Marine Pollution Bulletin 64 (2012) 16481653

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Marine Pollution Bulletin

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

Hydrophobic modication of polyurethane foam for oil spill cleanup

Hua Li, Lifen Liu , Fenglin Yang
MOE, Key Lab of Industrial Ecology and Environmental Engineering, School of Environmental Science and Technology, Dalian University of Technology, Dalian, China

a r t i c l e

i n f o

a b s t r a c t

Keywords:
Oil pollution
Oil sorbent
Polyurethane foams
Oleophilic

To improve the oleophilic/hydrophobic properties of polyurethane (PU) foams for oil spill cleanup, PU
samples were modied by grafting with oleophilic monomer Lauryl methacrylate (LMA) in solvent
and/or coating with LMA microspheres through heating and curing. Modied PU cubes were characterized by eld emission scanning electron microscopy (FE-SEM) and Fourier transform infrared spectroscopy (FTIR). The water sorption of modied PU cubes was decreased by 2450%, while the diesel or
kerosene sorption of modied PU cubes was increased by 1827%. In wateroil system, compared with
blank PU cubes, the sorption capacity of PU cubes grafted with LMA was increased by 44% for diesel
and 100% for kerosene. The sorption capacity of PU cubes coated with LMA microspheres was increased
by 20% for diesel and 7% for kerosene. The solvent sorption of modied PU cubes could reach 5069 g/g.
The modied PU cubes can be effectively used in oil/solvent spill cleanup.
2012 Elsevier Ltd. All rights reserved.

1. Introduction

and Burford, 2006). However, the oil sorption capacity of these synthetic organic sorbents is generally not very high.
The ultralight, open-cell, low-density and high-porosity polyurethane foams (PU) are thought as good oil sorbent. However, PU is
formed by the reaction of di-/poly-functional hydroxyl (polyol) or
amino-containing compounds with di-/poly-isocyanates. It has lots
of ether-, carbamate- and amide-groups, which make PU absorb both
oil and water. Although considerable research has devoted to the effect of the cell structure (Shimizu et al., 1997; Yang et al., 2005) and
foam density on oil sorption of PU (Duong and Burford, 2006), less
attention has paid to the surface modication of PU foams to make
it more oleophilic/hydrophobic for oil spill cleanup. The previous research about oil sorbent mainly focused on the sorption capacity of
oil, little research has demonstrated the difference among the sorption capacity in water, oil phase and wateroil system.
In this study, the following methods were introduced to develop
the oleophilic/hydrophobic properties of PU foams: (1) LMA, an alkyl
acrylate monomer with a long-chain alkyl group having a good afnity to oil or nonpolar solvents (Jang and Kim, 2000a,b; Atta et al.,
2006), was grafted onto PU in toluene. (2) LMA microspheres were
coated on the surface of PU. The commercial oil (diesel and kerosene)
samples were chosen for the tests and the sorption capacities of the
blank PU cubes and modied PU cubes in water, pure oil phase and
wateroil system were investigated and compared in details.

Recently, the pollution by oil spillage in the ocean has been

noted as a big environmental problem all over the world. To avoid
the adverse impacts of spilt oil on ecosystems and the long-term
effects of oil pollution, there is an urgent need to develop a wide
range of materials for cleaning up spilled oil effectively, as the
cleaning up treatment should vary with time, the type of oil, spill
scale, the location and weather conditions (Adebajo et al., 2003).
Representative treatments of spilt oil include usages of oil dispersant, oil gelling agent and oil sorbent (Shimizu et al., 1997). The use
of oil sorbents is considered as the most ideal solution because it
can efciently remove/recover oil from the sea. Oil sorbents can
be divided into two basic types: the synthetic ones and the natural
ones which include both inorganic and organic.
The natural inorganic/mineral sorbents such as clay (Carmody
et al., 2007), perlite (Bastani et al., 2006) and glass wool (Annunciado
et al., 2005), the natural organic sorbents including hay, feather,
straw and peat moss (Suni et al., 2004) are inexpensive and available
in large quantities. The synthetic sorbents include polymer-based
sorbent and carbon-based products. The disadvantage of natural
sorbents is that they are low in oil sorption capacity and dusty, difcult to use under windy conditions. In addition, as some natural organic sorbents absorb both oil and water, it may sink after
saturation. The synthetic organic sorbents such as polymeric ones
(polyurethane, polypropylene, polyethylene and cross-linked polymers) are the most commonly used commercial sorbents in oil spill
cleanup, due to their oleophilic and hydrophobic properties (Duong

2. Materials and methods

2.1. Materials

Corresponding author. Tel.: +86 411 84706173; fax: +86 411 84708083.
E-mail address: yuzhe25521@yahoo.com.cn (L. Liu).
0025-326X/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.marpolbul.2012.05.039

PU foams with the density of 15 kg/cm3 were purchased from

Dalian Lida Co. (China), cut to 1 cm  1 cm  1 cm and thoroughly

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H. Li et al. / Marine Pollution Bulletin 64 (2012) 16481653

rinsed with ethanol before being used. Lauryl methacrylate (LMA)

was purchased from Shanghai aoke Co. (China). Polyvinylpyrrolidone (PVP), Benzoyl peroxide (BPO) and anhydrous sodium sulfate
were purchased from Tianjin Fuchen Chemical Reagent Co. (China).
Divinylbenzene (DVB) was purchased from TCI Co. (Japan). All the
solvents (toluene, benzene, carbon tetrachloride, petroleum ether
boiling range 3060 C and ethanol) were purchased from Tianjin
Damao Chemical Reagent Co. (China). Diesel and kerosene were
purchased from the market of Dalian in China. Except PU foams
the materials were all used as received.

2.2. Grafting copolymerization

The reaction was carried out in a 100 ml three-necked reaction
ask equipped with a thermometer, nitrogen gas inlet and reux
condenser. 0.01 g of initiator BPO dissolved in 50 ml toluene was
added into the ask. 0.2 g of blank PU cubes were totally immersed
into the stirred reactive solution for 20 min at 80 C. Subsequently
a mixture containing 0.3 g of LMA and 0.003 g of cross-linker (DVB)
was added to the ask at once. After 6 h reactions under stirring
(500 rpm) and nitrogen atmosphere at 80 C, the cubes were
washed with ethanol and deionized water for several times, then
dried at 60 C under vacuum for 48 h. The sorbents were named
as PU-g-LMA. The grafting reaction scheme was shown in Fig. 1.

2.3. Preparation of LMA microspheres and its coating on PU cubes

LMA microsphere colloidal solution was prepared by emulsier-free emulsion polymerization. Briey, 0.2 g of PVP dissolved
in 100 ml of ethanol was poured into a 250 ml four-necked reaction ask equipped with a dropping funnel, nitrogen gas inlet
and reux condenser. Then, 5.0 g of LMA was slowly added within
30 min though a dropping funnel and then heated to 80 C, followed by the dropwise addition of BPO solution (0.05 g of BPO in
5.0 g of ethanol). The reaction was conducted at 80 C for 4 h under
nitrogen atmosphere. Finally, the obtained LMA colloidal solution
was diluted by ethanol at a concentration of 0.1 wt.%.
At room temperature, 0.2 g of blank PU cubes were immersed
and soaked in the LMA colloidal solution (100 ml) for 4 h. After
that, the prepared PU cubes were heated at 100 C for 30 min to allow the LMA beads to adhere well to the PU foams. The sorbents
were named as PU-LMA microspheres.

2.4. Sorption capacity test

The method developed for the measurement of oil and water
sorption capacity of the sorbent was based on ASTMF726-99: Standard Test Method for Sorbent Performance of Adsorbents.
For oil sorption tests, diesel or kerosene (50 ml) was poured into
a 100 ml beaker. The sorbent was weighed and the value recorded,
then it was immersed into the oil. In general, after 30 min 208 s
of immersion, the sorbent was removed and allowed to drain for
30 3 s. The saturated sorbent was then immediately transferred
to a pre-weighed weighing bottle and weighed. The oil sorption
of sorbent was calculated using the following equation:

Oil sorptiong=g

St  S0
S0

where S0 is the initial dry weight of a sorbent and St is the weight of

sorbent with oil absorbed. Solvent sorption capacity measurements
were carried out similarly.
For water sorption tests, the sorbent was rst weighed then
placed into a 100 ml Erlenmeyer ask which was lled with
50 ml of deionized water. The sealed ask was then placed in a
shaker (150 rpm) and shaken for 15 min 20 s. The contents of
the ask were allowed to settle for a period of 2 min. The sorbent
was removed and allowed to drain for 30 3 s, then immediately
transferred to a pre-weighed weighing bottle and weighed. The
water sorption was calculated using the following equation:

Water sorptiong=g

Swt  S0
S0

where S0 is the initial dry weight of sorbent and Swt is the wet
weight of sorbent (after water sorption).
In wateroil system sorption tests, 4.0 g of diesel or kerosene
was poured into a 100 ml Erlenmeyer ask which was lled with
50 ml of deionized water, the thickness of the oil lm was
23 mm. The sorbent was rst weighed and placed into the
Erlenmeyer ask. The sealed ask was then placed in a shaker
(150 rpm) and shaken for 30 min 20 s. The contents of the ask
were allowed to settle for a period of 2 min. Then sorbent was removed to an Erlenmeyer ask and then extracted by petroleum
ether (boiling range 3060 C) several times, subsequently the sorbent was removed and squeezed out the absorbed petroleum
ether. Anhydrous sodium sulfate was added to the petroleum ether
solution until there was no agglomeration, and then the
Erlenmeyer ask was sealed for 30 min to dehydrate. Next, after
ltration, the ltrate was collected by a dry beaker with a constant
weight. The beaker was placed in a 65 5 C water bath to vaporize
petroleum ether, then the beaker was placed in a 65 5 C drying
oven until it reached constant weight. Finally, the oil sorption in
wateroil system was calculated using the following equation:

Oil sorptiong=g

Mt  M0
S0

where M0 is the constant weight beaker, Mt is the weight of constant weight beaker with absorbed oil and S0 is the initial dry
weight of sorbent.
All tests were performed at 23 4 C and carried out in triplicate, the average value and standard deviation (0.541.65) were
calculated. If the value of any run (g/g) deviated by more than
15% from the mean of the three runs, the sample data would be rejected and the test would be repeated with three new specimens.
2.5. Characterization

Fig. 1. Reaction scheme for grafting polymerization of LMA onto PU surface.

The morphology of the blank PU cubes and modied PU cubes

were examined by eld emission scanning electron microscopy
(FE-SEM) (S-4800, Hitachi Ltd., Japan). FTIR spectra of blank PU

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H. Li et al. / Marine Pollution Bulletin 64 (2012) 16481653

cubes and modied PU cubes were recorded by a FT-IR spectrometer (IRPrestige-21, Shimadzu, Japan.).

partly coated microsphere, the weight of PU-LMA microspheres

was increased by 3%.

2.6. Sorption rate and video recording

3.3. Water sorption capacity

To examine the oil-wettability of the blank PU cubes and modied PU cubes, video recording was used to record how long the
blank PU cubes and modied PU cubes takes to totally immerse
into the diesel. In the video, the blank PU cubes was placed into
beaker a, the PU-g-LMA and PU-LMA microspheres cubes were
placed into beaker b and c, respectively. Timing started when
the sorbent was put into the oil.

The water sorption capacity was 14.13 g/g for blank PU cubes,
7.03 g/g for PU-g-LMA and 10.69 g/g for PU-LMA microspheres, it
decreased by 50% after the grafting treatment and 24% after the
coating treatment (Fig. 4), because the grafted or coated LMA
was oleophilic and hydrophobic. However, PU cubes grafted with
LMA was more hydrophobic than PU cubes coated with LMA
microspheres.
It was known that the grafting copolymerization of hydrophilic
polymers with various hydrophobic monomers proceeded by a free
radical mechanism, the free radicals abstract hydrogen atoms from
the polymer. Macro-radicals were formed and acted as the grafting
sites for the functional monomers (Pulat and Babayigit, 2001; Zhao
et al., 2011). Free radicals generated by peroxide, initiated homogeneous grafting reaction on the PU cubes, while the coating of LMA
microspheres was not as homogeneous as the grafting. There was
still uncoated area that had no LMA microspheres (Fig. 3f).

3. Results and discussion

3.1. Fourier transform infrared spectroscopy (FTIR)
FTIR spectra of blank PU cubes and modied PU cubes were
presented in Fig. 2. All of the samples had absorption peaks at
30003500 cm1 (NH stretching)/10701150 cm1 (CO stretching), 16901740 cm1 (urethane groups)/16501710 cm1 (C@O
stretching) and 28802890 cm1 (CH stretching) (Pulat and
Babayigit, 2001). In PU-g-LMA sample the intensity of NH groups
became weak as the grafting of LMA. The relative intensity for peaks
of C@O and CH2 chain at around 15001750 cm1 was increased
after grafting polymerization modication, due to the ester group,
aliphatic chain and aromatic ring from LMA and DVB. FTIR spectra
of PU-g-LMA was indicated that grafting copolymerization with
LMA proceeded by abstracting hydrogen atoms from the NH
groups (Alves et al., 2009) and LMA was successfully grafted on PU
cubes.
3.2. SEM analysis
From the SEM micrographs of blank PU cubes and modied PU
cubes shown, the pentagonal dodecahedron cell structure of the
blank PU cubes was not ideal. There remained polymer lm
between the cells, the size of the cell was mainly from 400 to
700 lm. Furthermore, the Fig. 3c had shown that the grafting copolymerization caused certain destruction of the cell structure/backbone of the PU cubes. And the modication with coated LMA
microspheres (Fig. 3e) had more severe destruction of the cell
structure by shrink during heating and cooling. The surface of
the blank PU cubes (Fig. 3b) were very smooth, the surface of
PU-g-LMA and PU-LMA microspheres were rougher (Fig. 3d and
f). Grafted polymer distributed more evenly on the surface of PUg-LMA (Fig. 3d). Oppositely, the coated LMA microspheres, left
uncovered surface on PU-LMA microspheres (Fig. 3f). Due to the

3.4. Oils sorption capacity and sorption rate in oil phase

As expected, modied PU cubes showed superior performance
in absorbing diesel and kerosene (Fig. 5). Compared with blank
PU cubes, the sorption capacity of PU-g-LMA increased 18% for diesel and 27% for PU-LMA microspheres. At the same time, the sorption capacity of PU-g-LMA increased 3.8% for kerosene and 18% for
PU-LMA microspheres. The increase of PU-g-LMA was much smaller than PU-LMA microspheres. That was due to the low yield of
grafting copolymerization, the weight increase on PU-g-LMA was
much lower (<1%) than the PU-LMA microspheres (3%).
In Table 1, a comparison of the maximum sorption capacity of
modied PU cubes with other previously reported sorbents was
listed. It was clear that the modied PU cubes had a very high oil
sorption capacity compared with the other polymer sorbents.
The sorption rate for diesel was shown in Fig. 6. When the time
was about 1 min, the sorption capacity reached more than 95% of
maximum capacity. The results indicated that the sorption rates
for blank PU cubes and modied PU cubes were fast and the maximum sorption capacity was achieved in about 2 min. The modication process did not inuence the sorption rate of PU cubes, but
the sorption capacity.
The contact angle of sorbents with water or oil is useful indicator of the improvement in hydrophobicity of oil sorbents. However,
PU cubes had a macrospore cell size ranging from 400 to 700 lm,
which made the contact angle measurement difcult. In order to
examine the oil-wettability of blank PU cubes and modied PU

Fig. 2. The FTIR spectra of the blank PU cubes and modied PU cubes.

H. Li et al. / Marine Pollution Bulletin 64 (2012) 16481653

1651

Fig. 3. SEM photographs of the blank PU cubes (a, b), PU-g-LMA (c, d) and PU- LMA microspheres (e, f).

Fig. 4. The water sorption capacity of the blank PU cubes and modied PU cubes.

cubes, video recording was used to examine how long it takes to

totally immersed in diesel (see Supplementary video). From the
videos recorded, it was clear that PU-g-LMA (b) immersed immediately in the diesel (around 6 s), the immersion of PU-LMA microspheres (c) was slower (around 10 s) and the rate to immerse the
blank PU cubes (a) was the slowest (about 15 s). This test proved
that the oleophilic and hydrophobic properties of blank PU cubes
and modied PU cubes followed an order of: PU-g-LMA > PULMA microspheres > blank PU cubes.

Fig. 5. The oil sorption capacity of the blank PU cubes and modied PU cubes in oil
phase.

3.5. Oils sorption capacity in wateroil system

In the wateroil system, due to competitive sorption of water,
the oil sorption of blank PU cubes and modied PU cubes were decreased (Fig. 7), the decrease order followed the sequence: blank
PU cubes > PU-LMA microspheres > PU-g-LMA.
However, modied PU cubes still showed higher oil sorption.
Compared with blank PU cubes, diesel and kerosene sorption
capacities of PU-g-LMA were increased by 44% and 100%. The die-

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H. Li et al. / Marine Pollution Bulletin 64 (2012) 16481653

Table 1
Oil sorption capacities of some sorbents reported in literature.
Oil sorbent

Oil
studied

Sorption
capacity (g/g)

Reference

Nonwoven
polypropylene

Crude oil

Wei et al., (2003)

Cotton grass ber

Gasoline
Diesel

19
20

Suni et al., (2004)

Organo-clays

Diesel
Hydraulic
oil
Engine oil

7.2
2.2

Carmody et al., (2007)

Carbonized pith
bagasse

Gasoline

23.86

Hussein et al., (2008)

Macroporous
organogel

Toluene
Crude oil

20.6
18.2

Tuncaboylu and Okay,

(2009)

PU-g-LMA

Diesel
Kerosene

46.98
41.42

This study

PU-LMA
microshperes

Diesel
Kerosene

50.40
47.27

This study

PU

Diesel
Kerosene

39.75
39.9

This study

2.1

Fig. 8. The solvent sorption capacity of the blank PU cubes and the modied PU
cubes.

The solvent sorption of modied PU cubes was also very high

(Fig. 8). Solvent sorption of modied PU cubes could reach 50
69 g/g. Comparing with the blank PU cubes, solvent sorption of
the modied PU cubes was increased by 3539%. The modied
PU cubes can also be effectively used in solvent spill cleanup.
4. Conclusions
PU cubes were successfully modied by grafting polymerization
with oleophilic monomer LMA in solvent and coating with LMA
microspheres. The oil sorption of modied PU cubes was enhanced
especially in the wateroil system, meeting the challenge for environmental protection of marine system and aqueous ecosystem. In
contrast to the blank PU cubes, water sorption capacity of PU-gLMA and PU-LMA microspheres was decreased by 50% and 24%,
respectively. The oil absorbed on PU-LMA microspheres increased
higher than PU-g-LMA in oil phase, but it increased lower than
PU-g-LMA in wateroil system. The solvent sorption of modied
PU-g-LMA cubes was also very high. The modied PU cubes are
applicable to cleanup the spill oil or solvent. And the modied
PU-g-LMA cubes are more suitable to cleanup the spill oil or solvent in wateroil system.

Fig. 6. The sorption rate of the blank PU cubes and modied PU cubes.

Acknowledgement
This work is supported by the National Natural Science Foundation of China (NO. 21177018).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the
online
version,
at
http://dx.doi.org/10.1016/
j.marpolbul.2012.05.039.
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Fig. 7. The oil sorption capacity of the blank PU cubes and modied PU cubes in
waterdiesel and waterkerosene system.

sel and kerosene sorption capacities of PU-LMA microspheres were

increased by 20% and 7%. Diesel sorption increase of modied PU
cubes was higher than kerosene because diesel was more viscous
than kerosene.

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