Article

pubs.acs.org/IECR

Degradation of Chemical Threats by Brominated Polymer Networks

Lev Bromberg, Natalie Pomerantz,+ Heidi Schreuder-Gibson,+ and T. Alan Hatton*,

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
+
U.S. Army Natick Soldier Research, Development & Engineering Center, Materials and Defense Sciences Division, Natick,
Massachusetts 01760, United States
*
S Supporting Information

ABSTRACT: Poly(N-bromomaleimide) (PMAi-Br), poly(N-vinylpyrrolidone)-bromine adducts (PVPBr), and poly(ethylene-

alt-N-bromomaleimide) (PEMAi-Br) and their cross-linked networks are introduced as reactive, self-decontaminating
components of protective barriers. Synthetic routes toward polymaleimides include free-radical copolymerization of maleimide
with divinyl cross-linkers as well as amidation of poly(ethylene-alt-maleic anhydride) with urea. The polymers are brominated by
bromine in carbon tetrachloride or by copper(II) bromide in dimethylformamide, with the active bromine contents up to and
above 4 mequiv/g, or >30 wt %. The brominated polymer networks exhibit considerable swelling in water and possess reversible
redox peak potentials in cyclic voltammetry experiments due to the redox reactions of the bromine present in the polymer
structures. In acidic aqueous media, PVPBr, PMAi-co-DVB-Br, and PEMAi-Br materials are able to degrade 100% of hydrazine,
monomethylhydrazine, and 1,1-dimethylhydrazine down to concentrations below detectable levels of 0.150.25 mM. The
hydrazine is converted to nitrogen gas. The insecticide malathion, tested as a simulant of a combat warfare agent VX, is eciently
and selectively oxidized to malaoxon in the presence of the brominated networks, whereas 2-(chloroethyl)ethyl sulde (CEES), a
simulant of the sulfur mustard agent, is rapidly oxidized, in both vapor and liquid states, into its less-toxic sulfone derivative, 1-
chloro-2-(ethylsulnyl)ethane (CEESO), with the only side product being 1,2-bis(ethylthio)ethane. The oxidation of CEES is
proven to be selective, in that no toxic overoxidized CEES analogue, 1-chloro-2-(ethylsulfonyl)ethane, is formed. The developed
brominated polymer networks are versatile materials with potential applications in coatings, lters, fabrics, and sorbents.

INTRODUCTION
The production and use of a wide range of chemical
compounds necessary for sustained economic development in
both developed and emerging nations can lead to signicant
contamination of the environment. Such chemical threats are
continual and ubiquitous, and eective means for their control
and eradication will go a long way to mitigate their health
implications. The immediacy of the problem is exacerbated
when chemical and biological compounds are released
deliberately over the short-term, either on the battleeld or in
civilian terrorist attacks, and rapid protection from, and
eradication of, these threats is imperative. These concerns
motivate the development of new protective materials that can
arrest the transport of the oending compounds and catalyze
their neutralization. Reactive and catalytic polymeric reagents
can fulll these demands.
In general, polymeric reagents possess the physical properties
of the high polymer and the functionality of the attached
reactive group(s); polymers are advantageous over their small
molecular weight counterparts due to their stability in the
reaction media, their recoverability, and ease of processing into
ready-to-use items. A polymer matrix can provide a specic
microenvironment that might induce selectivity in the chemical
reaction via steric eects arising from the macromolecular
structure, cross-link density, and pore size.1 In this study, we
focused on polymers with a mild oxidizing function, capable of
reacting with three classes of bioactive compounds such as
phosphorothioates, thioethers, and hydrazines possessing PS,
CSC, and RHN-NR2 (R = H or CH3) groups, respectively,
which occur in various types of pesticides,2 nerve and vesicant
chemical warfare agents (CWA), in the production of rocket
and jet propellants,3 nuclear fuel reprocessing, and many other
applications in the chemical, pharmaceutical, photographic, and
dye industries.
In this work, we report on the development of materials
capable of degrading phosphorothioates, thioethers, and
hydrazines on contact. There are a number of families of
polymeric systems capable of acting as oxidants.4 Among them,
polymer-bound halogenating and oxidizing agents such as
halamines (halogenated imide, amide, or amine groups),
pyridine- and pyrrolidone-based molecular halogen complexes,
and ion-exchange resins in anionic form, seem to be quite
amenable for utilization in protective materials and industrial
collective and individual protective equipment due to their
compatibility with a variety of other polymeric matrices and a
great multitude of available processing options.47 There is a
signicant body of literature related to the utilization of N-
haloamines as biocidal, antiseptic, halogenating and oxidizing
agents in polymeric coatings, resins, bers, paints, etc.812
Pyrrolidone-based molecular halogen complexes such as
poly(N-vinylpyrrolidone) (PVP)-bromine complexes have
been utilized in alcohol and acetal oxidation, alkene
dibromination, oxidative cleavage of silyl ethers, and conversion
Special Issue: Ganapati D. Yadav Festschrift
Received: March 11, 2014
Revised: April 9, 2014
Accepted: April 15, 2014

XXXX American Chemical Society A dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Industrial & Engineering Chemistry Research
Figure 1. Structures of chemical threats such as hydrazines, pesticides, CWAs (VX and HD), and mustard-gas simulant, CEES.
of dithioacetals to oxothioesters.1318 Functionality of PVP
stems from its hydrophilicity, benign nature, lm-forming
properties, ease of cross-linking, and ability to form adduct-type
complexes with halogens.19,20 PVP-based networks are water-
dispersible and can be synthesized in situ by UV-initiated
polymerization. Monomer and cross-linker solutions of such
systems can be applied to porous surfaces such as in textiles by
either batch coating or dip coating, followed by cross-linking
and halogenation.21 This results in bactericidal textiles.
There are no reports on activity of PVPhalogen adducts or
halamines in the degradation of chemical threats. We have
explored bromine-containing polymeric oxidants tailored for
reactivity in water- or polar solvent-containing systems for
specic reactions such as oxidation of hydrazines as well as
phosphinothioate, phosphonodithioate, or sulfane groups
present in pesticides, and nerve and vesicant chemical warfare
agents (CWA) (Figure 1).
The ecient hydrolysis of VX and other organophosphate
CWAs by -nucleophilic polymers and gels has been reported
in our previous work,22 but such polymers lack redox properties
and are ineective for HD degradation.
The high reactivity of N-bromosuccinimide (NBS) as an
oxidant and brominating agent in a multitude of reactions is
well-known.2332 In this work, we replicated the NBS reactivity
with its polymeric counterpart, brominated polysuccinimide
(alternatively called polymaleimide, PMAi) and its copolymers,
with a focus on the processability of the polymer into functional
networks and lms that can be incorporated into multilayered
fabrics and other items capable of degrading chemical threats.
Polymaleimides are conventionally prepared by either homo-
polymerization of maleimide,31,32 or by thermolysis or
hydrolysis of substituted maleimide homopolymers.3336 As
an alternative, to avoid the need to polymerize maleimide (a
relatively expensive starting material), polymaleimide (PMAi)
synthesis with high degrees of conversion has been reported via
amidation of poly(maleic anhydride) homopolymers by urea.37
We investigated both the copolymerization of monomeric
maleimide with divinyl cross-linkers and amidation of a
commercially available, lm-forming maleic anhydride copoly-
B dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
mer, poly(ethylene-alt-maleic anhydride) (PEMA). Anhydride
group chemistry of PEMA oers a range of possibilities
including esterication, aminolysis, hydrolysis, and amidation
reactions.38,39 PMAi homopolymers are water- and polar
solvent-soluble and possess a softening point at around 120
C.37 PMAi, PEMAi, and their copolymers, blends, and
networks are thermoplastic and thermosetting,40,41 which
make them suitable for melt extrusion and other processes of
ber production.
Following the homopolymer and network syntheses, the
resulting polymers were functionalized by bromination with a
bromine solution in carbon tetrachloride or a milder
bromination agent, copper(II) bromide in DMF. Bromination
by CuBr2 is known,42 but has not been reported for polymers
such as PMAi and analogues. The obtained brominated
polymers were capable of degrading hydrazines, pesticides
such as malathion (2-(dimethoxyphosphinothioylthio)-
butanedioic acid diethyl ester), which is a good VX- mimicking
agent, and 2-chloroethyl ethyl sulde (CEES), often used as a
simulant for the vesicant HD CWA.
EXPERIMENTAL SECTION
Materials. Malathion (99%, analytical standard), 2-chlor-
oethylethyl sulde (CEES, 99%), bromine (99.5%), copper-
(II) bromide (99%), maleimide (99%), divinylbenzene (80%),
dicumyl peroxide (98%), urea (99%, USP grade), 1-vinyl-2-
pyrrolidone (99%), poly(ethylene glycol) diacrylate (PEGDA,
average Mn 250), (Chelex 100 ion-exchange resin (sodium
form), poly(ethylene-alt-maleic anhydride) (PEMA, average
MW 100500 kDa, ethylene/maleic anhydride mol ratio of 1),
2-(4-dimethylaminophenylazo)benzoic acid (Methyl Red dye,
99%), polyvinylpyrrolidone (PVP, MW 1,3 MDa), potassium
bromate (ACS reagent, 99.8%), ammonium persulfate (99%),
hydrazine sulfate (99%), methylhydrazine sulfate (MHS, 99%,
Aldrich), and N,N-dimethylhydrazine (DMH, 98%) were all
purchased from Sigma-Aldrich Chemical Co. and were used as
received. Initiator Irgacure 2959 was obtained from Ciba
Specialty Chemicals. All other reagents, solvents, buer
Industrial & Engineering Chemistry Research
Figure 2. Synthesis of poly(maleimide-co-divinylbenzene) (PMAi-co-DVB) networks.
solutions, and gases were obtained from the commercial
sources and were of the highest purity available.
Syntheses. Polymaleimide-Based Cross-Linked Networks
(PMAi-co-DVB) (Figure 2). PMAi-co-DVB networks were
synthesized by free-radical copolymerization of maleimide and
divinylbenzene. In a typical synthesis, a solution of maleimide
(970 mg, 10 mmol), divinylbenzene (390 mg, 3 mmol), and
dicumyl peroxide (100 mg, 0.37 mmol) in 10 mL of 1,4-
dioxane was deoxygenated by nitrogen bubbling for 0.5 h and
then kept at 80 C in a sealed ask for 24 h. The resulting white
solid was twice dispersed in excess diethyl ether, separated, and
then dispersed sequentially in acetone and methanol. The
solids were separated by lter-suction and dried under vacuum
until constant mass. The yield of polymerization (Figure 2) was
measured to be approximately 90 wt % relative to the initial
maleimide loading. The eect of DVB concentration on the
solubility of the resulting networks by 24 h extraction in
methanol and acetonitrile was studied. At the initial DVB/
maleimide concentration ratio below 0.25 mol/mol, a
signicant fraction of the network (>1520%) appeared to
be soluble, and thus the DVB/maleimide mol/mol ratio of 0.3
to 0.5 was deemed to be suitable for the further network studies
reported throughout.
PMAi homopolymer was synthesized for characterization
purposes in a procedure identical to the one above, but without
the addition of DVB. The polymer was washed by diethyl ether
and acetone and dried under vacuum. Size-exclusion
chromatography was used to measure the weight-average
molecular mass of the resulting polymer in its DMF solutions,
which was found to be 120 kDa (polydispersity, 2.3). 1H NMR
(400 MHz, DMSO-d6), (ppm): 11.5 (m, C(O)OH,
minor), 10.9 (m, >NH), 7.42, 7.34, 7.24 (s, benzyl of dicumyl
peroxide), 2.53.3 (m, succinimide).
Poly(ethylene-alt-maleimide) (Figure 3). This polymer was
prepared in melts of PEMA and urea as reported previously,37
with variations.
Initial polymer (1.00 g) and urea (0.3 g) were ground in a
mortar and the resulting ne powder was placed in an oven at
180 C for 4 h. After being cooled to room temperature, the
reaction mixture was placed into ethanol overnight and then
Figure 3. Synthesis of poly(ethylene-alt-maleimide) (PEMAi) via
reaction of poly(ethylene-alt-maleic anhydride) with urea.
Article
ltered. The lter cake was dried under vacuum. 1H NMR (400
MHz, DMSO-d6), (ppm): 11.1 (m, C(O)OH), 8.5
(>NH, imide), 2.51 (m, CH of main chain), 1.61.8 (m, CH2
of main chain). Anal. Calcd: C, 60.6; H, 6.78; N, 9.92. Found:
C, 60.5; H, 6.63; N, 7.39. Content of carboxyls originating from
the hydrolysis of maleic anhydride relative to imide groups was
found to be below 10 mol %.
Synthesis of Poly(N-vinylpyrrolidone) (PVP) Networks. PVP
networks were synthesized from N-vinyl-2-pyrrolidone as a
main constituent and poly(ethylene glycol) diacrylate as a
cross-linker (Figure 4).
In a typical heat-initiated polymerization, an aqueous
solution containing N-vinyl-2-pyrrolidone (1.5 M), 16.6 wt %
Na2SO4, 10 wt % Na2HPO4, 0.1 M PEGDA, and 10 mM
azobis(isobutyronitrile) (AIBN) was deaerated by nitrogen
bubbling for 0.5 h and then equilibrated, while stirring, at 65 C
for 24 h. The resulting gel was washed extensively by water and
acetone and lyophilized.
Alternatively, a UV-initiated polymerization was carried out
at 25 C in deaerated, neat monomer/cross-linker (150/1 mol/
mol) solution in sealed glass Petri dishes using 1-[4-(2-
hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one
(Irgacure 2959). The solution was irradiated for 1560 min
using a UVGL-25 compact UV lamp (254365 nm, 4 W) from
a distance of 1 cm. UV-initiated polymerization resulted in
transparent gel lms, optionally lling the pores of a porous
support presoaked with the monomer/cross-linker solution.
Cotton/nylon (1:1) military-style fabric was found suitable as a
gel support.
PVP gels were also synthesized by the cross-linking of a high-
molecular-weight linear PVP; that is, a mixture of a 20 w/v%
aqueous solution of polyvinylpyrrolidone (MW 1.3 MDa) and a
5 w/v% ammonium peruslfate solution was equilibrated at 80
C for 4 h. A dramatic viscosication and gelation of the above
mixture was observed. The gel was snap-frozen in liquid
nitrogen and lyophilized. The resulting solid was cut into small
pieces suspended in water and dialyzed (MW cuto 1214
kDa). The puried gel was snap-frozen in liquid nitrogen and
lyophilized.
Polymer Bromination Using Bromine. Finely powdered, dry
PVP, PMAi, PMAi-co-DVB, or PEMAi (1 g) was carefully
suspended in a dark brown glass tube with chilled, freshly
prepared 15 wt % bromine solution in carbon tetrachloride (15
mL) at 0 C under constant stirring in the dark. The
suspension was sealed and brought up to ambient temperature
within 4 h under stirring, which continued for another 20 h.
The suspension of all polymers but PVP was rst washed by 2
M KOH,13,14 then ethanol and acetone, and the solids were
carefully separated by suction ltration. The yellowish solids
C dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Industrial & Engineering Chemistry Research
Figure 4. Synthesis of poly(1-vinyl-2-pyrrolidone-co-PEGDA) networks. Diethylene glycol diacrylate is depicted as a cross-linker, which is a close
analogue of PEGDA that was actually used.
Figure 5. Bromination of PMAi by copper(II) bromide.
were again washed by carbon tetrachloride and ethanol and
dried under vacuum. Bromine content in the resulting polymers
was measured by titration and is reported in what follows. The
yield of the bromination reactions was at least 94 wt % relative
to the initial polymer. For typical brominated poly(ethylene-alt-
maleimide) (PEMAi-Br), 1H NMR (400 MHz, DMSO-d6),
(ppm): 10.8 (m, C(O)OH), 3.35 (m, CH, imide main
chain), 2.51 (m, CH of main chain), 1.61.8 (m, CH2 of
main chain). Anal. Calcd.: C, 41.5; H, 4.1; Br, 31.8; N, 6.10.
Found: C, 42.2; H, 4.51; Br, 31.9; N, 5.58.
Bromination Using CuBr2 (Figure 5). The polymer to be
brominated such as PMAi, PMAi-co-DVB, or PEMAi was
dissolved or suspended in anhydrous N,N-dimethylformamide.
An equivalent amount of copper(II) bromide was placed in the
above solution or suspension and the resulting mixture was
kept under magnetic stirring for 3 h at 80 C. During the
progress of the reaction, the copper bromide completely
dissolved and the mixture changed color from dark-green to
dark-brown. After the solutions were cooled to ambient
temperature, the work-ups of the suspensions (in the case of
polymaleimide-co-DVB) and PMAi or PEMAi solutions were
dierent. The brominated polymaleimide-co-DVB suspension
in the DMF/CuBr2 solution was centrifuged at 15000 rpm for 1
min, and the solids were separated from the solution. The
solids were suction-rinsed with methanol using a pipet tted
with a glass lter separating beads of Chelex 100 ion-exchange
resin (sodium form) for more ecient removal of Cu2+ ions.
Then the network solids were washed with methylene chloride
and acetone and dried under vacuum. The solutions of
polymaleimide were mixed with Chelex 100 beads (eective
bead concentration, 30 wt %) and stirred for 3 h at room
temperature to facilitate removal of Cu2+ ions, at which point
the beads became dark-green. The beads were then separated
by centrifugation at 15000 rpm for 1 min and the supernatant
solutions were mixed with excess carbon tetrachloride, at which
point yellowish precipitates were observed. The solids were
ltered o, washed with carbon tetrachloride, methylene
chloride, and dried under vacuum. The yield of brominated
products, relative to the initial nonbrominated polymer weights,
was 80 to 84 wt % (brominated polymaleimide) or 92 to 95%
(brominated polymer network).
D dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
Methods. The equilibrium swelling degree of the cross-
linked networks was measured by weighing dry material (dry
mass, Md) that was placed in excess deionized water or
methanol or acetonitrile and equilibrated for 35 days at room
temperature. The material was removed from the solvent,
excess of which was gently wiped o the surface by a lter
paper, and the swollen mass (Ms) was measured by weighing.
The quilibrium swelling degree was dened as S (%) = (Ms/Md
1)100.
Cyclic voltammetry (CV) measurements were performed at
25 C with a VersaSTAT 3 potentiostat (Princeton Applied
Research, Oak Ridge, TN) using a three-electrode microcell
assembly (MF 1065, Bioanalytical Systems, Inc., West
Lafayette, IN) with a carbon paste working electrode, a
platinum wire auxiliary electrode, and a Ag/AgCl reference
electrode lled with an aqueous 3 M NaCl solution. The
reference electrode adhered to the acceptable range test relative
to a standard calomel electrode (SCE). The working electrode
was lled with 0.3 g/g of test sample thoroughly mixed and
compacted in oil-base carbon paste (BASi CF-1010); the tip of
the electrode was polished against lter paper. The electrolyte
solution used in the cell was aqueous 0.1 M HCl deaerated by
argon ow, and the CV was measured by applying a cyclic
potential between 1.5 and 1.5 V versus the Ag/AgCl
electrode. In some experiments, the argon ow was
discontinued after the deaeration, and the microcell was sealed
prior to the application of the potential in order to observe a
gas evolution during the voltammetry scans. Scan rates were
varied from 0.05 to 1.0 V/s.
Titration of Brominated Polymers by Hydrazine, MHS, and
DMH. We developed an analytical method for quantifying
accessible bromine groups in brominated polymers, based on
colorimetric titration.43,44 NBS and its polymeric analogues can
decolorize Methyl Red dye by bromination in aqueous acidic
medium, but oxidize hydrazines preferentially, so that the red
color of the titrant solution persists until all hydrazine has been
oxidized, but then disappears through decolorization by a
minor excess of available bromine.45 A 0.01% solution of
Methyl Red was prepared by dissolving 100 mg of the dye in 1
mL of 4.5 M NaOH, adding 1 mL of 4.25 M sulfuric acid and
diluting the resulting solution to 100 mL by deionized water. A
Industrial & Engineering Chemistry Research
Figure 6. Reaction between NBS and hydrazine, illustrating the titration stoichiometry.
measured amount of nely powdered PMAi-Br, PMAi-co-DVB-
Br, or PVPBr was suspended or dissolved in 50 mL of 0.425
M sulfuric acid solution and titrated by an aqueous solution of
hydrazine sulfate, methylhydrazine sulfate, or 1,1-dimethylhy-
drazine. Brominated PEMAi was found to be quite hydro-
phobic, with approximately 20% of its bromine content not
captured by titration in aqueous solutions only. Therefore,
powdered PEMAi-Br samples (1040 mg) were rst placed in
1 mL of methanol and briey sonicated, followed by mixing
with aqueous H2SO4 solution described above. All hydrazine
solutions were freshly made prior to titrations and deaerated for
510 min by nitrogen bubbling; MHS and DMH solutions
were not deaerated. Immediately prior to the start of titration,
0.1 mL of Methyl Red solution was added to the hydrazine
solution. The brominated material suspension was titrated with
0.1 w/v% hydrazine solution, added dropwise from a
microburet, with continuous stirring by a magnetic bar.
Initially, eervescence was observed during the titration due
to the nitrogen evolution, but it quickly ceased with the stirring.
A solution of N-bromosuccinimide was used as a titration
control.41 The end point of the titration was indicated by the
suspension turning colorless (Supporting Information, Figure
S-1). The volume of the hydrazine titrant, V (mL), required to
stoichiometrically react with a sample of the brominated
material of mass M (g) was calculated as
V = MQS /C
where Q (mmol/g) is the content of bromine in the sample, S
= 0.5 is the hydrazine-to-bromine equivalent stoichiometry (see
Figure 6), and C (mmol/mL) is the hydrazine concentration in
the titrant.
The bromine group content in the sample was calculated on
the basis of the values of elemental composition of C, H, N, and
Br (mol %) corresponding to the makeup of the polymer. In
the computation, the experimental elemental analysis data were
matched with the predicted ones using ChemBioDraw Ultra
software (version 13.0), yielding calculated bromine content
(Qcalc). The titrations were conducted in triplicate. An excellent
correspondence was found between the predicted bromine
content and the one obtained from the titrations. For instance,
Qfound/Qcalc ratio values obtained for NBS and PMAi-co-DVB-
Br were 0.99 0.013 and 1.03 0.070, respectively.
Degree of Hydrazine Elimination. By quantifying residual
hydrazine quantity (QfH, mmol) after its elimination by the
polymer using a hydrazine assay,45 we determined the eective
degree of elimination, E % = 100(1 QfH/Q0H), where Q0H is the
initial quantity of hydrazine or hydrazine derivative (in mmol)
set in the reaction mixture before the reaction commencement.
In brief, a polymer powder of a known weight (2040 mg) and
known bromine content (QpBr, mmol) was placed in 5 mL of
deaerated 0.425 M sulfuric acid solution containing a known
initial amount of hydrazine or hydrazine derivative (Q0H, mmol).
Initial conditions were set such that QpBr = (1.11.2)Q0H, that is,
bromine was in slight excess. After a 30 s sonication and a 24 h
equilibration under gentle shaking in a sealed vial in the dark at
room temperature, the solids were separated from the
E dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
suspension by centrifugation (14 000 rpm, 45 s) and the
supernatant was assayed for the hydrazine concentration
spectrophotometrically after addition of a freshly prepared
bromine (KBr/KBrO3) and Methyl Red solution. An Evolution
model 220 UVvis spectrophotometer (Thermo Scientic)
with sealed quartz cuvettes (path length, 1 cm; blank reading of
the reagent without hydrazine) was used. Calibration curves
using absorbances at = 515 nm were developed and the
published molar absorptivity of 9.95 104 L/molcm45 was
used for concentration measurement.
Degradation of Malathion. An assay was developed where
a weighed amount (2040 mg) of nely powdered brominated
polymer particles was allowed to equilibrate in a glass stoppered
vial with sodium acetateacetic acid buer (pH 3.7) for 10 min,
and these swollen particles were blended with 1 mL of freshly
prepared malathion emulsion in the buer. The mixture
contained 5 to 55 L (1545 mol) of malathion, but in
most experiments, malathion loading was 30 mg (25 L). The
suspension was sonicated for a specied time t using an
Aquasonic model 75T ultrasonic cleaner (power, 380 W,
VWR Scientic), to enable a proper contact between malathion
and polymer particles. In reactions that were conducted for
longer than 12 min, sonication was intermittent, to avoid
heating the reaction mixture. At specied time t2, the aqueous
suspension was mixed with 0.75 mL of CDCl3. Malathion was
extracted into the CDCl3 phase after additional 30 s sonication
and centrifugation of the blend at 15 000 rpm for 30 s. The
CDCl 3 phase (0.7 mL) was subjected to 31 P NMR
spectrometry using a Bruker Avance 400 spectrometer
operating at 161.98 MHz. The spectra were recorded by
accumulation of 200 scans. The degree of parathion conversion
was expressed as F = Ip/(Ir + Ip), where Ir and Ip are the
sums of the integrations of the signals corresponding to the
reactant (malathion, signals of stereoisomeric forms around
95.7 ppm46 and the products, in most reactions being solely
malaoxon (29.3 ppm) (Supporting Information, Figure S-2).
Replacing sulfur in the thionyl for the oxygen in the oxon group
leads to an over 66 ppm upeld shift in the 31P resonance.
Consequently, it easy to distinguish malathion from its oxidized
product when both compounds are present, and calculate the
degree of conversion from the spectrum integrations.
The observed apparent rate constant, kobs, is found from the
slope of the ln(1 F) vs t plot.47 After the reaction, the
aqueous phase containing polymer particles was washed with
acetone and dried under vacuum. The particles were subjected
to bromination by bromine in CCl4 as described above. After
bromination, the recycled particles were analyzed for bromine
content, weighed, and utilized in the next cycle of malathion
degradation, identical to the rst one. Three consecutive cycles
were conducted.
Reactivity of Materials toward 2-Chloroethyl Ethyl Sulde
(CEES). The ability of the materials to react with vapors of 2-
chloroethyl ethyl sulde in the presence of air was evaluated
using a Thermo Scientic DSQ II Series Single Quadrupole
GCMS (Thermo Fisher Scientic, Austin, TX). Samples were
prepared by placing 550 mg of each material to be tested into
Industrial & Engineering Chemistry Research Article

Table 1. Elemental Composition and Bromine Content (Q) of N-Bromosuccinimide and Brominated Polymers
bromine-containing species elemental composition (%) Q (meq/g)
N-bromosuccinimide (control) C, 27.0; H, 2.27; Br, 44.8; N, 7.83 5.6
a
PMAi-Br C, 34.8; H, 2.26; Br, 34.9; N, 8.42 4.3
a
PMAi-co-DVB-Br C, 36.9; H, 2.25; Br, 33.9; N, 8.17 4.2
b
PMAi-co-DVB-Br C, 38.7; H, 2.62; Br, 29.7; N, 9.15 3.7
a
PEMAi-Br C, 44.9; H, 4.62; Br, 26.2; N, 6.46 3.3
b
PEMAi-Br C, 46.4; H, 4.22; Br, 24.9; N, 7.12 3.1
c
PVPBr C, 45.2; H, 7.02; Br, 32.0; N, 5.71 4.0
d
PVPBr C, 44.2; H, 6.90; Br, 33.1; N, 5.26 4.1
a
Bromination by bromine in CCl4 bBromination by CuBr2 in DMF cPVP gel was synthesized by temperature-initiated copolymerization of 1-vinyl-2-
pyrrolidone and PEGDA, followed by bromination with Br2 in CCl4 (see Experimental Section). The degree of the gel cross-linking by PEGDA was
7 mol % relative to vinylpyrrolidone. dPVP gel was synthesized by cross-linking of aqueous polyvinylpyrrolidone solution with ammonium persulfate,
followed by bromination with Br2 in CCl4 (see Experimental Section).

capped GC vials. A small piece of cellulose sheet wiper

(Kimtech Science brand, Kimberly-Clark Worldwide, Inc.) was
suspended above the compound, and the vial was sealed with a
crimped septum cap. Then, 1 L of CEES was injected into the
vial onto the wiper. CEES evaporation from the wiper into the
vial supplied the vapor in the vial headspace and on the surface
of the tested material. A seven-point calibration curve was
developed for CEES in acetonitrile in a concentration range of
101000 ppm. A CEES control of 1 L on a wiper without any
reactive material was measured along with each reactive
compound. Blank samples of each material were also analyzed. Figure 7. Typical TGA and DSC thermograms of polyvinylpyrroli-
GC run parameters with an Rtx-5 ms column were as follows: done networks cross-linked by PEGDA (PVP1) or with ammonium
He carrier ow, 1 mL/min; split ow, 20 mL/min; injector inlet persulfate (PVP2) and PEGDA-cross-linked networks brominated by
temperature, 150 C; oven temperature, 85 C; ramp rate, 20 bromine in CCl4 (PVPBr). Heating scans, 10 C/min. Solid and
C/min until 220 C. Temperature of the transfer line to the dashed lines show TGA and DSC data, respectively.
MS was set at 250 C and the EI ion source was set at 200 C
for positive ion analysis. The reaction was monitored over a 24
h period. Upon completion of the vapor sorption and reaction,
both the reacted materials and the blanks were placed in evaporation of sorbed and bound water. Interestingly, the PVP
acetonitrile for extraction. The compounds in acetonitrile were network synthesized by the copolymerization of N-vinyl-
sonicated for 30 s and allowed to equilibrate at room pyrrolidone and poly(ethylene glycol) diacrylate (PEGDA, 7
temperature overnight to complete the extraction. The mol %) lost only 4% at 140 C, whereas the network prepared
extracted compounds were then analyzed by GCMS. by cross-linking PVP (1.3 MDa) by reaction with ammonium
persulfate lost approximately 18% at 140 C, indicating a much

RESULTS AND DISCUSSION

The synthesized polymeric species were characterized by
elemental analysis and bromine titration for composition, and
by thermogravimetric analysis (TGA) and dierential scanning
calorimetry (DSC) for thermal stability. The polymer materials
were also evaluated for their ability to swell in water and
methanol. The elemental compositions and bromine contents
of the polymers are collected in Table 1.
The bromine content of the halamine polymers (Table 1)
corresponded to 8090 mol % of the maleimide groups being
brominated, which is at or above the maximum bromination
levels reported previously for analogous polymers.13,14
Similarly, bromine content in the PVPBr material was
approximately the same as, or 510% higher than, the
maximum values reported previously.17 Note the longer time
and higher bromine concentrations used in the bromination
procedures herein.
The thermal properties of the dry polymers and their
brominated derivatives were studied using simultaneous TGA/
DSC heating ramps at 10 C/min (Figure 7 and Supporting
Information, Figure S-3). The thermal behavior of PVP and
PVPBr had features similar to those of other polymers studied
(Figure 7). The initial weight loss up to 120140 C indicated
F dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
larger content of water in this kind of network. The thermal
decomposition of the PVP network prepared with PEGDA
starts at above 220 C and a sharp mass loss resulting in about
95% change of the initial sample mass occurs between 350 and
520 C, where a well-dened endothermic DSC peak centered
at 448 C is observed. Thermal decomposition of the PVP
network prepared from long PVP homopolymer chains cross-
linked by hydrogen abstraction with persulfate followed by
macroradical recombination48 started above 200 C, and the
mass loss of about 97% of the initial sample mass occurred in
two steps: between 200 and 360 C and then between 377 and
650 C, where the network mass loss was 48% and 35%,
respectively. A broad exothermic DSC peak centered at 336 C
was observed, probably related to the melting of the PVP
crystallites and decomposition. The brominated PVPBr
species, which was prepared by bromination of the PVP
network cross-linked by PEGDA, lost approximately 30 wt %
from 150 to 335 C, which is attributed to the bromine
complexed to the polymer and liberated within this temper-
ature range.17 Liberation of bromine may have continued above
335 C, simultaneously with other decomposition processes.
Analogously, PEMAi-Br and PMAi-co-DVB-Br materials lost
approximately 35 and 42% of their initial mass, respectively,
attributable to bromine, in the temperature ranges 200354 C
Industrial & Engineering Chemistry Research Article

Figure 8. Cyclic voltammograms of NBS (a), PMAI-co-DVB-Br (b), PEMAi-Br (c), and PVPBr (d). Carbon paste working electrode (content of
material under study, 0.3 g/g) immersed in 0.1 M aqueous HCl was employed throughout; the initial potential and the potential scan rate were 1.5 V
vs SCE and 0.1 V/s, respectively. For NBS (a), directions of the rst scan are indicated by arrows. The rst and second forward and reverse scan data
are shown by blue and red lines, respectively. Background data (carbon paste only) are shown in green. In panel b, 10 CV scans are shown with
PMAi-co-DVB-Br (bromine content, 4.3 mequiv/g, blue lines) and its PMAi-co-DVB counterpart devoid of any bromine (red lines). In panels c and
d, PVPBr and PEMAi-Br contained 4.1 and 3.1 mmol/g bromine, respectively. CV data for brominated and parent, nonbrominated materials are
shown by blue and red lines, respectively.

and 284415 C, respectively (Supporting Information, Figure
S-3).
The aqueous solubility of PMAi, PEMAi, and PVP was
reduced by the polymer bromination, but was sucient to allow
access of water-soluble species such as hydrazine sulfate to all of
the available bromine in the heterogeneous titration (see
Experimental Section and Table 1). Water molecules retained
within the polymer particles after the synthesis might have
contributed to their ability to absorb liquid water. The
equilibrium swelling degree of PVPBr (cross-linked by
poly(ethylene glycol) diacrylate at monomer/cross-linker ratio
of 1:0.3 mol/mol, bromine content 4.0 mequiv/g), PMAi-co-
DVB-Br (monomer/cross-linker ratio of 13:1 mol/mol,
bromine content 3.7 mequiv/g) and PEMAi-Br (bromine
content, 3.3 mequiv/g) in deionized water was 360 50%, 230
40%, and 35 12%, respectively. The swelling in organic
solvents such as methanol and acetonitrile also decreased in the
sequence PVPBr > PMAi-co-DVB-Br PEMAi-Br. In the
titration experiments, PEMAi-Br was insuciently soluble in
water to allow access of hydrazine to all its reactive bromine
sites, and hence used methanol to assist in the swelling of the
gel particles. The bromine groups in the gel matrices were
accessible for redox reactions in cyclic voltammetry measure-
ments and for reactants such as malathion, as described below.
Redox Properties of Bromine-Functionalized Poly-
mers and Gels in Aqueous Media. When particles of a
brominated polymer were placed in deionized water, an acidic
pH of 1.55 in the suspension resulted due to the formation of
HBr; the equilibrium pH value depended on the polymer used
and polymer/water weight ratio. To alleviate the pH eects, we
studied redox properties of NBS and its polymeric counter-
parts, PMAi-co-DVB-Br, PEMAi-Br, and PVPBr, by cyclic
volammetry (CV) in aqueous HCl solutions. Figure 8 shows
representative CV data, collected for NBS and polymers loaded
G dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
into a carbon paste electrode immersed in 0.1 M HCl.
Voltammograms of NBS and polymers were signicantly
dierent with respect to the reversibility of the reactions. An
irreversible, one-electron NBS reduction leading to the
appearance of the NBS radical anion, [NBS] results in a
single reduction peak at around 0.6 V (Figure 8):49,50
NBS + e [NBS]
The unstable NBS anion radical decomposes into the
succinimide (S) radical and the bromide ion:
[NBS] S + Br
Succinimide is about 20-fold more soluble in water than NBS.
Succinimide and bromide ions diuse from the carbon paste
electrode, and the bromide ions undergo anodic oxidation
(peak potential at 1.19 V) to bromine radicals, which
recombine to produce bromine:
Br Br + e
Br + Br Br2
The described sequence of reactions results in irreversible
decomposition of NBS, which is illustrated by a dramatic
decrease in the oxidation and reduction peaks in the second
scan and disappearance of the peak potentials altogether in
subsequent scans. Under some specic (but dierent)
conditions, however, it is possible to brominate succinimide
electrochemically back into NBS in the presence of bromide
ions.51
In contrast to the behavior observed for NBS, the CV scans
of all brominated polymeric species exhibited reversible
patterns (Figure 8). The peak potentials for PMAi-co-DVB-
Br, a polymeric network analogue of NBS, were observed at
0.36 and 1.17 V, with a mean redox potential of 0.77 V,
corresponding to the cathodic reduction of the N-bromoma-
Industrial & Engineering Chemistry Research
leimide groups and anodic oxidation of bromine ions,
respectively. The peaks were broad and separated by 0.8 V.
The measured current response was stable over multiple
voltammetric scans. The electrochemical reactions in PMAi-co-
DVB-Br and PEMAi-Br involve N-bromomaleimide units
producing bromine and succinimide radicals, which recombine
and result in reconstitution of the N-bromomaleimide groups.
Since the N-bromomaleimide units are incorporated into the
polymer network and, thus, are unable to diuse into the
electrolyte after their reduction into succinimidyl units, the
redox processes are reversible.
It is interesting to observe the presence of the cathodic
reduction peaks in the 0.8 V area in the case of
nonbrominated PMAi-co-DVB material. These peaks, which
can be attributed to the irreversible reduction of the
succinimide units of the polymer (Figure 9),52 coincided with
gentle eervescence caused by the cathodic hydrogen evolution,
which was not observed with the brominated polymer species.
Figure 9. Reduction of maleimide units of PMAi-co-DVB.
The brominated polyvinylpyrrolidone network (PVPBr)
exhibited reversible redox peak potentials resembling those
found in the hydrobromic acidbromine system (S-4).
Polyvinylpyrrolidone is often used as a carbon paste or
electrode surface modier that amplies the electrochemical
response of the redox species capable of forming hydrogen
bonds with the PVP.53,54 Bromine and PVP gel form adducts
stabilized by hydrogen bonding in acidic media.17
The hydrobromic acid and bromine bound to the gel by
hydrogen bonds (Figure 10) are readily available for the anodic
Figure 10. Structure of PVPhydrobromic acid adducts.
oxidation of the bromide into bromine, which is reduced back
into bromide on the cathode (Figure 8, b):
anode: 2Br Br2 + 2e
cathode: Br2 + 2e 2Br
A linear dependence of the peak current on the square root of
the scan rate was observed with PVPBr (Supporting
H dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
Information, Figure S-5), which indicated that the electron
transport from the working, polymer-loaded paste electrode to
the counter electrode, primarily through the polymer particles,
was diusion-controlled, in accord with the RandlesSevcik
equation.55 However, PMAi-co-DVB-Br and PEMAi-Br materi-
als exhibited a linear dependence of the peak current on the
potential scan rate (Supporting Information, Figure S-5),
indicating prevalence of an electron adsorption mechanism in
these two polymeric materials, which was probably associated
with the reversible decomposition and reconstitution of the N-
bromomaleimide units on the polymeric surfaces.
Decontamination of Hydrazines. Hydrazine and its
methylated derivatives (methylhydrazine and 1,1-dimethylhy-
drazine, DMH) are used as components of jet and rocket
propellants, in nuclear fuel reprocessing and many other
applications in chemical, pharmaceutical, photographic, and dye
industries.56 These hydrazines are extremely toxic, carcinogenic,
and volatile, and thus their presence in the conned
environment can be an occupational hazard.57,58 In this work,
we exploited the redox activity of the brominated polymers for
elimination of hydrazines from aqueous media, aiming at the
potential application of these polymer materials for the
elimination of hydrazine spills. The reaction of the water-
insoluble polymer and network particles with aqueous acidic
solutions of hydrazine, methylhydrazine sulfate (MHS), and
DMH (Figure 11) results in the conversion of these
compounds into nitrogen, and hence, to the hydrazine
elimination from the solution. The eective degrees of
elimination, E, of hydrazine, MHS, and DMH by the polymers
under study were measured as described in the Experimental
Section. We used a slight excess eective concentration of
bromine in the acidic reaction medium relative to the
concentration of hydrazine in all experiments. Under tested
conditions (initial hydrazine, MHS, or DMH concentrations,
730 mM, 24 h at room temperature), the PVPBr, PMAi-co-
DVB-Br, and PEMAi-Br materials tested were able to remove
100% of hydrazine, MHS, and DMH down to concentrations
below detectable levels of 0.15 to 0.25 mM. The standard
deviations for E, determined in triplicate experiments, were
approximately 5%. In the control experiments, conducted with
nonbrominated species of PVP (synthesized by temperature-
initiated copolymerization of 1-vinyl-2-pyrrolidone and
PEGDA; the degree of gel cross-linking by PEGDA was 7
mol % relative to vinylpyrrolidone), the hydrazine, MHS, and
DMH elimination values, E, did not exceed 10%, indicating
poor anity of these hydrazines for the PVP gels. However, the
PMAi-co-DVB and PEMAi materials eliminated up to 2530%
of hydrazine and up to 20% of MHS and DMH in these
experiments, which can be attributed to the enhanced sorption
anity as well as chemical binding between the maleimide
groups of PMAi and PEMAi and residual maleic anhydride
groups in PEMAi and hydrazines.5961 However, the aerobic
conversion of hydrazines to nitrogen gas (Figure 11),
conducted without toxic catalysts such as Cu(II) is more
eective in eliminating the toxic eects of hydrazines than is
chemi- or physisorption.62 In that regard, the brominated
polymers and networks introduced in the present work are
extremely ecient.
Degradation of Malathion by Brominated Polymers.
Malathion is an organophosphorus pesticide that, in addition to
being an environmental problem in its own right, is considered
to be a less-toxic simulant for one of the most potent nerve
agents such as VX, since these two substances share some
Industrial & Engineering Chemistry Research
Figure 11. Reaction of methylhydrazine and 1,1-dimethylhydrazine with brominated polymer P.
structural and biological activity similarities (Figure 1).63,64
Although the hydrolytic reactions of VX with nucleophiles are
studied (and applied for decontamination) most often,22,6469
oxidative routes for the destruction of phosphonothiolates are
also well-documented.7075 Selective oxidation of the PS
bond, while avoiding the PO cleavage in VX, would be
valuable for devising decontamination strategies as it could
impede formation of toxic byproducts such as EA-2192 and the
like (Supporting Information, Figure S-6).74
Although oxidative degradation of malathion by Fe(II)/H2O2
as well as by N-bromosuccinimide in aqueous solutions has
been reported,76,77 oxidation of malathion with brominated
polymers in multiphase, heterogeneous reactions has not been
documented. Hydrolysis of malathion at acidic pH is
exceedingly slow,78 which is why the oxidation pathways are
best highlighted at slightly acidic pH that can, serendipitously,
help to minimize the cleavage of the PO bonds through
hydrolysis. When 1050 mg of the brominated polymer
particles were dispersed in 1 mL of phosphate-buered saline,
the resulting equilibrium pH was in the range of 3.15.5. To
eliminate pH uctuations, we studied oxidation kinetics in 0.05
M sodium acetateacetic acid buer solutions with pH
adjusted to 3.7. The oxidation of malathion to malaoxon by
the brominated polymers (Figure 12) was monitored by 31P
NMR.
Figure 12. Oxidation of malathion to malaoxon by brominated
polymers.
The substrate, malathion, was easily distinguishable from the
product, malaoxon (Supporting Information, Figure S-2).
Typical results of malathion oxidation by PVPBr particles
are shown in Figure 13. As is seen, the signal at around 95 ppm
corresponding to malathion rapidly disappeared while the
signal at 28 ppm corresponding to the oxidation product
malaoxon appeared and grew. Note that malathion is poorly
miscible with water (solubility of malathion in water is only 145
g/mL), so that the gel particles were suspended in an
emulsion of malathion in acetate buer, forming a three-phase
system. In order to enable a proper contact between the surface
of the solid oxidizing agent and malathion droplets, the samples
were sonicated for the specied time and then malathion and
its products were extracted into CDCl3 (see Experimental
Section). With PVPBr as an oxidant and at reaction times of
10 min or longer, signals corresponding to the decomposition
I dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
Figure 13. 31P NMR spectra illustrating the progress of malathion to
malaoxon conversion in suspensions of PVPBr (PEGDS cross-
linking, bromine content, 4.0 mequiv/g) in aqueous sodium acetate
acetic acid buer at 25 C, pH 3.7. The reaction time is given in
minutes. Initial polymer particle and malathion loadings were 25 mg
(0.1 mequiv of bromine) and 30 mg (0.09 mmol of malathion),
respectively.
products of malaoxon ( 20.9 ppm) also appeared, but the yield
of such products was minor (below 12 mol %) relative to
malaoxon. When reactions were conducted with brominated
polymers other than PVPBr, malaoxon was observed to be the
sole product of the malathion oxidation, which led us to
conclude that such oxidation was selective to the PS bond
and was not accompanied by the hydrolytic reactions. Under
ecient mass transfer by sonication and with slight excess of
bromine over malathion in the reaction medium, the reaction of
the malathion oxidation was complete within 10 min (Figure
13).
The PVPBr particles were used in three consecutive cycles
of reaction, polymer particle recovery, washing, and bromina-
tion, without loss of reactivity (Figure 14), which conrmed
that the brominated network was a reusable heterogeneous
oxidant for malathion.
The apparent observed rate constant of malathion oxidation
(kobs) by PVPBr was found to be approximately 0.3 min1 and
the reaction half-life was ca. 3.5 min. This value is dicult to
compare to that of other oxidants, as the rates of malathion
oxidation (unlike the rates of malathion hydrolysis) are seldom
reported and vary depending on conditions. Oxidation of
malathion to malaoxon by molecular oxygen from air in the
presence of water was found to be insignicant,78 yet oxidation
of malathion upon aerial spray application in small droplets was
reported to be fairly rapid.79
The rate of malathion oxidation could be aected by
sonication, which creates gasliquid cavitation bubbles with
interfaces enriched by hydroxyl radicals that could enhance
oxidative desulfuration. The observed rate constants and half-
lives of malathion-to-malaoxon conversion in apple juice at 15
C caused by sonication ranged from 2.4 103 to 5.0 103
min1 and 293 to 139 min, respectively, at a sonication power
of 100 and 500 W, respectively.80 However, the oxidation by
sonication alone, without bromine, appears to be 2 orders of
Industrial & Engineering Chemistry Research Article

overall bromine content in the polymer, which did not vary

Figure 14. Conversion (F) of malathion to malaoxon vs time in
aqueous acetic buer suspensions of PVPBr at 25 C, pH 3.7. Three
cycles consisting of malathion degradation for indicated time,
malathion extraction, solid particles separation, purication, bromina-
tion, and reuse were conducted. Cycle number is indicated on the
graph. In all cycles, initial polymer particle and malathion loadings
were 25 mg (0.1 mequiv of bromine) and 30 mg (0.09 mmol of
malathion), respectively. After each cycle, the particles were
brominated afresh and their bromine content was measured to be
4.04.1 mequiv/g. The initial curvature in the response curve is a
result of mass transfer limitations within the particles. For other details,
see the Experimental Section.
magnitude slower than in the present work. On the other hand,
malathion was 100% converted to malaoxon within 5 min or
less by a 50-fold molar excess N-bromosuccinimide.77 Overall,
the rate of heterogeneous oxidation reaction by PVPBr is of
the same order of magnitude as oxidation by water-soluble
NBS. We compared the eciency of all polymers of the present
study in malathion oxidation (Table 2).
PVPBr network species prepared either by cross-linking
premade PVP solution or by copolymerization of vinyl-
pyrrolidone and PEGDA, were most ecient in malathion
oxidation, followed by PMAi-Br, PMAi-co-DVB-Br, and then by
PEMAi-Br, which was the least ecient. It appears that the
signicantly, contributed less than the accessibility of the
bromine for malathion, which was reduced several-fold in the
case of PEMAi-Br. The latter polymer did not swell signicantly
in the aqueous medium or organic solvents.
Overall, we observed, for the rst time, that brominated
polymers and networks, PVPBr, PMAi-Br, and its cross-linked
counterpart, PMAi-co-DVB-Br, are ecient in malathion
oxidation in heterogeneous aqueous media, degrading up to
100% of the insecticide within minutes when sonicated.
Oxidation of CEES by Brominated Polymers. Decon-
tamination of 2-chloroethyl ethylsulde (CEES), a mustard
simulant, under ambient conditions can be achieved through a
catalytic aerobic oxidation process. Transition-metal-substituted
polyoxometalates (POMs) in the presence of NO2/NO3
species and/or combinations of bromide/bromate and nitrate
salts have been shown to be potent, yet selective catalysts for
such oxidation.8185 In the present work, we attempted to
replicate the activity of the POM and/or salt redox species, but
with polymers that can be engineered into protective materials
such as coatings, bers, lms, fabrics, etc. We were concerned
with reactivity of the polymers rather than their ability to act as
catalysts. That is, we intended the bromine-functionalized
polymers to participate in the reactions.
Figure 15 depicts typical chromatograms of the CEES vapors
allowed to equilibrate with a sample of PVPBr for varied time
periods at room temperature.

Table 2. Conversion (F, %) of Malathion to Malaoxon by

Brominated Polymers in Aqueous 0.05 M Sodium Acetate
Acetic Acid Buer at 25C, pH 3.7. Reaction Time, 10 min
brominea malathion/brominea
polymer species (meq) (mol/meq) F (%)b
PMAi-Br 0.13 0.70 85 9
c
PMAi-co-DVB-Br 0.13 0.72 83 12
d
PMAi-co-DVB-Br 0.11 0.82 73 6
c
PEMAi-Br 0.099 0.92 53
c
PEMAi-Br 0.20 0.46 11 4
d
PEMAi-Br 0.19 0.49 84
e
PVPBr 0.12 0.76 100
f Figure 15. Representative gas chromatograms of the CEES vapors
PVPBr 0.12 0.74 100
collected from the vial headspace where a PVPBr sample was
a suspended (a) and acetonitrile extracts from the same sample
Initial contents set up in the reaction. Polymers were loaded into the equilibrated with CEES vapors for 24 h (b). Sample bromine content,
buer as freshly prepared, nely ground weighed particles of known 4 mequiv/g; material weight, 52.6 mg, initial CEES load, 1 L = 8.6
bromine content. For bromine content in the polymers, see Table 1. mol, room temperature.
b
Conversion values were found in three independent measurements,
and standard deviations are shown, except for PVPBr, wherein a
complete conversion of malathion to malaoxon was observed in all The chromatogram of acetonitrile extracts from the polymer
measurements. cBromination by bromine in CCl4. dBromination by after 24 h equilibration with the CEES vapors is also presented.
CuBr2 in DMF. ePVP gel was synthesized by temperature-initiated
copolymerization of 1-vinyl-2-pyrrolidone and PEGDA, followed by
As is seen, relative CEES content in the air above the PVPBr
bromination with Br2 in CCl4 (see Experimental Section). The degree sample decreased over time, reecting sorption of the CEES on
of the gel cross-linking by PEGDA was 7 mol % relative to the polymer surface, and some of the chromatograms showed a
vinylpyrrolidone. fPVP gel was synthesized by cross-linking of aqueous peak identied as the CEES sulfoxide, 1-chloro-2-
polyvinylpyrrolidone solution with ammonium persulfate, followed by (ethylsulnyl)ethane (CEESO), which was observed after
bromination with Br2 in CCl4 (see Experimental Section). 1320 h. A complete depletion of the CEES vapor was
J dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Industrial & Engineering Chemistry Research
observed after 1320 h. A peak at 4.68 min appearing in the
vapor phase after 12 h of equilibration was assigned to 1,2-
bis(ethylthio)ethane (BEE, m/z = 150) using the GCMS
fragmentation pattern. Similar behavior of the CEES vapors was
observed when CEES was exposed to all of the brominated
polymer samples, with the initial eective bromine loading
signicantly exceeding the CEES loading, on the molar basis.
The apparent half-life of the CEES vapors leading to ca. 50%
vapor depletion on PVPBr and PMAiBr networks (solid
sample weight, 50 mg; bromine content, 4.04.2 mequiv/g)
was estimated to be 1.7 and 4 h, respectively. Parent PVP,
PMAi, and PEMAi networks devoid of bromine demonstrated a
strong sorption, but no oxidation of CEES. Analysis of the
CEES products extracted by acetonitrile from the brominated
polymer materials after 24 h of their exposure to the CEES
vapors demonstrated the presence of residual CEES, in
quantities decreasing with the increase of the initial bromine/
CEES loading ratio. The main product peak was CEESO, but
1,2-bis(ethylthio)ethane (BEE) was also present. The BEE
formation preceded the CEESO nal product formation, and
CEESO appeared in increasing concentrations with the
increasing initial brominated material loading.
The persistence of 1,2-bis(ethylthio)ethane (BEE) in both
the vapor phase and in the products extracted from the
brominated polymers indicates probable CEES degradation
route (Figure 16),86 which implies hydrolytic reactions in the
presence of trace amounts of water in the air.
Figure 16. Degradation scheme of CEES.
These reactions are well-established,87,88 and upon con-
densation of the CEES, 2-(ethylthio)ethan-1-ol and dehydro-
chlorination product, ethyl(vinyl)sulfane, produce sulfonium
cation intermediates that are further hydrolyzed into BEE.
Importantly, our experiments revealed that upon reaction of
CEES with brominated polymers no detectable formation of
the overoxidized CEES sulfone derivative, 1-chloro-2-
(ethylsulfonyl)ethane. The latter is a fairly potent vesicant,
and hence, the targeted oxidative decontamination process for
sulfur mustard is selective sulfoxidation.84 In the present work,
we discovered that brominated polymers such as brominated
poly(N-vinylpyrrolidone), poly(N-bromomaleimide), and poly-
(ethylene-alt-N-bromomaleimide) and their cross-linked net-
works are selective, that is, produce no overoxidized sulfones
(Figure 17).
K dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
Figure 17. Oxidation of CEES by a brominated polymer in the
presence of moisture. No overoxidized analogue, 1-chloro-2-
(ethylsulfonyl)ethane, is produced.
CONCLUDING REMARKS
Applications of oxidative compounds in detoxication of
chemical threats call for useful self-decontaminating formula-
tions, fabrics, cosmetics, lters, or coatings. Such oxidative
compounds should not be highly corrosive or toxic, and
preferably not require light or other conditions that may not be
normally encountered for the compounds to perform. In the
present work, we aimed at meeting all of the above
requirements, and in addition, set out the concept of devising
the oxidants to be in a readily synthesized polymeric system
that can be engineered into composite or multilayered materials
capable of withstanding some mechanical stress, thermal
degradation, and exposure to solvents. It appeared that
brominated networks of cross-linked poly(N-vinylpyrrolidone),
and poly(N-maleimide), as well as poly(ethylene-alt-malei-
mide) can be eective oxidants of hydrazine and its methylated
derivatives, organothiolate pesticide malathion, which acts as a
simulant of a combat warfare agent VX, and 2-chloroethyl
ethylsulde (CEES), a sulfur mustard mimic. The brominated
networks appeared to be selective as oxidants, producing no
products other than malaoxon from malathion and no
overoxidized products such as sulfones, from CEES. These
desirable features, along with a multitude of toxicants that can
be decontaminated, suggest potential applicability of the
studied brominated polymer networks.
ASSOCIATED CONTENT
* Supporting Information
S
UVvis and 31P NMR spectra and structures of malathion and
malaoxon; TGA thermograms of polymers; cyclic voltammetry
of 0.1 M HBr aqueous solution; dependencies of the oxidation
and reduction peak currents on scan rate. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: tahatton@mit.edu.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This work was supported by the Defense Threat Reduction
Agency under Army Research Oce Grant W911NF-13-D-
0001.
Industrial & Engineering Chemistry Research
REFERENCES
(1) George, B. K.; Pillai, V. N. R. Poly(N-bromoacrylamide): A new
polymeric recyclable oxidizing and brominating reagent. Macro-
molecules 1988, 21, 18671870.
(2) Pehkonen, S. O.; Zhang, Q. The degradation of organo-
phosphorus pesticides in natural waters: A critical review. Crit. Rev.
Environ. Sci. Technol. 2002, 32, 1772.
(3) Toth, B. A review of the natural occurrence, synthetic production
and use of carcinogenic hydrazines and related chemicals. In Vivo.
2000, 14, 299319.
(4) Taylor, R. T. Polymer-bound oxidizing agents. ACS Symp. Ser.
1986, 308, 132154.
(5) Liang, J.; Chen, Y.; Ren, X.; Wu, R.; Barnes, K.; Worley, S. D.;
Broughton, R. M.; Cho, U.; Kocer, H.; Huang, T. S. Fabric treated
with antimicrobial N-halamine epoxides. Ind. Eng. Chem. Res. 2007, 46,
64256429.
(6) Liu, S.; Sun, G. New refreshable N-halamine polymeric biocides:
N-chlorination of acyclic amide grafted cellulose. Ind. Eng. Chem. Res.
2009, 48, 613618.
(7) Hui, F.; Debiemme-Chouvy, C. Antimicrobial N-halamine
polymers and coatings: A review of their synthesis, characterization,
and applications. Biomacromolecules 2013, 14, 585560.
(8) Kocer, H. B. Residual disinfection with N-halamine based
antimicrobial paints. Prog. Org. Coat. 2012, 74, 100105.
(9) Badrossamay, M. R.; Sun, G. A study on melt grafting of N-
halamine moieties onto polyethylene and their antibacterial activities.
Macromolecules 2009, 42, 19481954.
(10) Tamami, B.; Shirazi, A. N.; Ebrahimzadeh, F. Synthesis and
applications of cross-linked poly(N-bromomaleimide) in oxidation of
various organic compounds. Iran. Polym. J. 2009, 18, 957967.
(11) Kocer, H. B.; Cerkez, I.; Worley, S. D.; Broughton, R. M.;
Huang, T. S. N-Halamine copolymers for use in antimicrobial paints.
ACS Appl. Mater. Interfaces 2011, 3, 31893194.
(12) Volkmann, A.; Ghosh, S. Antimicrobial coatings based on
hydantoin-containing polymer networks for textiles. J. Appl. Polym. Sci.
2011, 119, 16461651.
(13) Maslinska-Solich, J.; Rudnicka, I.; Nour, M. A. Acetals oxidation
into esters with poly(N-bromosuccinimide). React. Funct. Polym. 1995,
26, 4349.
(14) Yaroslavsky, C.; Patchornik, A.; Katchalski, E. Unusual
brominations with N-bromopolymaleimide. Tetrahedron Lett. 1970,
42, 36293632.
(15) Lakouraj, M. M.; Tajbakhsh, M.; Mokhtary, M. Poly-
(vinylpyrrolidone)bromine complex: A mild and efficient reagent
for selective bromination of alkenes and oxidation of alcohols. J. Chem.
Res. 2005, 8, 481483.
(16) Mathew, P.; Nair, S. K.; Sreedhar, K. M.; Pillai, V. N. R.; Asokan,
C. V. Bromine complexes of polyvinylpyrrolidone supports: A mild
reagent for the transformation of -oxoketene dithioacetals to -
oxothiolesters. Synth. Commun. 2005, 35, 21572161.
(17) Koshy, E. P.; Zacharias, J.; Pillai, V. N. R. Poly(N-
vinylpyrrolidone)-hydrotribromide: A new gel-type resin for alcohol
oxidation and alkene dibromination. React. Funct. Polym. 2006, 66,
845850.
(18) Lakouraj, M. M.; Mokhtary, M. Polyvinylpolypyrrolidone-
bromine complex, mild and efficient polymeric reagent for selective
deprotection and oxidative deprotection of silylethers. Lett. Org. Chem.
2007, 4, 6467.
(19) Haaf, F.; Sanner, A.; Straub, F. Polymers of N-vinylpyrrolidone:
Synthesis, characterization and uses. Polym. J. 1985, 17, 143152.
(20) Schenck, H.-U.; Simak, P.; Haedicke, E. Structure of
polyvinylpyrrolidoneiodine (povidoneiodine). J. Pharm. Sci. 1979,
68, 15051509.
(21) Volkmann, A.; Ghosh, S. Antimicrobial coatings based on
hydantoin-containing polymer networks for textiles. J. Appl. Polym. Sci.
2011, 119, 16461651.
(22) Bromberg, L.; Schreuder-Gibson, H.; Creasy, W. R.; McGarvey,
D. J.; Fry, R. A.; Hatton, T. A. Degradation of chemical warfare agents
by reactive polymers. Ind. Eng. Chem. Res. 2009, 48, 16501659.
L dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
(23) Djerassi, C. Brominations with N-bromosuccinimide and related
compounds. The WohlZiegler reaction. Chem. Rev. 1948, 43, 271
317.
(24) Dauben, H. J.; Layton, L.; McCoy, L. L. N-Bromosuccinimide. I.
Allylic bromination, a general survey of reaction variables. J. Am. Chem.
Soc. 1959, 81, 48634873.
(25) Barnes, R. A.; Buckwalter, G. R. Reactions of N-bromosucci-
nimide. II. J. Am. Chem. Soc. 1951, 73, 38583861.
(26) Stuckwisch, C. G.; Hammer, G. G.; Blau, N. F. Reaction of N-
bromosuccinimide with secondary alcohols. J. Org. Chem. 1957, 22,
16781680.
(27) Pinnick, H. W.; Lajis, N. H. N-Bromosuccinimide oxidation of
silyl ethers. J. Org. Chem. 1978, 43, 371372.
(28) Beebe, T. R.; Boyd, L.; Fonkeng, S. B.; Horn, J.; Mooney, T. M.;
Saderholm, M. J.; Skidmore, M. V. Selective oxidation of alcohols
using the 1:1 complex of N-bromosuccinimide and tetrabutylammo-
nium iodide. J. Org. Chem. 1995, 60, 66026603.
(29) Carreno, M. C.; Ruano, J. L. G.; Sanz, G.; Toledo, M. A.;
Urbano, A. N-Bromosuccinimide in acetonitrile: A mild and
regiospecific nuclear brominating reagent for methoxybenzenes and
naphthalenes. J. Org. Chem. 1995, 60, 53285331.
(30) Schmir, G. L.; Cohen, L. A. Oxidative degradation of imidazoles
by bromine or N-bromosuccinimide. Biochemistry 1965, 4, 533538.
(31) Tripathi, C. B.; Mukherjee, S. Lewis base catalysis by thiourea:
N-bromosuccinimide-mediated oxidation of alcohols. J. Org. Chem.
2011, 50, 124211242.
(32) Abdel-Hady, A. E. M. Kinetics and mechanism of oxidation of l-
proline by N-bromosuccinimide in aqueous acidic medium. Ind. Eng.
Chem. Res. 2011, 50, 1242112425.
(33) Haas, H. C.; Moreau, R. D. Maleimide polymers. 111. Color
reactions and kinetics. J.Poly.Sci.A 1975, 13, 23272334.
(34) Agarwal, P.; Yu, Q.; Harant, A.; Berglund, K. A. Synthesis and
characterization of polymaleimide. Ind. Eng. Chem. Res. 2003, 42,
28812884.
(35) Otsu, T.; Matsumoto, A.; Tatsumi, A. Synthesis and
characterization of poly(N-tert-alkylmaleimide)s. Polym. Bull. 1990,
24, 467474.
(36) Matsumoto, A.; Oki, Y.; Otsu, T. Polymaleimides bearing a
readily hydrolyzable side group: Synthesis and polymerization of N-
trialkylsilylmaleimides and characterization of the polymers. Polym. J.
1992, 24, 679688.
(37) Zhang, X. R.; Tang, B. T.; Zhang, S. F. A simple and practical
solvent-free preparation of polymaleimide. Molecules. 2011, 16, 1981
1986.
(38) Evenson, S. A.; Badyal, J. P. S. Solventless attachment of long-
chain molecules to poly(ethylene-alt-maleic anhydride) copolymer
surfaces. J. Phys. Chem. B 1998, 102, 55005502.
(39) Evenson, S. A.; Fail, C. A.; Badyal, J. P. S. Surface esterification
of poly(ethylene-alt-maleic anhydride) copolymer. J. Phys. Chem. B
2000, 104, 1060810611.
(40) Chattha, M. S. Thermosettable powder compositions of
polymaleimide and allyl-functional prepolymer, U.S. Patent
5,183,865; Feb 2, 1993.
(41) Mizori, F. G.; Dershem, S. M. Imide-linked maleimide and
polymaleimide compounds, U.S. patent 7,208,566; Apr 24, 2007.
(42) Bhatt, S.; Nayak, S. K. Copper (II) bromide: a simple and
selective monobromination reagent for electron-rish aromatic
compounds. Synth. Commun. 2007, 37, 13811388.
(43) Barakat, M. Z.; Shaker, M. The micro-determination of
hydrazine salts and certain derivatives. Analyst 1963, 88, 5963.
(44) Malone, H. E. Determination of mixtures of hydrazine and 1,l-
dimethyhydrazine. Anal. Chem. 1961, 33, 575577.
(45) George, M.; Nagaraja, K. S.; Balasubramanian, N. Spectropho-
tometric determination of hydrazine using bromine and methyl red.
Indian J. Chem. 2007, 46A, 16211624.
(46) Berkmant, C. E.; Thompson, C. M. Synthesis, Absolute
configuration, and analysis of malathion, malaoxon, and isomalathion
enantiomers. Chem. Res. Toxicol. 1993, 6, 718723.
Industrial & Engineering Chemistry Research
(47) Bromberg, L.; Straut, C. M.; Centrone, A.; Wilusz, E.; Hatton,
T. A. Montmorillonite functionalized with pralidoxime as a material for
chemical protection against organophosphorous compounds. ACS
Appl. Mater. Interfaces 2011, 3, 14791484.
(48) Anderson, C. C.; Rodrigues, F.; Thurston, D. A. Crosslinking
aqueous poly(vinyl pyrrolidone) solutions by persulfate. J. Appl. Polym.
Sci. 1979, 23, 24532462.
(49) Barry, J. E.; Finkelstein, M.; Moore, W. M.; Ross, S. D.; Eberson,
L.; Jonsson, L. Electrochemical reduction of N-bromosuccinimide.
Reaction mechanism for formation of the succinimidyl radical. J. Org.
Chem. 1982, 47, 12921298.
(50) Haque, I. U.; Akram, W.; Tariq, M.; Khan, A. Voltammetry on
N-bromosuccinimide in hexafluoropropan-2-ol. Electrochem. Sci. Trans.
2011, 33, 4148.
(51) Krishnamoorthy, S.; Srinivasan, R. K.; Noel, M. A comparative
evaluation of operating conditions for the electrochemical bromination
and chlorination of succinimide. Bull. Electrochem. 2000, 16, 544550.
(52) Moore, W. M.; Finkelstein, M.; Ross, S. D. The electrochemical
reduction of succinimide. Tetrahedron 1980, 36, 727730.
(53) Liu, Q.; Zhu, X.; Huo, Z.; He, X.; Liang, Y.; Xu, M.
Electrochemical detection of dopamine in the presence of ascorbic
acid using PVP/graphene modified electrodes. Talanta 2012, 97, 557
562.
(54) Wang, P.; Gan, T.; Zhang, J.; Luo, J.; Zhang, S.
Polyvinylpyrrolidone-enhanced electrochemical oxidation and detec-
tion of acyclovir. J. Mol. Liq. 2013, 177, 129132.
(55) Bard, A. J.; Faulkner, L. R. Electrochemical Methods.
Fundamentals and Applications; John Wiley & Sons, Inc.: New
York, 2001.
(56) Schmidt, E. W. Hydrazine and Its Derivatives: Preparation,
Properties, Applications, 2nd ed.; Wiley-Interscience: New York, 2001.
(57) Keller, W. C. Toxicity assessment of hydrazine fuels. Aviat. Space
Environ. Med. 1988, 59 (11Pt 2), A100106.
(58) Zelnick, S. D.; Mattie, D. R.; Stepaniak, P. C. Occupational
exposure to hydrazines: treatment of acute central nervous system
toxicity. Aviat. Space Environ. Med. 2003, 74, 12851291.
(59) Tillet, G.; Boutevin, B.; Ameduri, B. Chemical reactions of
polymer crosslinking and post-crosslinking at room and medium
temperature. Prog. Polym. Sci. 2011, 36, 191217.
(60) Feuer, H.; Rubinstein, H. Maleic hydrazide. I. Reactions with
selected electrophilic reagents. J. Am. Chem. Soc. 1958, 80, 58735877.
(61) Feuer, H.; White, E. H.; Wyman, J. E. The reactions of maleic
anhydride with hydrazine hydrate. J. Am. Chem. Soc. 1958, 80, 3790
3792.
(62) Moliner, A. M.; Street, J. J. Decompostion of hydrazine in
aqueous solutions. J. Environ. Qual. 1998, 18, 483487.
(63) Zhu, W.-C.; Wang, B.-R.; Xi, H.-L.; Pu, Y.-K. Decontamination
of VX surrogate malathion by atmospheric pressure radio-frequency
plasma jet. Plasma Chem. Plasma Process. 2010, 30, 381389.
(64) Gephart, R. T.; Coneski, P. N.; Wynne, J. H. Decontamination
of chemical-warfare agent simulants by polymer surfaces doped with
the singlet oxygen generator zinc octaphenoxyphthalocyanine. ACS
Appl. Mater. Interfaces 2013, 5, 1019110200.
(65) Yang, Y. C.; Szafraniec, L. L.; Beaudry, W. T.; Bunton, C. A.
Perhydrolysis of nerve agent VX. J. Org. Chem. 1993, 58, 69646965.
(66) Yang, Y. C.; Szafraniec, L. L.; Beaudry, W. T.; Rohrbaugh, D. K.;
Procell, L. R.; Samuel, J. B. Autocatalytic hydrolysis of V-type nerve
agents. J. Org. Chem. 1996, 61, 84078413.
(67) Groenewold, G. S.; Williams, J. M.; Appelhans, A. D.; Gresham,
G. L.; Olson, J. E.; Jeffery, M. T.; Rowland, B. Hydrolysis of VX on
concrete: Rate of degradation by direct surface interrogation using an
ion trap secondary ion mass spectrometer. Environ. Sci. Technol. 2002,
36, 47904794.
(68) Gershonov, E.; Columbus, I.; Zafrani, Y. Facile hydrolysis-based
chemical destruction of the warfare agents VX, GB, and HD by
alumina-supported fluoride reagents. J. Org. Chem. 2009, 74, 329338.
(69) Kim, K.; Tsay, O. G.; Atwood, D. A.; Churchill, D. G.
Destruction and detection of chemical warfare agents. Chem. Rev.
2011, 111, 53455403.
M dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
(70) Yang, Y. C.; Szafraniec, L. L.; Beaudry, W. T.; Rohrbaugh, D. K.
Oxidative detoxification of phosphonothiolates. J. Am. Chem. Soc.
1990, 112, 66216627.
(71) Blasko, A.; Bunton, C. A.; Kumar, A. Oxidative hydrolysis of
phosphorus (V) esters of thiols by peroxymonosulfate ion. Reactions
of peroxymonosulfate ion with phosphorus (V) esters of thiols. J. Phys.
Org. Chem. 1997, 10, 427434.
(72) Yang, Y.-C.; Berg, F. J.; Szafraniec, L. L.; Beaudry, W. T.;
Bunton, C. A.; Kumar, A. Peroxyhydrolysis of nerve agent VX and
model compounds and related nucleophilic reactions. J. Chem. Soc.,
Perkin Trans. 1997, 2, 607613.
(73) Cassagne, T.; Cristau, H.-J.; Delmas, G.; Desgranges, M.; Lion,
C.; Magnaud, G.; Torreilles, E.; Virieux, D. Destruction of chemical
warfare agents VX and soman by a-nucleophiles as oxidizing agents.
Heteroatom Chem. 2001, 12, 485490.
(74) Yang, Y.-C. Chemical detoxification of nerve agent VX. Acc.
Chem. Res. 1999, 32, 109115.
(75) Wagner, G. W.; Sorrick, D. C.; Procell, L. R.; Brickhouse, M. D.;
Mcvey, I. F.; Schwartz, L. I. Decontamination of VX, GD, and HD on a
surface using modified vaporized hydrogen peroxide. Langmuir 2007,
23, 11781186.
(76) Noradoun, C. E.; Mekmaysy, C. S.; Hutcheson, R. M.; Cheng, I.
F. Detoxification of malathion a chemical warfare agent analog using
oxygen activation at room temperature and pressure. Green Chem.
2005, 7, 426430.
(77) Kralj, M. B.; Trebse, P.; Franko, M. Oxidation as a pre-step in
determination of organophosphorus compounds by the AChETLS
bioassay. Acta Chim. Slov. 2006, 53, 4351.
(78) Wolfe, N. L.; Zepp, R. G.; Gordon, J. A.; Baughman, G. L.;
Cline, D. M. Kinetics of chemical degradation of malathion in water.
Environ. Sci. Technol. 1977, 11, 8893.
(79) Brown, M. A.; Petreas, M. X.; Okamoto, H. S.; Mischke, T. M.;
Stephens, R. D. Monitoring of malathion and its impurities and
environmental transformation products on surfaces and in air
following an aerial application. Environ. Sci. Technol. 1993, 27, 388
397.
(80) Zhang, Y.; Xiao, Z.; Chen, F.; Gea, Y.; Wu, J.; Hu, X.
Degradation behavior and products of malathion and chlorpyrifos
spiked in apple juice by ultrasonic treatment. Ultrason. Sonochem.
2010, 17, 7277.
(81) Gall, R. D.; Faraj, M.; Hill, C. L. Role of water in
polyoxometalate-catalyzed oxidations in nonaqueous media. Scope,
kinetics, and mechanism of oxidation of thioether mustard (HD)
analogs by tert-butyl hydroperoxide catalyzed by H5PV2Mo10O40.
Inorg. Chem. 1994, 33, 50155021.
(82) Boring, E.; Geletii, Y. V.; Hill, C. L. Catalytic aerobic oxidation
of 2-chloroethyl ethylsulfide, a mustard simulant, under ambient
conditions: Effect of solvents, ligands, and transition metals on
reactivity. J. Mol. Catal. A: Chem. 2001, 176, 4963.
(83) Okun, N. M.; Anderson, T. M.; Hill, C. L. Polyoxometalates on
cationic silica: Highly selective and efficient O2/air-based oxidation of
2-chloroethyl ethyl sulfide at ambient temperature. J. Mol. Catal. A:
Chem. 2003, 197, 283290.
(84) Hill, C. L.; Okun, N. M.; Hillesheim, D. A.; Geletii, Y. V.
Catalysts for aerobic decontamination of chemical warfare agents
under ambient conditions. ACS Symp. Ser. 2007, 980, 198209.
(85) Luo, Z.; Geletii, Y. V.; Hillesheim, D. A.; Wang, Y.; Hill, C. L.
Mechanistic studies of O2-based sulfoxidations catalyzed by NOx/Br
systems. ACS Catal. 2011, 1, 13641370.
(86) Karote, D.; Walker, B.; Dai, H.; Krishnamoorthi, R.; Voo, J.,
Rajagopalan, S. J. Chemical warfare agent simulants in gambles uid:
Is the uid toxic? Can it be made safer by inclusion of solid
nanocrystalline metal oxides? J. Chem. 2013, Article ID 641620, 14
pages, http://dx.doi.org/10.1155/2013/641620.
(87) Yang, Y.-C.; Szafraniec, L. L.; Beaudry, W. T. A comparison of
the oxidative reactivities of mustard (2,2-dichlorodiethyl sulfide) and
bivalent sulfides. J. Org. Chem. 1990, 55, 36643666.
Industrial & Engineering Chemistry Research Article

(88) Yang, Y.-C.; Szafraniec, L. L.; Beaudry, W. T.; Ward, J. R.

Kinetics and mechanism of the hydrolysis of 2-chloroethyl sulfides. J.
Org. Chem. 1988, 53, 32933297.

N dx.doi.org/10.1021/ie501055g | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX