Chapter 11 Polymers Chemistry

WATER-BASED DRILLING FLUIDS
POLYMERS CHEMISTRY
(NON INHIBITING)
Well Area Operations

Agip KCO Drilling Supervisors Training Course
Drilling Muds RPW2021A 1
INTRODUCTION
The use of polymers in drilling fluids began in 1937 when starch was introduced for
the control of filtration.
Nowadays, polymers are an integral part of each water-based fluid.
At present, a large numbers of polymers is available:
Starch → natural origin
¾Special polymers obtained through modification of natural polymers
¾Synthetic origin
¾Polymers technology

POLYMERS FUNDAMENTAL STRUCTURE
A polymer is a substance that consists of large molecules formed from smaller molecules
in repeating structural units (monomers)
Polymerization reaction = when monomers are linked one to the other to form the largest
polymeric molecule.

Linear CMC (carboxymethylcellulose), PHPA

(Partially Hydrolyzed Polyacrylamide) and
HEC (Hydroxyethylcellulose)
Branched Starch and Xanthan gum
Cross-linked Cross-linked Xanthan gum

Linear Polymer
Chemical
Monomers modification
Cross.linked
agent
Cross-linked
polymer
Polymers fundamental structure

number of molecules Tight distribution
Wide distribution
Molecular Weight
Distribution of the different molecular weights

Polar Group
Class Group
Name Formula
Non-ionic oxhydryle - OH
ether R-O-R
ester -O-CH3??
Anionic OH phenolic C6H5OH- C6H5O-

Carboxyl COOH COO-
Sulphonic SO3H- -SO3-
Phosphate PO3H- -PO3-
Cationic Amine -NH3 NH4+

Carboxylic ionized group

Insoluble Soluble
Polymer solubility

POLYMERS STRUCTURE AND FUNCTIONS IN
DRILLING FLUIDS
Function Main Characteristics
Viscosity High Molecular Weight
Viscosity and gel function High molecular weight and structure at high
ramification agent or cross-linkage
Viscosity in saline solution High molecular weight and non ionic or anionic
types at high substitution
Deflocculation, dispersion or fluidification Low molecular weight and negative charges in

alkaline ambient
Flocculation High molecular weight with groups which bring

charges for the absorption on the clays
Surfactants (surface-active agent) Presence of hydrophobic and hydrophilic

groups on the same molecule
Addittives to control the filtrate Particles in colloidal shape
Relationships between the functions of use in drilling fluids and essential outlines of
the polymeric structure

DRILLING FLUIDS
VISCOSITY
High Molecular Weight
Viscosity Solution
Low Molecular Weight

DRILLING FLUIDS
DEFLOCCULANTS
Deflocculants or fluidizers in alkaline clay-based systems, results as absorption of

polymers with negative charge on clay lamines which neutralize the positive charges
obtaining a global negative charge.

DRILLING FLUIDS
FLOCCULANTS
Flocculants are characterized by a high molecular weight through which the polymer can
form a connection from particle to particle.

DRILLING FLUIDS
Surfactants (Surface active agent)

Surfactants are polymers in which each molecule contains two sets of atoms
or groups.
A group is called polar when attracted towards polar surfaces such as water
In this case they are called hydrophilic groups.
The others are not polar but hydrophobic .
The nature of the surfactant is linked to the type of hydrophobic or hydrophilic

group and the combination of the groups.

DRILLING FLUIDS
Non-polar groups Polar Groups
Hydrocarbons chain CH3 - (CH2) hydroxil -OH

Often derived from oils or natural phenolic R.OH
greases. ether - CH2 - CH2 - 0- CH2CH2OH
They can contain connections in the carboxylic – R – COO-
molecule - CH = CH- esterification – R - COOR1
sulphonate - OSO3~
sulphate -SO3-
Sulphosuccinate
CH2COOR
O3S - CHCOOR
Amine –R -NH2
Certain non-polar and polar groups can be incorporated in a molecule of surfactant.

DRILLING FLUIDS
Interface
Non pol. Pol. Surfactant function
oil water Direct or inverse emulsifier
air water Foaming or anti-foam agent
steel water Lubricant
steel clay Detergent
clays water Dispersant
oil clay Oil-based wetting agent
Interfaces in the drilling fluids modified by the surfactants

DRILLING FLUIDS
FILTRATE ADDITIVES
Polymeric additives can affect filtrates with three different mechanisms.

A deflocculated cake transforms in a thinner but more permeable cake so that the
polymers act as deflocculant such as the low viscosity CMC or the
lignosulphonates. If the liquid phase, which passes through the cake, is viscous, it
will reduce also the filtrate.
A third mechanism of reduction of the filtrate consists in adding colloidal particles
which can deform, to plug the pore cake.

POLYMERS CLASSIFICATION
Polymers in drilling muds can be classified into three different criteria. The classification
can occur in accordance with their chemical characteristics, (for instance, anionic and
non-ionic) according to their function as viscosifiers or additives to control the filtrate, or
easily according to their origin. There are three types of polymers in drilling:
• Natural origin
• Natural origin modified.
• Synthetic origin.

NATURAL POLYMERS
Glucose

Amylose

Amylopectine

Xanthan rubber

MODIFIED NATURAL POLYMERS
The use of modified natural polymers is common in drilling muds.

Starch cellulose → natural polymers.
A modified polymer can have different properties compared to the original.
Polyelectrolytes.

Cellulose derivates
Carboxylmethylcellulose (CMC)
Cellulose

Sodium carboxylmethylcellulose, D.S. = 1.0

(HEC - Hydroxyethylcellulose)
Hydroxyethylcellulose

Cellulose derivates
(CMS – carboxymethyl starch)
carboxymethyl starch

Hydroxypropyl starch
Another example of modified starch is the HPS – hydroxypropyl

starch)
For reaction between starch and propylene oxide.
The product is non-ionic and soluble in water.
Modifications are summed to the starch water-solubility.

SYNTHETIC POLYMERS
CH2 = CH
|
A
Sodium polyacrylate

Polyacrilate
Flocculation

Clay SPA interaction

Copolymerization

Copolymer polyacrylamide/polyacrylate
Sodium Acrylate/Acrylamide

PHPA

TYPES AND FUNCTIONS OF POLYMERS IN
DRILLING FLUIDS
Types and functions of polymers in drilling fluids
Type of polymer Description Examples Functions

Carboxymethyl COO groups linear polymers High viscosity Viscosifier additive
Ether anionic, polysaccharides CMC Filtrate additive
Cellulose CMC High molecular weight Low viscosity
Low molecular weight CMC
Hydroxyethyl Ether, Non-ionic ether group linear HEC Viscosifier in
Cellulose HEC polymer polysaccharide. particular for brines
High molecular weight.
Starch Branched polysaccharide Corn, potatoes, Filtrate control in
which forms a colloidal tapioca etc. with salt solutions
solution, normally C00- or variable
ionic or anionic. chemical
changes
Bacterial gum Polysaccharide Xanthan Gum Viscosifier
Polysaccharides Complex branched structure especially for salt
– some anionic groups. High water and where
molecular weight suspension
properties are
needed

DRILLING FLUIDS
(CONT’D)
Natural gums from Branched Polysaccharide, GUAR, Gums arabic Viscosofoer

trees high molecular weight,
complex structure with some
anionic groups
Lignosulfonate Sulphonate soluble at 1', Calcium lignosulfonate, Fluidizer,
water coming from lignin. chromium deflocculant, control
Metallic salts lignosulfonates,
ferrochromium
Polymer type Description Examples Functions

Mineral Lignines Metallic salts of branched Chromium lignite, potash Filtrate control,
humic acid lignite, caustic lignite fluidizer
Tannine Extracts and tree bark Quebracho Fluidizer
Polyphosphates Molecularly dehydrated Pyrophosphate sodium Fluidizer

phosphates acid
Polymeric Vinyl Acrylic acid polymer CH2=CH -CH2-CH-CH2-CH- Low molecular
COOH C=0 C=0 weighti<1000,
O-Na O-Na fluidizer, flocculante
with high P.M.

DRILLING FLUIDS
(CONT’D)
Polymeric Vynil Acrylic acid copolymer and -CH2-CH-CH2-CH Flocculant clay

C=0 C=0 stabilizer
O-Na+ NH2
Co . Polymer Acetate vinyl - anhydride -CH2-CH-CH-CH- Flocculant bentonite

High molecular weight CO CO CO expandent
O = CCH3OH OH
Surfactant Resin soap, lecithin lime Synthetic polymers Emulsifier for water in
soap, bread-fruit tree resin, emulsifier for oil in
nonilfenoletoxilate the detergents for
alkilsulphonate water-based muds.
Surfactant Ethanol Synthetic polymers Foaming

n-Tricedil polioxi, ethylene
ether, nonyilfenol-
polyethylene glycol
Surfactant Superior alcohols, vegetable Synthetic polymers Anti-foaming

oils, sulphates
Surfactant Fatty acids glycerides, Synthetic polymers Corrosion inhibitoe
alkydiamina etoxilato lubricant


Chapter 11 Polymers Chemistry

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WATER-BASED DRILLING FLUIDS

Well Area Operations

Nowadays, polymers are an integral part of each water-based fluid.

At present, a large numbers of polymers is available:

Starch → natural origin

¾Special polymers obtained through modification of natural polymers

Well Area Operations

Well Area Operations

Linear CMC (carboxymethylcellulose), PHPA

Branched Starch and Xanthan gum

Cross-linked Cross-linked Xanthan gum

Well Area Operations

Polymers fundamental structure

Well Area Operations

number of molecules Tight distribution

Distribution of the different molecular weights

Well Area Operations

Anionic OH phenolic C6H5OH- C6H5O-

Cationic Amine -NH3 NH4+

Well Area Operations

Carboxylic ionized group

Well Area Operations

Well Area Operations

Function Main Characteristics

Viscosity High Molecular Weight

Deflocculation, dispersion or fluidification Low molecular weight and negative charges in

Flocculation High molecular weight with groups which bring

Surfactants (surface-active agent) Presence of hydrophobic and hydrophilic

Addittives to control the filtrate Particles in colloidal shape

Well Area Operations

High Molecular Weight

Low Molecular Weight

Well Area Operations

Deflocculants or fluidizers in alkaline clay-based systems, results as absorption of

Well Area Operations

Well Area Operations

Surfactants (Surface active agent)

In this case they are called hydrophilic groups.

The others are not polar but hydrophobic .

The nature of the surfactant is linked to the type of hydrophobic or hydrophilic

Well Area Operations

Non-polar groups Polar Groups

Hydrocarbons chain CH3 - (CH2) hydroxil -OH

Certain non-polar and polar groups can be incorporated in a molecule of surfactant.

Well Area Operations

Non pol. Pol. Surfactant function

oil water Direct or inverse emulsifier

air water Foaming or anti-foam agent

steel water Lubricant

steel clay Detergent

clays water Dispersant

oil clay Oil-based wetting agent

Interfaces in the drilling fluids modified by the surfactants

Well Area Operations

Polymeric additives can affect filtrates with three different mechanisms.

Well Area Operations

Well Area Operations

Well Area Operations

Well Area Operations

Well Area Operations

Well Area Operations

MODIFIED NATURAL POLYMERS

The use of modified natural polymers is common in drilling muds.