Surfactants

Classification of surfactants?

A_Ionic surfactant B_Nonionicsurfactants

Anionic

Cationic

Zwitterionic(amphoteric)
 A_Ionicsurfactant

Anionic
*In solution, the head is negatively charged. This is the most
widely used type of surfactant for laundering, dishwashing
liquids and shampoos because of its excellent cleaning
properties and high
(based on sulfate, sulfonate or carboxylate anions)

Anexample:Sodiumdodecylsulfate(SDS)
*The most commonly used anionic surfactants are alkyl
sulphates, alkyl ethoxylate sulphates and soaps.
 Cationic

*In solution, the head is positively charged.

(based on quaternary ammonium cations)

An example : Benzethonium chloride (BZT)

 Zwitterionic (amphoteric)
*These surfactants are very mild, making them particularly
suited for use in personal care and household cleaning
products.
*They can be:
_anionic (negatively charged),
_cationic (positively charged) or
_non-ionic (no charge) in solution,
depending on the acidity or pH of the water.
*An example of an amphoteric/zwitterionic surfactant is alkyl
betaine

e.g.:Cocamidopropylbetaine
B_ Non-ionic surfactants

*These surfactants do not have an electrical charge, which

makes them resistant to water hardness deactivation.

*They are excellent grease removers that are used in

laundry products, household cleaners and hand
dishwashing liquids.
Micelle

*A micelle (rarely micella, plural micellae) is an aggregate of

surfactant molecules dispersed in a liquid colloid.
* A typical micelle in aqueous solution forms a roughly spherical
or globular aggregate with the hydrophilic "head" regions in
contact with surrounding solvent, sequestering the
hydrophobic tail regions in the micelle center.
How do surfactants work in detail?

Surfactants can work in three different ways:

a_ roll-up,
b_ emulsification, and
c_ solubilization.
A_Thesurfactantlowersthe
Roll-up mechanism
oil/solutionandfabric/solution
interfacialtensionsand
inthiswayliftsthestainofthe
fabric.
B_ Emulsification

The surfactant lowers the oil-

solution interfacial tension
and makes easy
emulsification of the oily
soils possible.
 C_ Solubilization

Through interaction with the micelles of a

surfactant in a solvent (water), a substance
spontaneously dissolves to form a stable and
clear solution.
Applications of Surfactant
Detergent

*is a compound, or a mixture of

compounds, intended to
assist cleaning. The term is
often used to differentiate
between soap and other
chemical surfactants used for
cleaning purposes.
 Fabric softener

(also called Fabric Conditioner)

*is used to prevent static cling and makes the
fabric softer.
An emulsifier

*(also known as an
emulgent or
surfactant) is a
substance which
stabilizes an
emulsion.
An adhesive

*is a compound that adheres or bonds two items

together.
 An ink

*is a liquid containing various pigments and/or

dyes used for colouring a surface to render an
image or text. Ink is used for drawing or
writing with a pen or brush.
 What is a Polymer?
A polymer is formed by the combination of a
large number of smaller units called
monomers linked through covalent linkages

Monomers should have minimum

bifunctionality i.e.two functional groups or
one double bond
Monomer, Constitutional Repeat Unit,
Degree of Polymerization
(i) M onomer : Vinyl Chloride
CH2 CH

Cl
( ii ) DP : 1000

[ CH2 CH ]1000

Cl
PVC ( iii ) M olecular W eight of Polymer
= Mol. Wt. of Monomer x DP
= 62.5 x 1000
= 62,500
( iv ) CRU : ( CH2 CH )
Cl
The Polymer Parameters
Chemical Composition
Homopolymers

Copolymers

Terpolymers

Molecular Weight
- Different averages
Isomerisms
Head to tail and Head to head

Isomeric polyisoprenes

Geometrical isomers

Configuration - atactic, isotactic, syndiotactic

Topology
Chains, Branches - star, comb, random, Network
Classification of Polymers
Addition and Condensatiom
Natural and Synthetic
Homochain and Heterochain
Monodispersed and Polydispersed
Homopolymers, Copolymers and Terpolymers
Linear, Branched and Network Polymers
Charged and Uncharged Polymers
Thermoplasts and Thermosetts
Crystalline and Amorphous Polymers
Fibres, Plastics and Elastomers
Isotactic, Syndiotactic and Atactic Polymers
Classification of Polymers
Homopolymers
~AAAAAAAAAAAAAAAAAAAAAAAAAAA~
Copolymers
Random
AAABBBBAABBBBBBABABBBAAABBBBB~
Block
~AAAAA~~~~~~AAAABBBBB~~~~~~BBBB~
Graft
~AAAAAAAAAAAAAAAAAAAAAAAAAAAA~
B
B
BBBBBBBBBB~
Terpolymers
ABCACBAACBBCCACBBBCCAACBCA
 Classification of Polymers
Addition Polymers Condens. Polymers
Or
Or
Chain Polymers
Step Polymers

Monomer Monomer(s) contain

Unsaturated atleast 2 functional
groups
Polymer Classification Stereochemistry
Geometrical isomers
Configuration - atactic, isotactic, syndiotactic

A B A B A B A B

isotactic

A B B A A B B A

syndiotactic

A B A B B A A B

atactic
Classification of Polymers

Chains ( Linear)

Branches - star, comb, random

Network
Classification of Polymers
Thermoplastic
Linear architecture

Processable at moderate temperatures

Soluble and Melt

Polyethylene, PVC, PET

Thermosetting
Cross-linked architecture

Not processable after forming

Insoluble and Infusible

Polyurethane, Formaldehyde resins

Thermoplastics
Often formed by addition polymerisation
leading to long linear chain polymers with
no crosslinks
Soften on heating readily, because
secondary forces between the individual
chain can break easily by heat or pressure.
Can be reshaped and reused
Usually soft, weak and less brittle
Thermosetts

Often formed by condensation

polymerisation and three dimensional
network structures are formed
Can not be reshaped and reused . Can not be
reclaimed from wastes
They do not soften on heating. On prolonged
heating, however charring of polymers is
caused
Insoluble in almost all organic solvents
LDPE (Low-density polyethylene)

LDPE is found in grocery bags, bread

bags, shrink wrap, margarine tub tops...
LDPE can be recycled into new grocery
bags...
 High-density polyethylene

HDPE is found in milk jugs, butter tubs,

detergent bottles, motor oil bottles...

HDPE can be recycled into flower pots,

trash cans, traffic barrier cones,
detergent bottles...
 Polyvinyl chloride

PVC is used in shampoo bottles,

cooking oil bottles, fast food service
items...

for pipes in plumbing

PVC can be recycled into drainage
and irrigation pipes...
 Molecular weight
Small mol wt substances vs Polymers
Molecular weight is a characteristic of a

compound.
All small mol wt compounds have a

definite molecular weight. It is not so in

case of polymers.
Even a particular sample of polymer has

molecules of different size.

 Polydispersity Index = Mw/ Mn

For monodispersed polymers PDI =1

Mn< Mw< Mz< Mz+1

 Copolymerization & Copolymers?
The process of polymerising two or more than
two monomers together is copolymerisation
and the polymer formed copolymer

The term copolymer is better referred to

addition polymers.

The copolymers often possess the properties

shown by the homopolymers made from the
constituent monomers of the copolymer.
Why Copolymers?

Practical Importance
Variety of copolymers by varying nature
and amounts of each monomer
Produce properties not available with

Homopolymers
Types of copolymers

AABBBAAABABBAAABBA
Random
ABABABABABABABA
Alternating
AAAAAAAAABBBBBBBAAAAAABBBB

Block
AAAAAAAAAAAAA

B
Graft BBBBBBBBBBBBB
Diblockcopolymers Block Copolymer:
Macromolecule, that is composed of
at least two different monomers
in a block-like structure.
Triblockcopolymers (AB, ABA, ABC...)
ABC=(A)x(B)y(C)z

ABA=(A)x(B)Y(A)z showphaseseparation
inthesolidstate,
inselectivesolvents,
ABC=(A)x(B)y(C)z onsurfaces.
Block Copolymer Properties
change
With the type of structure Di, Tri, Multi,

Radial..
With the total molecular weight and % Block

With the different monomers used in making

blocks

Thus there is need for tailor-made polymers

Block copolymers have
become important in recent
years
Advances in polymerization
techniques
Newer applications in green
chemistry, nanoscience and
biotechnology
Block Copolymer Characterization

Type,Total mol wt, % Blocks, Microstructure,

Spectroscopy NMR &IR

Thermalanalysis DSC&TGA
Light scattering SLS,DLS,SAXS,SANS
Chromatography GPC
Properties in Solution
Adsorption characteristics on to
surfaces
Aggregation in solution

Distinct structural moieties in

block copolymers make them
behave like surfactants
( Amphiphiles)
Hydrophilic- Hydrophobic Copolymers

or

Amphiphilic Block Copolymers

Block copolymer adsorption
Water soluble copolymeric surfactants like
pluronics adsorb at air/water interface and
significantly reduce surface tension.

Water insoluble copolymeric surfactants

form insoluble monolayers thar can have
different phases.

Block copolymers can efficiently adsorb on

to the solid/liquid or liquid/liquid surfaces,
thus sterically stabilize sols, latexes and
emulsions.
Amphiphiles at Interfaces e.g. Air / Water
CMC = critical micelle
conc.
KP = Krafft point
cmc
Micellar
Characteristics:
- size (3-5 nm)
- shape (sphere,
rod,..)
- agg number (20-...)
- dynamics (s to
ms)
- amphiphiles reduce surface energy

-hydrophobic effect = entropy

loss of oriented water-molecules
around the hydrophobic tail
Aggregation behaviour
In selective solvent , block copolymers
aggregate to form micelle
Hydrophilic-hydrophobic block
copolymers form micelle in water.
PEO-PPO-PEO ( Pluronics) block
copolymers form micelle in water and
are commercially available surfactants
 Surfactant Aggregates
Unimers Normal micelles
Cylindrical
Spherical

Inverted hexagonal phase

Reverse micelles
Bilayer lamella
4 nm
Aggregation in solution
Apart from spherical and rod like micelles,
concentrated copolymers solutions form
different liquid crystalline phases that
control the rheology of solutions.

Micelle shape and size and the existence

of lc phases depends on the molecular
characteristics of copolymer and external
factors like temperature, pressure, pH ,
presence of additives etc.
Phase Diagram of an Oil/Water/Amphiphile Mixture
 APPLICATIONS
Block Copolymers
Several commercial products are
available as thermoplastic elastomers
(e.g. styrene- diene block polymers as
Solprene Philips; Kraton; Shell.
 The use of styrene- butadiene and styrene-
isoprene block copolymer as thermoplastic
elastomers in footwear is well known.

The other thermoplastic elastomers are

polyether-polyester and polyether-polyamide.

Thermoplastic elastomers combine the properties

of a rubber and the processing characteristics of
a thermoplastic which make these materials of
great industrial importance.
 Styrene-diene and styrene-hydrogenated
diene triblock copolymers are reportedly
good pressure sensitive adhesives and are
used for bitumen modification.
The interfacial characteristics make block
copolymers useful materials as polyblends,
as adhesives, sealants, binders for laminates,
as constituent of coating materials, surface
modifiers for fillers and fibers.
Blending of block copolymers with other
polymers provides new polymeric materials
with desired properties. Some grades of high
impact polystyrene are such systems
 Surfactant based applications of block
copolymers are as colloid stabilizers,
in dispersion polymerization in
aqueous and nonaqueous media ,
in emulsion stabilization,
in microemulsion polymerization
in polymeric emulsions.
 EO/PO block copolymers find
numerous applications in medical,
pharmaceutical, textile, cosmetic,
detergents and pesticidal formulations.
Their reversible thermorheological
feature makes them potential
candidates for controlled release.
 Block Copolymer:
Macromolecule, that is composed of at least two different
monomers
in a block-like structure.

(AB, ABA, ABC...)

Triblock copolymers
Diblock copolymers
ABC=(A)x(B)y(C)z

ABA=(A)x(B)Y(A)z

ABC=(A)x(B)y(C)z
 Block Copolymer properties depends on

1. Change in the structure (Di, Tri, Multi, Radial, .. etc.

2. Change in the molecular weight and the % block.

 PEO-PPO-PEO (Pluronic)
CH 3
HO C H 2C H 2O CH CH 2O CH 2CH 2O H

m/2 n m/2

PEO hydrophilic and PPO hydrophobic

Form core shell micelle in dilute solutions. Micellization strongly
concentration and temperature dependent
Show reversible thermorheological behaviour and various LC
phases in concentrated solutions
Prepared by the reaction of preformed polypropylene glycol and
ethylene oxide.
Typical mol mass of PPO group 4000

3625

3250

2750

2250

2050

1750

1450

1200

950
0 10 20 30 40 50 60 70 80

% PEO
 Pluronics: Applications
Stimulus response leads to the formation of
core-shell nanoaggregates (Micelles)

Above CMT/CMC

Hydrated Shell
Block
copolymer in Hydrophobic
solution core
before
CMT/CMC
 The performance based properties of Pluronics can
be enhanced in presence of various stimulies.

Temperature
Concentration

Salts

Surfactants

Hydrotropes

Urea and its derivatives.

 The hydrophobic core can solubilize water
insoluble organic compounds.
Nanoparticle synthesis
Metal oxide nanoparticles viz, Titania, Silver,
Zirconia could be synthesized using block
copolymers.