Chapter 2.

Synthesis of polymers
Dr. Van-Tien Bui
Email: [email protected]
Phone: 84‐911552201

Vietnam National University Ho Chi Minh City

Ho Chi Minh City University of Technology
Faculty of Materials Technology
2.1 2.3

Chain-growth Methods and

polymerization technologies
Content
2.2 2.4

Step-growth Modification of
polymerization polymer
 Types of Polymerization

Addition Condensation
(Chain-growth ) (Step-growth)
polymerization polymerization

Radical
Polymerization

Ionic
Polymerization

Cationic
Polymerization

Anionic
Polymerization
2.1. Addition or Chain-growth polymerization
 Definition: is a process by which
monomer units are attached one at a
Initiation
time in chain-like fashion to form a
linear macromolecule. Three steps of
Addition Propagation
 No molecule is eliminated and no by- polymerization via chain
transfer
product is generated.
Deactivation
via
combination

via
disproportionation
a. Radical Polymerization

Initiation involves the formation of radicals Propagation is the rapid and

followed by the radical's reaction with a progressive addition of
vinyl monomer monomers to the growing
polymer chain without a
change of the active center
The two most common initiators (I)
are benzoyl peroxide (BPO) and 2,2'-
Termination is the destruction
azo-bis-isobutyrylnitrile (AIBN).1 Both
of the growth active center,
molecules have a strong tendency to
usuallyby combination or
fall apart into two fragments with
coupling of the radicals of two
unpaired electrons, the so-called free
growing polymer chains or
radical initiators:
by disproportionation
I → 2 R·
a. Radical Polymerization

Initiation involves the formation of radicals Propagation is the rapid and

followed by the radical's reaction with a progressive addition of
vinyl monomer monomers to the growing
polymer chain without a
change of the active center
The two most common initiators (I)
are benzoyl peroxide (BPO) and 2,2'-
Termination is the destruction
azo-bis-isobutyrylnitrile (AIBN).1 Both
of the growth active center,
molecules have a strong tendency to
usuallyby combination or
fall apart into two fragments with
coupling of the radicals of two
unpaired electrons, the so-called free
growing polymer chains or
radical initiators:
by disproportionation
I → 2 R·
a. Radical Polymerization

Initiation involves the formation of radicals Propagation is the rapid and

followed by the radical's reaction with a progressive addition of
vinyl monomer monomers to the growing
polymer chain without a
change of the active center
The two most common initiators (I)
are benzoyl peroxide (BPO) and 2,2'-
Termination is the destruction
azo-bis-isobutyrylnitrile (AIBN).1 Both
of the growth active center,
molecules have a strong tendency to
usuallyby combination or
fall apart into two fragments with
coupling of the radicals of two
unpaired electrons, the so-called free
growing polymer chains or
radical initiators:
by disproportionation
I → 2 R·
The free radical mechanism for
the polymerisation of ethene.
Radical polymerization
b) Ionic Polymerization
 Cationic Polymerization
 Anionic Polymerization
  Cationic Polymerization
In cationic vinyl polymerization, the initiator is a cation (positive electrical charge - A+).
A pair of electrons, negatively charged, from the carbon-carbon double bond will be attracted to
this cation, and will leave the carbon-carbon double bond to form a single bond with the initiator,
as shown. This leaves one of the former double bond carbons at a loss for electrons, and carrying a
positive charge. This new cation will react with a second monomer molecule in the same manner
as the initiator reacted with the first monomer molecule.

Carbocation
 Cationic vinyl polymerization
The initiator used is Aluminum trichloride, or AlCl3
The aluminum atom in AlCl3 is sharing
electron pairs with only three other
atoms, leaving it with only six electrons,
two short of the magical octet. As it sits,
it has a whole orbital empty and ready
for something to come along and fill it. It
just so happens, much to the delight of
that aluminum atom, that a very small
amount of water is usually present in the
system. Now the oxygen atom in water
has two unshared pairs of electrons, and
it most graciously donates a pair to the
aluminum atom, forming an AlCl3 and
H2O complex.
 Cationic vinyl polymerization
 Initiation Propagation Termination

The AlCl3/H2O complex

forms and reacts with the
first monomer molecule
 Cationic vinyl polymerization
 Initiation Propagation Termination
Monomer after monomer is added to form a polymer
Cationic vinyl polymerization
 Chain transfer to monomer
 Cationic vinyl polymerization
 Chain transfer to initiator
 Cationic vinyl polymerization
 Initiation Propagation Termination
  Anionic Polymerization
Anionic vinyl polymerization is a method of making polymers from small molecules
containing carbon-carbon double bonds.

Initiator:

Carbanion forming:
 Anionic vinyl polymerization
 Initiation

 Propagation
 The Chain That Wouldn't Die
In order to stop them, something like water, which reacts with the
carbanions, has to be added to the polymer. Systems like this are called
living anionic polymerizations.
2.2. Condensation or Step-growth polymerization
 Definition: is the formation of polymers by stepwise intermolecular
chemical reactions that may involve more than one monomer species.
 There is usually a low-molecular-weight by-product such as water that is
eliminated (or condensed).
Structure of the Condensation Polymerization of Adipic acid and
Hexamethylendiamin to Nylon 6,6

Adipic acid Hexamethylendiamin

Nylon 6,6
The formation of the polyester poly(ethylene terephthalate) (PET) from the reaction
between dimethyl terephthalate and ethylene glycol to form a linear PET molecule
with methyl alcohol as a by-product; the intermolecular reaction is as follows:
Condensation polymerization
 Comparation
Step-growth polymerization Chain-growth polymerization

Growth by addition of monomer

Chain growth profile Growth throughout matrix only at one end or both ends of
chain
Usage of monomer in Rapid loss of monomer early in Some monomer remains even at
the reaction the reaction long reaction times
Different steps operate at different
Similar steps repeated throughout stages of mechanism (i.e. initiation,
Reaction steps
reaction process propagation, termination, and
chain transfer)
Average molecular weight
Molar mass of backbone chain
increases slowly at low
Average molecular increases rapidly at early stage and
conversion and high extents of
weight remains approximately the same
reaction are required to obtain
throughout the polymerization
high chain length
Active chain remains Ends remain active (no
Chains not active after termination
after reaction? termination)
Initiators required? No initiator necessary Initiator required
Comparation
2.3 Polymerization techniques
Polymerization
techniques

Addition Condensation
(Chain-growth ) (Step-growth)
polymerization polymerization

Bulk(or mass) Melt

polymerization polycondensation
Homogeneous
Solution
polymerization Interfacial-Solution
polycondensation
Suspension
polymerization
Heterogeneous
Emulsion
polymerization
a) Bulk polymerization
Bulk polymerization or mass polymerization is carried out by adding a soluble initiator to pure monomer in liquid state.
i. The initiator should dissolve in the monomer.
ii. The reaction is initiated by heating or exposing to radiation.
iii. Once the reaction starts, heating is stopped as the reaction is exothermic.
iv. The heat generated is dissipated by circulating water jacket.
v. Viscosity increases dramatically during conversion.

Bulk polymerization of styrene

The method is used for the polymerization of liquid state monomers.
It is usually adopted to produce polystyrene, polyvinyl chloride, polymethyl methacrylate and low
density polyethylene.
 Advantages & Limitations
Advantages Limitations
 High molecular mass polymer is obtained with
wide range  Heat transfer and mixing become difficult as
the viscosity of reaction mass increases.
 The system is simple and only requires thermal
insulation.  The problem of heat transfer is compounded
by the highly exothermic nature of free
 The polymer obtained is having higher purity and radical addition polymerization.
minimum by-product
 The polymerization is obtained with a broad
 Large castings may be prepared directly. molecular weight distribution due to the
 Molecular weight distribution can be easily high viscosity and lack of good heat transfer.
changed with the use of a chain transfer agent.  Very low molecular weights are obtained.
 The product obtained has high optical clarity  Gel effect should be there
b) Solution polymerization
Some disadvantages of bulk polymerization are
eliminated in solution polymerization.
i. Monomer along with initiator dissolved in
solvent, formed polymer stays dissolved.
ii. The mixture is kept at polymerization
temperature & constantly agitated.
iii. Depending on concentration of monomer the
viscosity of solution does not increase.
iv. After the reaction is over, the polymer is used
as such in the form of polymer solution or the
Monomer+ Polymerization Polymer+
polymer is isolated by evaporating the solvent.
solvent solvent
v. Polymer so formed can be used for surface
coating

It is used for the production of Polyacrylonitrile, PVC, Polyacrylic acid, Polyacrylamide, Polyvinyl
alcohol, PMMA, Polybutadiene, etc
 Advantages & Limitations
Advantages Limitations

 Solvent has low viscosity, reaction mixture can be  Reduce monomer concentration which
stirred results in decreasing the rate of the reaction
and the degree of polymerization
 Solvent acts as a diluent and aids in removal of
heat of polymerization  Mobility is reduced and this can affect
termination events, so the rate of reaction is
 Solvent reduces viscosity, making processing increased
easier
 Solvent may terminate the growing polymer
 Thermal control is easier than in the bulk and chain, leading to low molecular weight
 “Cheap” materials for the reactors (stainless steel polymers
or glass lined.)
 Difficult to remove solvent from final form,
causing degradation of bulk properties
 Small yield per reactor volume
 The requirements for a separate solvent
recovery step
 c. Suspension polymerization
 Suspension polymerization is a heterogeneous
radical polymerization process that uses mechanical
agitation to mix a monomer or mixture of monomers
in a liquid phase, such as water, while the monomers
polymerize, forming spheres of polymer.
 The monomer droplets (size of the order 10-1000 μm)
are suspended in the liquid phase. The individual
monomer droplets can be considered as
undergoing bulk polymerization. The liquid phase
outside these droplets help in better conduction of
heat and thus tempering the increase in
temperature.
 The dispersion is maintained by continuous agitation
and the droplets are prevented to coalesce (unite
or merge) by adding small quantity of stabilizers. The
stabilizers used are PVA, gelatin, cellulose are used
along with inorganic stabilizers such as kaolin,
magnesium silicate, aluminum hydroxide,
calcium/magnesium phosphate, etc if necessary.

 The product separated out in the form of spherical pearls or beads of polymer. The products are
small uniform spheres.
 Suspension polymerization
SEM-Picture of
This process is used in PMMA-particles, that
the production of many started to coalesce
during suspension
commercial resins, polymerization, close
including polyvinyl to a single bead
chloride (PVC), a widely
used plastic, styrene
resins, including
polystyrene, expanded Light microscopic
polystyrene, and high- picture of a PMMA-
impact polystyrene, as Equipment used for copolymer, made by
well as poly(styrene- a Suspension suspension
Polymerizaion polymerization
acrylonitrile) and poly
reaction
(methyl methacrylate).
 Advantages & Limitations
Advantages Limitations

 The process is comparatively cheap as it  The method can be adopted only for water
involves only water instead of solvents. insoluble monomers.
 Viscosity increase is negligible.  It is difficult to control polymer size.
 Agitation & temperature control is easy.  Polymer purity is low due to the presence of
suspending & stabilizing additives that are
 Product isolation is easy since the
difficult to remove completely.
product is insoluble in water.
 Suspension polymerization reaction is highly
agitation sensitive.
 Larger volume of reactor is taken up by water.
 The method cannot be used for tacky
polymers such as elastomers because of the
tendency for agglomeration of polymer
particles.
d. Emulsion polymerization
 The system consists of water insoluble
monomer, dispersion medium & emulsifying
agents or surfactants (soaps and detergents) and
a water soluble initiator (potassium persulphate /
H2O2, etc).

 The monomer is dispersed in the aqueous

phase, not as a discrete droplets, but as a
uniform emulsion. (Monomer droplet diameter ~ 0.5 to
10 μm depending upon the polymerization temperature &
rate of agitation.)
 The emulsion of monomer in water is stabilized
by a surfactant. (A surfactant has a hydrophilic and
hydrophobic end in its structure. When it is put into a water,
the surfactant molecules gather together into aggregates
called micelles. The hydrocarbon tails (hydrophobic) orient
inwards & heads (hydrophilic) orient outwards into water.)
The monomer molecules diffuse from monomer
droplets to water & from water to the
hydrocarbon centre of micelles.
Application
• Some grades of styrene-butadiene (SBR)
• Some grades of Polybutadiene
Synthetic rubber • Polychloroprene (Neoprene)
• Nitrile rubber
• Acrylic rubber
• Fluoroelastomer (FKM)

• Some grades of PVC; polystyrene; PMMA

• Acrylonitrile-butadiene-styrene terpolymer (ABS)
Plastics • Polyvinylidene fluoride
• Polyvinyl fluoride
• PTFE

• polyvinyl acetate
• polyvinyl acetate copolymers
Dispersions • polyacrylates
• Styrene-butadiene
• VAE (vinyl acetate – ethylene copolymers)
Advantages & Limitations
Advantages Limitations
 High molecular weight polymers can be made at fast  For dry (isolated) polymers,
polymerization rates. water removal is an energy-
 In others lie a tradeoff between molecular weight and intensive process
polymerization rate.  They are usually designed to
 The continuous water phase is an excellent conductor of operate at high conversion
heat that allows the heat to be polymer molecules are of monomer to polymer.
contained within the particles, so it is method to increase  It may result in significant
the rate of many reactions. chain transfer to polymer.
 Since polymer molecules contained within water viscosity
remains close to that of water and is not dependent on
molecular weight.
 The final product can be used as is and does not
generally need to be altered or processed.
Examples of different kinds of advanced emulsion systems that
can be designed using food-grade ingredients

High internal phase emulsions

Methods for the synthesis of cross-linked

PS particles spanning a range of sizes.

Emulsion Polymerization
Condensation polymerization
Schematic representation of the interfacial
polycondensation reaction in the miniemulsion.
 2.4
Modification
of polymers
 Surface modification

Surface properties of any polymers have an

imminent influence over key properties such
as wetting, adhesion, friction, and
biocompatibility, therefore affecting
the applicability of a polymer material.
 Physical Routes
Advantages: simple, cost-effective, scalable
and ecofriendly (does not require the use of
any chemicals).
While it cannot change the inherent chemical
nature of the polymer, modifying the polymer
surface by physical methods alters its
wettability by inducing roughness in micro-
and nanoscale.
Application: Superhydrophobic surfaces;
antifouling, and ice-phobic surfaces for
industrial

Chematic showing the replication process and the process

parameters andSEM images showing the silicon (Si)
master pattern structure and the replica of the pattern in
polypropylene (PP).
 Chemical Treatment on Polymers
a) Wet chemical treatment of
polymers in selective
functionalization of surfaces,
inhibit bacterial and fungal
growth and cleans the surfaces
by actively removing dust and
grime.
b) Selective treatment of polymer
(PET) resulting in a positively,
and negatively charge surface
with different wet chemicals with
simultaneous enhancement in
wettability.
c) SEM microscopy images of a dip
coated epoxy cresol novolac
resin: i) before and ii) after
swelling and etching with hot
KMnO4/NaOH solution.
 Surface Treatment of Polymers by Plasma
• Advantages: relatively simple process that is clean,
solvent-free, fast, and environmentally friendly.
• In surface plasma treatment, inert gases such as
oxygen, nitrogen, and hydrogen are used to
dissociate and react with the substrate surface and
to change its properties such as wettability,
printability, and adhesion

Schematic overview of plasma surface interactions.

 Treatment of Polymers with Corona
a) Mechanism of spatially selective
hydrophilic surface modification of PDMS
by corona discharge. PDMS was found to
show more hydrophilic character than
oleophilic, a condition not normally
achieved due to very low surface tensions
of oil.
b) Schematic of the setup and chemical
phase reaction of corona in air.
c) Mechanism of rear side treatment of a
rough porous substrate. Corona discharge
penetrates partially through the substrate
via pores, consequently ionizing the air
between the backing roll and substrate.
 Ultraviolet (UV) Treatment of Polymers
 UV treatment is an effective,
economical and an efficient
noncontact polymer surface
modification method with
fewer processing steps.
 UV treatments are usually
performed for curing photo
(light-sensitive) polymers,
for increasing the surface
adhesiveness
(hydrophilicity),and for
functionalizing the surface
by photoinitiated polymer
grafting in the presence of
photoinitiator/photosensitizer.
Treatment through Thermal Annealing
Representations of woven and nonwoven fabrics.
a) Woven fabrics with more regularly
compartmentalized free space between the
fibers.
b) Nonwoven fabrics with interconnected
continuous free space between the fibers.
c) Nonwoven electrospun mat detail visualizing a
soldering-like attachment of the nanofibers at
their junction points through interpenetration
and entanglement of polymer chains after
annealing.
d) Cross-linking of fluorinated polymer after
annealing.
Surface Modification through Patterning
Patterned polymeric surfaces have numerous applications in
electronics, optical devices, and biomedical fields, masks and
templates

Evaporation Dewetting Photolithography

Block Microcontact
Laser
copolymers printing
 Evaporation
Evaporation of solvents from
thin films of polymer, leaving
the nonvolatile solutes
assembled, can produce
unique patterns.
Dewetting
Schematic representation of the fabrication of ordered
arrays of holes with tunable size and depth by colloidal
imprinting on P4VP/ PS bilayers followed by dewetting
of P4VP fi lms on PS fi lms via thermal annealing.
i) Self-assembly of single-particle colloidal crystals on
P4VP/ PS bilayers.
ii) Colloidal imprinting of the P4VP/PS bilayers by
thermal annealing.
iii) Particle removal by sonication.
iv) Tuning of the both the hole diameter and depth
by dewetting of P4VP on top of PS.

Application: Dewetting method has been used to

fabricate polymeric patterned structures for
potential applications in memory
storage devices, optical devices, electronics, and
membranes.
 Photolithography
This process uses the light to transfer patterns to a photoresist film using a photomask or optical
interference (holographic) and then subsequently removes selected area of the film through
dissolution in an appropriate solvent. The light irradiation causes photopolymerization, photo-cross-
linking, functionalization, and decomposition.

Application: light emitting displays (LEDs),polymer dispersed liquid-crystal displays

(LCDs), optical components, sensors and actuators, and 3D photonic crystals.
 Block copolymers
Block copolymers
(BCPs) are prepared
by polymerization of
one monomer in a
controlled manner,
then followed by
chain extension with
a different monomer
to form copolymers.
As a result, blocks of
two or more
polymeric chains are
formed side-by-side,
which are chemically
different and
covalently attached
to each other.
 Pattern transfer using block copolymer Block copolymers

Block copolymers (BCPs) are self-assembled at

various structures such as micelles, spheres,
cylinders, lamellae, with dimensions from a few
nanometers to above 100 nm

Applications: BCPs are used as templates for

fabrication of nanoscale metal, ceramic
nanodots and wires, photonic crystals, and
high density information storage media.

Isoporous block copolymer membranes.

 Laser Surface Texturing

The fundamental process of LST

relies on a focused laser beam
aimed on the surface of the
polymer where
radiation from the laser beam is
absorbed into the topmost
layer, inducing heat. The
inducted heat causes melting or
even vaporization, which in-turn
modifies the surface.
 Microcontact printing
Schematics depicting the microcontact
• In microcontact printing, a rigid or elastic printing (µCP) technique
polymeric stamp with relief features transfers
the polymer solution to the substrate which
makes it a very straightforward and cost-
effective method.
• PDMS is the most used microcontact stamp
due to its transparency, flexibility, and ability
to make conformal contact with rough
surfaces.
• Advantages: Faster processing times, lower
consumption of ink molecules, and ability to
impart high resolution patterns on the
largearea surfaces are the advantages of this
method.
• Application: Microcontact printing technique
is majorly used for manufacturing of the
organic electronics, LEDs, transistors,
electronic papers, and integrated circuits