section 9

polymer

polymer
chemistry

contents
introduction ..........................................................................................................................1
polymer types .......................................................................................................................1
polyacrylate, polyacrylamide, and phpa ............................................................2
carboxymethylcellulose (cmc) and polyanionic cellulose (pac) ................2
hydroxyethylcellulose (hec) ...................................................................................4
starch .............................................................................................................................4
guar gum .......................................................................................................................5
xanthan gum ...............................................................................................................5
other naturally derived polymers ........................................................................5
polymer uses .........................................................................................................................5
viscosity .........................................................................................................................6
bentonite extension ..................................................................................................6
occulants .....................................................................................................................6
deocculants ...............................................................................................................6
surfactants ....................................................................................................................6
ltration control .........................................................................................................7
shale stabilisation ......................................................................................................7
polymer limitations ............................................................................................................7

Section 9

polymer chemistry

Section 9

01

polymer chemistry

introduction
A polymer is a molecule consisting of a series of repeating units. The
number of units can vary from several to tens of thousands with
corresponding variance in chain length and molecular weight. The
polymer can be linear or branched and can be synthetic or naturally
derived.
The lower molecular weight polymers are used as deocculants;
whereas, the high molecular weight molecules are used as viscosiers
and occulants.
The repeating unit need not always be the same. Copolymers consist of
two or more different groups joined together and may be random or
block depending on how the groups are distributed on the chain.

The two major mechanisms for manufacturing polymers are

condensation, which alters the makeup of the repeating units, and
addition which utilises the presence of a double bond in the reacting unit
to form a long chain. The addition process will generally yield higher
molecular weight polymers than will condensation. The condensation
process produces a polymer in which the repeating units contain fewer
atoms than the monomers from which they were formed. Frequently,
water is formed as a by-product of the process. The process requires two
or more compounds which react chemically and does not depend upon
the presence of a double bond for propagation of the chain.
This mechanism is susceptible to interruption by impurities or any outside
inuence which would reduce the efciency of the process.
Many commercially available polymers are not readily soluble in water.
This is an undesirable property for drilling uid chemicals. Fortunately,
many of the polymers available have been chemically treated in order to
make them water-soluble. The solubility of these polyelectrolytes will be
affected by the chemical makeup of the drilling uid, pH, salts and
presence of divalent cations, etc.

polymer types
Each type of polymer has its own characteristics in terms of how it
functions in a particular type of drilling uid. Therefore, selection of the

polymer chemistry

correct type of polymer is critical to good performance. Below are listed

ve general types of commonly used polymers.

polyacrylate, polyacrylamide, and phpa

Polyacrylates are used as dispersants (low mol. weight), uid loss reducing
agents (medium mol. weight) or occulants (high molecular weight).
Simple ones are cheap, but calcium sensitive. Copolymers are common,
e.g. vinyl sulphonate vinyl acrylate copolymers used as high temperature
uid loss reducing agent.
High molecular weight, partially hydrolysed polyacrylamides (PHPA)
are very effective shale stabilisers, clay extenders, occulants, and
encapsulating colloids. More correctly they are block copolymers of
polyacrylamide (c. 70%) and polyacrylate (c. 30%). The presence of excess
PHPA can be monitored via various tests and is reported on the mud
report form.
Hydrolysis
CH2 - CH alkali
C=N n

n CH2 = CH - C = N
Acrylonitrille
(Monomer)
CH2
CH

CH2
CH

Co _

Na

Na

CONH

Co _

Co _

Na +

Na

CH

CH

CH

CH

CH2

CH2

CH2

CH2
CH

Co _

Polyacrylonitrile (Polymer)

CONH

Co _

Na

PHPA Polymer

carboxymethylcellulose (cmc) and polyanionic

cellulose (pac)
These are widely used as viscosiers and uid loss reducing agents.
Carboxymethyl cellulose and polyanionic cellulose are both produced
by carboxymethylation. The quality of the product is determined by the
degree to which the reaction is carried out (degree of substitution) and
by whether the salt by-product is removed or not. Viscosity can be either
high or low depending on chain length.

Section 9

02

Section 9

03

polymer chemistry

When cellulose is reacted with sodium monochloroacetate, a sodium

methylacetate group is substituted on one of the three hydroxyl groups.
Cellulose Structure
H

OH

HO
4

CH2OH

H
OH
H

H1
O

CH2OH

H
OH H

CH2OH

OH

OH
H

OH

CH2OH

O
H
OH

OH

H.OH

The degree of substitution (DS) refers to the number of hydroxyl groups

upon which substitution takes place divided by the number of repeating
units in the molecule.
Carboxymethylcellulose Structure
H

OH

HO
4

CH2O

H
OH
H

H1

CH2COO-Na+

CH2O

CH2COO-Na+

H
H

OH

OH

OH
H

CH2O

H
OH H

H
O

CH2COO-Na+

CH2O

CH2COO-Na+

H
OH

OH

H.OH

The degree of substitution will range from zero to a maximum of

three. Generally, CMC will have a DS in the range of 0.4 to 0.8 with 0.45
being required for solubility. The degree of polymerisation (DP) will
range from 500 to 5000. The polymers with the greater DP will impart
more viscosity to the uid. High DS on the other hand, will permit more
tolerance to salts and cation contamination. Thermal degradation
accelerates above 250 F.
Polyanionic cellulose is similar to CMC but generally has a degree of
substitution (DS) of about 1.0. The PAC materials generally are more
expensive than CMC due to higher processing costs, but show a greater
tolerance to hardness and chlorides. PAC begins to thermally degrade at
250 F.

polymer chemistry

hydroxyethylcellulose (hec)
Hydroxyethyl cellulose. This is used mainly as a viscosier for completion
uids. Its non ionic nature means that it is not affected by salt. Key factors
are purity and high acid solubility.
HEC is formed by causticising cellulose and reacting it with ethylene oxide
which replaces one or more of the hydroxyl groups present on the cellulose
molecule.
Hydroxyeathylcellulose Structure
CH2OCH2CH2OCH2CH2OH H

Cellulose +

H
OH

OH

H
H

Ethylene oxide

OCH2CH2OH

OH

CH2OCH2CH2OH

Hydroxyethylcellulose

Although HEC is non ionic, it is still water soluble due to the hydroxy
ethyl groups. HEC imparts high viscosity to water or brines but exhibits
no gel strengths. It is prone to degradation through shear or heat and
has a maximum thermal stability of about 225 F.

starch
Widely used as uid loss reducing agents, particularly in salty muds. Can
be potato or grain derived. Quality and temperature stability can be
improved by various processes.
The starches are pre-gelatinised in order to permit them to readily hydrate.
Starches are peptised chemically or by exposure to heat. The peptisation
ruptures the microscopic sacks which contain the amylose and amylopectin
allowing them to contact with water and hydrate.
Starches are used mainly for uid loss control and are effective in a large
range of uid systems, such as seawater, saturated saltwater, KCl muds
and lime muds. Starches are thermally stable to about 250 F. Starches,
unless chemically modied are not resistant to bacteria and require a
biocide to prevent fermentation, except in saturated salt and high pH
muds.

Section 9

04

Section 9

05

polymer chemistry

guar gum
Viscosier used to make spud muds. Derivatives (eg.hydroxy propyl guar)
may be used in certain completion /workover uids.
Guar gum is manufactured from the seed of the guar plant. Guar is a
naturally occurring non ionic polymer used as a viscosier in waters
ranging from fresh to saturated salt (NaCl). High levels of hardness and
alkalinity will slow or even eliminate the hydration process and can cause
a signicant decrease in viscosity.
Guar has a maximum thermal stability of about 200 F and a biocide is
necessary to retard fermentation.

xanthan gum
Excellent viscosier giving shear stable rheology with progressive gels.
It is derived from bacteria.
Xanthan Gum is a biopolymer and is a product of the action of a bacteria
(Xanthomonas Campestris) on sugar. It may be used in a variety of brines
and salinity levels. Xanthan gum begins to degrade thermally at
temperatures of about 225 - 250 F. Xanthan gum is the only polymer that
provides thixotropy, i.e., formation of gel structures.

other naturally derived polymers

Other products which may loosely be described as polymers include:
Lignosulphate - used as a dispersant
Lignite - used a uid loss reducer and dispersant
Lignin (esp. polyanionic lignin) - used for uid loss control
Tannin/ Quebracho - used as dispersants

polymer uses
Some of the major uses of polymers in drilling uids are:

Viscosity
Bentonite Extension
Deocculation
Filtration Control
Shale Stabilisation

polymer chemistry

viscosity
Viscosity is due to the interactions between the polymer molecules and
water, between the polymers themselves and between polymers and
solids.
The longer the molecules the greater the viscosity. The interaction
between the polymers, water and solids can be disrupted by applying
energy or shear. The result is that the higher the shear, the lower the
viscosity.

bentonite extension
The bentonite extenders work by cross-linking bentonite particles to
increase the physical interaction between particles. There is a narrow
band of concentrations which allow this cross-linking to occur, but above
which a viscosity decrease may occur.

occulants
These polymers are characterised by a anionic high molecular weight
which will enable the polymer to bridge from particle to particle. The ionic
groups of the polymer will allow it to absorb strongly on the ionic sites of
solids and form an aggregate. The aggregates will settle or be removed by
shakers or centrifuges.
It is possible to have either total or selective occulation. Selective
occulation removes some of the drill solids.

deocculants
The deocculants or thinners are usually negatively charged polymers.
These products absorb onto the edges of clay particles resulting in an
overall negative charge.
Deocculants are anionic polymers. Polymer deocculants are shorter
molecules with a greater charge density.
These characteristics facilitate adsorption onto the clay particle without
causing cross-linking. These polymers are sensitive to divalent cations
and are less effective when hardness exceeds about 400 mg/l.

surfactants
These are discussed in the OBM Fundamentals section. They are polymers
with a polar, water loving end and a non polar oil soluble end.

Section 9

06

Section 9

07

polymer chemistry

These polymers will stabilise emulsions either direct or indirect depending

on the length of each entity.

ltration control
Three mechanisms can be envisaged for polymers to act as uid loss
additives.
a.
b.
c.

Deocculants. These pack down the lter cake forming a atter, less
permeable medium.
Viscosity of the ltrate. The thicker the liquid phase being forced
through the lter cake, the lower rate of ltration.
Colloidal particles. Compressible colloidal particles will deform to plug
pores in the lter cake.

Often a combination of mechanisms will provide the most effective

control.
Starches, CMC, PAC, and hydrolysed polyacrylates are effective ltration
control agents.
Anionic polymers control ltration by viscosifying the water phase to
restrict uid ow through the lter cake. Non ionic materials such as the
starches, some anionic materials such as PAC and CMC, work by hydrating
and swelling and physically plugging pores in the lter cake.

shale stabilisation
Shale stabilisation is provided through polymer attachment to the
positively charged sites on the edge of clay particles in shales. This
attachment minimises water invasion into the clay particle and reduces
hydration and dispersion. These polymers have been used with success
in conjunction with salt and potassium-based muds for added inhibition.

polymer limitations
Polymers have many advantages, particularly for formulating drilling
uids from sea water or salt saturated brine or for making highly
inhibitive muds such as the KCl/PHPA systems. They do have limitations
however.

Rheological Characteristics
Linear polymers such as CMC, PAC, HEC , produce almost ideal power law
uids with poor viscosities at low shear rates and at, low gel strengths.
Thus suspension properties are poor. Xanthan gum is the exception and
has good suspension characteristics. Note, however, that gels increase as
the low gravity solids build up.
Tolerance to Contaminants
Most polymers tolerate salt or KCl very well, but the anionic ones e.g.
CMC or PAC can be precipitated by calcium if the pH is high. Cement is
the worst contaminant. Calcium values over 1000 mg/l (as in, for
example, gyp muds) can be tolerated if the pH is below 10. Polymer yields
are higher in fresh water than in saturated salt.
Temperature
The polysaccharides have relatively poor temperature stability max. BHT
250 - 300 F depending on grade). This can be increased by using stabilisers.
The synthetic polymers can tolerate much higher temperatures (350 F
500 F).
Bacteria
Starch, guar gum and Xanthan gum are quite easily attacked. The use
of a biocide is recommended. CMC and PAC are more resistant to attack.
Shear Degradation/ Absorption
Some polymers do undergo shear degradation and are absorbed onto
cuttings and drill solids. Consequently their viscosifying effects are
reduced (but inhibition is increased). High molecular weight, linear
polymers such as PAC and PHPA are most susceptible.
Cost
Polymer muds are generally more expensive in terms of cost/bbl than
bentonite muds. However, the advantages obtained by their use (better
hole stability, ROP etc.) will normally outweigh the extra cost.

08
Section 9

polymer chemistry