Polymer Degradation and Stability 146 (2017) 69–77

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Degradation of fluorinated polyoxadiazole in wet acidic media MARK

∗
Guillaume Raynel , Debora Salomon Marques, Tulay Yilmaz Inan, Qasim Saleem
Saudi Aramco, Research and Development Center, Dhahran, 31311, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: The chemical degradation of poly(2,5-(4,4’-(hexafluoropropylidene)diphenyl)-1,3,4-oxadiazole) (F-POD) was

Fluorinated polyoxadiazole studied in wet acidic media using a variety of analytical techniques. It was found that in aqueous acidic solution,
Oxadiazole F-POD degradation increased with higher acidity (lower pH) and can reach levels of up to 20% in mild acidic
Polymer degradation conditions (pH 5.5). Furthermore, residual water present in chloroform was found to be capable of inducing
Hydrolysis
degradation in the fluorinated polymer as well. A mechanistic explanation of the hydrolysis is proposed, which
Cross-linking
Polymer characterization
implicates the electron withdrawing effect of the hexafluoroisopropylidene group in the oxadiazole ring opening.
The initially linear polymer is suggested to be transformed into a bi- or three-dimensional polymer (i.e., a
branched or cross-linked structure) due to the attack of 1,3,4-oxadiazole ring by carboxylic hydrazide, causing a
considerable loss of its solubility in organic solvents. Finally, we demonstrate that F-POD is susceptible to cross-
link via relatively simple chemistry.

1. Introduction other polymeric membranes yield higher salt rejection capability

Polyoxadiazoles (POD) are a class of hetero-aromatic polymers first
reported in 1961 [1]. This class of polymers was developed during the
cold war in the search for lightweight and thermal resistant materials
for aerospace applications. Polyoxadiazoles are known to have high
thermal and hydrolytic stability, strong mechanical properties and re-
latively low density [2–4]. The ability to form films and fibres with POD
quickly gave rise to applications such as fabrication of heat-resistant
fibres used in fire-retardant clothing [5,6]. In the recent decades, doped
POD has also been used as an advanced material for organic electronics
and optoelectronic applications [7]. This is due to the high charge and
photoconductivity exhibited by these materials, which can be used for
charge storage, electrochemical sensors and electroluminescent devices
such as LED and OLED [7–10].
The properties of POD were especially impactful in the field of
membrane science. In addition to being resistant to high temperatures,
POD membranes are suited for harsh environments such as acids, bases
and organic solvents [11]. Gas permeation membranes made from poly-
1,3,4-oxadiazole can be tailored by the addition of functional groups to
the polymer backbone to obtain a wide range of permeability and se-
lectivity [12,13]. Polyoxadiazoles are also attractive to fuel cell appli-
cations when doped or sulfonated to increase proton conductivity
[14–16]. In the presence of doping with phosphoric acid, the con-
jugated heterocyclic ring facilitates the transport of protons in proton
electrolyte membrane fuels cells [14]. Membranes made of POD were
also considered for reverse osmosis, but enjoyed limited success since
[17,18]. Nevertheless, POD is considered as a substitute for ceramic
membranes for processes requiring temperatures up to 300 °C, such as
those used for catalysis, chemical synthesis, and other processes in the
petrochemical and pharmaceutical industries [19].
Polyoxadiazoles are soluble only in certain acids, such as sulfuric,
trifluoroacetic and phosphoric acids. The fluorinated polyoxadiazoles
(F-POD), by virtue of the incorporated hexafluoroisopropylidene
groups, are soluble in a wider range of organic solvents, allowing for
easier processing into fibres and membranes [20]. It is also believed
that the F-POD fibres have decreased combustibility [21]. The added
hexafluoroisopropylidene groups in F-POD also increase the void spaces
in the membrane matrix of gas permeation membranes, increasing
permeability and selectivity [12,13]. Another interesting property of F-
POD is its high hydrophobicity, which coupled with its high thermal
stability, strong mechanical properties and ease of processability, make
this polymer an attractive option for low-energy water treatment
membrane processes [22–24].
In the past, F-POD was usually synthesized through condensation of
hydrazine with dibasic acids in oleum, since thermal dehydration of
perfluoropolyhydrazides was not possible due to decomposition
[25,26]. Other synthetic routes included the cyclisation of poly-
hydrazides and condensation of a diacid chloride with bistetrazole [26].
In recent years, an easier synthetic methodology was adopted to pro-
duce F-POD, which involved the condensation of a diacid with hy-
drazine sulfate using poly(phosphoric) acid as solvent and dehydrating
agent [27,28].

∗
Corresponding author.
E-mail address: guillaume.raynel@aramco.com (G. Raynel).

http://dx.doi.org/10.1016/j.polymdegradstab.2017.09.021
Received 19 July 2017; Received in revised form 24 September 2017; Accepted 26 September 2017
Available online 28 September 2017
0141-3910/ © 2017 Elsevier Ltd. All rights reserved.
G. Raynel et al.
Although POD is considered to be very chemically stable, the hy-
drolysis of POD is known to occur, leading to the opening of the 1,3,4-
oxadizaole ring in the presence of acids [3,29]. In this work, a similar
mechanism is detected in F-POD. The electron withdrawing effect of the
hexafluoroisopropylidene group weakens the carbon bonds in the ox-
adiazole ring, leading to a further degradation of the molecule through
hydrolysis in acidic media. The vulnerability of F-POD is demonstrated
in different acidic media, along with how this degradation property can
be explored as a method to crosslink the polymer.
2. Experimental
2.1. Materials
The synthesis of F-POD is reported elsewhere [19,28]. Acetic acid
(Sigma Aldrich, USA, > 99.8%), hydrochloric acid (Fisher scientific,
USA, 37%), deuterated chloroform (CDCl3) (Merck Sharp and Dohme,
Montreal, > 99.8% D), deuterated dimethylsulfoxide (DMSO-d6)
(Wilmad Glass Co., USA, > 99.8% D), tetrahydrofuran (THF) (Sigma
Aldrich, USA, > 99.9%), hexylamine (Sigma Aldrich, USA, 99%), 1,8-
diaminooctane (Sigma Aldrich, USA, 98%) and iron sulfide (Sigma
Aldrich, USA, > 95%) were used without further purification. Ultra-
pure water was purified on a Milli-Q® Integral 15 water system.
2.2. F-POD degradation
2.2.1. Aqueous acidic F-POD degradation (pH 1.5 & 5.5)
A small sample of F-POD (25 mg) was added to 20 mL of an aqueous
solution of hydrochloric acid (31.7 mmol/L) and acetic acid
(872.5 mmol/L). The pH of the solution was 1.5. Another F-POD sample
was added to 20 mL of an aqueous solution of hydrochloric acid
(31.7 mmol/L) and iron sulphide (187.1 mg, 2.13 mmol). The pH was
5.5. Both mixtures were left overnight at 25 °C. The treated F-POD
samples were then rinsed with pure water and left to dry overnight.
Both samples were analysed by differential scanning calorimeter (DSC),
thermogravimetric analyser (TGA) and attenuated total reflection
Fourier-transform infrared spectroscopy (ATR FTIR) spectroscopy. The
average molecular weights of the samples were subsequently de-
termined using gel permeation chromatography (GPC).
2.2.2. Non-aqueous acidic F-POD degradation
An F-POD sample (25 mg) was added to 1 mL of CDCl3. This liquid
mixture was analysed by NMR spectroscopy immediately after dis-
solution and by FTIR spectroscopy after being left overnight at 25 °C.
The remaining solution was left to evaporate at 25 °C. The resulting
beige solid was not soluble in CDCl3. The solid was partially dissolved
at 60 °C in DMSO-d6 and was analysed again by NMR spectroscopy.
2.2.3. Reaction of F-POD with hexylamine
An F-POD sample (23.1 mg) was added to 1 mL of a deuterated
chloroform solution with 29.2 mg (286 μmol) of hexylamine. The
mixture was left overnight at 25 °C. An off-white solid precipitated
immediately. This precipitate was analysed by FTIR and NMR spec-
troscopy in DMSO-d6.
2.2.4. Crosslinking reaction of F-POD
An F-POD sample (26.2 mg) was added to 1 mL of a deuterated
chloroform solution with 1.8 mg (12.2 μmol) of 1,8-diaminooctane. The
mixture was left overnight at 25 °C. An off-white solid precipitated
immediately. This precipitate was analysed by FTIR and NMR spec-
troscopy in DMSO-d6.
2.3. Analytical methods
2.3.1. NMR spectroscopy
Samples for NMR were prepared by dissolving the solid material in
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Polymer Degradation and Stability 146 (2017) 69–77
either CDCl3 or DMSO-d6. For DMSO-d6 samples, heating at elevated
temperatures was employed at times to homogenize the sample. All
spectra were acquired on a Varian 500 MHz NMR spectrometer,
equipped with a 5 mm liquids probe. The 1H NMR spectra were ac-
quired with a single 90° pulse, a 60 s recycle delay and a 5 s acquisition
time. Generally, a line broadening of 0.5 Hz was applied to the FID
before Fourier transformation. The spectra were typically calibrated to
the TMS signal (0 ppm).
2.3.2. FTIR spectroscopy
Samples for FTIR were analysed as received in solid form. For the
sample dissolved in CDCl3, the solvent was evaporated prior to the test.
FTIR spectroscopic data were collected for all samples using a Varian
FT-IR spectrophotometer equipped with mercury cadmium telluride
(MCT) detector and Golden gate accessory with an average of 128 scans
at a resolution of 4 cm−1.
2.3.3. Gel permeation chromatography
Samples for GPC were prepared by dissolving the solid material in
THF (2 mg/mL). The samples were left for 30 min to ensure complete
dissolution and then filtered through a 0.45 μm syringe filter prior to
injection of 100 μL. The Agilent 1260 Infinity GPC/SEC system was
equipped with a degasser, an isocratic pump, an autosampler, a ther-
mostatted column compartment and a refractive index detector. The
pump was used to achieve a THF eluent flow rate of 1 mL/min through
two GPC columns (type 100 Å and 10,000 Å), each 30 cm long and
connected in series. The columns were packed with highly cross-linked
polystyrene-divinylbenzene (PhenogelTM) 5 μm particles. The tempera-
ture of the column oven was maintained at 30 °C. Calibration was
achieved using Agilent EasiCal polystyrene standards (molecular
weights: 580; 1390; 2780; 4830; 9970; 19,540; 51,150; 113,300;
224,900 and 483,400 g/mol) dissolved in THF. The average molecular
weight of the samples was calculated from the plot of molecular weight
versus relative retention time, using the integrated Agilent software.
2.3.4. Differential scanning calorimeter
Glass transition temperatures were determined by a TA instruments
DSC Q20 coupled with refrigerated cooling system, following ASTM
D3418 standard method. Scans were run with 5 mg of sample under a
nitrogen purge (20 cm3/min) as follow a heating cycle at a heating rate
of 10 °C/min to 400 °C, a cooling cycle at a rate of 100 °C/min to
20.0 °C, and finally a heating cycle at a heating rate of 10 °C/min to
400 °C. Reported values were obtained from a second heating run.
2.3.5. Thermogravimetric analysis
The samples were analysed using a TA instruments TGA Q500 that
was programmed to run at a heating rate of 10 °C/min between 20 °C
and 800 °C under a nitrogen atmosphere to determine the weight losses
of the samples. About 5 mg of each sample was uploaded into TGA
sample pan.
3. Results & discussions
The water-insoluble poly(2,5-(4,4’-(hexafluoropropylidene)di-
phenyl)-1,3,4- oxadiazole) (F-POD in Fig. 1) was exposed to acidic
aqueous solutions (pH 1.5 and 5.5). In parallel, a similar amount of F-
POD was added to pure water as a reference sample.
Fig. 1. F-POD chemical structure.
G. Raynel et al.
Fig. 2. Reference sample of F-POD (left) and F-POD treated in acidic conditions (right) in
pure water.
After rinsing the material with clear water, the F-POD treated in
acid conditions sunk to the bottom of the vial (right sample vial in
Fig. 2). In comparison, the reference sample (left sample vial in Fig. 2)
floated on the water. This change in the physical behaviour between the
treated F-POD and the untreated sample could indicate the possibility
of a chemical change of the polymer (i.e., loss of hydrophobicity). If the
polymer becomes more hydrophilic, water molecules can adsorb on the
surface of the material [30], therefore increasing the apparent mass of
the sample (i.e., mass of the polymer plus mass of the water adsorbed
on the polymer) for the same effective volume.
After air drying the samples, thermal and molecular weight analyses
were performed. The DSC of both F-POD samples showed one glass
transition temperature (Tg) at 287 °C for untreated F-POD and 282 °C
for treated F-POD samples (Fig. 3). The decrease in glass transition
temperature is explained by a decrease in molecular weight, which is a
Fig. 3. DSC thermograms for untreated F-POD (blue) and treated F-POD (red). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version
of this article.)
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Polymer Degradation and Stability 146 (2017) 69–77
Fig. 4. GPC chromatograms for treated F-POD (red) and untreated F-POD (blue). (For
interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
sign of decomposition of the F-POD polymer. A GPC analysis was per-
formed on both F-POD samples to calculate the molecular weights of
the two polymers (Fig. 4). The average molecular weight values were
323,992 g/mol for untreated F-POD and 192,445 g/mol for treated F-
POD. The TGA results (Fig. 5) revealed that the percentage of weight
loss of the volatile and light hydrocarbons below 200 °C was about 2 wt
% for both samples. The total weight loss value at 800 °C was de-
termined to be 53.3 wt % for untreated F-POD and 58.2 wt % for
treated F-POD. The percentage residue value was 46.8 wt % for un-
treated F-POD and 42.1 wt % for treated F-POD, according to the coke
amount formed for each polymer. In conclusion, the thermal analysis
(DSC and TGA) and GPC results all indicate that F-POD has undergone
degradation.
An ATR FTIR was performed on each sample to analyse the change
of functionality on the polymer surface (Fig. 6). The peak of the ox-
adiazole C=N stretching at 1665 cm−1 significantly decreased in
G. Raynel et al. Polymer Degradation and Stability 146 (2017) 69–77

Fig. 5. TGA thermograms for untreated F-POD (blue) and treated F-POD (red). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version
of this article.)

intensity (19% ± 1% in pH 5.5 and 23% ± 1% in pH 1.5) for F-POD
samples exposed to aqueous acidic solution. This effect was more sig-
nificant as the pH of the aqueous solution decreased. Furthermore, the
infrared spectra peak at 1725 cm−1 marginally increased. This nascent
peak was attributed to the C=O stretching of carboxylic acid. Brown
et al. showed that the hydrolysis of 2,5-bisperfluoroalkyl-1,3,4-ox-
adiazoles occurs readily in basic or acidic conditions to yield bis(per-
fluoroalkanoic acid) hydrazides, which can undergo a subsequent
hydrolysis to give the corresponding perfluoroalkanoic acids and hy-
drazinium salt in acidic conditions; or the resultant perfluoroalkanoate
salt and hydrazine in basic conditions [31,32].
The build-up of the carboxylic acid functionality at the F-POD's
surface indicates a similar mechanistic path of degradation (Scheme 1)
as observed in the hydrolysis of 2,5-bisperfluoroalkyl-1,3,4-oxadiazoles
in acidic conditions. In this scenario, the carbons, which constitute the
1,3,4-oxadiazole ring, become more electrophilic due to the electron

Fig. 6. Infrared spectrum superposition of untreated F-POD (blue), F-POD treated with acid (red pH 5.5 & purple pH 1.5). (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)

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G. Raynel et al. Polymer Degradation and Stability 146 (2017) 69–77

Scheme 1. Acid hydrolysis of F-POD.

Scheme 2. Acid hydrolysis of POD.

Fig. 7. 1H NMR spectra of F-POD in CDCl3 (a), F-POD degraded in DMSO-d6 (b), hexylamine reaction product in DMSO-d6 (c), and cross-linked F-POD in DMSO-d6 (d).

withdrawing effect of bis(trifluoromethyl)methylene groups in the para
position. The nucleophilic attack of water on F-POD (1) gives, as an
intermediate, the polyhydrazide (2). Readily, a carbonyl group of 2
undergoes another nucleophilic addition of water to form the corre-
sponding acid (3) and hydrazide (4). Finally, the hydrolysis of 4 yields
3 and a hydrazinium ion (5).
The hydrazinium salts formed can be assumed to be washed away in
the various aqueous solutions used to clean the treated F-POD. With
time, the hydrazinium salts (pKa: 8.1 [32–34]) in equilibrium with its
base form, will slowly oxidize in the presence of oxygen to produce
nitrogen and water [35]. The presence of hydrazine in F-POD, as a
decomposition product was discussed by Gomes et al. [28] during the
sulfonation of F-POD to explain the increase of the N/C ratio from 0.119
to 0.138. In comparison, it was reported that poly(1,4-phenylene-1,3,4-

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G. Raynel et al. Polymer Degradation and Stability 146 (2017) 69–77

Fig. 8. FTIR spectra of reference F-POD, F-POD after NMR in CDCl3, reaction with hexylamine and cross-linked F-POD.

Scheme 3. Nucleophilic attack of carboxylic hydrazide onto F-POD.

Scheme 4. Reaction of F-POD with excess of hexylamine.

oxadiazole) (6) hydrolyzed to the matching polyhydrazide (7) in acidic
conditions (25–75% sulfuric acid) at room temperature (Scheme 2) [3].
The degradation of 6 into diacid (8) occurs in acidic conditions at
higher temperature (i.e., reflux of aqueous sulfuric acid solution) [29].
A 1H NMR of the reference F-POD material was performed in CDCl3
(top spectrum of Fig. 7). The F-POD polymer dissolved fully in aprotic
non-polar solvent, such as chloroform. The spectrum showed the main
product (80% of F-POD 1, 1H NMR: 8.19 & 7.61 in CDCl3) some traces
of unreacted diacid (11% of 3, 1H NMR: 8.05 & 7.49 ppm in CDCl3) and
polyhydrazide (9% of 2, 1H NMR: 8.11 & 7.54 ppm in CDCl3) [28,36].
An FTIR measurement of the resultant deuterated solution was per-
formed and showed an unexpected partial decomposition (Fig. 8). The

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G. Raynel et al. Polymer Degradation and Stability 146 (2017) 69–77

13
Fig. 9. C{1H} and 1H NMR spectra of 11 in DMSO-d6.

Scheme 5. Cross-linking reaction of F-POD with 1,8-diaminooctane.

peak of the oxadiazole C=N stretching at 1665 cm−1 disappeared,
while four peaks were observed to increase: the peak previously en-
countered in the degradation of F-POD in acidic water (i.e. 1725 cm−1),
attributed to the C=O stretching of carboxylic acid (3); two peaks at
1645 cm−1 and at 1619 cm−1, attributed to C=O stretching of car-
boxylic hydrazide functionality existing in 2 and 4; and a peak at
3071 cm−1, attributed to N-H stretching of hydrazine species (5) [37].
It is posited that the F-POD polymer in CDCl3 reacted with the trace
residual water in the solvent (0.066 %w of water in chloroform [38] at
20 °C) [39,40], contributing to the opening of 1,3,4-oxadiazole [41]. As
the limiting factor of this acidic hydrolysis was water (12.6%, 3.6 mmol
of water for 28.6 mmol of 1), only a partial decomposition of F-POD
was observed.
The terminal amino group of the carboxylic hydrazide (4) is a good
nucleophile [42], which may attack the 2 (or 5) position(s) on the
1,3,4-oxadiazole ring, as shown on Scheme 3, to form a 1-((4,4’-(hex-
afluoropropylidene)diaryl)amidinyl)-2-((4,4’-(hexafluoropropylidene)
diaryl)carboxyl) hydrazine (9) [32,43]. The change of solubility of the
resulting solid (i.e., no longer soluble in CDCl3) indicates that the linear
F-POD 1 was transformed through partial acid hydrolysis into a

75
G. Raynel et al.
reticulated polymer (e.g. branched or cross-linked polymer). The F-POD
decomposition in wet acidic chlorinated solvent resulted in a beige
coloured solid, which was slightly soluble in DMSO-d6. The 1H NMR
spectrum (Fig. 7(b)) showed the diacid 3 remaining from the reference
F-POD material as the main product (56%, 1H NMR: 8.05 & 7.48 ppm in
DMSO-d6), with minor products of unreacted F-POD (24% of 1, 1H
NMR: 8.17 & 7.60 ppm in DMSO-d6) and carboxylic hydrazide (20% of
4, 1H NMR: 8.27 & 7.66 ppm in DMSO-d6).
The formation of 1,2,4-triazole from 2,5-disubstituted-1,3,4-ox-
adiazole [43–45], or 1,2-disubstituted carboxylic hydrazide [46],
usually requires heating to circumvent the sterics between the aromatic
protons in ortho position of the triazole ring and the R group attached
to the nitrogen, which would be positioned at the 4 position on the 2,5-
disubstituted-1,2,4-triazole ring. These steric interactions don't allow
for maximum orbital overlap of the phenyl-triazole-phenyl aromatic
rings, consequently destabilizing slightly the molecule (i.e., increasing
its energy of formation) [47]. The reaction of F-POD (1) with an excess
of hexylamine (10) shown in Scheme 4 was performed to investigate
the potential ring formation, which would yield the corresponding
1,2,4-triazole (12) at room temperature. The resulting off-white powder
was analysed by FTIR and NMR spectroscopies (IR spectrum on Fig. 8
and 1H NMR spectrum on Fig. 7).
An FTIR was performed on the sample and is shown at the middle of
Fig. 8. The peak of the oxadiazole C=N stretching at 1665 cm−1 has
disappeared. In addition, two peaks increased: one peak at 1735 cm−1,
attributed to C=N stretching of amidinyl group of 11; one peak at
1377 cm−1, attributed to C-N stretching of amidine species (11). The
1
H NMR spectrum of the reaction product (Fig. 7(c) and Fig. 9) showed
a shielding of the aromatic peaks in 11 (1H NMR: 7.90 & 7.27 ppm in
DMSO-d6) compared to F-POD (1H NMR: 8.17 & 7.60 ppm in DMSO-d6).
Furthermore, the 13C NMR spectrum of this product (Fig. 9) showed a
peak at ∼168 ppm in DMSO-d6, attributed to C=N of the two amidinyl
group of 11, compared to the C=N peak of F-POD at 153 ppm in CDCl3.
When the NMR sample was heated at 50 °C, no change in the NMR
spectrum was observed. The cyclisation of the hydrazide intermediate
(e.g. 9, 11, or 14) to form the corresponding 1,2,4-triazole didn't occur
at temperatures lower than 50 °C, which corroborate with the structures
of the products in the various proposed mechanisms.
Using a similar mechanistic approach to the nucleophilic attack of
carboxylic hydrazide onto F-POD (Schemes 3 and 4), the cross-linking
reaction of F-POD shown in Scheme 5 was performed with of 1,8-dia-
minooctane (13) and F-POD (1). The resulting powder (14) was off-
white in colour and was analysed by FTIR and NMR spectroscopies (IR
spectrum on Fig. 8 and 1H NMR spectrum of the soluble fraction on
Fig. 7(d)).
An FTIR was performed on the sample and is shown at the bottom of
Fig. 8. The peak of the oxadiazole C=N stretching at 1665 cm−1 was
found to have disappeared. In addition, four peaks increased related to
14: one peak at 1594 cm−1, attributed to C=N stretching of the ami-
dinyl group; two peaks at 1545 cm−1 and at 1502 cm−1, attributed to
C=O stretching of carboxylic hydrazide functionality; and a peak at
1379 cm−1, attributed to C-N stretching of amidine species. The 1H
NMR spectrum of the soluble fraction of the crosslinked product (15,
Fig. 7(d)) showed a shielding of the aromatic peaks (1H NMR:
7.90 & 7.28 ppm in DMSO-d6) compared to 11 (1H NMR:
7.90 & 7.27 ppm in DMSO-d6 – Fig. 7(c)) and F-POD (1H NMR:
8.17 & 7.60 ppm in DMSO-d6). Furthermore, the cross-linked product,
which wasn't fully soluble in DMSO-d6, swelled with the addition of the
deuterated solvent (Fig. 8).
4. Conclusions
In this work, the degradation of F-POD in the presence of aqueous
acidic media is demonstrated by a variety of analytical techniques. The
F-POD degradation increased as the pH of the aqueous acidic solution
decreased. This surface degradation can be as significant as 20% in mild
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Polymer Degradation and Stability 146 (2017) 69–77
acidic conditions (pH 5.5). This effect should be considered for appli-
cations where F-POD is used as a material in contact with acidic water
(e.g., membranes for waste water treatment or fuel cell membranes in
humid environments). In addition, we also demonstrated that when F-
POD is dissolved in aprotic non-polar solvent (i.e., chloroform), the
residual water present in the solvent is capable of inducing degradation.
The initially linear polymer is transformed into a reticulated polymer
(e.g., branched or cross-linked polymer), considerably losing its solu-
bility, except for partial solubility in a highly polar solvent such as
DMSO. Furthermore, the product of degradation yielded the substituted
amidinyl carboxyl hydrazide, or the substituted bis-amidinyl hydrazide
in the presence of an excess of amines under mild reaction conditions.
Lastly, the crosslinking of F-POD using a diamine compound (1,8-dia-
minooctane) was successfully induced by taking advantage of the me-
chanistic pathway of degradation shown in this work.
Acknowledgments
The authors would like to thank Mr. Amer A. Tuwailib, Dr. Saroj K.
Panda and Mr. Thunayyan A. Al-Qunaysi from the Saudi Aramco
Research and Development Center for their support with sample ana-
lysis; Mr. Phil Embleton from the Saudi Aramco Public Relations
Department for proofreading and Dr. Regis Vilagines from the Saudi
Aramco Research and Development Center for endorsing this research.
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