Scheme 3.32  Synthetic scheme BABSA-based co-SPIs [242].

To understand the effect of –CF3 moiety on a

Figure 3.18 Temperature dependence of proton
conductivity for co-SPIs and Nafion® 115 mem-
branes at 100% RH. Reproduced with permission
from Ref. [242].
conductivity (0.18–0.22 S/cm in water at 80 °C) that
was better than SPI-B membranes (0.13–0.14 S/cm in
water at 80 °C) because of the higher IEC values of
the former, even though they had the same DS. Fur-
thermore, the SPI-N membranes had higher proton
conductivity than Nafion® 115 at 40 °C (Fig. 3.18).
The highly proton-conducting performance of SPI-N
membranes was attributed to their good hydropho-
bic/hydrophilic microphase-separated structure.
particular polymer structure, Liu et al. synthesized
three fluorinated sulfonated polynaphthalimides
with different fluorene contents and compared
their properties with their non-fluorinated ana-
logues [251]. Two new sulfonated diamine mono-
mers, 2,5-bis(4-amino-2-trifluoromethylphenoxy)
benzenesulfonic acid (BAFPBS) and 2,5-bis(4-
aminophenoxy)benzenesulfonic acid (BAPBS),
with flexible ether linkages were successfully syn-
thesized as precursor materials for polymerization.
Scheme 3.33 shows the synthetic route for prepar-
ing polynaphthalimides. The researchers designated
the fluorinated polyimide series CF3-SPI-X and the
corresponding non-fluorinated series SPI-X, where
X represents the molar proportion of synthesized
diamine to a commercial diamine, ODA (e.g., X = 1,
BAFPBS/ODA = 4:1; X = 2, BAFPBS/ODA = 2:1;
and X = 0 represents the homo-polyimide without
ODA). They reported that both series of SPIs exhib-
ited acceptable or good thermal stability, oxidative
stability, mechanical integrity, and proton conduc-
tivity (up to 0.085 S/cm at 80 °C for CF3-SPI-0).
However, the fluorinated SPI series (CF3-SPI-X)
had higher dimensional stability and lower metha-
nol permeability compared with the non-fluorinated
ones (SPI-X) at the same –SO3H group content
(Table 3.14).
160 Handbook of Specialty Fluorinated Polymers

5 5

+ 1 2 2 1+  + 1 2 1+ 

+2 6
2 2

7($3K&22+
2 2
PFUHVRO 5 &)+

2 2

2 2 5 5 2 2

1 1 2 2 1 1 2
Q Q
2 2 +2 6 2 2

Scheme 3.33  Synthetic route of sulfonated polynaphthalimides with –CF3(CF3-SPI-X) and without –CF3 groups
(SPI-X) [251].

Table 3.14  Methanol Permeability and Swelling fluorene-containing quadriphenyldiamine (QA) [252].
Ratio of Sulfonated Polynaphthalimides
The structure of the prepared fluorinated five-member
Swelling Ratio co-SPI is shown in Scheme 3.34(a).
Methanol (%) A homopolymer without the fluorinated group
Permeability was also prepared comparison. All of the resulting
Polymer (cm2/s) 20 °C 100 °C SPI membranes, as casted from DMAc, were trans-
CF3-SPI-0 2.03 × 10−7 8.9 13.4 parent, tough, and mechanically strong, with a high
CF3-SPI-1 9.81 × 10−8 4.7 6.9
TS (ranging from 41.7 to 66 MPa in dry state) and
Young’s modulus (1.44–1.67 GPa), which was higher
CF3-SPI-2 7.37 × 10−8 3.8 4.8 than Nafion® 117 (TS, 38 MPa; Young’s modulus,
SPI-0 2.77 × 10−7 10.8 18.9 0.18 GPa) and a few other reported non-fluorinated
six-member SPIs [255]. All of the SPIs had good
SPI-1 1.05 × 10−7 7.5 12.5
solubility in common organic solvents, which was
SPI-2 8.21 × 10−8 6.7 9.3 attributed to the combined effects of ether linkages
and the bulky –CF3 pendant groups in the backbone,
Data taken from Ref. [251]. which disrupted the regularity of the molecular chains
and hindered dense chain packing, thereby improv-
Over the past few years, Banerjee et al. have been ing solubility. All of the SPIs had high thermal stabil-
involved in synthesizing and developing new fluori- ity with the onset of decomposition of sulfonic acid
nated random co-SPI membranes to be used as PEMs moieties at around 290–300 °C and above 570 °C for
for fuel cells [252–254]. They prepared several series the polymer backbone. The Tg for all of the SPIs was
of fluorinated co-SPIs by varying the co-SPI structures in the range 220–227 °C, which indicated the amor-
(Scheme 3.34). They also fine-tuned the DS of the phous nature of the polymers. However, the close Tg
resulting co-SPI by adjusting the molar proportion of value was attributed to the fact that with an increase
sulfonated diamine to non-sulfonated fluorene contain- in DSDSA, the expected increase in Tg resulting from
ing diamine to understand the optimum composition the slight increase in intermolecular interactions of
for the better performance of PEM. First, they synthe- pendant ‒SO3H groups was almost counterbalanced
sized a series of random fluorinated co-SPIs with con- by an increase in flexible C]C double bonds in the
trolled DS (designated as DQB-XX, where XX = 50, structure. Furthermore, the effect from the molecular
60, 70, 80, and 90) using a commercially available sul- bulkiness of the –SO3H group was adjusted for by the
fonated diamine, 4,4′-diaminostilbene-2,2′-disulfonic bulky pendant –CF3 groups in the non-sulfonated part
acid (DSDSA), aromatic dianhydride (BPADA), and of the polymer chain. Water uptake of the DQB-XX
3: Fluorinated Polyimides 161

2 2 &) 2 2
2 2 2 2 62+
1 1 2 2 1 1

2 +& &+ 2 )& P 2 +& &+ 2 P

62+
D>@
2 2 &) 2 2
+26
1 1 2 2 1 1
P
2 2 )& 2 2 62+ P
E>@
2 2 )& 2 2
+26
1 1 2 2 1 1
P
2 2 &) 2 2 62+
F>@
Scheme 3.34  Repeat unit structures of fluorinated co-SPIs.
series of polymers increased with an increase in IEC
values. For DQB50 to DQB100, the water uptake
value increased from 14% to 41.27%. However, the
hydration number (λ) was unchanged after reaching
a certain value, probably owing to the higher rigidity
of the aromatic SPI chain and the strong ionic inter-
action among sulfonic acid groups, which limited the
free volume for water uptake surrounding the ionic
‒SO3H groups beyond a certain limit. Anisotropic
membrane swelling was observed for all of the DQB-
XX membranes with a relatively larger dimensional
change in the direction of thickness than in-plane
and the anisotropic degree (Δtc/Δlc) was in the range
2.4–5.75. Upon transmission electron microscopic
analysis, excellent nanophase-separated morphol-
ogy was observed for this series of co-SPIs, which
consisted of large amounts of bigger ionic clusters
(20–25 nm) and a certain amount of smaller ionic
clusters (2–5 nm) along with medium-size clusters
(10–12 nm). In addition, with an increase in DS, the
isolated ionic clusters gradually became closer to
each other, which was favorable for water-keeping
and proton transport. The proton conductivity of
the DQB-XX membranes was reported to be in the
range 3.96–34.55 mS/cm at 30 °C and 100% RH, and
showed an increasing trend with an increase in IEC
from 0.96 to 1.93 mEq./g. It was also noticed that for
similar IEC values, proton conductivity of the syn-
thesized SPIs were comparable to or even better than
many other five-member SPIs [227,256], but the val-
ues were still lower than for Nafion® 117 (45 mS/cm
at 30 °C) under similar experimental condition [257].
To improve hydrolytic-oxidative stability, Baner-
jee et al. synthesized another series of fluorinated
co-SPIs (designated DQN-XX, where XX = 40, 50,
60, 70, 80, and 90) based on a six-member dianhy-
dride, NTDA [253]. The co-SPIs were synthesized
P
through one-pot high temperature polycondensation
in m-cresol solvent and in the presence of triethyl-
amine and benzoic acid, as presented in Scheme
3.35. By adjusting the monomer feed ratio of sulfo-
nated diamine (DSDSA) to non-sulfonated diamine
(QA), the DS of the resulting co-SPIs was controlled.
All of the synthesized co-SPIs had high molecular
weight with polydispersity indices (PDIs) between
1.3 and 3.5 and good solubility in polar aprotic sol-
vents such as DMAc, DMSO, DMF, and NMP. The
co-SPIs had good thermal stability; the onset of ther-
mal decomposition of sulfonated moieties occurred
at around 300–340 °C, which is well above the ser-
vicing temperature for a PEM fuel cell (70–120 °C).
No melting temperature or Tg was observed from
DSC thermograms, which might be because of the
strong interactions of ionic groups, naphthalimide
groups, and rigid backbones. The co-SPI membranes
displayed excellent mechanical properties that were
better than many other non-fluorinated six-member
SPIs [258,259] and were superior to some reported
fluorinated six-member SPIs [242]. Furthermore, the
co-SPI membranes had good dimensional stability
and fairly good oxidative stability, which were bet-
ter than those of many other SPIs [258,260]. The
relatively higher oxidative stability of the co-SPIs
resulted from the presence of hydrophobic –CF3
moiety, which could protect the polymer main chain
from being attacked by water molecules containing
highly oxidizing radical species (HOO· and HO·).
The oxidative stability showed an increasing trend
with an increase in the proportion of the –CF3 group
in the repeat unit of the co-SPI structure.
Transmission electron spectroscopy analyses of the
membranes showed excellent nanophase-separated
morphology containing well-dispersed hydrophilic
domains in a hydrophobic matrix (Fig. 3.19). Such
162 Handbook of Specialty Fluorinated Polymers

&)
+26
+1 2 2 1+ +1
 1+
)& 62+
4$
2 2 '6'6$

 2 2 1IORZ
2 2 1(WPFUHVROEHQ]RLFDFLGR&K
17'$ R&K
PQ+2 R&K

2 2 &) 2 2
(W+126
1 1 2 2 1 1
P
2 2 )& 2 2 621+(W P
6XOIRQDWHGSRO\LPLGH'41;;6DOWIRUP

<LHOG 
$FLGWUHDWPHQW
2 2 &) 2 2
+26
1 1 2 2 1 1
P
2 2 )& 2 2 62+ P
6XOIRQDWHGSRO\LPLGH'41;;$FLGIRUP
Scheme 3.35  Reaction scheme for synthesis of DQN-XX copolymers [253].
hydrophilic clusters were mainly responsible for water
uptake and may have formed interconnecting ionic
channels by absorbing water, which was favorable
for proton transport. It was also observed from the
micrographs that with an increase in the DS, the num-
ber and size of the ionic clusters gradually increased
and allowed aggregation, which in turn favored the
proton conductivity of the membranes. The research-
ers showed that the presence of hydrophobic –CF3
groups in the polymer backbone led to the nanophase-
separated structure improving proton conductivity.
The water uptake of the co-SPI membranes gradually
increased with an increase in IEC values (Fig. 3.20).
The DQN40–DQN90 exhibited an increase in water
uptake from 14.2% to 42%. The proton conductivity
of the co-SPI membranes showed the comprehensive
effect of IEC and water uptake and the conductivity
value increased with temperature. The proton conduc-
tivity values were in the range 5–81.9 mS/cm at 30 °C
P '41
 '41
 '41
 '41
 '41
 '41
and 9.4–108.2 mS/cm at 80 °C, respectively. It was also
noticed that for similar sulfonation degrees, the proton
conductivity values of the DQN-XX series of co-SPIs
were comparable to or better than many other SPIs
under similar experimental conditions [252,261,262].
In addition, for the DQN-90 membrane, the proton
conductivity value was comparable to the commer-
cially available Nafion® 117 membrane under similar
experimental conditions.
A further improvement in proton conductivity was
accomplished by designing a new series of co-SPIs
(DHNH-XX, where XX = 40, 50, 60, and 70) using
NTDA, DSDSA, and a flexible fluorinated diamine,
1,4-bis(2′-trifluoromethyl-4′-[4″-aminophenyl]phe-
noxy)benzene (HQA) [254]. The repeat unit struc-
ture of the co-SPI is shown in Scheme 3.34(c). All
of the DHNH-XX membranes showed high thermal
stability (desulfonation temperature above 270 °C)
and good mechanical properties (TS in the range
 3: Fluorinated Polyimides 163

Figure 3.19 Transmission electron spectroscopy micrographs of co-SPI membranes (cross-section, in Ag+

form). Reproduced with permission from Ref. [253].

90 the increased fluorene content in DHNH-XX mem-

80 branes, leading to high hydrophobicity and a more
Proton conductivity (mS/cm)

70 flexible backbone structure. In addition, fairly

60 at 30 OC good oxidative stability of the HQA-based co-
50 SPI membranes was observed (τ1 = 2.9–4.6 h and
40 τ2 = 6.3–20.5 h), which was better than that of other
30 reported SPIs [242,263]. As presented in Table 3.15,
20 the proton conductivity of the DHNH-XX mem-
10
branes was in the range 5–46 mS/cm at 30 °C and
12–129 mS/cm at 90 °C, and showed an increas-
0
Inflection point 4045 )
1.0
1.5 30
35
t. % ing trend with an increase in DS and temperature.
IEC 2.0 20
25
k e (w Proton conductivity values of the DHNH-XX mem-
theo (mm 2.5 15 u pta
ol/g) 3.0 10 ter branes were better than many other SPIs reported
Wa
in the literature with similar IECs, but were slightly
Figure 3.20 Correlation plot of IEC, water uptake, lower than Nafion® 117 (150  mS/cm at 90  °C)
and proton conductivity of DQN-XX samples. Repro- under similar experimental conditions [253,262].
duced with permission from Ref. [253]. However, the increased proton conductivity of
DHNH-XX series of membranes compared with the
44–88 MPa and Young’s modulus = 1.23–2.36 GPa previously reported DQN-XX series of membranes
in a dry state). Also, the prepared membranes exhib- [253] could be attributed to the relatively higher
ited better hydrolytic stability (up to 450 h) despite water uptake values and morphology difference,
having high IEC values (1.1–2.1 mEq./g), which was as observed in the TEM, which showed largely
even better than previously reported DQN-XX series aggregated clustered morphology with average
of membranes (Table 3.15). This was attributed to cluster sizes ∼35–50 nm.
164 Handbook of Specialty Fluorinated Polymers

Table 3.15  Proton Exchange Membrane Properties of co-SPI and Nafion® 117 Membranes
Proton Conductivity (mS/cm)
IECW, Theo. Hydrolytic Water Uptake
Polymer (mEq./g) Stability (h) (wt.%, 30 °C) 30 °C 80 °C
DHNH-40 1.10 >450 15.23 5 10
DHNH-50 1.41 >450 20.57 10 28
DHNH-60 1.75 >450 26.29 28 60
DHNH-70 2.10 ∼417 33.61 46 99
DQN-40 1.03 >400 14.16 5 9.4
DQN-50 1.34 >400 18.97 6.5 13.2
DQN-60 1.67 >400 23.84 7.6 17
DQN-70 2.03 >400 29.73 22.8 39.6
DQN-80 2.42 ∼120 35.61 54.5 80.6
Nafion 117 0.91 – 19 60 135

&+
3.3.3.2.2  Fluorinated Sulfonated Block/ 2 & 2
Graft Copolyimides &+
+1 1+
M. Pineri and co-workers prepared a series of
%LV>DPLQRSKHQR[\SKHQ\O@LVRSURS\OLGLQHP$3,
sequenced sulfonated naphthalenic block poly-
imides with improved solubility by introducing &)
ether linkages into the main chain or bulky groups 2 & 2
as substituents using specifically designed aromatic &)
diamines containing phenylether bonds with or with- +1 1+
out –CF3 groups, NTDA, and 4,4′-diamino-biphenyl
2,2′-disulfonic acid (BDSA) [261]. They synthesized
several new aromatic diamines to prepare SPI block
copolymers with different block lengths and thor-
oughly investigated their PEM properties. The struc-
ture of the two diamines is presented in Scheme 3.36,
designated mAPI and mAPFI. Also, the IEC varied
between 0.56 and 1.73 mEqn./g with a constant sul-
fonated chain length (x = 5). A few other co-SPIs were
synthesized with different sulfonated chain lengths
(x = 3, 5, and 9) with a constant IEC (0.86 mEq./g)
from the diamines. The water uptake for mAPI and
mAPFI-based co-SPI was between 14% and 46.5%
at 25 °C with a constant block length, x = 5. For a
given polymer structure, water uptake increased with
an increase in IEC (Table 3.16) but the hydration
number (λ) remained almost constant, which sug-
gested that water was mainly located in the hydro-
philic domains. The researchers reported that despite
the large IEC, proton conductivity values were weak
as presented in Table 3.16. Water uptake and pro-
ton conductivity values for the co-SPIs according to
%LV>DPLQRSKHQR[\SKHQ\O@KH[DIOXRURLVRSURS\OLGLQHP$3),
Scheme 3.36 Aromatic diamines containing phenyl
ether bonds with or without –CF3 groups [261].
block length are also given in Table 3.16. The authors
reported that proton conductivity exhibited a maxi-
mum value for ionic block average length equal to
three monomer units (x = 3).
The research group of H. Kawakami extensively
studied fluorinated block/graft co-SPIs with vari-
ous structures [260,264,265]. First, they synthesized
fluorinated block co-SPI by chemical imidization
using a two-pot procedure with NTDA, BDSA, and
2,2′-bis(4-aminophenoxy)hexafluoropropane (6FAP)
by varying the diamine compositions and block
lengths (m/n = 112/48, 70/30, and 49/21) and exam-
ined their physical and PEM properties [264]. The
repeat unit structure of the block co-SPI is shown in
Scheme 3.37. A random variety of similar co-SPI was
also prepared to compare their properties. The proton
conductivity of block co-SPI was strongly influenced
3: Fluorinated Polyimides 165

Table 3.16  Water Uptake and Conductivity Values of Block co-SPIs

Acronyms IEC (mEq./g) Water Uptake (%) λ σ (mS/cm)
CH3 5 20/80 0.63 13.5 12.5 0.32
CH3 5 30/70 0.96 19.0 11.5 1.3
CH3 5 40/60 1.30 27.0 12.0 6.5
CH3 5 50/50 1.64 42.0 15.0 5.9
CF3 5 20/80 0.56 14.0 14.0 0.40
CF3 5 30/70 0.86 22.0 14.0 1.7
CF3 5 40/60 1.17 31.0 15.0 4.6
CF3 5 50/50 1.51 41.0 15.0 7.1
CF3 5 60/40 1.86 46.5 14.0 8.3
CF3 1 30/70 0.86 19.5 12.5 1.1
CF3 3 30/70 0.86 17.0 11.0 2.7
CF3 5 30/70 0.86 22.0 14.0 1.7
CF3 9 30/70 0.86 20.0 13.0 0.36

Data taken from Ref. [261].

2 2 +26 2 2
&)
1 1 1 1

P &)
P
2 2 62+ 2 2

Scheme 3.37  Repeat unit structure of fluorinated block co-SPI [264].

by the block length and showed an increasing trend
with an increase in block length. The researchers
reported that the proton conductivity of the block
co-SPI membranes was in the range 190–350 mS/
cm at 80 °C, which was better than the correspond-
ing random analogue. For example, at an IEC value
of 2.44, proton conductivity of a block co-SPI was
250 mS/cm, whereas its random analogue with the
same IEC value had a proton conductivity value of
150 mS/cm, which was much lower under similar
experimental conditions. The prepared block co-SPI
had significantly high proton conductivity that was
even better than that of Nafion® 117 (σ = 150 mS/cm
at 90 °C). The relatively higher proton conductivity
of the block co-SPI compared with that of the ran-
dom analogue was attributed to the larger hydration
number (λ = 15) of block co-SPI compared with the
corresponding random variety (λ = 11), in favor of
better water management for block co-SPI. However,
the increase in proton conductivity with an increase
in block length was contrary to the results reported
by Genies et al. [261], who observed a decreasing
trend in proton conductivity with an increase in block
length. In this study, at higher block lengths, the size
and length of ionic domains increased, giving better
phase-separated morphology that formed a favorable
path for proton transport leading to an increase in
proton conductivity.
In a further study, the researchers analyzed the
proton conductivity and membrane stability of low
IEC containing fluorinated block co-SPI membranes
and compared their PEM properties with a corre-
sponding random analogue [265]. The structure of
the co-SPIs investigated is presented in Scheme 3.38.
The authors observed much a higher value of proton
conductivity for the block co-SPI membrane than for
the random membrane, even though the same IEC
values existed for both polymers. In particular, the
166 Handbook of Specialty Fluorinated Polymers

2 2 +26 2 2

1 1 1 1 5
P Q
2 2 62+ 2 2
[
5
&)  &) 
2 & 2 &
&)  &) 

$33) )$3

Scheme 3.38  Chemical structure of sulfonated block copolyimides [265].

2 )& &) 2 2 )& &) 2

1 1 1 1
Q Q
2 2 2 2+ 2 2 2 2+
2 2

2 +1
[

1
2

2
1
2

+26
62+

Scheme 3.39  Chemical structure of 6FDA-HABA-g-NTDA-BDSA [260].

proton conductivity of the low-IEC (0.8 mEq./g) block
copolyimide membrane (σ = 100 mS/cm) at 80 °C and
98% RH was 16 times larger than that measured in the
low-IEC random copolyimide membrane (σ = 6 mS/
cm), whereas that of the high-IEC (2.1 mEq./g) block
copolyimide membrane (σ = 420 mS/cm) at 98% RH
was four times that of the high-IEC random copoly-
imide membrane (σ = 110 mS/cm). From this result,
the researchers suggested that the protons in the
low-IEC block copolyimide were effectively trans-
ported through the membrane. Again, effective pro-
ton mobility (μeff) through the low-IEC block co-SPI
membrane at approximately 20% water uptake was
superior to that of the high-IEC block co-SPI mem-
brane, which may be because dissociation of the pro-
tons from sulfonic acid groups in the low-IEC block
co-SPI is more facilitated compared with those in
the high-IEC co-SPI. Furthermore, it was reported
that hydrolytic and oxidative stability of the low-
IEC block copolyimide membranes was significantly
improved compared with that in the high-IEC mem-
branes. From these studies, the researchers concluded
that block co-SPI consisting of a small amount of sul-
fonic acid groups (i.e., with low IEC) is desirable for
the development of PEMs, when considering the bal-
ance between the proton conductivity and membrane
stability of the PEMs.
Kawakami et al. also synthesized novel fluori-
nated graft co-SPIs by controlling the grafting ratio
between the fluorinated polyimide as the main chain
polymer and the sulfonated polyimide as the side
chain polymer [260]. Scheme 3.39 shows the repeat
unit structure of the graft co-SPI, designated 6FDA-
HABA-g-NTDA-BDSA. In that study, they reported
that the proton and oxygen transport properties of the
graft copolyimide membranes strongly depended on
3: Fluorinated Polyimides 167

2 )& &) 2 2 )& &) 2

1 1 1 1
Q Q
2 2 2 2+ 2 2 2 2+
2 2

2 +1
1

\
2

2
62+ 1
2
2

2
62+

Scheme 3.40  Chemical structure of 6FDA-HABA-g-NTDA-BSPB [260].

the molecular weight of the side chain polymer and
the grafting ratio. The grafting ratio between the fluo-
rinated polyimide and the sulfonated polyimide was
controlled by changing the reaction time of the side
chain and main chain polyimides. Three different
graft copolymers, 6FDA-HABA-g-NTDA-BDSA
(1), (2), and (3), were synthesized with a similar IEC
(approximately 2.4 mEq./g) but different side chain
lengths, to explain the effect of the side chain length
on proton conductivity and oxygen permeability. On
the other hand, 6FDA-HABA-g-NTDA-BDSA (4)
was prepared with a higher IEC (3.14 mEq./g) and
grafting ratio (14%) to explain the effects of IEC and
grafting ratio on proton conductivity and oxygen per-
meability. All of the graft copolyimide membranes
had significantly high proton conductivity exceeding
that of Nafion® 117. In particular, the graft copoly-
imides, 6FDA-HABA-g-NTDA-BDSA (3) and (4),
had proton conductivity values of 1.1 and 1.2 S/cm,
respectively, at 90 °C and 98% RH, which is seven
times more than that of Nafion® 117. In addition, the
oxygen permeability (P(O2 ) = 0.14 Barrer at 35 °C,
76 cm Hg) of 6FDA-HABA-g-NTDA-BDSA (4) was
approximately one-eighth the value of Nafion® 117
owing to significantly low oxygen diffusivity, and the
membrane had excellent gas barrier properties. Also,
the selectivity ratio of the 6FDA-HABA-g-NTDA-
BDSA (4) copolymer, as calculated from the proton
and oxygen transports of the graft copolyimide mem-
brane, was 66 times more than Nafion® 117.
However, the water stability of the 6FDA-HABA-
g-NTDA-BDSA membrane was low, which was
attributed to the lower stability of the sulfonated
diamine, BDSA. To improve the membrane stability
of the sulfonated graft copolyimide, they also synthe-
sized a novel sulfonated graft copolyimide, 6FDA-
HABA-g-NTDA-BSPB (Scheme 3.40), composed
of the side chain-type sulfonated diamine. It was
observed that the oxidative and the hydrolytic sta-
bilities of 6FDA-HABA-g-NTDA-BSPB exhibited
4.5 and 80 times larger values than those determined
for 6FDA-HABA-g-NTDA-BDSA, which indicated
that the 6FDAHABA-g-NTDA-BSPB membrane
had good membrane stability. Considering the bal-
ance between the proton conductivity, oxygen per-
meability, and membrane stability of the PEM, they
concluded that such a side chain-type graft co-SPI is
promising as a PEM material and may have potential
application for use in fuel cells.
In their next study, Kawakami et al. addressed
issues surrounding the design of the PEM for fuel
cells, and more specifically, the role of the polymer
architecture in proton conductivity and gas perme-
ability [266]. From the previous study, Kawakami
et al. showed that the polymer architecture (for exam-
ple, graft polymer structures) helped enhance proton
conductivity and suppressed gas permeability [260].
Taking that idea one step further, they synthesized
and examined the PEM properties of sulfonated block
(S-b-PI), graft (S-g-PI), random-graft (S-rg-PI), and
168 Handbook of Specialty Fluorinated Polymers

block-graft (S-bg-PI) copolyimides. The chemical polymer architectures. To systematically understand

structures of different varieties of co-SPIs are sum- the relationship between the architecture of polymers
marized in Scheme 3.41. The frame formats of these and their PEM properties, all four varieties of poly-
co-SPIs are illustrated to identify differences among mer series were designed to possess almost similar

2 2 2 62+ 2 2 2 2

1 1 1 1 1 1

P ] ]Q
2 2 +2 6 2 2 2 Q2 2
Q
62+ +1 2 +2 2
<
2 ;
2 2

1
+2 6
2
2
1
6EJ3,
2

2 2 2 62+ 2 2 2 2

1 1 1 1 1 1

2 2 +2 6 2
P 2 2 J2 2
QJ

62+ +1 2 +2 2

2 ;
2 2

1
+2 6
2
2
1
6UJ3,
2
2 2 2 2 2 2
&)
1 1 2 2 1 1 1 1
&) P J QJ
2 2 2 2 2 2

62+ +1 2 +2 2
;
2
2 2
1
+26
2
2
1

2 6J3,
2 2 2 62+ 2 2
&)
1 1 1 1 2 2
&)
P 2 Q
2 2 +2 6 2 2 <

6E3,
Scheme 3.41  Chemical structures of sulfonated co-SPIs [266].
3: Fluorinated Polyimides 169

IEC values. Graft co-SPI membranes had higher
proto conductivities than the block co-SPIs at high
humidity (viz. 98% RH) and exceeded that of Nafion®
117 at all temperatures (Table 3.17). For example,
fluorinated graft co-SPI (S-g-PI) and block co-SPI
(S-b-PI) had proton conductivities of 0.45 and 0.17 S/
cm, respectively, at 98% RH and 80 °C. On the other
hand, block-type co-SPI membranes had higher pro-
ton conductivity than graft-type co-SPI membranes at
a low humidity (viz. 30% RH). In addition, the graft
co-SPI membranes had remarkably low gas permea-
bility compared with that of block co-SPI membranes
as well as Nafion® 117, as presented in Table 3.17.
However, the oxidative stabilities of the novel sulfo-
nated block/graft co-SPI membranes were reported
to be insufficient for use in practical fuel cell appli-
cations. The authors concluded that although there
was a stability issue for the prepared membranes,
the outstanding low gas permeability and reasonably
high proton conductivity of the novel membranes
show promise for future applications in fuel cells by
improving stability.
In work by Hansen et al., a series of multi-block
copolymers based on fluorinated co-SPI was syn-
thesized and its detailed morphological analysis and
PEM properties were thoroughly examined [267].
The structure of the multi-block co-SPI is presented
in Scheme 3.42. A random variety of co-SPI was pre-
pared to compare their properties. The block length
of the co-SPI was carefully varied from five to 50
repeat units whereas the IEC of the each co-SPI was
kept constant. The researchers observed that proton
conductivity was increased with an increase in block
length, especially under low RH conditions, and the
performance of the random co-SPI was inferior com-
pared with its block counterparts.
For example, at 5% RH, the conductivity of co-
SPI-50 (50 represents the hydrophilic block length)
was more than 12 times higher than that mea-
sured for the random copolyimide (4.6 × 10−6 vs
3.7 × 10−7 S/cm). Such a difference in proton con-
ductivity was attributed to the enhanced microphase-
separated morphology for membranes with longer
blocks, pointing toward a channel-like morphology
(Fig. 3.21). The better quality of phase separation
with growing domain size was also supported by
solid-state NMR analysis. However, above 60% RH,
both the random and block co-SPIs had approxi-
mately the same proton conductivity (>0.05 S/cm at
90% RH) (Fig. 3.22).
3.3.3.2.3  Fluorinated Sulfonated
Copolyimides Based on Electrospun
Nanofibers
Tamura and Kawakami made a novel attempt
to develop uni-axially aligned electrospun nanofi-
ber composite membranes composed of fluorinated

Table 3.17  Proton Exchange Membrane Properties of Sulfonated co-SPIs

Proton Conductivity (S/cm) Oxygen
Oxidative Permeability
Polymer IEC (mEq./g) Stabilitya (h) 80 °C, 98% RH 80 °C, 30% RH Coefficientb
S-bg-PI 2.51 3.0 0.44 1.0 × 10−3 0.032
S-rg-PI 2.48 3.5 0.43 1.7 × 10−5 0.033
S-g-PI 2.32 3.0 0.45 8.3 × 10−6 0.25
S-b-PI 2.21 3.0 0.17 2.6 × 10−4 1.3
Nafion® 117 0.91 – 0.15 6.4 × 10−3 1.1

aOxidativestability was measured by the time when the membranes completely dissolved in Fenton reagent at 80 °C.
bMeasured at 35 °C and 76 cm Hg; unit: 10−10 (cm3 [STP] cm/[cm2 s cm Hg]).
Data taken from Ref. [266].

62+ 2 2 2 2
&)
2 1 1 1 1

[ &) \
+2 6 2 2 2 2

Scheme 3.42  Chemical structure of multi-block co-SPI [267].

170 Handbook of Specialty Fluorinated Polymers

D F H

E G I

Figure 3.21  Atomic force microscopy and TEM images of membranes based on (a, b) co-SPI-r, (c, d) co-SPI-5,
and (e, f) co-SPI-50. Reproduced with permission from Ref. [267].

The oxidative and hydrolytic stability of the com-

Figure 3.22  Proton conductivity as a function of RH at
50 °C of synthesized co-SPI membranes and Nafion®
117. Reproduced with permission from Ref. [267].
SPI-nanofibers and SPI for PEM fuel cells [268].
First, uni-axially aligned SPI-nanofibers were pre-
pared by electrospinning and deposited onto the glass
plate. A schematic representation of the co-SPI nano-
fiber and its chemical structure (designated NTDA-
BDSA-r-APPF) is shown in Fig. 3.23. Thereafter,
composite membranes containing uni-axially aligned
SPI-nanofibers were prepared by solvent casting.
posite membrane was significantly improved with an
increase in nanofiber, and the oxygen permeability of
the composite membrane decreased compared with
that determined in the membrane without nanofibers.
Furthermore, the proton conductivity of the mem-
brane in the parallel direction indicated a signifi-
cantly higher value compared with that determined
for the membrane in a perpendicular direction or for
the membrane without nanofibers prepared by the
conventional solvent-casting method (Fig. 3.24). In
addition, phase separation in the polymer with both
hydrophobic and hydrophilic domains was facilitated
for that kind of uni-axially aligned electrospun nano-
fiber (Fig. 3.23(c) and (d)). The authors showed that
that kind of aligned electrospun nanofiber could be
considered a promising material as a PEM and the
composite membrane containing nanofibers may
have potential application for use in fuel cells.
In a further study, Kawakami et al. reported another
kind of uni-axially aligned 6FDA-based co-SPI nano-
fiber fabricated by electrospinning [269]. The co-SPI
(designated 6FDA-BDSA-r-APPF, Mw = 3.4 × 105 g/
mol, PDI = 1.8, IECexp. = 1.65 mEq./g) was synthe-
sized by imidization of the precursor poly(amic acid)
in the presence of benzoic acid and triethylamine;
3: Fluorinated Polyimides 171

Figure 3.23  (a) Chemical structure of NTDA-BDSA-r-APPF; (b) schematic representation of co-SPI nanofiber;
(c,d) TEM image of cross-sectional aligned nanofiber in the radial and axial direction, respectively; (e) SEM image
of aligned nanofiber electrospun on specially designed collector. Reproduced with permission from Ref. [268].

its chemical structure is shown in Fig. 3.25. To pre-

Figure 3.24 Proton conductivity of the composite
membrane containing aligned nanofibers for parallel
(σ//) and perpendicular (σ⊥) directions at 80 °C and
98% RH. Reproduced with permission from Ref. [268].
pare uni-axially aligned nanofibers, the authors used
parallel aluminum electrodes on a glass plate as a
grounded collector to which high voltage (V2) could
be applied between parallel electrodes (Fig. 3.25).
They observed that the proton conductivity of the
co-SPI nanofibers (>1 S/cm at 30–90 °C and 95%
RH) was two orders higher than those of correspond-
ing co-SPI membranes at all temperature ranges
(Fig. 3.26). Furthermore, a higher applied voltage
(V2) between the parallel electrodes during electros-
pinning gave higher proton conductive co-SPI nano-
fibers owing to the formation of an effective proton
conduction pathway by molecular orientation in the
nanofibers. The polarized ATR Fourier transform
infrared spectroscopy study supported the molecu-
lar orientation of the polymer backbone along the
nanofiber axis, which was mainly responsible for the
ultra-high proton conductivity in the co-PSI nanofi-
bers owing to the formation of a better proton con-
duction pathway.
172 Handbook of Specialty Fluorinated Polymers

O CF3 O HO3S O CF3 O

CF3 the aerospace industry and in membrane-based appli-
N N N N O O
O
CF3
O SO3H 0.7n O
CF3
O
CF3
0.3n
cations. Polymers containing pendant hexafluorois-
6FDA-BDSA-r-APPF / DMF propyledene groups (–C[CF3]2) or trifluoromethyl
(–CF3) groups have increased solubility, higher Tg,
higher thermal and thermo-oxidative stability, lower
dielectric constant and water uptake, better optical
V1 F1
transparency, and higher gas permeability and flame
Aligned resistance compared with their non-fluorinated ana-
Aluminum Glass
type F2
plate nanofibers logues. Because of the bulky free volume of –C(CF3)2
and –CF3 groups and the low polarizability and hydro-
phobicity of fluorene, these polyimides have better sol-
ubility, a lower dielectric constant, a lower refractive
H+ index, and lower moisture absorption compared with
Parallel SO3-
electrodes
Proton conduction in nanofiber their non-fluorinated counterparts. The –C(CF3)2, –
V2 CF3-substituted diamines and dianhydrides are key
monomers for the preparation of fluorinated poly-
Figure 3.25 Schematic illustration of SPI (6FDA- imides. Researchers have immense interest in the
BDSA-r-APPF) nanofiber preparation. Reproduced properties of fluorinated polyimides and understand
with permission from Ref. [269]. the structure–property correlation of these polymers.
It has been observed that membranes made from poly-
imides are the most attractive materials for gas separa-
tion because they have high gas selectivity for different
gas pairs (CO2–CH4, O2–N2 etc.) along with a number
of outstanding properties such as excellent thermal and
thermo-oxidative stability, solvent resistance, fire retar-
dant qualities, and mechanical and electrical properties.
Fluorinated polyimides have attracted much attention
as basic materials for gas separation membranes owing
to their high gas permeability with relatively high selec-
tivity for pairs of gas. Innovative research in the field
of fluorinated polymers is ever increasing. Currently,
it is well-established that incorporation of fluorene in
the form of trifluoromethyl –C(CF3)2 or –CF3 groups
in the polymer backbone enhances the FFV, solubility,
thermal stability, and so on. In addition, the bulkiness of
these groups facilitates gas permeability.
Fluorinated polyimide membranes are also good
candidate for pervaporation for the separation of close
boiling solvent mixtures and for dehydration. The
Figure 3.26 Temperature dependence of proton presence of bulky fluorinated groups in the polyimide
conductivity of co-SPI nanofibers at 95% RH. Repro- structure has caused significant improvement in per-
duced with permission from Ref. [269]. vaporation properties compared with non-fluorinated
polyimides. Using –C(CF3)2 containing aromatic
3.4 Summary dianhydrides (viz. 6FDA) to synthesize polyimides,
polymer chain mobility and chain packing can be
Aromatic polyimides are an important class of restricted, which in turn results in an improvement
high-performance polymers with interesting proper- in pervaporation selectivity. Furthermore, permeabil-
ties such as good chemical and solvent resistance, ity is simultaneously enhanced as a result of the high
high thermal and mechanical properties, and high FFV produced by the bulky –C(CF3)2 groups.
optical transparency. These excellent properties make Sulfonated polyimides are well-known polymer
them suitable for engineering plastics to be used in materials for fabricating PEMs because of their high
3: Fluorinated Polyimides
proton conductivity, good thermomechanical stabil-
ity, excellent dimensional stability, superior solvent
resistance, low fuel crossover, and outstanding film-
forming ability. Sulfonated polyimides with pendant
–C(CF3)2 or –CF3 groups enhance the oxidative and
dimensional stability of the membrane and increase
proton conductivity by facilitating better phase-sep-
arated morphology. Many structural modifications
of sulfonated polyimides by fluorene/fluorinated
groups and their effect on PEM properties have been
discussed in the last section of this chapter. Also,
their properties with a few non-sulfonated analogues
and Nafion were compared. Fluorinated sulfonated
polyimides have high conductivity at moderately
high temperatures and humidity that is comparable
to or better than that of Nafion and exhibits lower
methanol permeability compared with Nafion. This
chapter summarizes the synthesis and properties of
fluorinated polyimides and their applications in vari-
ous fields. The chapter provides further direction for
research for polymer and material scientists in the
field of fluorinated high-performance polyimides.
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