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Chap - 06 Polimer Kimyasi
Chap - 06 Polimer Kimyasi
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
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Polymer Chemistry and Applications 6.2 Revision No: A-0 / Revision Date: 03·31·98
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_______________________
…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-SAL has greater tolerance
not water- the protective shell coating of amy- to hardness and a slightly higher tem-
soluble… lopectin to release the inner amylose. perature stability than MY-LO-JEL. It also
The starch granules are heated until the 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.
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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-0 / Revision Date: 03·31·98
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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 “drill-in” and workover/completion
— in the drillstring, for instance — the fluid applications. It viscosifies brines,
viscosity of the mud system decreases. including seawater, NaCl, KCl, CaCl2,
Under the very high shear rates experi- NaBr and, to some extent, even CaBr2. It
enced in the drill bit nozzles, the fluid is degradable with oxidizers (bleach) or
thins dramatically until it behaves enzymes, and is acid-soluble for easy
almost like water. Under lower-shear- clean-up. It develops gel strengths and
rate conditions — in the annulus, for easily suspends acid-soluble materials
instance — hydrogen bonding forms like CaCO3. FLO-VIS is a special, clarified
again and viscosity increases. Under version of xanthan. The clarified version
static conditions, xanthan fluids dis- has been processed to remove any bac-
play thixotropic characteristics provid- terial residue for clean fluid applications.
ing gels. Xanthan gum and a similar
MODIFIED NATURAL POLYMERS
biopolymer called welan gum are two
Modified of only a few commercial polymers Modified natural polymers are very
natural that produce thixotropic properties common in drilling fluids. Cellulose
(gels) in water-base fluids. and starch are two natural polymers
polymers that frequently are used to produce
The concentration of xanthan neces-
are very sary to develop thixotropic properties modified natural polymers. The modi-
common depends on the makeup water. Only fied versions can have substantially
0.5 lb/bbl may be sufficient for a highly different properties than the original,
in drilling natural polymers. For drilling fluids,
weighted freshwater system while it
fluids. may take 2 to 3 lb/bbl in a KCl or a nonionic natural polymers — such as
high-salinity NaCl system. In high- cellulose and starch — are modified
salinity brines, xanthan polymer — like to polyelectrolytes.
other water-base polymers — does not Polyelectrolytes. Many polymers are
hydrate easily and, to some extent, not water-soluble and therefore are not
remains coiled. In freshwater, the applicable to water-base drilling fluids
polymer expands and the polymer — unless they are modified. To obtain
branches come in contact, allowing water solubility, polymers are some-
hydrogen bonding and the resulting times modified to polyelectrolytes. This
thixotropy to develop more easily. modification involves an alteration of
Xanthan gum (such as DUO-VIST and the repeating unit of the polymer. A
FLO-VIST) is added to drilling fluids for a polyelectrolyte is a polymer that dis-
number of applications. Most often, it solves into water, forming polyions and
is used as a clay substitute to impart counter ions of the opposite charge. A
thixotropic properties. Xanthan gum is polyion has charges that repeat along
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CHAPTER
the polymer chain. The charges can be occurs when polymers become entan-
positive, as in a cationic polymer, or gled with one another by clinging to
negative, as in an anionic polymer. A a limited amount of water.
few examples of cationic polymers exist,
PH EFFECTS
but most often polymers in drilling
Polymer fluids are negatively charged. Polymer solubility is affected by pH.
solubility The effectiveness of a polyelectrolyte The pH often determines the extent of
depends on the number of available the ionization of the functional groups
is affected along the polymer chain. For instance,
sites on the polymer which, in turn,
by pH. depends on the following factors: the most common functional group
• The concentration of the polymer. found in water-base polymers is the
• The concentration and distribution carboxyl group. The ionized carboxyl
of the ionizable groups. group is a distinguishing feature in
• The salinity and hardness of the fluid. most anionic polymers including
• The pH of the fluid. CMCs, PHPAs and xanthan gums,
to name a few.
With an increasing number of ionized
sites on the polymer, it tends to extend
O–
and uncoil. This is due to mutual charge
repulsion that elongates and stretches C
the polymer into a configuration that
O
gives the maximum distance between
like charges. In spreading out, the poly- Figure 5: Ionized carboxyl group.
mer exposes the maximum number of
charged sites. Spreading out allows the As seen in Figure 5, the ionized car-
polymer to attach to clay particles and boxyl group has a double-bonded oxy-
to viscosify the fluid phase. gen and a single-bonded oxygen on the
terminal carbon. Ionization is accom-
CONCENTRATION EFFECTS plished by reacting the carboxyl group
As discussed, polymers assume a with an alkali material such as caustic
stretched or elongated configuration soda. By ionizing the previous insolu-
when dissolved in the water phase of ble carboxyl group, solubility of the
a drilling fluid. This configuration is polymer occurs (see Figure 6).
not rod-like but twisted and curled
to obtain the maximum distance O O–
between like charges on the polymer. C
NaOH
C
In dilute concentrations, the polymer
OH O
hydrates a thick envelope of water
(about 3 or 4 water molecules). There Insoluble Soluble
is an electrostatic repulsion between
these envelopes, whose surfaces are Figure 6: Polymer solubility.
large when the fully extended shape
The sodium carboxylate group draws
is assumed. This large surface area
water to it through its anionic charged
contributes to the viscosity effects
site. When the polymer is added to
As the of the polymer.
water, the sodium ion releases from the
polymer As the polymer concentration
polymer chain and leaves behind a neg-
increases, the envelopes of water sur-
hydrates rounding the polymers decrease. As
atively charged site. The polymer is now
anionic and free to hydrate water. As the
water… more polymer vies for less water, the
polymer hydrates water, the envelope
viscosity effect is an increase in viscosity. This
increases.
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_______________________ 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
_______________________
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_______________________
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
_______________________
_______________________
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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 THERMPAC 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), THERMPAC 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.
_______________________
_______________________
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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
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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).
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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.
TACKLE is an pH and can tolerate temperatures to TACKLE 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
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Polymer Chemistry and Applications 6.14 Revision No: A-0 / Revision Date: 03·31·98
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C C C
O NH2 O O– O NH2
n
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Overtreat with polymer, and the system • Geometry and size of the settling pit.
thins out too much. • Retention time.
The degree of bentonite extension • Temperature.
depends on the following factors:
It is recommended that FLOXIT be
• The MW and the ratio of acrlyamide
mixed in dilution water at a concen-
to acrylate.
tration of 1 to 2 lb/bbl before adding
• The size and hydration of the particle.
it to the system. Again, pilot testing is
• The salinity and hardness of the
necessary to determine the optimum
makeup water.
concentration.
• The concentration of the PHPA
polymer. HIGH-TEMPERATURE
SYNTHETIC POLYMERS
PHPA also FLOXIT.E PHPA also can be used as a
flocculant. Flocculation is the process by Due to the thermally stable carbon-
can be used carbon linkage that makes up the
which individual particles are connected
as a in loosely bound, large aggregates by a backbone of synthetic polymers, high-
flocculant. flocculating polymer. The resulting mass temperature polymers are synthetically
of linked particles increases to the point derived. Several high-temperature poly-
at which the solids agglomeration falls mers are available for drilling fluids. A
out of suspension. Settling is most number of them are prepared from the
effective when the system is static. AMPS (2-acrylamido-2-methyl propane
The mechanism involved in floccula- sulfonic acid) monomer. AMPS was
tion is very much like the mechanism covered earlier in this chapter in con-
used for bentonite extension. PHPA is junction with TACKLE. AMPS is used in
also effective in both applications. It the preparation of TACKLE to improve
should be noted that PHPA is not as tolerance to solids, salinity and hard-
effective at flocculating systems that ness at high temperatures.
contain bentonite. Since bentonite AMPS is also used to improve the
breaks up into colloidal-size, hydrated high-temperature tolerance to conta-
solids, bentonite does not settle. The minants in fluid-loss-control additives.
small hydrated particles do not have Examples of copolymers and terpoly-
enough density to settle. mers that incorporate the AMPS
The use of FLOXIT is limited to clear- monomer or other sulfonated monomers
water drilling applications. Once solids are the Hoechst’s Hostadrill 2825,
build in the water or the system is Drilling Specialties’ Driscal-D and SKW’s
weighted, the product is no longer use- Polydrill. The manufacturers of these
ful. Determining the optimum concen- materials claim that their respective
tration of FLOXIT must be determined by polymers withstand salt and hardness
pilot testing. The effectiveness of the at temperatures to 400°F (204°C).
flocculation depends on the interaction Chemical structures for Hostadrill and
of the polymer with the solids, which Polydrill are given in Figures 19 and 20.
in turn depends on the following: 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
• Rheological properties of the system. extended period of time. It has the effect
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CH CH CH2 CH
O=C C=O
O SO3Na
n
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