Article

pubs.acs.org/EF

Novel Solution to Oil Spill Recovery: Using Thermodegradable

Polyolefin Oil Superabsorbent Polymer (Oil−SAP)
Xuepei Yuan and T. C. Mike Chung*
Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United
States
*
S Supporting Information

ABSTRACT: This paper discusses a novel approach that may provide a complete solution to combating oil spills. The
technology is centered on a cross-linked polyolefin terpolymer (x−OS−DVB), containing 1-octene, styrene, and divinylbenzene
units, which is an oil superabsorbent polymer (oil−SAP) with aliphatic and aromatic side chains that have similar solubility
parameters (oleophilic and hydrophobic properties), with the hydrocarbons in crude oil. Some x−OS−DVB terpolymers, with
desirable morphology (amorphous, low Tg, and high free volume) and lightly cross-linked (complete network) structure, show
rapid oil absorption and swelling to reach a capacity 45 times their weight. The capacity of oil uptake (swelling) is inversely
proportional to the cross-linking density. The combination of selective oil absorption (without water) and tough mechanical
strength offers buoyancy, stability, and easy recovery on water surfaces. The recovered oil-swelled gel, containing more than 98%
oil and 2% x−OS−DVB, is suitable for regular oil-refining processes (an economic, no waste, and no pollutant approach). The
bulk side chains in x−OS−DVB result in a relatively low ceiling temperature for depolymerization and zero heating residue at
450 °C, well below the first distillation step (>600 °C) in oil refining. Furthermore, polyolefins are the most inexpensive
polymeric material, with a large production capability around the world. Overall, this cost-effective new polyolefin oil−SAP
technology shall dramatically reduce the environmental impacts from oil spills and help recover one of our most precious natural
resources.

■ INTRODUCTION
In light of the 2010 BP oil spill in the Gulf of Mexico, more
than 20 years after the Exxon Valdez disaster in Alaska, we still
have no effective technology for removing, recovering, and
cleaning up oil spills or oil slicks from the surfaces of water
bodies and shorelines. Despite the government’s “all hands on
deck” approach to combating the oil spill, currently used
methods (booms and skimmers, dispersants, and in situ
burning) are decades old, low-technology, and manpower-
intensive, some with unknown environmental consequences.
On the basis of these current methods, most spilled oil is
wasted and becomes pollutants in our air and waters.
Furthermore, any small fraction that is actually recovered
generates a large quantity of solid and liquid waste itself, from
tons of soiled boom and other oily waste. It is treated as
industrial waste and buried at specially designated dumps, some
near residential neighborhoods. In fact, oil spill accidents
around the world are actually more frequent than the few
highly publicized cases in United States. As shown in Figure S1
of the Supporting Information, every few years, there has been
a major oil spill, as a result of storage tanks and cracked pipes,
oil tanker collisions or wrecks, and even from war with delivery-
destroying oil facilities. The Exxon Valdez spilled 11 million
gallons of oil into the Prince William Sound, but even that case
did not make the top 10 list of the largest oil spills (the smallest
spill on the list was 4 times larger than that of Exxon Valdez).
Indeed, more than 30 oil spills were measured as larger and
more devastating in the past 40 years.
There have been some reports discussing the sorption of
crude oils, which is an attractive approach to the actual removal
of spilled oil. Two general sorption mechanisms include
adsorption (surface sorption) mechanism by employing porous
or fibrous (high surface area) materials and absorption (matrix
sorption/swelling) mechanism using cross-linked oleophilic
and hydrophobic materials.1 The economic and environmental
concerns surrounding oil spills encouraged many researchers to
investigate natural sorption materials, such as multifarious
inorganic porous products (i.e., clay, talc, zeolites, silica aerogel,
calcium fly ash, etc.),2,3 and organic biodegradable products
(straw, hull, corncob, peat moss, sugar cane bagasse, wood/
cotton fibers, wool-based materials, silkworm cocoon waste,
etc.).4−10 However, most of them show limited oil sorption
capacity and also absorb water, thus making the recovered
solids unsuitable for calcinations; most of them end up in the
landfills. Meltblown polypropylene (PP) pads and booms11,12
are the most commonly used oil sorbent materials, adsorbing
oil in their interstices via capillary action. Because of the weak
oil−substrate interaction (adsorption mechanism), the fiber-
based adsorbers exhibit many disadvantages, including failure to
maintain oil of low viscosity and easy rebleeding of adsorbed oil
under a slight external force. There are also some reports
disclosing the usage of hydrophobic alkyl acrylate oil
absorbents,13−16 such as cross-linked styrene/acrylate, 1-
octene/acylate, and octadecene/maleic anhydride co-polymers.
However, these resins contain some hydrophilic polar groups
and require an additional procedure for the cross-linking
Received: March 5, 2012
Revised: June 30, 2012
Published: July 9, 2012

© 2012 American Chemical Society 4896 dx.doi.org/10.1021/ef300388h | Energy Fuels 2012, 26, 4896−4902
Energy & Fuels
Scheme 1. Synthesis of Cross-Linked x−OS−DVB Terpolymer Material for Oil Absorption
reaction after co-polymerization. In addition, this method has
the drawback of a long absorbing time, especially for aliphatic
hydrocarbon components. Some synthesized rubbers,17−22 such
as polybutadiene, butyl rubber, styrene−butadiene rubber
(SBR), and ethylene propylene diene monomer (EPDM),
were also modified (grafting and cross-linking) to achieve the
network structure for oil absorption. However, the solution
cross-linking is hardly controlled; they usually require extensive
solvent extraction to remove the soluble fraction. The resulting
sol-free materials possess various degrees of cross-linking
density, reducing the overall oil swelling capability. Some
methods, i.e., milling, electric-spinning, and foaming of the oil
absorbents to increase surface area, have also been applied to
improve oil-absorbing speed. However, many materials,23−25
similar to that of meltblown PP, only physically adsorb oil at
the surface by capillary action. Recently, several papers applied
the high surface area materials, including nanowire mem-
branes,26 nanocellulose aerogels,27 and carbon nanotube
aerogels,28 to increase oil adsorption capacity. The treatment
of the recovered solid materials is always a major concern,
including waste disposal, recyclability, and biodegradability.
Overall, it is still a major scientific challenge to identify a
suitable oil superabsorbent polymer (oil−SAP) material that
can offer a comprehensive solution for combating future oil
spills.
■
EXPERIMENTAL SECTION
Materials and Instrumentation. All O2- and moisture-sensitive
manipulations were carried out inside an argon-filled vacuum
atmosphere drybox. 1-Octene, styrene, and p-divinylbenzene (Sigma-
Aldrich) were distilled over CaH2 under argon. Toluene (Wiley
Organics) was dried via refluxing over sodium metal for 48 h under
argon. TiCl3·AA (AA = activated by aluminum metal), AlEt2Cl (25 wt
% in toluene) (Sigma-Aldrich), hexane, benzene, cyclohexane, and
petroleum (VWR) were used as received. Gasoline (octane number of
98) and diesel were purchased from a service station of the Shell Oil
Company. Meltblown PP pads were kindly provided by Newpig
Corporation in Pennsylvania.
All 1H spectra were recorded on a Bruker AM-300 instrument in
chloroform-d at room temperature. The thermal properties of the
polymers were measured by differential scanning calorimetry (DSC)
using a Perkin-Elmer DSC-7 instrument controller with a heating and
cooling rate of 20 °C/min under nitrogen. The molecular weight of
the polymer was determined using Waters gel permeation
chromatography (GPC). The columns used were Phenomenex
Phenogel of 105, 104, 103, and 500 Å. A flow rate of 0.7 mL/min
was used, and the mobile phase was tetrahydrofuran (THF). Narrow
molecular-weight polystyrene standards were used to estimate the
molecular weight.
Synthesis of 1-Octene/Styrene/Divinylbenzene (OS−DVB)
Terpolymers. In a typical 1-octene/styrene/DVB terpolymerization
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reaction, 50 mL of toluene, 5 mL of 1-octene, 5 mL of styrene, and 0.2
mL of DVB were charged into a Parr 450 mL stainless autoclave
equipped with a mechanical stirrer in an argon-filled drybox. The
reactor was sealed, moved out of the drybox, and then purged with
nitrogen gas at 25 °C. About 0.101 g of TiCl3(AA) and 4 mL of
AlCl2Et (25 wt % in toluene) were added under nitrogen pressure to
initiate the polymerization. After agitation for 3 h at elevated
temperature (∼45 °C), the reaction was terminated by adding 100
mL of dilute HCl solution in methanol. The polymer was isolated by
filtration, washed completely with methanol, and then dried under
vacuum for 8 h. About 4 g of OS−DVB terpolymer was obtained. The
terpolymers were completely soluble in common organic solvents,
including toluene, THF, and decalin. They were analyzed by 1H NMR
and GPC to determine their molecular structures.
Oil Absorption Evaluation. Oil absorption tests were conducted
following the standard method [American Society for Testing and
Materials (ASTM) F726-06] using various oils. Typically, a piece of
polymer around 0.2 g was put into gasoline. After a certain time, the
sample was picked up with a tweezer and laid on a filter paper to
remove the excess gasoline before weighing it on a balance. Oil
absorbency (g/g) was calculated by the weight ratio between the
absorbed oil and the original dried materials. To study swelling
kinetics, the above measurements were carried out from time to time.
In addition, the absorption study was also extended to the individual
crude oil components, including alkanes (such as heptane), cyclo-
alkanes (such as cyclohexane), and aromatic hydrocarbons (toluene
and xylene). Evidently, these amorphous x−OS−DVB-based oil−SAP
samples are very effective at absorbing both aliphatic (linear and
cyclic) and aromatic hydrocarbon molecules, and their capacities are
basically controlled by cross-linking density (swelling ability), lower
cross-linking density higher swelling, and absorption capacity.
■
RESULTS AND DISCUSSION
Our research approach has been focused around the design of a
new oil−SAP that can simultaneously exhibit a combination of
several essential properties, including (a) high oil absorption
capacity, (b) fast kinetics, (c) no water absorption, (d)
buoyancy and good mechanical strength for easy recovery
from the water surface, (e) recovered oil/oil−SAP mixture
suitable in a regular oil-refining process, and (f) cost-
effectiveness. The study has been centered on new polyolefin-
based oil−SAP polymers that are petroleum downstream
products, having similar solubility parameters (oleophilic and
hydrophobic properties), with the hydrocarbon components in
crude oil and low production cost. With a suitable polyolefin
structure and morphology, the polymer shall rapidly absorb oil
(without water) and swell its volume to accommodate a large
quantity of absorbed oil. The resulting oil/oil−SAP mixture
(pure hydrocarbons) will float on the water surface with good
stability for easy recovery. In addition, it is highly desirable that
the oil−SAP polymer can be thermally decomposed back to
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Table 1. Synthesis and Oil Absorption Evaluation of Cross-Linked 1-Octene/Styrene/DVB Terpolymersa

polymerization condition absorption capacity (weight times)b
d
run monomer A/B/ terpolymer [A]/[B]/[C] yield Mwe f
gel
number Cc (mL) (mol ratio) (g) (kg/mol) (%) gasoline petroleum diesel toluene hexane benzene cyclohexane
A-1 5/5/0.2 82.3/17.4/0.3 3.07 330 100 41.3 40.3 41.1 47.1 42.8 40.7 43.5
A-2 5/5/0.5 79.3/20.2/0.5 3.76 410 100 21.1 19.6 20.0 22.7 20.4 19.8 22.0
A-3 5/5/1 78.4/20.7/0.9 3.94 420 100 13.7 11.6 11.9 11.6 11.9 14.1 14.1
A-4 5/5/2.5 76.3/22.3/1.4 4.02 460 100 6.41 6.28 6.39 6.24 5.62 5.59 7.02
A-5 5/5/5 74.1/24.0/1.9 4.56 520 100 5.45 5.34 5.40 4.75 5.10 5.21 5.80
PPg 9.21 9.71 9.09 10.0 8.10 10.4 11.3
a
Polymerization condition: TiCl3(AA)/AlCl2Et = 0.101 g/4 mL (25 wt % in toluene), 50 mL of toluene, and 45 °C for 3 h. Cross-linking condition:
240 °C for 2 h. bAbsorption time = 24 h cA, 1-octene; B, styrene; and C, DVB. dDetermined by 1H NMR spectra. eMeasured by GPC with a
standard polystyrene calibration curve. fAfter the thermal cross-linking reaction, the gel content was determined from the toluene-insoluble part after
Soxhlet extraction. gCommercial meltblown PP pad (adsorption mechanism).

Figure 1. 1H NMR spectrum of an OS−DVB terpolymer (run A-5).

low-molecular-weight hydrocarbons (monomers) at <600 °C requirement of an expensive solution removal of hydrocarbon-

during the first refining (distillation) step. Therefore, the
recovered oil/oil−SAP mixtures shall be suitable for regular oil-
refining processes and resolving concerns regarding disposal,
recyclability, biodegradability, and environmental issues caused
by the initial oil spill.
As illustrated in Scheme 1, a series of amorphous OS−DVB
terpolymers (I) were systematically synthesized using a
common heterogeneous Ziegler−Natta catalyst that shows
suitablity for preparing high-molecular-weight OS−DVB
terpolymers with good control of composition and random
structure and only engaging mono-enchainment for DVB. As
will be discussed, a lightly cross-linked oil−SAP material (an
oil-swellable network) is crucial for achieving a high oil
absorption capability, which requires a high-molecular-weight
OS−DVB terpolymer (I) with few DVB cross-linker units in
every polymer chain. The resulting OS−DVB terpolymer (I),
containing some pendent styrene moieties (thermal cross-
linkers), is completely processable (soluble) in forming various
product sizes and shapes (II). However, upon thermal heating
(>220 °C), it becomes a completely insoluble network
structure (III) by engaging in a Diels−Alder [2 + 4] interchain
cycloaddition reaction between two pendent styrene units in
the adjacent polymer chains.28−30 This solid-state cross-linking
reaction (effective and without any byproduct) eliminates the
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soluble fractions shown in many papers, in which the cross-
linking reactions were usually carried out in dilute solutions
with a considerable amount of intrachain coupling activities.
Table 1 summarizes the experimental results of the
terpolymerization reaction with 1-octene, styrene, and DVB
using a heterogeneous Ziegler−Natta catalyst [i.e., TiCl3(AA)/
AlCl2Et]. This traditional Ziegler−Natta catalyst shows an
effective incorporation of both 1-octene and styrene co-
monomers and mono-enchainment of DVB to form the
homogeneous OS−DVB terpolymer (I) solution with a rather
narrow molecular weight and composition distribution. In
general, the terpolymerization results are quite consistent with
the previous observation in the co-polymerization reactions
between 1-octene and styrene 31 and 1-octene and p-
methylstyrene.32 Although 1-octene exhibits higher reactivity
than styrenic monomers (styrene and p-methylstyrene), the
styrenic co-monomers can be homogeneously incorporated in
the co-polymer with high molecular weight and a broad range
of co-polymer compositions using heterogeneous Ziegler−
Natta catalysts. Figure S2 in the Supporting Information shows
a typical GPC curve of the terpolymer (run A-1) with high
molecular weight (Mw ∼ 330 000 g/mol) and relatively narrow
molecular weight distribution (Mw/Mn ∼ 2.1). As will be
discussed, the DSC curves also show a sharp Tg that is
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Figure 2. (Left panel) DSC curves of four OS−DVB terpolymers (runs A-1, A-2, A-3, and A-4). (Right panel) TGA thermographs of an OS−DVB
terpolymer (run A-1) under nitrogen atmosphere.
proportional to the styrene content and the styrene and DVB
contents are directly proportional to the monomer feed ratios.
The high OS−DVB terpolymers, containing more than 20 mol
% aromatic units (styrene and DVB), have been prepared
without any detectable cross-linking reaction. All resulting OS−
DVB terpolymers were completely soluble in common
hydrocarbon solvents, such as hexane and toluene, at ambient
temperature.
Figure 1 shows a typical 1H nuclear magnetic resonance
(NMR) spectrum of OS−DVB terpolymer (run A-5). There
are several aliphatic proton chemical shifts at 0.8 ppm,
corresponding to CH3 in the 1-octene units, and a band
between 0.9 and 1.7 ppm, corresponding to CH2 and CH in the
polymer backbone and 1-octene side chains. In the expanded
region, there are three minor bands around 5.2 and 5.7 ppm
(CHCH2) and 6.7 ppm (CHCH2), corresponding to the
vinyl groups in the pendent styrene groups (after mono-
enchainment of DVB units). There is also a broad aromatic
proton band between 6.9 and 7.4 ppm (C6H4) from both
styrene and DVB units. The integrated intensity ratio between
all three vinyl protons from the DVB units and the phenyl
protons from both styrene and DVB units determines the
styrene and DVB mole ratio. The mole ratio of 1-octene was
determined by the CH3 chemical-shift intensity at 0.8 ppm.
Figure 2 shows thermal properties of the OS−DVB
terpolymers in Table 1, including differential scanning
calorimetry (DSC) and thermogravimetric analysis (TGA)
measurements. On the left panel of Figure 2, all DSC curves
exhibit only one sharp Tg transition in the flat baselines. There
was no detectable melting point up to 200 °C. The Tg (−80
°C) of poly(1-octene) linearly increases with its aromatic co-
monomer content. All OS−DVB terpolymers (Table 1) exhibit
low Tg values (< −50 °C), even with 25 mol % of aromatic
(styrene and DVB) content. The combination implies a
homogeneous terpolymer microstructure with a completely
amorphous morphology and high free volume. The right panel
of Figure 2 shows the TGA curve of an OS−DVB sample (run
A-1). Under an inert atmosphere, the OS−DVB terpolymer
starts its thermal decomposition at 300 °C and rapidly
decreases its weight around 400 °C. At 450 °C, the OS−
DVB terpolymer was completely decomposed without any
residue, indicating the formation of volatile small hydrocarbon
molecules. On the basis of the mass spectrum, the main volatile
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components are the 1-octene and styrene monomers, with their
derivatives having a molecular size below C20. Overall, the
thermal decomposition profile resembles those of poly(1-
octene) and polystyrene homo-polymers. The bulky side chains
in 1-octene and styrenic monomer units weaken the C−C
bonds along the backbone, which may result in chain scission
and the subsequent free-radical-mediated depolymeriza-
tion33−35 at a relatively low pyrolysis temperature. It is
interesting to note that the OS−DVB terpolymer (I) shall
engage in rapid cross-linking activities during the thermal
process (>200 °C). However, the resulting cross-linking
structure appears to have little effect on the overall thermal
degradation.
Before oil absorption evaluation, the OS−DVB terpolymer
(I) solids were divided in 1/4 in. particles and then heated at
240 °C under N2 for 2 h to complete the cross-linking reaction.
The resulting x−OS−DVB samples (III) were subjected to a
vigorous solvent extraction by refluxing toluene for 36 h to
examine any soluble fraction that was not fully cross-linked into
the network structure. Evidently, all x−OS−DVB samples in
Table 1 show no detectable soluble fraction, even in the
terpolymer (run A-1) with only 0.3 mol % DVB units (about 5
DVB units per polymer chain), indicating a very efficient
thermal cross-linking reaction under a polymer melt state
condition. The extensive chain entanglement among many
polymer chains significantly enhances the interchain Diels−
Alder [2 + 4] cycloaddition reaction between two pendent
styrene units from adjacent polymer chains. The high-
molecular-weight terpolymer with narrow molecular weight
and composition distributions certainly also helps in achieving
the complete network structure.
The resulting x−OS−DVB terpolymers (runs A-1−A-5)
were subjected to contact with various oils and pure
hydrocarbons to understand their oil absorption capability
and kinetics. Because crude oil is predominantly a mixture of
aliphatic and aromatic hydrocarbons with various molecular
weights, the exact molecular composition varies widely from
formation to formation. Thus, we decided to examine a broad
range of petroleum products, including some representative of
pure aliphatic and aromatic compounds. Table 1 summarizes
the experimental results with several individual aliphatic and
aromatic hydrocarbons (i.e., hexane, cyclohexane, benzene, and
toluene) and some common petroleum products (i.e., gasoline,
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petroleum, and diesel). Figure 3 compares the oil uptake versus
time for five x−OS−DVB samples (runs A-1−A-5) with a
crude containing approximately 70% volatile light oils and 30%
nonvolatile heavy oils.
Figure 3. Oil uptake versus time for a comparative set of x−OS−DVB
samples (runs A-1−A-5) with a crude containing approximately 70%
volatile light oils and 30% nonvolatile heavy oils.
Seemingly, the oil absorbency and swelling capacity in x−
OS−DVB is largely controlled by cross-linking density,
reversely proportional to the cross-linking density. There is a
very minor dependence upon the absorbates, either the
aliphatic or aromatic hydrocarbons, or even the mixed oil
products. All of the x−OS−DVB samples contain both aliphatic
and aromatic side chains with similar mole ratios but with
different cross-linking densities. The lowest cross-linking
density of x−OS−DVB (run A-1), with 82.3/17.4/0.3 1-
octene/styrene/DVB mol %, exhibits a high absorbent capacity
and the largest degree of swelling, forming a softer and more
cohesive gel formation. Conversely, the x−OS−DVB sample
with high cross-link density (run A-5) shows lower absorbent
capacity and swell. The gel strength is firmer and can maintain
particle shape, even under modest pressure.
Figure 4 compares the oil absorption performance of the x−
OS−DVB sample (run A-1) with a state-of-the-art meltblown
PP pad that is fabricated from a nonwoven fibrous PP textile
with a highly crystalline polymer structure and porous
morphology (high surface area). They were examined side by
side for comparison. The meltblown PP pads (adsorption
mechanism) show rapid oil adsorption in their interstices by
capillary action, saturating at 10 times the weight of uptake
without any visible volume enlargement. The adsorption
mechanism happens only on the PP fiber surfaces (not inside
the crystalline matrix), which is advantageous with fast kinetics
but with limited capacity, and the weak oil−PP interaction
results in some adsorbed oil rebleeding under a slight external
force. On the other hand, the lightly cross-linked oil−SAP
sample (run A-1), with amorphous morphology, gradually
absorbs oil in its matrix, increasing its weight by more than 10
times within 10 min and reaching 40 times its weight after 12 h.
Its oil sorption capacity is superior (>4 times) to that of the
state-of-the-art meltblown PP pad.
Figure 5 shows the action of this x−OS−DVB sample (run
A-1) during the oil absorption. The starting 1/4 in. oil−SAP
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Figure 4. Oil uptake for (a) x−OS−DVB (run A-1) and (b)
commercial meltblown PP pad.
sample (Figure 5a) can effectively absorb crude oil from the
water surface with a large expansion of its volume (>40 times).
Subsequently, the resulting oil/oil−SAP mixture floating on the
water surface (Figure 5b) is ready for collection and can be
picked up with a tweezer without leaking oil (Figure 5c). The
combination of good mechanical strength (cross-linked elastic
structure) and a strong affinity between the oil and polymer
matrix ensure its structure integrity and oil absorption stability.
In a real-world context, it shall also be stable under ocean
environments (waves, wind, sunlight, etc.) and easily removed
from the water surface. Had this material been applied to the
top of the leaking well head in the Gulf of Mexico during the
2010 spill, this oil−SAP could have effectively transformed the
gushing brown oil into a floating gel for easy collection and
minimized the pollution consequences to our air and waters.
In addition to effective oil recovery, the resulting oil-swelled
gel mixture can be treated as crude oil, suitable for regular
refining processes (distillation and cracking). The mixtures
contain no water and have nearly the same composition as the
original crude oil. During refinery, the minor component (2−
3%) of x−OS−DVB polymer will be thermally decomposed
back to <C20 hydrocarbon molecules (typically existing in crude
oil) without residue (Figure 2), well below the typical crude-oil-
refining temperature (>600 °C). This process has multifarious
benefits: it eliminates the concern surrounding solid waste
disposal, recyclability, and biodegradability and maintains our
reservations of natural resources. Furthermore, polyolefin
products are the most inexpensive of polymeric materials and
are capable of large-scale production around the globe. With
conservative estimates, the production cost of new oil−SAP
material comes below $2/lb in large-scale industrial production.
A total of 1 lb of oil−SAP, with a 40 times absorption capacity,
can recover more than 5 gallons of spilled oil (currently treated
as a pollutant instead of a useable resource) to regular crude oil
that is worth more than $12 (on the basis of $80/barrel).
In this study, we have developed a new oil−SAP technology
based on polyolefin-based x−OS−DVB terpolymers that can be
effectively prepared by a conventional Ziegler−Natta catalyst
and then thermally cross-linked into the oil−SAP materials.
The combination of oleophilic and hydrophobic properties with
amorphous morphology, high free volume, and a cross-linked
network offers a desirable matrix for oil absorption and
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Energy & Fuels
Figure 5. (a) Starting x−OS−DVB oil−SAP sample (run A-1). (b) After soaking with crude oil, this swelled oil−SAP is floating on the surface of
water and (c) picked up by a tweezer. The background grid is used for the scale reference.
swelling. The oil uptake is inversely proportional to the cross-
linking density. Oil uptake with up to 45 times that of the
polymer weight and fast kinetics has been observed in a lightly
cross-linked x−OS−DVB terpolymer. Overall, this new oil−
SAP technology exhibits a combination of benefits in oil
recovery and cleanup, including (i) high oil absorption
capability, (ii) fast kinetics, (iii) easy recovery from the water
surface, (iv) no water absorption, (v) no waste in natural
resources, and (vi) being cost-effective and economically
feasible. This new oil−SAP technology shall fundamentally
address the multiple issues created by mega oil spills, whether
seen from an environmental or economic standpoint.
■
ASSOCIATED CONTENT
*
S Supporting Information
Major oil spills and polymer structure characterization (GPC
and TGA curves) of OS−DVB terpolymers. This material is
available free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: chung@ems.psu.edu.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support of this
work by a National Science Foundation (NSF) Research Grant
(CBET-1067554) and commercial feasibility study by Ben
Franklin Foundation under its Translational Research in Energy
Support Program.
■ REFERENCES
(1) Karan, C. P.; Rengasamy, R. S.; Das, D. Indian J. Fibre Text. Res.
2011, 36, 190−200.
(2) Arbatan, T.; Fang, X.; Shen, W. Chem. Eng. J. 2011, 166, 787−
791.
(3) Karakasi, O. K.; Moutsatsou, A. Fuel 2010, 89, 3963−3970.
(4) Chol, H. M.; Cloud, R. M. Environ. Sci. Technol. 1992, 26, 772−
776.
(5) Teas, C.; Kalligeros, S.; Zanikos, F.; Stournas, S.; Lois, E.;
Anastopoulos, G. Desalination 2001, 140, 259−264.
(6) Inagaki, M.; Kawahara, A.; Konno, H. Carbon 2002, 40, 105−111.
4901
Article
(7) Adebajo, M. O.; Frost, R. L.; Kloprogge, J. T.; Carmody, O.;
Kokot, S. J. Porous Mater. 2003, 10, 159−170.
(8) Deschamps, G.; Caruel, H.; Borredon, M. E.; Bonnin, C.;
Vignoles, C. Environ. Sci. Technol. 2003, 37, 1013−1015.
(9) Suni, S.; Kosunen, A. L.; Hautala, M.; Pasila, A.; Romantschuk,
M. Mar. Pollut. Bull. 2004, 49, 916−921.
(10) Sun, X. F.; Sun, R. C.; Sun, J. X. J. Mater. Sci. 2003, 38, 3915−
3923.
(11) Bayat, A.; Aghamiri, S. F.; Moheb, A.; Vakili-Nezhaad, G. R.
Chem. Eng. Technol. 2005, 28, 1525−1528.
(12) Wei, Q. F.; Mather, R. R.; Fotheringham, A. F.; Yang, R. D. Mar.
Pollut. Bull. 2003, 46, 780−783.
(13) Jang, J.; Kim, B. S. J. Appl. Polym. Sci. 2000, 77, 903−913.
(14) Atta, A. M.; Arndt, K. F. J. Appl. Polym. Sci. 2005, 97, 80−91.
(15) Atta, A. M.; El-Hamouly, S. H.; AlSabagh, A. M.; Gabr, M. M. J.
Appl. Polym. Sci. 2007, 105, 2113−2120.
(16) Farag, R .K.; EI-Saeed, S. M. J. Appl. Polym. Sci. 2008, 109,
3704−3713.
(17) Shan, G. R.; Xu, P. X.; Weng, Z. X.; Huang, Z. M. J. Appl. Polym.
Sci. 2003, 90, 3945−3950.
(18) Ceylan, D.; Dogu, S.; Karacik, B.; Yakan, S.; Okay, O. S.; Okay,
O. Environ. Sci. Technol. 2009, 43, 3846−3852.
(19) Essawy, H. A.; Essa, M. M.; Abdeen, Z. J. Appl. Polym. Sci. 2010,
115, 385−392.
(20) Zhou, M. H.; Cho, W. J. J. Appl. Polym. Sci. 2002, 85, 2119−
2129.
(21) Zhou, X. M.; Chuai, C. Z. J. Appl. Polym. Sci. 2010, 115, 3321−
3325.
(22) Fouchet, B. J. Appl. Polym. Sci. 2009, 111, 2886−2891.
(23) Lin, C.; Huang, C. L.; Shern, C. C. Resour., Conserv. Recycl. 2008,
52, 1162−1166.
(24) Zhu, H.; Qiu, S.; Jiang, W.; Wu, D.; Zhang, C. Environ. Sci.
Technol. 2011, 45, 4527−4531.
(25) Tanobe, V. O. A.; Sydenstricker, T. H. D.; Amico, S. C.; Vargas,
J. V. C.; Zawadzki, S. F. J. Appl. Polym. Sci. 2008, 111, 1842−1849.
(26) Yuan, J.; Liu, X.; Akbulut, O.; Hu, J.; Suib, S. L.; Kong, J.;
Stellacci, F. Nat. Nanotechnol. 2008, 3, 332−336.
(27) Korhonen, J.; Kettunen, M.; Ras, R.; Ikkala, O. ACS Appl. Mater.
Interfaces 2011, 3, 1813−1816.
(28) Gui, X. C.; Wei, J. Q.; Wang, K. L.; Cao, A. Y.; Zhu, H. W.; Jia,
Y.; Shu, Q. K.; Wu, D. H. Adv. Mater. 2010, 22, 617−621.
(29) Chung, T. C. Functionalization of Polyolefins; Academic Press:
London, U.K., 2002.
(30) Lin, W. T.; Shao, Z.; Dong, J. Y.; Chung, T. C. Macromolecules
2009, 42, 3750−3754.
(31) Chung, T. C.; Lu, H. L.; Hong, S Rubber Chem. Technol. 1999,
72, 283−298.
dx.doi.org/10.1021/ef300388h | Energy Fuels 2012, 26, 4896−4902
Energy & Fuels Article

(32) Fu, Z.; Zhu, L.; Deng, J.; Xu, J.; Wang, Q.; Fan, Z. J. Appl. Polym.
Sci. 2011, 119, 677−684.
(33) Faravelli, T.; Pinciroli, M.; Pisano, F.; Bozzano, G.; Dente, M.;
Ranzi, E. J. Anal. Appl. Pyrolysis 2001, 60, 103−121.
(34) Guaita, M. Br. Polym. J. 2007, 18, 226−230.
(35) Yuan, X. P.; Chung, T. C. Appl. Phys. Lett. 2011, 98, 62901−
62903.

4902 dx.doi.org/10.1021/ef300388h | Energy Fuels 2012, 26, 4896−4902