Journal of Minerals & Materials Characterization & Engineering, Vol. 1, No.2, pp97-109, 2002
Printed in the USA. All rights reserved
Gerard T. Caneba and Jay Axland
Department of Chemical Engineering, Michigan Technological University,
1400 Townsend Drive, Houghton, MI 49931
This paper pertains to the possible use of newly-synthesized vinyl
acetate/acrylic acid (VA/AA) copolymer to help recover trapped crude oil, an
important mineral resource. The proposed approach is to use the copolymer as a
foaming surfactant (in water or brine), which will be driven by a gas, such as
carbon dioxide or nitrogen. Neutralized forms of the copolymer result in an
anionic surfactant, which has been found to have minimal adsorption onto the
rock matrix. The neutralized VA/AA copolymers synthesized in this study are
found to outperform other anionic surfactants and even more adsorbing nonionic
surfactants. Due to the long chain nature of the hydrophilic groups of nonionic
surfactants, they are found to produce better foams than anionic ones. Since
VA/AA copolymers have long chain hydrophilic groups, it is not surprising that
they are good foaming agents as well. Optical microscopy of VA/AA emulsions
reveal that they form microscopic network surface structures, which are
presumably due to liquid crystalline formation in macromolecular scale.
Gerard T. Caneba and Jay Axland Vol. 1, No. 2
At a time when the economic recovery is threatened by potentially high crude oil prices
due to increased demand, the authors are compelled to put on-line promising new oil production
technologies. Current domestic production levels have been dropping in recent years, even
though it is widely known that there are still about 377 billion barrels of oil trapped within
mineral rock matrices.1 New more efficient production technologies are needed to recover more
of the oil originally in place (OOIP) from domestic sources.
Recently, authors developed an efficient manufacturing method for producing
amphiphilic copolymers of vinyl acetate (VA) and acrylic acid (AA) at AA contents as low as 4
wt %. A process and composition-of-matter patent has recently been submitted to the U.S.
Patent and Trademark Office.2 The conceptual basis of the synthesis method is the so-called free-
radical retrograde-precipitation polymerization (FRRPP) process.3-6 Early studies have indicated
that these block copolymers have good foaming capabilities, especially for micellar foam-based
enhanced oil recovery applications.7
Aside from the widely positive oil recovery performance characteristics of VA-AA
copolymers that will be described below, a review of the raw material cost structure also points
to its possibility of being commercially available in the future. Table 1 below shows selling
prices of some monomers and polymers in the market.
In terms of the manufacturing method used, the VA-AA-based copolymers would be
similar in cost structure to those used for producing general purpose propylene and crystal
polystyrene. These two materials are diluted in a solution environment, just as the VA-AA
system is. Differences between polymer and monomer prices for these materials is in the
$0.114-0.27/lb range. This is the same cost/lb associated with the formation of the VA-AA
copolymers from the monomers. With a 30% profit (based on figures from industry contacts),
the cost of producing the VA-AA copolymers is in the order of $1/lb.
Based on the prices given in Table 1 and comparisons of manufacturing procedures with
the method used in this paper, it is possible that poly(vinyl acetate) can be produced and sold at
$2.00/kg. If copolymerization is made with acrylic acid, $0.20/kg will be added to the cost (As
indicated in Reference B of Table 1). This translates to an overall cost of $1.00/lb of dry VA-
AA copolymer. Therefore, we have two approaches to the estimation of the same selling price
for the VA-AA copolymers at $1.00/lb.
In CO2 flooding oil recovery operations, the VA/AA copolymers are supposed to be good
foaming surfactants. Its polymeric nature results in the capability to form surfaces with
relatively large radii of curvature. Since its hydrophobic part is an ester, the interface is
relatively stable in the presence of hydrocarbons from the crude oil. After neutralization of the
acid, the polymer is stable in brine solutions, since brine acts as a buffering agent. It is worth
noting that good foaming surfactants for CO2 flooding operations have oxygenated hydrophobic
groups.8 The more the oxygenated groups, the better. The drawback is that the cost of the
foaming surfactant increases as well. It is possible that the VA/AA copolymer will be cost-
effective because the raw material cost is relatively low, while manufacturing process occurs
under mild operating conditions at reasonable yields (currently up to 29 wt % in solution, almost
100% yield in solid). Final product can be in the form of a concentrated self-emulsion (with
some alcohol) in water or as a dried solid.
Vol. 1, No. 2 Vinyl Acetate-Acrylic Acid Copolymer for Enhanced Oil Recovery
Table 1. Selling prices of some commodity monomers and polymers
Type of Monomer
or Polymer
Monomer or Polymer Selling PriceA
Ethylene $0.19/lb
Propylene $0.145/lb
Vinyl Chloride $0.20/lb
Styrene $0.23/lb
Acrylonitrile $0.385/lb
Vinyl Acetate $0.49/lb
Methyl Methacrylate $0.60/lb
Methyl Acrylate $0.83/lb
Propylene Oxide $0.64/lb
Ethylene Oxide $0.45/lb
Acrylic Acid $0.87/lb
Acrylamide $0.80
Polyethylene, Low
Polyethylene, High
Polypropylene, General
Polystyrene, Crystal $0.50/lb
Polystyrene, Expandable
to Foams
General Purpose
Poly(vinyl acetate)
(dry basis)B
Poly(vinyl acetate) beads
and other dry forms
ABased on March 25, 2002 issue of Chemical Market Reporter
BFrom “Concise Encyclopedia of Polymer Science and Engineering”, J.L. Kroschwitz, Ed., John
Wiley and Sons, New York, 1990, pp. 1264-1270.
Estimates indicate that over the next 20 years, U.S. oil consumption will increase by
33%.9 This increase amounts to an additional rate of consumption of 6 million barrels per day or
2.19 billion barrels per year. At the same time domestic production has been decreasing at the
rate on 1.5 million barrels per day or 548 million barrels per year.
This increasing dependence on foreign sources of crude oil coupled with the uncertain
political and military situation in the Middle East exposes the United States to future oil price
volatility. The availability of improved production methods should at least have a stabilizing
effect on petroleum prices, and it might also help fill in temporary foreign production shortfalls.
Gerard T. Caneba and Jay Axland Vol. 1, No. 2
For the relatively mild situation of increase of oil prices from early1999 to late 2000 by
about $20/barrel (reaching $30/barrel at the end of the year 2000), the effect translated to an
import of roughly $80 billion/year or a difference of 0.9% of the gross domestic product. More
specific effects of this oil price increase include:10
1. Heating bills of New Englanders, who depend on heating oil, rose by 27%.
2. Du Pont, a chemical company that is dependent on petrochemical products, faced an increase
of $1.3 billion in raw materials cost.
3. Georgia-Pacific’s Northwest paper mill closed down and laid off 800 workers until diesel
generators could be installed.
4. Trucking bankruptcies in the year 2000 was at an all-time high of 3,500 due to a 140%
increase in diesel cost.
5. Farm production cost increased by 30%.
In this work, the potential of using VA/AA-based copolymers as foaming surfactants in
the recovery of crude oil that is trapped in various rock formations is investigated. Exploitation
of new technologies for the recovery of such an important mineral resource has recently attained
an urgent prominence, due to decreasing domestic production amidst increasing demand.
Background experimental work for the formation of the VA/AA copolymer used in this
work are presented elsewhere.2,7 An atmospheric static foam test method8 has been employed in
order to determine comparative performance of the neutralized VA/AA surfactant. In a 25-ml
graduated cylinder, 10 ml of 0.5 wt % surfactant in brine (1.5X, which contained 15.57 wt %
NaCl and 1.14 wt % CaCl2) and 3 ml crude oil were mixed by vertical shaking, and the foam
volume measured vs. time. Two kinds of crude oil were used, a heavy one and a light one. Both
were obtained from Citgo Corporation.
Emulsions from VA/AA copolymers in distilled water were viewed using an optical
microscope (Zeiss Axioplan 2 from Zeiss, Thornwood, NY) at 100X and 400X magnifications.
A drop of emulsion was placed between glass slides. Frames were captured using the Scion
ImagePC computer software and stored onto disks as an image files.
Vol. 1, No. 2 Vinyl Acetate-Acrylic Acid Copolymer for Enhanced Oil Recovery
Results and Discussion
Table 2 shows the results of the static foaming test in comparison with literature values.
Table 2. Comparative foaming performance of VA/AA block copolymer compared with other
oxygenated surfactants.
Surfactant Temperature,
oC Organic Material Foam Volume, ml
VA/AA (B6-1)A 67 Bear Lake CrudeB 4-5
VA/AA (B6-1) 20 Bear Lake Crude 2.3
Tergitol XDC 20 Bear Lake Crude 1.6
VA/AA (B6-1) 20 50/50 v/v
75 50/50 v/v
75 50/50 v/v
75 50/50 v/v
75 50/50 v/v
Alcohol Ethoxylate,
75 50/50 v/v
AThe Code B6-1 is the neutralized VA/AA block copolymer with 6 wt % AA content
BThis is a crude oil condensate from Bear Lake, Michigan
CTergitol XD is an ethylene oxide/propylene oxide block copolymer that is produced by Union
Carbide, which is a relatively expensive nonionic surfactant
It can be seen from Table 2 that the neutralized VA/AA block copolymer outperforms (B6-1)
other oxygenated surfactants. It is worth noting that the higher the proportion of oxygenated
material in the surfactant the better is its foaming performance.8
In another set of experiments, light and heavy crude oil (from Citgo Corp.) were used in
the static foam test column. Here, the foam volume vs. time was monitored. VA/AA-based
surfactants were compared with commercial alcohol ethoxylates (Brij 78 and 721) and
ethoxylated alkylphenols (Triton X-155 and X-705, and Igepal DM-880, DM-970, and CA-890),
which are some of the better nonionic foaming surfactants in the market at reasonable prices.
The test was conducted at 70oC. Figure 1 shows that VA/AA surfactants (B6-1 and 6/25/02
Products) surfactant systems have higher foam volumes compared other nonionic foaming
surfactants in both light and heavy crude. It is worth mentioning that the Tergitol XD surfactant
Gerard T. Caneba and Jay Axland Vol. 1, No. 2
used to generate data in Table 2 resulted in a negligible foam volume at the higher operating
temperature of 70oC.
Figure 2 shows results of comparison of foam volumes vs. time between VA/AA-based
surfactants and commercially available anionic surfactants. Features of the anionic surfactants
used are:
1. Triton H55 – Phosphate Esters, potassium salt
2. Rhodacal DS10 – Sodium Dodecyl Benzene Sulfonate
3. Rhodapex CO436 – Sulfates and Sulfonates of Oils and Fatty Acids
Again, VA/AA-based surfactants outperform some of their anionic counterparts. The difference
here and Figure 1 is that nonionic surfactants seem to be better foam formers than anionic types.
Also, it is evident that longer chain nonionics (higher numbered Brij, Triton, and Igepal) and
anionics tend to be better foaming surfactants than their shorter counterparts.
Figure 3 shows a network surface structure of a VA/AA-based emulsion with 6.6 wt %
solids. The repeat unit in the network structure is between 5 and 10 µm. The formation of the
network or bicontinuous surfactant structure is well-established in relatively high molecular
weight ethylene oxide/propylene oxide segmented block copolymer nonionic surfactants, and it
has been ascribed to the formation of liquid crystalline macromolecular assemblies.12 Upon
dilution, the emulsion showed 10 µm spherical domains that could form aggregates up to about
60 µm in size (Figure 4). In Figure 5, bubble surfaces are shown with the network surfactant
Gas-flooding enhanced oil recovery has been commercialized in the 1980s, and it has
become a great success story.13 The continued success depends on the availability of better-
performing and lower cost surfactants. Estimates vary, but the amount of oil recoverable from
gas-flooding operations is in the tens of billions of barrels here in the United States. The
incremental cost of surfactant-flooding operations had been pegged at $8-12/barrel of oil,14 in
which a substantial fraction of that is the cost of surfactants and other chemicals. These figures
translate to possible demand for surfactants in the order of billions of pounds per year. More
efficient, lower cost surfactants can amount to billions of dollars in savings, and it may involve
less surfactant use per barrel of oil recovered.
Newly synthesized vinyl acetate-acrylic acid-based copolymers have been shown to be
attractive foaming surfactants for the recovery of crude oil that is trapped within rock matrices.
Results were obtained, based on static foaming tests, and optical microscopy of emulsions.
These new copolymer materials could put micellar foam flooding in the forefront of enhanced oil
recovery, if fully developed.
Vol. 1, No. 2 Vinyl Acetate-Acrylic Acid Copolymer for Enhanced Oil Recovery
1. Obtained from
2. Caneba, G.T. and Dar, Y., 2002, “Free Radical Retrograde Precipitation Copolymers and
Process for making Same”, submitted to U.S. Patent and Trademark Office, January.
3. Caneba, G.T., 1992, “Free-Radical Retrograde-Precipitation Polymerization Process”, U.S.
Patent No. 5,173,551, December;
4. Caneba, G. T., 1992, Adv. Polym. Tech., 11, 277-286;
5. Aggarwal, A., R. Saxena, B. Wang, and G. T. Caneba, 1996, J. App. Polym. Sci., 62, 2039-
6. Wang, B., Y. Dar, L. Shi, and G. T. Caneba, 1999, J. App. Polym. Sci., 71, 61-74.
7. Caneba, G.T., 2002, Proceedings of the American Institute of Chemical Engineers Annual
Meeting, Indianapolis, IN, November 3-8.
8. Borchardt, J.K., Bright, D.B., Dickson, M.K., and Wellington, S.L., 1988, “Surfactants for
Carbon Dioxide Foam Flooding”, in: Surfactant-Based Mobility Control – Progress in
Miscible-Flood Enhanced Oil Recovery, D.H. Smith, Ed., ACS Symposium Series, 373,
Washington, D.C., Chapter 8.
9. “National Energy Policy: Report of the National Energy Policy Development Group”, U.S.
Government Printing Office, Washington, D.C., May, 2001, p. x.
10. Ibid., Chapter 2.
11. Obtained from
12. Chu, B. and Z. Zhao, 1996, “Nonionic Surfactants”, Nace Vaugn, Ed., Marcel Dekker, NY,
pp. 67-143.
13. Klins, M.A. and C.P. Bardon, 1991, “Carbon Dioxide Flooding”, in:Basic Concepts in
Enhanced Oil Recovery Processes, M. Baviere, Ed., Elsevier Applid Science, New York.,
14. Obtained from
Gerard T. Caneba and Jay Axland Vol. 1, No. 2
The authors wish to acknowledge Mr. David Colquhoun in the research group of Dr.
Susan Bagley in the Michigan Tech Department of Biological Sciences, for his assistance in the
use of their optical microscope for viewing the surfaces of our VA/AA-based emulsions and
Vol. 1, No. 2 Vinyl Acetate-Acrylic Acid Copolymer for Enhanced Oil Recovery
Time, min
Foam Volume, ml
Brij 78, Heavy
Brij 78, Light
Brij 721, Light
Brij 721, Heavy
B6-1, Light
B6-1, Heavy
6/24/02, Light
Igepal DM970,
Igepal CA890,
Triton X705,
Igepal DM880,
Triton X155,
Figure 1. Static foam volume vs. time for the VA/AA-based copolymers (B6-1 and 6/24/02
Emulsions) and commercially available nonionic surfactants (Brij, Triton, and Igepal surfactants)
at 70oC. Light and heavy crude oil was used in this test.
Gerard T. Caneba and Jay Axland Vol. 1, No. 2
Time, min
Foam Volume, ml
Triton H55
Rhodacal DS10
Figure 2. Static foam volume vs. time for the VA/AA-based copolymers (B6-1 and 6/24/02
Emulsions) and commercially available anionic surfactants (Triton, Rhodacal, and Rhodapex
surfactants) at 70oC. Light crude oil was used in this test.
Vol. 1, No. 2 Vinyl Acetate-Acrylic Acid Copolymer for Enhanced Oil Recovery
Figure 3. Optical micrograph of a surface of a VA/AA-based emulsion (6.6 wt % solids) at
400X magnification, showing a bicontinuous network structure with 5-10 µm open cells.
Gerard T. Caneba and Jay Axland Vol. 1, No. 2
Figure 4. Optical micrograph of a surface of a VA/AA-based diluted emulsion (from 6.6 wt %
solids) at 400X magnification, showing about 10 µm spherical domains and aggregates up to
about 60 µm in size.
Vol. 1, No. 2 Vinyl Acetate-Acrylic Acid Copolymer for Enhanced Oil Recovery
Figure 5. Optical micrograph of a surface of a VA/AA-based diluted emulsion (from 6.6 wt %
solids) at 100X magnification, showing a surface of a bubble that has a bicontinuous network