SPE 80206
Development of a Hydrophobically Modified Water-Soluble Polymer as a Selective
Bullhead System for Water-Production Problems
Larry Eoff, Dwyann Dalrymple, and B.R. Reddy, Halliburton, Jim Morgan and Harry Frampton, BP Amoco
Copyright 2003, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 5–7 February 2003.
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Abstract
For many years, bullhead systems have received a great deal
of attention from the oil and gas industry. Because of the
completion techniques used in many wells, protecting the
hydrocarbon interval effectively during a water control
treatment is not always practical or cost-effective. Bullhead
systems offer the option of a treatment without zonal isolation
and are designed to decrease water production with little or no
decrease in oil or gas production. This paper describes the
laboratory development of a new polymer that shows promise
as a bullhead system.
The material falls into the class of hydrophobically
modified water-soluble polymers; that is, a water-soluble
polymer into which water-insoluble moieties have been
introduced. The unique associative and adsorptive properties
of this class of polymers are well documented, but they have
not been commercially exploited to a great extent in oil
field applications.
These materials offer improvements over the hydrophilic
polymers traditionally used for permeability modifications.
For example, hydrophobic modification appears to improve
cleanup of the polymer that penetrates an oil saturated core,
resulting in less risk of damage to oil permeability.
Hydrophobic modification, depending on the structural
features, also increases reduction to water flow in comparison
to the unmodified polymer. This paper includes a general
description of hydrophobically modified polymers and their
properties, as well as detailed descriptions of the development
and laboratory testing of the new system.
Introduction
Controlling water production has been an objective of the oil
industry almost since its inception. Produced water has a
major economic impact on the profitability of a field.
Producing 1 bbl of water requires as much or more energy as
producing the same volume of oil. Often, each barrel of
produced water represents some lesser, but significant, amount
of unproduced oil. In addition, water production causes other
related problems such as sand production, the need for
separators, disposal and handling concerns, and the corrosion
of tubulars and surface equipment.
Many methods are available to mitigate water production
problems. Among the chemical methods, both sealing and
nonsealing systems have been in use for many years.
Nonsealing systems are also referred to as bullhead systems,
disproportionate permeability modifiers, and relative
permeability modifiers (RPMs). These nonsealing systems
(referred to in this paper as RPMs) are typically dilute
polymer solutions, which perform due to adsorption onto the
pore walls of the formation flow paths. A large number of
such polymer systems have been promoted throughout the
years, and a large volume of literature has been devoted to this
topic. One relatively common theme mentioned for such
systems has been that they are best applied to layered,
heterogeneous formations without reservoir crossflow.
A previous paper described an RPM polymer that
consisted of polydimethylaminoethyl methacrylate derivatized
with methoxypolyethylene glycol.1 This system was shown to
provide significant permeability reduction in relatively low-
permeability sandstone cores at 100% water saturation as well
as at residual oil saturation. Subsequent testing showed much
lower levels of permeability reduction in higher-permeability
sandstone cores that contained residual oil saturation.
Therefore, a development project was initiated to investigate
systems that could provide a minimum of 80% brine
permeability reduction in sandstone cores in a broad range of
permeabilities, while showing minimal effect on oil
permeability (preferably no effect, but in any case <50%
reduction). Several types of chemical systems were
investigated, but eventually a class of materials known as
hydrophobically modified water-soluble polymers became the
focus of attention.
Hydrophobically Modified Water-Soluble Polymers
The solution properties, such as rheology and viscosities, of
both ionic and nonionic water-soluble polymers, are uniquely
modified when hydrophobic groups are introduced into the
polymer chains.2-5 The primary factor responsible for the
property modification is the associative tendency between the
hydrophobic groups when placed in aqueous medium. The
associative interactions of the hydrophobic groups may lead to
2 SPE 80206
either lower or to higher solution viscosities depending on the
polymer concentration, which determines whether intra- or
inter- molecular interactions dominate. These attractive
interactions are often depicted as transient and reversible
crosslinks among polymer chains that form under static or low
shear conditions, but rupture at high shear rates. At
concentrations that result in viscosity increase of the solutions
under low shear conditions, the polymer solutions still behave
as traditional shear-thinning fluids under high shear. This
property is useful in oil field applications requiring particle
transport, such as fracturing or transport of drill cuttings.
Commercially, however, this property has found extensive
applications in the coatings industry.
Another unique property of hydrophobically modified
water-soluble polymers is their behavior in aqueous brines.
The viscosity of a polyelectrolyte solution decreases with
added salts due to the screening of the charges on the polymer
chain by the component ions of the salt. While this
phenomenon still occurs with hydrophobically modified ionic
polymers, the decrease in viscosity due to charge screening is
more than compensated by the increased intermolecular
associations among the hydrophobic groups due to the
presence of salts. Thus, hydrophobically modified polymers
find use as viscosifiers for brines such as those used in drill-in
or drilling fluids.6,7
The shear dependent rheological properties of
hydrophobically modified water-soluble polymers can be
modified without altering their behavior towards salts by the
addition of surfactants. This result has found use in polymer
flooding application for enhanced oil recovery.8,9
The adsorption behavior of hydrophilic water-soluble
polymers can also be modified in a unique manner by the
introduction of hydrophobic groups. Rather than reaching a
plateau adsorption isotherm as is common for hydrophilic
polymers, hydrophobic modification appears to result in
continued increase in adsorption with increase in polymer
concentration. This behavior is attributed to associative
adsorption of polymer chains on previously adsorbed layers
of polymers.10
In general, hydrophobic modification of water-soluble
polymers adds new properties while retaining features typical
for hydrophilic polymers. The extent of these new properties
can be controlled by the synthesis method, polymer
concentration, hydrophobe type and amount, the quality of the
solvent, and the monomer distribution along the polymer
chain. Based upon their unique properties, especially the
adsorption and associative properties, this class of compounds
was chosen for investigation as an improved RPM.
Experimental Procedures
Core Flow Tests. All flow tests were carried out using
multipressure-tap Hassler sleeves. All tests utilized sandstone
cores. (Typical X-ray diffraction analysis is shown in Table 1,
and physical properties of the cores are shown in Table 2.)
Core lengths were approximately 5 to 6 inches, and the
diameter was approximately 1 inch. API brine was used to
establish the initial and final permeabilities in all cases. 2%
KCl was used as the treatment mix water in all cases.
Kerosene was used as the oil phase in all flow tests. In these
tests, brine and oil initial permeabilities were determined in
the normal production direction with the flow from segment 1
to segment 4 (from reservoir to well). The treatment is
pumped in the reverse direction, from segment 4 to segment 1
(from well into reservoir). Final assessment of the treatment’s
effect reverts to flow from segment 1 to segment 4.
All core tests were performed at residual water saturation
or residual oil saturation. The following test procedure
was used:
1. Record the core dimensions, and place the core in the
multi-tap Hassler sleeve apparatus.
2. Place sufficient overburden pressure on the core to
ensure that no fluid bypasses the core.
3. Determine the viscosities (at temperature) of the
brine and oil to be used in the flow tests. Perform all
flow series at the desired test temperature.
4. Stabilize the flow of brine through the core in the
normal production direction.
5. Stabilize the flow of oil through the core in the
normal production direction.
6. Repeat Steps 4 and 5 until reproducible brine
permeabilities and oil permeabilities have been
achieved, ending with either brine or oil depending
on the test being performed.
7. Pump the treatment through the core in the reverse
flow direction. Overdisplace the treatment through
the core with 100 cm3 of brine and 25 cm3
of kerosene.
8. Repeat Step 4 or 5.
9. Use Eq. 1 to determine the shutoff percentage:
[(pretreatment permeability – post-treatment permeability) /
pretreatment permeability] × 100 …………………………(1)
Rheological Measurements. All rheological measurements
were run on a Haake RS 150 Rheostress Rheometer, using a
cone and plate arrangement, at 73ºF.
Hydrophobically Modified Polymer Development
Polyacrylamide Modification. Hydrophobically modified
polyacrylamide was selected as the first type of polymer to be
evaluated, to determine whether hydrophobic modification
could improve RPM functionality. It was chosen because the
use of polyacrylamide in bullhead operations has been well
documented, and for its ease of polymerization.11 Several
variations were synthesized in an effort to determine whether
the hydrophobic modification had a positive effect on the
brine permeability reduction. The screening test method used
for this phase of the project incorporated a multi-tap core flow
test using Berea sandstone cores in a brine-oil-brine-treatment-
brine flow sequence, at 175ºF. As described in previous
papers, using the multi-tap Hassler sleeve reveals the depth of
penetration of the treatment into the core.1,12
A large number of modified polyacrylamides were tested,
with polymers containing variations in both the levels of
hydrophobe and the hydrophobe chain length. Representative
examples of the test results are shown in Fig. 1. The first entry
in Fig. 1 is for an in-house synthesized unmodified
polyacrylamide. This polymer was not extensively
characterized, but it was compared to a commercially
available polyacrylamide with molecular weight of ~6 million,
SPE 80206
which had been utilized in previous core flow tests.1 Based
upon solution viscosities, the in-house synthesized sample has
a molecular weight considerably less than 6 million. The
remainder of the data in Fig. 1 is for polyacrylamide modified
with various levels of C18 hydrophobe groups. For these
samples, the synthesis conditions (temperature and initiator
concentration) were the same as those used for the unmodified
polyacrylamide. Therefore, the molecular weights of the
unmodified and modified polymers may be somewhat similar
and any differences in performance can be attributed to the
hydrophobic modification.
As shown in Fig. 1, the hydrophobic modification did
increase levels of brine permeability reduction, and also
increased thermal stability. In these tests, the initial %
permeability reduction (% Kw reduction) was calculated after
flowing a minimum of 130 pore volumes of brine through the
core after the treatment sequence. The cores were then shut-in
overnight, at temperature, and flow was re-established the
following day. As has been seen previously, the unmodified
polyacrylamide is not thermally stable at 175ºF, and the level
of brine permeability reduction drops by almost 80% after the
overnight shut-in.1 However, the hydrophobic modification
resulted in an increase in thermal stability. The polymer with
4% C18 hydrophobe shows only a very slight decrease in
effectiveness after the shut-in. The exact reasons for these
improvements are not known, but it is speculated that the
superior retention of the brine permeability reduction is due to
increased levels of permanent adsorption, resulting from
hydrophobic associations.10
Based on all the data generated during this phase of the
project, the conclusion that the hydrophobic modification was
improving the level of brine permeability reduction was
reached. However, the target goal of 80% minimum reduction
had not been met. The hydrophobic modification also
appeared to be increasing the temperature stability of the base
polymer (polyacrylamide) at the screening temperature of
175ºF. The next development phase led toward seeking a
polymer base that would have better thermal stability
than polyacrylamide.
Polydimethylaminoethyl Methacrylate Modification. Based
on previous experience, polymers based on
dimethylaminoethyl methacrylate (polyDMAEMA) were
investigated.1 Several variations of hydrophobically modified
polyDMAEMA (HMpolyDMAEMA) and hydrophobically
modified copolymers of DMAEMA and vinyl pyrollidone
were synthesized. The previous tests with polyacrylamide had
shown that both C16 and C18 hydrophobic groups imparted
improvements to brine permeability reduction. With
polyDMAEMA, the addition of C10 hydrophobic groups was
also tested. These tests revealed that the C10 hydrophobe was
not effective at imparting brine permeability reduction
characteristics; the highest level of permeability reduction was
~25%. Apparently, a minimum chain length is needed to
provide the necessary associations between polymer chains,
which imparts the ability to reduce core permeability. After
extensive testing, polyDMAEMA modified with a C16
hydrophobe was determined to meet the desired minimum
requirements of at least an 80% reduction to brine
permeability with little or no damage to the effective
3
permeability to oil. Following are examples of flow tests run
during the evaluation of this polymer.
As shown in Fig. 2, in a low-permeability berea core the
polymer brought about the desired permeability reduction to
brine throughout the core. Continued testing showed that the
polymer treatment resulted in excellent brine permeability
reduction from 90º to 200ºF, even in high-permeability
sandstone cores. Figs. 3 through 5 illustrate that the target goal
of 80% permeability reduction was met in all of these tests. In
addition, no decline in the effective brine permeability
blockage has been seen with continued flow through the cores,
at temperatures up to 210º F.
As shown in Figs. 3 through 5, a variable in these three
tests was the treatment volume. This variation relates to a test
method mentioned in previous publications from this
laboratory.1,12 The previous method was a parallel test used to
mimic a layered reservoir containing water-producing and oil-
producing layers without crossflow. In this test, a core at
100% water saturation or residual oil saturation and a second
core at residual water saturation are connected so that the
treatment can be pumped into both cores with a single pump.
This is the laboratory equivalent of bullheading a treatment
into a well with layered water-producing and
oil-producing zones.
Several of these tests have been performed with various
polymer treatments, with successful results. However, in an
effort to test the most variations in the least amount of time, an
alternate test procedure was adopted. In some tests, 500 mL
of the HMpolyDMAEMA treatment was required to achieve
the desired level of >80% brine permeability reduction. When
cores were treated with the HMpolyDMAEMA, a significant
pressure increase was often seen during the treatment phase
before the planned injection of 500 mL of treatment was
completed. In a relatively few cases, the full 500 mL was
pumped with no pressure increase. In the field, a limit would
usually be imposed on the rise in injection pressure considered
acceptable during treatment (usually about 200 psi below the
fracture pressure). Therefore, the test procedure adopted was
to limit the treatment to 500 mL or 500 psi, whichever
occurred first. A wide variation in the volume of treatments
actually pumped has been seen with this method. While no
definitive reason for this variation in pressure increase has
been determined, it is most probably due to variations in the
cores used in the evaluation.
This method was also chosen for treating cores at residual
water saturation. Limiting the oil cores to the same pressure
limit as the water cores seems reasonable. During an actual
treatment, if the target water-producing zone is of higher
permeability than the oil-producing zone, most of the
treatment should go into the water zone. Therefore, if and
when pressure buildup occurs during a treatment, both zones
will experience the same pressure. Not only does this test
method seem practical, it greatly simplifies the test in regard
to equipment and time.
Testing at Residual Water Saturation. Fig. 6 shows results
of the treatment of a berea core at residual water saturation. As
shown, the treatment resulted in minimal damage to the oil
flow (many of these tests were run and this result is typical of
most of the tests).
4 SPE 80206
Oxidizer Treatments. The ability to remove water shutoff
treatments is a commonly raised topic. In the case of sealants
(crosslinked polymers, monomer solutions, silicates, etc.), the
treatments are essentially permanent. The gel in the rock
matrix cannot be removed because fluid cannot flow into the
treated zone to contact the gel. However, with treatments of
dilute, nongelling polymers, flow through the treated zone can
be achieved because the treatment is not a total sealant. Fig. 7
shows the results of treating a core with an oxidizer (sodium
hypochlorite) after a polymer treatment. In this case, a high
permeability sandstone core was treated with 6,000 ppm
polymer at 200ºF. After brine flow to obtain the %
permeability reduction, the core was treated with 2 pore
volumes of 5% sodium hypochlorite. The core was shut-in
overnight, and brine flow resumed the next day. As shown in
Fig. 7, overall permeability reduction fell from 85% to almost
zero after the oxidizer treatment.
Rheological Measurements. As previously mentioned,
hydrophobically modified polymers show unique rheological
properties. Fig. 8 shows viscosity measurements over a 30-
minute time period for polyDMAEMA and two
hydrophobically modified polyDMAEMA samples. The
polyDMAEMA test revealed essentially constant viscosity for
30 minutes at shear rates ranging from 20 to 1,000 sec-1. The
HMpolyDMAEMA samples initially showed constant
viscosity, but a rapid increase in viscosity was seen after a
period of time. For the 5% C16 modified polymer, the
viscosity increase was observed at a shear rate of 200 sec-1.
For the 7% C16 modified polymer, the increase occurred at 50
sec-1. While more extensive investigation of the rheological
properties is not presented here, the hypothesis is that this
viscosity increase is due to a change from intra- to inter-
molecular hydrophobic associations. Under low shear
conditions, intramolecular associations dominate. However,
under higher shear conditions these associations break,
allowing the polymer chains to stretch and experience
intermolecular associations. These intermolecular associations
are believed to result in the rapid increase in
viscosity observed.
This rheological phenomenon could have implications in
the use of this polymer system. As mentioned previously, in
some core flow tests no pressure increase was seen even after
500 mL of treatment had been flowed into the core. One test
has been run to investigate the effect of treatment flow rate. In
this test, 245 mL of treatment was pumped at 2 mL/min, with
no pressure increase. The flow rate was then increased to
4 mL/min, and after pumping only 40 additional mL of
treatment the pressure had increased to 400 psi (in this case
the treatment was stopped at 400 psi rather than 500 psi). This
phenomenon is not new, and a recently published paper
discusses a “flow induced adsorption” of polymers at various
treatment flow rates.13
Conclusions
At this point, the hydrophobically modified polyDMAEMA
has been successfully taken through the scale-up procedures to
commercial quantities and is awaiting field trials. Based upon
the laboratory investigation, the following conclusions can
be drawn:
• Hydrophobic modification appears to improve the
brine permeability reduction for both polyacrylamide
and polyDMAEMA.
• The hydrophobic modification of polyDMAEMA
improves the brine permeability reduction in high-
permeability sandstone cores at residual oil
saturation, as compared to a previously disclosed
hydrophilically modified polyDMAEMA.
• The target goals of 80% brine permeability reduction
and much lower oil permeability reduction have been
met with the HMpolyDMAEMA.
Acknowledgements
The authors thank Halliburton and British Petroleum for their
support and permission to publish this work.
References
1. Eoff, L. et.al.: “Structure and Process Optimization for the Use of
a Polymeric Relative-Permeability Modifier in Conformance
Control,” paper SPE 64985 presented at the 2001 SPE
International Symposium on Oilfield Chemistry, Houston, Texas,
13-16 February.
2. Wang, T.K, Iliopoulos, I., and Audebert, R.: In Water-Soluble
Polymers. Synthesis, Solution Properties and Applications,
Shalaby, S.W., McCormick, C. L, and Butler, G.B., eds. ACS
Symposium Series 467, American Chemical Society,
Washington, DC (1991) p 218.
3. Polymers in Aqueous Media: Performance Through Association,
Glass, J.E., ed. Advances in Chemistry Series 223, American
Chemical Society, Washington, DC (1989).
4. McCormick, C.L, Bock, J, and Schulz, D.N.: Encyclopedia
Polymer Science and Engineering, 2nd Ed., Mark, H.F., Bikales,
N.M., Overberger, C.G., and Menges, GT., eds. Wiley-
Interscience: New York (1989) vol. 17, p 730.
5. Hydrophilic Polymers: Performance with Environmental
Acceptance, Glass, J.E., ed.. Advances in Chemistry Series 248,
American Chemical Society: Washington, DC (1996).
6. Taylor, K.C. and Nasr-El-Din, H. A. J.: “Water-Soluble
Hydrophobically Associating Polymers for Improved Oil
Recovery: A Literature Review.” J. Petro. Sci. Eng. (1998) 19,
289. Paper SPE 29008 presented at the 1995 SPE International
Symposium, San Antonio, Texas, 14-17 February.
7. Audibert-Hayet, A. et al.: “Novel Hydrophobically Modified
Natural Polymers for Non-damaging Fluids,” paper SPE 56965
presented at the 1999 Offshore Europe Conference, Aberdeen,
Scotland, 7-9 September.
8. WO 00/73623 (2000) Issued to ExxonMobil Research and
Engineering Company, New Jersey.
9. Lijian, D. and Biao, W.: “Hydrophobically Associating
Terpolymer and its Complex with a Stabilizer in Brine for
Enhanced Oil Recovery,” paper SPE 29007 presented at the 1995
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Antonio, Texas, 14-17 February.
10. Volpert, E. et al.: “Adsorption of Hydrophobically Associating
Polyacrylamides on Clay.” Langmuir (1998) 14, 1870.
11. Zaitoun, A., Kohler, N. and Guerrini, Y.: “Improved
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Recovery Symposium, Tulsa, 3-5 April.
SPE 80206 5

13. Chauveteau, G., Denys, K. and Zaitoun, A.: “New Insight on presented at the 2002 SPE/DOE Improved Oil Recovery
Polymer Adsorption Under High Flow Rates,” paper SPE 75183 Symposium, Tulsa, 13-17 April.

Table 1—X-Ray Diffraction Table 2—Core Physical Properties

Analysis of Sandstone Cores Figure Core Core Core Permeability
Sample Berea Brown Number Length (in.) Diameter (in.) Before Treatment (md)
(%) Sandstone Sandstone 2 5.8 1.0 18 (Sor)
Quartz 74 95 3 5.5 1.0 830 (Sor)
K Feldspar 8 2 4 5.8 1.0 610 (Sor)
Na Feldspar 1 — 5 5.5 1.0 650 (Sor)
Calcite — — 6 5.7 1.0 149 (Swi)
Aknerite 7 Trace 7 5.4 1.0 875 (Sor)
Siderite Trace —
Kaolinite 7 1
Mica 3 Trace
Goethite Trace 2
Soluble Fe 1 1

Fig. 1—Effective permeability to water reduction vs. % hydrophobe substitution at Sro, using polyacrylamide polymers at 175°F in
Berea sandstone.
6 SPE 80206

Fig. 2—Sro, Berea core, 230°F, 4,000-ppm HMpolyDMAEMA, 400-mL treatment.

Fig. 3—Sro, brown sandstone core, 90°F, 2,000-ppm HMpolyDMAEMA, 35-mL treatment.
SPE 80206 7

Fig. 4—Sro, brown sandstone core, 150°F, 2,000-ppm HMpolyDMAEMA, 250-mL treatment.

Fig. 5—Sro, brown sandstone core, 200° F, 6,000-ppm HMpolyDMAEMA, 53-mL treatment.
8 SPE 80206

Fig. 6—Swi, berea core, 200°F, 6,000-ppm HMpolyDMAEMA, 8-mL treatment.

Fig. 7—Sro, brown sandstone core, 200°F, 6,000-ppm HMpolyDMAEMA, 500-mL treatment, followed by 25 mL of oxidizer.
SPE 80206 9

Fig. 8—1% solution viscosities of polyDMAEMA and 5% C16 and 7% C16 modified polyDMAEMA.