Introduction
Polymers have been used in drilling sources. Other, more-specialized poly-
fluids since the 1930s, when cornstarch mers are modified natural polymers,
was introduced as a fluid-loss-control while still other more-sophisticated
additive. Since that time, polymers have polymers are derived from synthetics.
become more specialized and their The unlimited potential of polymer
acceptance has increased accordingly. development makes polymers applicable
Polymers are part of practically every to virtually every drilling fluid function.
water-base system in use today. Indeed, With polymer technology, it is possible
some systems are totally polymer- to analyze a situation on a molecular
dependent and are termed broadly level and design a polymer with the spe-
as polymer systems. cific properties to address the situation.
A wide array of polymers is available For this reason, polymers have an
today. Some polymers — like starch, unlimited future in drilling fluids.
for instance — originate from natural
Polymer Chemistry and Applications 6.1 Revision No: A-0 / Revision Date: 03·31·98
CHAPTER
Polymer Chemistry and Applications 6.2 Revision No: A-0 / Revision Date: 03·31·98
CHAPTER
_______________________
…O
OH H α O
OH H
O
OH H
O
OH H
…
_______________________
_______________________ H OH H OH H OH H OH
_______________________
Figure 2: Amylose.
_______________________
O…
_______________________
6
_______________________ CH2 Oα O O
H•OH
_______________________
O
O O O
_______________________
O
x
_______________________
_______________________
O
α y
_______________________
O
_______________________ O O
4
αO 3
H•OH
O
O O O 1
x
O
y
…O
Figure 3: Amylopectin.
source for drilling fluids. Starch con- pregelatination. Once dispersed, the
sists of two polysaccharides: amylose starch hydrates water. It is subsequently
and amylopectin. Amylose, a chain dried and bagged as the final product. It
of carbohydrate rings, makes up the is non-ionic and soluble in saturated
straight chain backbone of the starch saltwater as well as freshwater.
molecule. Amylopectin is a highly MY-LO-JELE is a cornstarch consisting
branched chain of carbohydrate rings of an average of about 25% amylose and
that branches off from an amylose 75% amylopectin. POLY-SALE is a potato
backbone. The ratios of the amylose starch which is slightly different from
and amylopectin fractions determine cornstarch. Potato starch has a slightly
the properties of the starch. higher molecular weight than corn-
Starch in Starch in its raw form is not water- starch and also has a higher concentra-
its raw soluble; it simply floats around as starch tion of amylose to amylopectin. For
particles. To make starch effective in these reasons, it functions somewhat
form is drilling fluids, it is necessary to rupture differently. POLY-SALE has greater toler-
not water- the protective shell coating of amy- ance to hardness and a slightly higher
soluble… lopectin to release the inner amylose. temperature stability than MY-LO-JELE. It
The starch granules are heated until the also produces slightly more viscosity.
cells rupture, which allows the amylose The biggest drawback to the use of
to disperse. This process is known as starches is their tendency to ferment.
Polymer Chemistry and Applications 6.3 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
CH2OH CH2OH
O O
O O
OH
OH OH
O
CH2OCCH2 O
O
OH
HO
COOOM⊕
O
O
OH
CH2
COOOM⊕ O
O O OH
C
M⊕ ≡ Na, K, 1⁄2/Ca
OH OH
CH2 O
Polymer Chemistry and Applications 6.4 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
attractive forces holding the polymers used instead of loading a fluid with clay
together are pulled apart. As the hydro- solids to obtain viscosity and suspen-
gen bonding breaks, the viscosity of the sion. This is beneficial in many ways,
fluid thins. When the shear is removed, most notably by maintaining optimum
the polymer chains resume their inter- suspension and carrying capacity in flu-
molecular hydrogen bonding and their ids without increasing solids loading.
original viscosified state returns. This property makes xanthan gum the
Xanthan polymer produces pseudo- polymer of choice for increasing viscos-
plastic or shear-thinning fluids and gel ity in extended-reach and horizontal
structures. As the shear is increased, vis- wells, especially when the wells involve
cosity is progressively decreased. When low annular velocities.
the shear is removed, the original vis- Xanthan has several properties that
cosity of the fluid is completely recov- make it an ideal polymer for clay-free
ered. Under high-shear-rate conditions “reservoir drill-in” and workover/com-
— in the drillstring, for instance — the pletion fluid applications. It viscosifies
viscosity of the mud system decreases. brines, including seawater, NaCl, KCl,
Under the very high shear rates experi- CaCl2, NaBr and, to some extent, even
enced in the drill bit nozzles, the fluid CaBr2. It is degradable with oxidizers
thins dramatically until it behaves (bleach) or enzymes, and is acid-solu-
almost like water. Under lower-shear- ble for easy clean-up. It develops gel
rate conditions — in the annulus, for strengths and easily suspends acid-
instance — hydrogen bonding forms soluble materials like CaCO3. FLO-VIST
again and viscosity increases. Under is a special, clarified version of xan-
static conditions, xanthan fluids dis- than. The clarified version has been
play thixotropic characteristics provid- processed to remove any bacterial
ing gels. Xanthan gum and a similar residue for clean fluid applications.
biopolymer called welan gum are two
Modified MODIFIED NATURAL POLYMERS
of only a few commercial polymers
natural that produce thixotropic properties Modified natural polymers are very
(gels) in water-base fluids. common in drilling fluids. Cellulose
polymers and starch are two natural polymers
The concentration of xanthan neces-
are very sary to develop thixotropic properties that frequently are used to produce
common depends on the makeup water. Only modified natural polymers. The modi-
0.5 lb/bbl may be sufficient for a highly fied versions can have substantially
in drilling different properties than the original,
weighted freshwater system while it
fluids. may take 2 to 3 lb/bbl in a KCl or a natural polymers. For drilling fluids,
high-salinity NaCl system. In high- nonionic natural polymers — such as
salinity brines, xanthan polymer — like cellulose and starch — are modified
other water-base polymers — does not to polyelectrolytes.
hydrate easily and, to some extent, Polyelectrolytes. Many polymers are
remains coiled. In freshwater, the not water-soluble and therefore are not
polymer expands and the polymer applicable to water-base drilling fluids
branches come in contact, allowing — unless they are modified. To obtain
hydrogen bonding and the resulting water solubility, polymers are some-
thixotropy to develop more easily. times modified to polyelectrolytes. This
Xanthan gum (such as DUO-VIST and modification involves an alteration of
FLO-VIST) is added to drilling fluids for a the repeating unit of the polymer. A
number of applications. Most often, it polyelectrolyte is a polymer that dis-
is used as a clay substitute to impart solves into water, forming polyions and
thixotropic properties. Xanthan gum is counter ions of the opposite charge. A
Polymer Chemistry and Applications 6.5 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
polyion has charges that repeat along occurs when polymers become entan-
the polymer chain. The charges can be gled with one another by clinging to
positive, as in a cationic polymer, or a limited amount of water.
negative, as in an anionic polymer. A
PH EFFECTS
few examples of cationic polymers exist,
Polymer but most often polymers in drilling Polymer solubility is affected by pH.
solubility fluids are negatively charged. The pH often determines the extent of
The effectiveness of a polyelectrolyte the ionization of the functional groups
is affected along the polymer chain. For instance,
depends on the number of available
by pH. sites on the polymer which, in turn, the most common functional group
depends on the following factors: found in water-base polymers is the
• The concentration of the polymer. carboxyl group. The ionized carboxyl
• The concentration and distribution group is a distinguishing feature in
of the ionizable groups. most anionic polymers including
• The salinity and hardness of the fluid. CMCs, PHPAs and xanthan gums,
• The pH of the fluid. to name a few.
With an increasing number of ionized
O–
sites on the polymer, it tends to extend
and uncoil. This is due to mutual charge C
repulsion that elongates and stretches
O
the polymer into a configuration that
gives the maximum distance between Figure 5: Ionized carboxyl group.
like charges. In spreading out, the poly-
mer exposes the maximum number of As seen in Figure 5, the ionized car-
charged sites. Spreading out allows the boxyl group has a double-bonded oxy-
polymer to attach to clay particles and gen and a single-bonded oxygen on the
to viscosify the fluid phase. terminal carbon. Ionization is accom-
plished by reacting the carboxyl group
CONCENTRATION EFFECTS with an alkali material such as caustic
As discussed, polymers assume a soda. By ionizing the previous insolu-
stretched or elongated configuration ble carboxyl group, solubility of the
when dissolved in the water phase of polymer occurs (see Figure 6).
a drilling fluid. This configuration is
not rod-like but twisted and curled O O–
to obtain the maximum distance C
NaOH
C
between like charges on the polymer.
OH O
In dilute concentrations, the polymer
hydrates a thick envelope of water Insoluble Soluble
(about 3 or 4 water molecules). There
is an electrostatic repulsion between Figure 6: Polymer solubility.
these envelopes, whose surfaces are
The sodium carboxylate group draws
large when the fully extended shape
water to it through its anionic charged
is assumed. This large surface area
site. When the polymer is added to
As the contributes to the viscosity effects
water, the sodium ion releases from the
polymer of the polymer.
polymer chain and leaves behind a neg-
As the polymer concentration
hydrates increases, the envelopes of water sur-
atively charged site. The polymer is now
anionic and free to hydrate water. As the
water… rounding the polymers decrease. As
polymer hydrates water, the envelope
viscosity more polymer vies for less water, the
effect is an increase in viscosity. This
increases.
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CHAPTER
Polymer Chemistry and Applications 6.7 Revision No: A-0 / Revision Date: 03·31·98
CHAPTER
_______________________ HO H H
O
H H
O
H O H
OH H OH H
_______________________
_______________________ OH H OH H
H H
O O
_______________________ H H H
O O
_______________________
H OH CH2OCH2COO–Na+ H OH CH2OCH2COO–Na+
_______________________
O O
HO H H H H
_______________________ H O H
OH H OH H
_______________________ 4 I
H OH H H OH H
_______________________ O O
H H H
O O
_______________________ CH2OCH2COO–Na+ H OH CH2OCH2COO–Na+ H OH
n
_______________________
Polymer Chemistry and Applications 6.8 Revision No: A-0 / Revision Date: 03·31·98
CHAPTER
_______________________
CH2OCH2CH2OCH2CH2OH H OCH2CH2OH
_______________________ O
H H
_______________________ H H H O OH H
_______________________
Cellulose + C C OH H H O
_______________________ H H
O O
H H
_______________________ H OH CH2OCH2CH2OH
Ethylene oxide n
_______________________
_______________________
Polymer Chemistry and Applications 6.9 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
which makes it ideally suited for gravel- structure. Also like CMC, the sub-
packing and other operations where the stitution occurs most readily at the
completion fluid contacts the produc- hydroxymethyl group.
…HEC…does tion interval. Since HEC is non-ionic, it THERMPACT UL, a carboxymethyl
not react as does not react as strongly with charged starch, controls fluid loss with a
surfaces as do ionic polymers. This fur- minimum increase in viscosity in
strongly with ther enhances its role as a completion most water-base drilling fluids. It is
charged fluid additive. an alternative to PAC materials in
surfaces HEC has a temperature limitation of systems requiring tight filtration con-
250°F (121°C). It is not affected greatly trol and low rheological properties.
as do ionic by pH (above 10 pH, there may be a THERMPACT UL performs more like a
polymers. minor loss of viscosity) and it is resistant CMC material than a starch. It has a
to bacteria. It is not a thixotropic poly- temperature stability similar to CMC
mer (does not generate gel structures for and PAC (up to 300°F (149°C)) and
suspension) and, in fact, provides little if does not require a bactericide.
any Low-Shear-Rate Viscosity (LSRV), THERMPACT UL is most effective when
although it produces a great deal of applied in drilling fluids containing less
overall viscosity. than 20,000 mg/l Cl– and 800 mg/l
Starch derivatives. As stated earlier in Ca2+. It performs at any pH level and is
this chapter, starch is useful in many compatible with all water-base systems.
applications without chemical modifi- Hydroxypropyl starch. Another
cation. But with chemical modification, example of modified starch is
starch derivatives can be made to have Hydroxypropyl (HP) starch. It is pro-
different properties. Starch can be mod- duced by reacting starch with propylene
ified in such a way that it no longer is oxide. The resulting modified starch is
susceptible to bacterial degradation. It nonionic and is water-soluble. The mod-
also can be made significantly more ification actually adds to the water solu-
temperature-stable with simple modifi- bility of the starch. As with CMS and
cations. A few examples of modified HEC, the substitution occurs at either
starches are given below. the hydroxymethyl group or at either
_______________________ Carboxymethyl Starch (CMS). of the two available hydroxyl groups
Another example of a modified polymer on the ring structure. Also like CMC
_______________________
is carboxymethyl starch. Like CMC, and CMS, the substitution occurs most
_______________________ carboxymethyl starch undergoes a readily at the hydroxymethyl group.
_______________________ carboxylate substitution at either the The result is a substitution of
hydroxymethyl group or at either of propoxylated groups. The D.P. of the
_______________________
the two hydroxyl groups on the ring propoxylated groups is known as the
_______________________
_______________________
…O
OH H α O
OH H
O
OH H
O
OH H
…
_______________________
_______________________ H OH H OH H OH H OH
n
_______________________
Figure 10: Carboxymethyl starch, D.S. = 1.0.
_______________________
_______________________
Polymer Chemistry and Applications 6.10 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
O O O O
H H H H H H H H
H H H H
…O
OH H α O OH H
O
OH H
O
OH H
…
H OH H OH H OH H OH
n
Molar Substitution (M.S.). The M.S. is is better than most starch materials. It
the average number of propylene oxide is thermally stable to 250°F (121°C) in
molecules that have reacted with each brine applications.
starch unit. Once a hydroxypropyl Mor-Rex.E An enzyme-hydrolyzed
group is attached to each unit, it can cornstarch which has been chemically
react further with additional groups modified to a maltodextrin. The hydrol-
in an end-to-end formation. The reac- ysis of the starch results in a product
tion of propylene oxide with starch that is much lower in molecular weight
has similarities to the reaction of cel- (less than 5,000) and imparts a slightly
lulose with ethylene oxide. In each anionic character to the polymer.
case, substitution occurs with a repeat- Mor-RexE has been used in lime-
ing structure that must be defined by base drilling fluids almost exclusively.
its M.S. This is due primarily to its tendency
Many types of HP starch are avail- to increase the calcium solubility in a
able. The properties vary with the D.P., lime-base fluid environment. In such
the D.S. and the degree of polymeriza- an environment, the Mor-RexE poly-
tion of the substituted group (M.S.). mer is further hydrolyzed and Ca2+
FLO-TROLT. An HP starch used primar- attaches to the free carboxylate groups
ily for fluid-loss-control in FLO-PROT formed during hydrolysis. This results
systems. It works in conjunction with in an increased concentration of soluble
calcium carbonate to form an easy-to- calcium. In other words, a lime-base
remove, acid-soluble filter cake. Like system treated with Mor-RexE contains
starch, FLO-TROLT is compatible with more soluble calcium than the same
most makeup brines including seawa- lime-base system without Mor-Rex.E It
ter, NaCl, KCl, CaCl2, NaBr, CaBr2 and is thought that the additional Ca2+ pro-
formate brines. It does not require a vides additional inhibition benefits.
bactericide. Functionally, Mor-RexE acts as a
FLO-TROLT has unique viscosifying deflocculant, which is consistent with
characteristics that make it suitable its size and anionic character. Typical
for “reservoir drill-in” fluid applica- concentrations for Mor-RexE in a lime/
…FLO-TROLT tions. Unlike PAC products, FLO-TROLT Mor-RexE system are 2 to 4 lb/bbl. Like
contributes contributes to LSRV. It works synergis- traditional starch, it is thermally stable
tically with FLO-VIST to increase Low- to about a 200°F (93°C) circulating
to LSRV. Shear-Rate Viscosity (LSRV). temperature and requires a bactericide.
Recommended FLO-TROLT concentra-
SYNTHETIC POLYMERS
tions are 2 to 4 lb/bbl for most applica-
tions, although higher concentrations Synthetic polymers are chemically
are used to achieve lower filtration synthesized, usually from petroleum-
rates. Temperature stability for FLO-TROLT derived products. Unlike natural and
modified natural polymers, synthetic
Polymer Chemistry and Applications 6.11 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
polymers are “built up” from relatively During the drilling of a well, the
Synthetic smaller molecules. Synthetic polymers interaction between the drilled solids
polymers afford an almost unlimited flexibility has a profound effect on the proper-
in their design. They can be tailor- ties of the mud. There is a natural ten-
afford an made to fit almost any application. dency for flocculation to occur (see
almost Their size and chemical composition Figure 13). Flocculation results in an
unlimited can be made to produce properties for overall increase in the rheological
almost any function. properties of the drilling fluid.
flexibility in Frequently, synthetic polymers are
their design. prepared from substituted ethylene. The
polymerization process occurs through
an addition reaction wherein the substi-
tuted ethylene groups are added to the
end of the polymer chain. In the figure
below, the substituted group “A” can be
any functional group.
CH2 = CH
|
A
Note the carbon-carbon backbone and
the unlimited substitution possibilities.
The carbon-carbon backbone is a more
stable linkage than the carbon-oxygen
linkage encountered earlier with starch-
and cellulose-base polymers. The carbon-
carbon linkage is resistant to bacteria
and has temperature stability in excess
of 700°F (371°C). The substitution
groups most likely will degrade before
the carbon-carbon linkage. Figure 13: Flocculation of drill solids.
Polyacrylate. The polymerization of
SPA functions as a deflocculant at low
acrylic acid and the subsequent neutral-
molecular weights (less than 10,000).
ization with sodium hydroxide yields
It is highly anionic and adsorbs on
the polymer Sodium Polyacrylate (SPA).
the active solids in drilling fluids. The
SPA is an anionic polymer that can
adsorbed polymer neutralizes the posi-
function either as a deflocculant or a
tive charges on aggregated particles,
fluid-loss control additive, depending on
which results in mutual repulsion and
the molecular weight of the polymer.
deflocculation. This is best accom-
H H H H
plished with a small polymer. Short-
chain polymers create maximum
adsorption on the particle surfaces and
C CH C CH eliminate the flocculating effect that
occurs when one polymer adsorbs to
COO–Na+ COO–Na+ several particles (see Figure 14).
Polymer Chemistry and Applications 6.12 Revision No: A-0 / Revision Date: 03·31·98
CHAPTER
SPA
20 lb/bbl bentonite equivalent and the
– mud weight is less than 12 lb/gal.
–
+
– TACKLET is also affected by soluble cal-
+ – +
–
+
+ cium, although it is still effective in
+ –
+
+ seawater applications.
+ –
– Copolymerization. So far, this chap-
+
+ – ter has dealt only with homopolymers,
–
+
–
i.e., polymers prepared from identical
– – –
+
+ + + units (or monomers). It is possible to
+ –
start with more than one type of
monomer and undergo polymerization
A copolymer and end up with a copolymer. A copoly-
contains Figure 14: Diagram of SPA and clays.
mer contains two or more different
types of monomers.
two or more Many mud companies use low- Through copolymerization, polymers
different molecular-weight sodium polyacrylate can be made which have different prop-
types of as their primary deflocculant for low- erties than any of the homopolymers
solids, non-dispersed and other poly- alone. Adding more monomers creates
monomers. mer systems. It can be prepared as a a completely new dimension for design
dry powder but usually is available in possibilities. It is possible to use more
liquid form. than a single monomer to impart spe-
SPA functions at much lower concen- cific properties to the finished polymer
trations than lignosulfonates. Typically, product. For instance, one monomer
concentrations of 0.25 to 1.0 lb/bbl are can be used to extend temperature sta-
sufficient to control rheological proper- bility and a second monomer can be
ties. SPA does not depend on alkaline used to inhibit shale.
TACKLET is an pH and can tolerate temperatures to TACKLET is an example of a copolymer.
example of a 500°F (260°C). It performs best in poly- It is prepared from two monomers:
mer systems but is sometimes used as a sodium acrylate (as in SPA) and a
copolymer. stand-alone product in spud mud and monomer known in the industry as
in geothermal applications. AMPS (2-acrylamido-2-methyl propane
SPA is sensitive to high concentrations sulfonic acid). The AMPS monomer
of solids. Since it is a surface-active provides a sulfonate group that imparts
material, it can get overwhelmed in a greater temperature stability and toler-
high-solids environment. It works best ance to solids, salinity and hardness
when the CEC of the mud is less than than the sodium acrylate group alone.
x y x y
Monomer A Monomer B n
Polymer Chemistry and Applications 6.13 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
Polymer Chemistry and Applications 6.14 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
C C C
O NH2 O O– O NH2
n
Polymer Chemistry and Applications 6.15 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
Polymer Chemistry and Applications 6.16 Revision No: A-0 / Revision Date: 03·31·98
CHAPTER
Polymer Chemistry and Applications 6.17 Revision No: A-0 / Revision Date: 03·31·98
CHAPTER
Overtreat with polymer, and the system • Rheological properties of the system.
thins out too much. • Geometry and size of the settling pit.
The degree of bentonite extension • Retention time.
depends on the following factors: • Temperature.
• The MW and the ratio of acrlyamide
It is recommended that FLOXITE be
to acrylate.
mixed in dilution water at a concen-
• The size and hydration of the particle.
tration of 1 to 2 lb/bbl before adding
• The salinity and hardness of the
it to the system. Again, pilot testing is
makeup water.
necessary to determine the optimum
• The concentration of the PHPA
concentration.
polymer.
HIGH-TEMPERATURE
PHPA also FLOXIT.E PHPA also can be used as a
SYNTHETIC POLYMERS
can be used flocculant. Flocculation is the process by
which individual particles are connected Due to the thermally stable carbon-
as a in loosely bound, large aggregates by a carbon linkage that makes up the
flocculant. flocculating polymer. The resulting mass backbone of synthetic polymers, high-
of linked particles increases to the point temperature polymers are synthetically
at which the solids agglomeration falls derived. Several high-temperature poly-
out of suspension. Settling is most mers are available for drilling fluids. A
effective when the system is static. number of them are prepared from the
The mechanism involved in floccula- AMPS (2-acrylamido-2-methyl propane
tion is very much like the mechanism sulfonic acid) monomer. AMPS was
used for bentonite extension. PHPA is covered earlier in this chapter in con-
also effective in both applications. It junction with TACKLE.T AMPS is used in
should be noted that PHPA is not as the preparation of TACKLET to improve
effective at flocculating systems that tolerance to solids, salinity and hard-
contain bentonite. Since bentonite ness at high temperatures.
breaks up into colloidal-size, hydrated AMPS is also used to improve the
solids, bentonite does not settle. The high-temperature tolerance to conta-
small hydrated particles do not have minants in fluid-loss-control additives.
enough density to settle. Examples of copolymers and terpoly-
The use of FLOXITE is limited to clear- mers that incorporate the AMPS
water drilling applications. Once solids monomer or other sulfonated monomers
build in the water or the system is are the Hoechst’s Hostadrill 2825,
weighted, the product is no longer use- Drilling Specialties’ Driscal-D and SKW’s
ful. Determining the optimum concen- Polydrill. The manufacturers of these
tration of FLOXITE must be determined materials claim that their respective
by pilot testing. The effectiveness of polymers withstand salt and hardness
the flocculation depends on the inter- at temperatures to 400°F (204°C).
action of the polymer with the solids, Chemical structures for Hostadrill and
which in turn depends on the follow- Polydrill are given in Figures 19 and 20.
ing: An example of a high-temperature
• Hydratability of the solids. polymer that functions to prevent high-
• The concentration of the solids. temperature gelation is a Sulfonated
• Salinity of the water. Styrene Maleic Anhydride (SSMA)
• Hardness of the water. copolymer. Generally, it is applied to
• Chemical characteristics of the wells at high temperatures prior to log-
polymer. ging runs and at other times when the
• Polymer concentration. drilling fluid is not circulated for an
Polymer Chemistry and Applications 6.18 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER
_______________________ OH R’
_______________________
CH2 C CH2 C
_______________________
_______________________
SO3–Na+ SO3–Na+
n
Polymer Chemistry and Applications 6.19 Revision No: A-1 / Revision Date: 02·28·01