Polymer

Engineering
Ch.E- 433
Dr. Hirra Anjum
hirra.anjum@uet.edu.pk
 Course Outline
• Basic principles of polymerization processes, polymer molecular weight,
& structure
• Polymer synthesis and characterization
• Types of polymerization
• Dependance of properties on molecular structure & microstructure
• Polymer rheology
• Unit processing operations, formulation, & uses of polymers
• Mechanical properties
• Degradation & failure methods
• Analysis and identification of polymers.
 Mapping
Mapping with
COURSE LEARNING OUTCOMES (CLOs)
with PLO Bloom’s
Taxonomy

CLO-1: To have basic knowledge of the polymers, their properties,

PLO-1 C2
and polymer characterization techniques available for testing.

CLO-2: Understand the mechanical properties of polymers and

PLO1 C1
gain an insight into the thermodynamics of polymer solution.

CLO-3: To analyze and identify the polymer through

characterization techniques and study the degradation & failure PLO-2 C2
methods.
 Polymer age
• Natural Polymers
• Protien (methane,Ammonia, carbon dioxide)
• Wood, Cotton, Cellulose,Starch
• Instinct to Survive: Before (Animal skin), Now (polyester/Nylon)
• Joseph Priestley: Weeping wood (exuade from a tree) may remove
pencil marks, (rubber/yen)
• Christian Schonbein: Cotton to combustible gun cotton (nitro
derivative of naturally occurring cellulose
• Jhon Wesley Hyatt: Elephant tusks (Celluloid)
• Leo Baekeland: Phenol+formaldehyde (Bakelite)
Spectrum of plastic articles used in our daily life
 Polymer age
• Polymers can be converted into strong solid articles, flexible
rubber-like masses, soft and resilient foams, smooth and fine
fibers, clean and clear glass-like sheets, swollen, jelly-like
food materials, and so on.

• They can be used to bond objects, and real joints, fill cavities,
and bear loads, in fact, anything from clothing to space
vehicles even replaces human organs. This explains why this
age could pass as the polymer age.
 What are polymers
• Complex and giant molecules and are different from low molecular
weight compounds (common salt).
• These macromolecules are made up of much smaller molecules.
 Classification
• Polymers cannot be classified under one category because of their
complex structures, different behaviors and vast applications. We can,
therefore, classify polymers based on the following considerations.
• Based on processing
• Based on polymerization mechanism
• Based on polymer structure
 Classification Based on Processing
1. Thermoplastic polymers
2. Thermoset polymers
 1. Thermoplastic polymers
• Thermoplastic pellets soften when heated and become more fluid as more
heat is administered.
• The curing process is 100% reversible as no chemical bonding takes place.
• This characteristic allows thermoplastics to be remolded and recycled
without negatively affecting the material’s physical properties.
• There are a variety of thermoplastic resins that offer various performance
benefits, but the majority of materials commonly used offer high strength,
shrink-resistance, and easy flexibility.
• Depending on the resin, thermoplastics can serve low-stress applications
such as plastic bags or can be used in high-stress mechanical parts.
• Examples of thermoplastic polymers include polyethylene, PVC, and nylon.
 Applications of thermoplastic polymers
• Thermoplastics are considered to be a favorable substitute to minimize
these costs. Certain properties of thermoplastics that make them a
suitable substitute material are:
• Their ability to withstand corrosive materials and corrosive environments.
• Being able to carry materials of extreme temperatures (hot or cold).
• Their capacity to handle virtually any type of fluid transport application.
• Common materials used to produce these pipes are PVC or CPVC.
Additional materials include polypropylene, PVDF, ABS, nylon, and
polyethylene. Polyethylene gas tanks are used to transport natural gas for
use in residential and commercial applications
Pros and Cons of Thermoplastic Materials
 Common Thermoplastic
• Some of the most common thermoplastic materials in use include:
1. Polycarbonate
2. Acetal Copolymer Polyoxymethylene
3. Acetal Homopolymer Polyoxymethylene
4. Acrylic
5. Nylon
6. Polyethylene
7. Polypropylene
8. Polystyrene
9. Polyvinyl chloride (PVC)
10. Teflon
 2. Thermoset Polymers
• thermoset polymers as implied by their name become set in their
physical and chemical properties after an initial heat treatment and
therefore are no longer affected by additional heat exposure.
• The process is very similar to hard boiling an egg. Once the egg is
boiled, additional reheating does not cause disfiguration – similar to
the curing process associated with a thermoset part.
• After initial heat forming, thermoset material’s ability to exhibit
resistance to heat, corrosion, and mechanical creep make them
perfectly suitable for use in components that require tight tolerances
and excellent strength-to-weight characteristics, while being exposed
to elevated temperatures.
 Applications of thermoset plastics
• Thermoset plastics offer enhanced high-performance combination of thermal
stability, chemical resistance, and structural integrity.
• Thermoset components are used extensively in a wide range of industries – and
are used for applications in the automotive, appliance, electrical, lighting, and
energy markets due to excellent chemical and thermal stability along with
superior strength, hardness, and moldability.
• Thermoset plastic composites are capable of meeting the specifications of a wide
range of production materials at a very low cost.
• Their use allows for an assortment of small and large parts to be fabricated with
high production volume while maintaining their repeatability consistently from
batch to batch.
• Thermosets provide an alternative process when complex and geometric shapes
cannot be achieved through metal fabrication or the use of thermoplastics but
can be manufactured in a mold.
Pros and Cons of thermoset polymers
 Common Thermoset polymers
• Epoxy (e.g., carbon fiber epoxy resin)
• Phenolics
• Bismaleimide (BMI)
• Fluoropolymers
• Polytetrafluoroethylene (PTFE)
• Polyvinylidene fluoride (PVDF)
• Melamine
• Silicone
• Urea Formaldehyde
2. Based on polymerization mechanism
• The reaction of combining these monomers to form long chains
or three-dimensional networks is known as polymerization. Broadly
polymerization can be classified into two categories,

• Step-Growth or Condensation Polymerization

• Chain-Growth or Addition Polymerization
 Addition Polymerization
• As the name suggests addition polymers form when an addition reaction
occurs. The repeating monomers form a linear or branch structure
depending on the type of monomer. During addition polymerization, the
monomers rearrange themselves to form a new structure. But there is no
loss of an atom or a molecule. Again there are four types of addition
polymerizations which are

• Free Radical Polymerization

• Cationic polymerization
• Anionic Vinyl Polymerization
• Coordination Polymerization
 Free Radical Polymerization
• the addition polymer forms by addition of atoms with a
free electron in its valence shells. These are known as free radicals.
They join in a successive chain during free radical polymerization.
 Cationic polymerization
• A polymerization where a cation is formed causing a chain reaction.
• It results in forming a long chain of repeating monomers
 Anionic Polymerization
• Involves the polymerization of particularly vinyl polymers with a
strong electronegative group to form a chain reaction
 Coordination Polymerization
• This method was invented by two scientists Ziegler and Natta who
won a Nobel Prize for their work.
• They developed a catalyst which let us control the free radical
polymerization.
• It produces a polymer which has more density and strength
Coordination Polymerization
 Condensation Polymerization
• It is a form of a step-growth polymerization where smaller molecules
or monomers react with each other to form larger structural
units (usually polymers) while liberating by-products such as water,
gas or saltmolecule. The by-products are normally referred to as
condensate.
• These polymers are obtained by random reaction of two molecules.
• Common examples are esterification, amidation.
 Classification based on Polymer Structure
• Polymers are also classified by Chemical structure of their backbone
as
• Linear polymers
• Branched polymers
• Crosslinked polymers
• Network polymers
 Homochain polymers
• Polymers having all carbon atoms along their backbone are
homochain polymers
• If these carbon chain polymers exist with only single bond along the
backbone called as polyalkylenes.
• Examples are polystyrene, polyolefins, poly vinyl chloride.
• Carbon chain polymers with double bonds such as diene elastomers
are called polyalenylenes
• Carbon chain with triple bond are called polyalkynylenes
(polyacetylene)
 Hetrochain polymers
• Polymers that contain more than one atom typein their backbone are grouped
according to the type of atoms and chemical groups
• Carbon oxygen polymers
• Polyethers
• polycarbonates
• Carbon sulfer polymers
• Polythioethers
• polysulfones
• Carbon nitrogen polymers
• Polyamines
• Polyimines
• Polyamides
• polyureas
 Review of Previous Lecture
Introduction to polymeric materials

1/20/2023 34
 What are polymers made from?
Many polymers are formed from alkenes, which are a family of
hydrocarbon molecules with the general formula CnH2n.
Alkenes contain at least one double covalent bond between carbon
atoms. The double bond makes them very reactive.
⚫ The simplest alkene is ethene
(C2H4).

double
covalent
bond

⚫ The second simplest alkene is

propene (C3H6).

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Polymer Families
Recall polymer categories:
Plastics:
Thermoplastics
Engineered and commodity
Thermosets
Engineered and commodity
Elastomers:
Thermosets and thermoplastics

1/20/2023 36
 Introduction
• Most of polymers need to add with specific ingredients to obtain desirable properties.

• Additives were used:

• To improve or modify the mechanical, chemical, and physical properties
• To prevent degradation (both during fabrication and in service)
• To reduce materials costs
• To improve the processability

• Each of the additives in formulation has specific functions either during processing or end products
applications

• Typical additives include

• Plasticizer
• filler materials,
• stabilizers,
• colorants
• flame retardants.
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 Plasticizers
➢ Can be in liquid, half solid or solid form.

➢ It must be compatible with the polymeric materials and other

compounding ingredients → incompatibility will result in poor processing
properties.

➢ Plasticizer were used for:

1. ‘extender’ (large amount >20 pphr)→ to make the end products cheaper
2. Processing aid (small amount 2-5 pphr)→ to make the processing easier

3. Modifier → to modifies some polymeric properties.

1/20/2023 38
oThe aid of additives called plasticizers can :
oimprove the flexibility, ductility, and toughness
o produces reductions in hardness and stiffness

olowers the glass transition temperature → at ambient conditions the polymers

may be used in applications requiring some degree of flexibility and ductility.

oThese applications include thin sheets or films, tubing, raincoats, and

curtains.

1/20/2023 39
 •Reduces vander waal’s
Primary forces
plasticizers •Allow greater mobility

•Provide mechanical
Secondary separation between
plasticizers the molecules
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 Fillers

➢Fillers normally add in polymeric materials for economical

or technical reasons.

➢Filler materials are most often added to polymers to

improve tensile and compression strengths, abrasion
resistance, toughness, dimensional and thermal stability
and other properties.

1/20/2023 43
 Fillers

• Materials used as particulate fillers → include wood flour (finely powdered sawdust), silica
flour and sand, glass, clay, talc, limestone, and even some synthetic polymers.

• Particle sizes range all the way from 10 nm to macroscopic dimensions

• Because these inexpensive materials replace some volume of the more expensive polymer,
the cost of the final product is reduced.

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 Stabilizers
• Some polymeric materials under normal environmental conditions →are subjected to rapid
deterioration in mechanical properties.

• Most often this deterioration is a result of exposure to light → in particular ultraviolet

radiation and oxidation

• Ultraviolet radiation →
• causes a severance of some of the covalent bonds along the molecular chain
• also result in some crosslinking.

• Oxidation deterioration is a consequence of the chemical interaction between oxygen atoms and the
polymer molecules.

• Additives that counteract these deteriorative processes are called stabilizers.

1/20/2023 47
 Colorants
o Colorants impart a specific color to a polymer

o They may be added in the form of:

o dyes
o The molecules in a dye actually dissolve and become part of the molecular structure of the
polymer. Suitable for coloring transparent polymers

o Organic pigments.
o Pigments are filler materials that do not dissolve → but remain as a separate phase; they are
opaque

o have a small particle size, high heat and light stability

o Others may impart opacity as well as color to the polymer.

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 • Inorganic pigments

1/20/2023 49
 Anti static agents

• Are used to increase the surface conductivity

• It prevents the attraction of dust particles
• Reduces the risk of explosion in hazardous environment

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General properties of polymeric materials

1. Electrical insulation
2. Strength/weight ratio
3. Corrosion resistance

1/20/2023 51
 Rubber

“I have seen a substance excellently

adapted to the purpose of wiping from
paper, the marks of a black lead
pencil” (Joseph Priestley)

1/20/2023 52
 Rubbers

• “ a material which can be elastically deformed a large amount and when the
force is released, it comes back to its original position is known as
elastomer”

• Examples: Natural Rubber, SBR, Polyisoprene etc.

1/20/2023 53
 Rubber as Elastomer

• A soft elastomer can be turned as rigid and brittle thermoset e.g. SBR is
soft and flexible, but after vulcanization with sulfur it turns rigid and
brittle
• Fully vulcanized Natural Rubber is called “Ebonite”

1/20/2023 54
 Flexibility and Elasticity

• A polymer is flexible if it can yield to force without breaking.

• A polymer is elastic if it regains its original shape after a distorting force is
removed.
• Elastomers are flexible as well as elastic materials.
• The natural polymer rubber is the prototype for this kind of material.
• Natural rubber is soft and tacky when hot. It can be made harder in a
reaction with sulfur, called vulcanization.

1/20/2023 55
 Vulcanization

1/20/2023 56
Polymer Engineering
Chemistry of polymerization
 Contents of the lecture
• Types of Polymerization
1. Chain Polymerization
2. Step Polymerization
3. Miscellaneous Polymerization
• Polymerization Techniques
1. Bulk Polymerization
2. Solution Polymerization
3. Emulsion Polymerization
4. Melt Polycodensation
5. Solution Polycondensation
6. Interfacial Condensation
7. Solid & gas phase polymerization
 Polymerization
• Polymerization is a process which allows simple low
molecular weight compounds to combine and form
high molecular complex compounds.
 Types of Polymerization

1. Chain Polymerization
2. Step Polymerization
3. Miscellaneous Polymerization
Free Radical Polymerization
Initiators
List of free radical initiators
List of free radical initiators
List of free radical initiators
List of free radical initiators
 Ways to liberate Initiator
1. Thermal Decomposition
2. Photo Decomposition
3. Catalytic Decomposition
4. Excitation of monomer
5. Redox Initiators
Thermal Decomposition
Rate of Decomposition
Decomposition behaviour of certain initiators at
different temperatures
Decomposition behaviour of certain initiators at
different solvents
Photochemical Decomposition
Direct excitation of monomers
Induction of Initiator by suitable
catalyst
Induction of Initiator by suitable
catalyst
 Redox Initiators
Redox polymerisation
Steps Involving Free radical polymerization
• Initiation
• Propagation
• Termination
• Chain transfer
• Inhibitors
Initiation
Initiation
Initiation
Propagation
Propagation
Propagation
Propagation
Propagation
Termination
Termination
Termination
Termination
Polymer Engineering
Ch.E-410
Dr. Hirra Anjum
Chain Transfer
Chain Transfer
Chain Transfer
inhibitors
Inhibitors
Inhibitors
Inhibitors
Inhibitors
Inhibitors
Inhibitors
 Industrial practice-Inhibitors
Short stops
Ionic Polymerization
 Ionic Polymerization

Chain Reactions
Ionic Polymerization

Co Catalyst
Ionic Polymerization Initiation
Ionic Polymerization
Ionic Polymerization Termination
Ionic Polymerization-Proton donation

Dead Polymer Molecule

Ion Pair Precipitation
Ionic Polymerization-Formation of
covalent bond
Cationic Polymerization
Anionic Polymerization
Anionic Polymerization
Anionic Polymerization
Anionic Polymerization & Cationic
Polymerization differences
Anionic Polymerization
Anionic Polymerization-Termination
Anionic Polymerization-Termination
Coordination Polymerization
Coordination Polymerization
Insertion Polymerization
Coordination Polymerization
Zieglar Natta Catalyst
Zieglar Natta Catalyst

Coordination Complexes
Zieglar Natta Catalyst Structure
Natta Mechanism
Cossee Monometallic mechanism
Factors , depend, formation of syndiotactic polymer
Stereo-Regularity Formed
Mechanism Of the active centre formation
Mechanism of the active centre formation
Polymer Engineering
Ch.E-410
Dr. Hirra Anjum
Zieglar Natta Catalyst
Zieglar Natta Catalyst

Coordination Complexes
Zieglar Natta Catalyst-Structure
Natta Mechanism
Cossee Monometallic mechanism
Factors , depend, formation of syndiotactic polymer
Stereo-Regularity Formed
Mechanism Of the active centre formation
Mechanism Of the active centre formation
 Step Polymerization
• The polymer build up proceeds through a reaction between functional
groups of monomers.
• The reaction takes place in step wise manner and polymer buildup is
therefore slow.
• Although many known reactions with organic functional groups can be
made use of in step polymerization,
a. condensation,
b. addition,
c. ring-opening,
d. amidation, and
e. ester interchange reaction are the most commonly used ones.
 Step Polymerization
• Step polymerization reaction are mostly accompanied
by the elimination of small molecules.
• Whether the elemental composition of polymer
formed and that of the monomers are the same or not
depends on whether the reaction is accompanied by
the elimination of small molecules or not.
Polycondensation
Polycondensation
Polycondensation
Polycondensation-Generic Reactions
Polycondensation-Generic Reactions
Polymer Engineering
Ch.E-410
Dr. Hirra Anjum
 Polyaddition Polymerization
• Polyaddition polymerization is brought about by the
migration of one monomer molecule to another, or to the
intermediate product.
• Vinyl monomers and monomer pairs with reactive
functional groups undergo polyaddition polymerization.
• No free radiacal, carbanium or carbonium ion formation.
• Like chain polymerization, monomer units are simply
added one after another to form a polymer without
eliminating any small molecule.
Styrene Styrene
 Polyaddition Polymerization
• Since polymer is formed by the migration of hydrogen atom from the
monomer and its addition at the double bond this process involves a
higher activation energy as compared to free radical or ionic
polymerization.
• The polymer growth is rather gradual and is brought about step by
step, as against the rapid chain growth in chain polymerization.
Pairs of monomers with reactive
functional groups
diisocyanate diol

Polyurethane
Polycondensation

Polyaddition
 Limitations of polyaddition
• Both vinyl monomers as well as monomer pairs with reactive
functional groups can undergo polyaddition polymerization.
• However, the hydrogen atom in a methylene group of vinyl
monomer is not that mobile, it is not that easy to get really high
molecular weight polymers from vinyl monomers by this
technique.
• Oligomers are the best example prepared from this technique.
• On the contrary, monomers (polyhydric alcohols and polyamines)
can easily undergo polyaddition with polyisocyanates, yielding
polyurethanes and polyureas of a very high molecular weight.
Polyurea
 Ring opening Polymerization
• Monomers having ring structure can be opened up and polymerized if the
conditions are feasible.
• Condensing a bifunctional low molecular weight compounds having a strain
free configuration
 Example 1-anionic chain polymerization
• Initiation step:
Sodium methoxide when dissolved in dioxane attacks on ethylene oxide
which is the heterocyclic oxirane ring compound and cleaves to form a
ring.

Ethylene oxide Sodium methoxide Methoxy ethane

 Example 1-anionic chain polymerization

• Propagation step:
The newly formed anion attacks the fresh ethylene ring, which will be
opened up and added on with the simultaneous formation of anion and
this process goes on and on.
 Example 1-anionic chain polymerization

• Termination step:
When the anion is caged by the addition of proton in the form of HCl,
termination occurs.

• Note:
This polymerization is similar to the anionic chain polymerization the only
difference is that in the latter, the attack by the anion is on the π electron
pair, while in this case, it is on the activated ring.
 Example 2- by anion polymerization
o In this case, the attacking anionic species is the caprolactam anion (I)
introduced in the form of sodium caprolactam and N-acetyle
caprolactam (1%).

o The Anion attacks the caprolactam molecule and abstracts a proton,

generating a new capralactam anion (II).
 Example 2- by anion polymerization
o This new anion opens up the ring in the dimer (III) formed between
sodium caprolactum and N-acetylecaprolactam.
 Example 2- by anion polymerization

o The anion on the trimer carries the attack on the fresh caprolactam molecule and
abstracts a proton, generating a new monomeric anion, followed by proton
abstraction.
Example3- ring opening by catalytic quantities
Polymer Engineering
Dr. Hirra Anjum
 POLYMERISATION TECHNIQUES
• The terminology included terms such as polymerization
system, catalyst system and solvent system.
• These refer to the physical aspects of polymerization
reactions which decide
o whether the monomer is polymerized in its condensed or
gaseous state,
o whether it is polymerized as such or along with other inert
components such as solvents and non-solvents.
Factors influencing the physical conditions
of polymerization
• There are some factors that dictate the physical conditions
under which polymerization is to be carried out.

• Nature of the monomer,

• The type of polymerization mechanism chosen,
• The required physical form of the polymer,
• Viability of the process for industrial production
 Types of polymerization techniques
• These varying physical conditions lead to different polymerization
techniques, as enumerated in the following sections.
1. Bulk polymerization
2. Solution polymerization
3. Suspension polymerization
4. Emulsion polymerization
5. Melt polycondensation
6. Solution polycondensation
7. Interfacial condensation
8. Solild & gas phase polymerization
 1. Bulk polymerization
• The monomer is taken in the liquid state and the initiator is
dissolved in the monomer.
• The chain transfer agent, whenever used to control the
molecular weight, is also dissolved in the monomer itself.
• The whole system is, therefore, in a homogeneous phase.
• The reaction mass is heated or exposed to a radiation
source for initiating the polymerization and is kept under
agitation for proper mass and heat transfers.
 1. Bulk polymerization
• This whole phenomenon is called 'auto-acceleration' and,
sometimes, the uncontrolled exothermic reaction can lead
to an explosion.
• Bulk polymerization, however, is quite simple and the
product obtained has a high purity since, except the
initiator and the chain transfer agent, no other additive that
could contaminate the product is used.
 1. Bulk polymerization-Disadvantages
1. As the polymerization proceeds, the viscosity of the medium
increases and mixing becomes progressively difficult, leading to
products with very broad molecular weight distribution.

2. Another disadvantage of bulk polymerization is that as the medium

gets viscous, the diffusibility of the growing polymer chains
becomes restricted, the probability of chain collision becomes less,
termination becomes difficult, active radical sites accumulate and
the rate of polymerization increases enormously.
 1. Bulk polymerization
• The polymer obtained can also be used as such since no isolation from
other components is involved.

Application:
• The bulk polymerisation technique is used in
• the free radical polymerisation of methyl methacrylate or styrene to
get transparent moulding powders and
• cast sheetings
• vinyl chloride to get PVC resin.
 2. Solution polymerization
• In solution polymerization, the monomer is dissolved in a
suitable inert solvent along with the chain transfer agent,
whenever used.
• The free-radical initiator is also dissolved in the solvent
medium, while the ionic and coordination catalysts, can either
be dissolved or suspended.
• The presence of the inert solvent medium helps to control
viscosity increase and promote a proper heat transfer.
 2. Solution polymerization- Disadvantage
• The major disadvantage of the solution polymerization
technique is that, however inert the selected solvent involved
in chain transfer to the solvent, cannot be completely ruled
out and, hence, it is difficult to get very high molecular
weight products.
• The polymer formed will also have to be isolated from the
solution either by evaporation of the solvent or by
precipitation in a non-solvent, and removal of their final
traces is always extremely difficult.
 2. Solution polymerization-Advantages
• Solution polymerization techniques, nevertheless, can
advantageously be used
1. where the polymer is used in its solution form,
2. as in the case of certain adhesives and coating compositions,
3. in systems where the polymer formed is insoluble in its
monomer,
4. solvent and precipitates out as a slurry and is amenable for
easy isolation.
 2. Solution polymerization-Applications
• Industrial production of polyacrylonitrile by free-radical
polymerization,
• Industrial production of polyisobutylene by cationic
polymerisation,
• Block co-polymers are also made exclusively by this
technique.
 3. Suspension polymerization
• Only water-insoluble monomers can be polymerized by this
technique.
• The monomer is suspended in water, in the form of fine droplets,
which are stabilized and prevented from coalescing by using
suitable
• water-soluble protective colloids,
• surface active agents
• stirring.
 3. Suspension polymerization-size of
monomer droplets

The size of the monomer droplets formed depends on

• the monomer-to-water ratio,

• the type and concentration of the stabilising agents
• the type and speed of agitation employed.
 3. Suspension polymerization-Initiators
• The initiators are monomer soluble.

• Since each monomer droplet is isolated and independent of

the other droplets, it can be visualized to act as an
independent bulk polymerization nucleus.
 3. Suspension polymerization
• The continuous aqueous phase separating the monomer droplets
acts Ad as an efficient heat transfer medium and, hence, the
exothermicity is well controlled.
• Since water is used as the heat transfer medium, the process is
also economical as compared to solution polymerization.
• As the entire bulk of the monomer is divided into innumerable
tiny droplets, control on the kinetic chain length of the polymer
formed is also quite good, resulting in a fairly narrow molecular
weight distribution of the product.
 3. Suspension polymerization- bead or
pearl polymerization
• Polymerization proceeds to 100% conversion and the product is
obtained as spherical beads or pearls.
• For this reason, this technique is also known as bead or pearl
polymerization.
• Isolation of the product becomes easy as this involves only filtration
of the beads and removal of the surface active agents and protective
colloids by water washing.
• The water- washed and dried product can be used as such for
moulding purposes or can be dissolved in a suitable medium for use
as adhesives and coatings.
 3. Suspension polymerization- Products
1. Expandable polystyrene beads (from which polystyrene
foams are made),
2. styrene-divinyl benzene co-polymer beads (for the pre-
paration of ion-exchange resins)
3. polyvinyl acetate beads (for further conversion into
polyvinyl alcohol) are produced by the suspension
technique using free-radical initiators.
 Emulsion Polymerization
• As in the case of suspension polymerisation, in emulsion
polymeri- sation too, the monomer is dispersed in the
aqueous phase not as discrete droplets, but as a uniform
emulsion.
• The emulsion is stabi- lised by surface active agents
(surfactants), protective colloids and of fatty acids and of aryl
and alkyl sulfonic acids), cationic (alkyl amine
hydrochlorides and alkyl ammonium halides) or non-ionic
(alkyl glycosides and saccharose esters of fatty acids).
 Emulsion Polymerization
oSurfactants serve the purpose of lowering the surface tension at the
monomer- water interface and facilitate emulsification of the monomer-in
water.
oOwing to their low solubility, surfactants get fully dissolved or molecularly
dispersedly at low concentrations.
oBeyond a particular concentration, the excess quantity does not get
molecularly dispersed.
oBut forms molecular aggregates known as 'micelles', and an equilibrium is
set up between the dissolved surfactant molecules and the aggregated ones.
oThe highest concentration, wherein all the molecules are in a dispersed
state, or the concentration beyond which only micelle formation is possible,
is known as the 'critical micelle concentration' (CMC).
oTypical examples of surfactants and their CMC values are given in Table
Emulsion Polymerization
 Emulsion Polymerization-Emulsifier
molecule
• Emulsifier molecules are made of two parts:
• a long non-polar hydrocarbon chain to which is attached a
polar group such as -COONa -SO,Na,-NH,HCl or -NBr.
• In micelle formation, the emulsifier molecules aggregate in
such a way that the polar end of the molecules align
themselves outward and the hydrocarbon ends come close to
each other at the interior.
micelles
Polymer Engineering
Dr. Hirra Anjum
hirra.anjum@uet.edu.pk
 Emulsion Polymerization
• Due to the close proximity of the hydrocarbon ends of all emulsifier
molecules, the interior of the micelle acts as a hydrocarbon phase
where the monomer can be solubilized.
• Now, when the monomer is added and agitated, emulsification takes
place, The resultant emulsion is a complex system:
a) a molecular solution of the emulsifier in water is the
continuous phase wherein the monomer drop-lets and
micelles (having the solubilized monomer at their interior)are
uniformly dispersed.
b) If the monomer is slightly soluble in water, then the aqueous
emulsifier solution phase will also contain a part of the
monomer dissolved in it.
Emulsion Polymerization
 Difference b/w suspension & emulsion
• The difference between the suspension system and the emulsion system is
that, while both have monomer droplets, the emulsion system has, in
addition, micelles in which the monomer is solubilized.
• If the quantity of the emulsifier added is less than the CMC, the system
becomes one of suspension polymerization and only when there is enough
emulsifier to form the micelles, can we get an emulsion system.
• Emulsion systems generally utilize water-soluble initiators such as
persulfates or hydrogen peroxide.
• Redox initiators are also widely used.
 Mechanism Involved
• In the emulsion polymerization technique, the monomer is present as
suspended droplets and solubilized at the micelle's interior.
• When the initiator is water soluble and monomer insoluble, there is
hardly any initiator in the monomer droplet; hence, no appreciable
polymerization occurs inside the monomer droplet.
• At the micelle, however, we have a very favorable condition for
polymerization. The surface layer of the micelle formed by the polar
ends of the emulsifier molecules is highly hydrophilic.
• Thus, an appreciable concentration of the initiator is found at this place.
At the same time, the interior of the micelle is filled with the solubilized
monomer.
 Mechanism Involved
• Polymerization, therefore, starts at the surface layer of the micelle and
proceeds inwards.
• As and when the monomer inside the micelle is consumed, more
monomer diffuses into the micelle from the monomer droplets present
in the aqueous phase.
• The chain growth continues till another radical species enters and
arrests the chain growth. With more and more polymer formation, the
polymer chains agglomerate into fine particles.
• Get surrounded and then stabilized by the emulsifier layer of the micelle.
• As the polymer particle concentration increases, it absorbs the monomer
and swells in size, which, in turn, enlarges the size of the micelle.
 Mechanism Involved
• At a particular stage, however, the micelle bursts and loses its
identity; all the emulsifier molecules originally forming the micelle
now form an absorption layer around the polymer particles.
• Further supply of the monomer to the growing chain inside the
swollen polymer particle comes, again, from the monomer
droplets.
• Monomer droplets in this emulsion system act only as a reservoir
where the monomer diffuses into micelles or polymer particles.
 Latex & its use
• At the end of the polymerization, we have fine particles of the polymer,
stabilized by the emulsifier layer and dispersed uniformly in the aqueous
phase.
• This milky white dispersion is often called ‘latex’.
• The latex can either be used as such for making adhesives, water-soluble
emulsion paints, etc.
• the polymer can be isolated from the latex by
1. destabilizing the emulsion (using some electrolytes),
2. spray drying
3. freezing.
 Factors influencing the Mechanism
The actual mechanism is quite complicated and varies from system
to system.
The simplicity or complexity of the system Depends upon
a) Whether the monomer is slightly soluble or completely insoluble
in water,
b) whether the initiator is soluble in water or monomer or in both,
the monomer/water and emulsifier/ water ratios.
 Chances of occurrence of
polymerization
The polymerization can occur at one or more of the following spots:
• (a) at the dissolved phase of the monomer in water;
• (b)at the interface between the monomer droplet and water;
• (c) inside the monomer droplet;
• (d) at the surface layer of the micelle;
• (e) at the hydrocarbon phase of the micelle;
• (f) at the surface of the polymer particle;
• (g) at the interior of the swollen mass.
 The Outcome

The ultimate result, however, is the

same in that the monomer droplets as
well as the micelles lose their identity
and the polymer is formed as fine
particles and is then stabilized into an
emulsion.
 Advantages of Emulsion Polymerization
oHeat transfer is very efficient, and the viscosity build-up of the
polymerization mass is quite low compared to the bulk and solution
techniques.

oSince the polymerization proceeds at the micelles, where the

surface/volume ratio is very high, the rate of polymerization is quite
high.

oSince the number of radicals in a micelle is very much limited and since
there is a continuous supply of monomer to the growing chain, a very
high molecular weight product is achieved by this technique.
Applications of Emulsion Polymerization
• Emulsion polymerization is the most widely used industrial
technique and monomers such as
• vinyl chloride,
• butadiene,
• chloro-prene,
• vinyl acetate,
• acrylates and
• methacrylate is polymerized by this technique.
 Melt Polycondensation
• This technique is used for the polymerization of monomers which have
at least one solid component and do not decompose around their
melting points.
• The temperatures involved in melt polycondensation are rather high
• Hence, the reaction has to be carried out in an inert atmosphere of N2
or CO2, to avoid such side reactions as can lead to oxidation,
decarboxylation, and degradation, etc .
• In some cases, the reaction is carried out under reduced pressure to
facilitate the removal of the byproduct, which becomes essential if a
high molecular weight product is aimed.
 Problems associated to MP
• Removal of the by-product becomes extremely difficult at later
stages of the reaction as there is a considerable increase in the
viscosity of the medium, like in bulk polymerization.
• The polymer formed is in the molten state at the reaction
temperature and is discharged from the reactor while hot, as
otherwise, it will solidify inside the reactor, and removal will
become extremely difficult.
• In most of cases, the hot melt from the reactor is passed on
directly to the processing equipment for extrusion, casting, or
spinning.
 Applications
• Production of polyethylene terephthalate from dimethyl
terephthalate and ethylene glycol is carried out by the melt
condensation technique.
• Preparation of nylon 6, 6 is another example, illustrative of the melt
condensation technique.
 Solution Polycondensation
• In the solution polycondensation technique, the reactants are taken as a
solution in a suitable inert solvent.
• The reaction can be carried out at comparatively lower temperatures
during which heat and mass transfer processes are easier than in the melt
technique.
• The solvent can also serve as an entrapping agent for the byproduct
formed and, hence, the removal of the byproduct becomes easy.
• Owing to the presence of the solvent phase, however, the kinetic
probability of chain growth is low and this leads to a reduced rate and a
low degree of polymerization.
Applications of Solution Polymerization
• Many of the liquid polyester resins based on glycols
and unsaturated dicarboxylic acid are prepared by
this technique using high-boiling aromatic
hydrocarbons as a solvent with which the
water(byproduct) forms an azeotrope and, hence,
can be removed easily.
 Interfacial Condensation
• In this technique, polymerization is allowed to proceed at the interface
between an aqueous and an organic medium.
• Reactants having highly reactive functional groups, which can readily
react at ambient temperatures to form condensation products, are
suited to this technique.
• Preparation of fully aromatic polyamides from terephtholoyl chloride
and para-phenylene diamine is a typical example:
 Interfacial Condensation
• ‘The diamine is dissolved in water and the acid chloride in chloro-form or
carbon tetrachloride.
• When the two solutions are brought in contact with each other, at the
interface, the diamine molecules diffuse into the organic phase and react
with the acid chloride, resulting in the formation of a polymer that
precipitates out immediately.
• The byproduct formed (HCI) diffuses back into the aqueous phase and gets
dissolved.
 Interfacial Condensation
• The precipitate is formed at the interface in the form of a thin film and,
when removed from the system, exposes a fresh surface of acid
chloride to the organic phase, resulting in the formation of a fresh
quantity of the polymer.

• Since the polymer formation at the interface is a diffusion-controlled

process, very high molecular weight products can be achieved by this
technique.
 Interfacial Condensation
• In actual production, the two solutions are very thoroughly agitated
so as to form an emulsion wherein the interface surface/volume ratio
is increased tremendously and,
• hence, both the rate and degree of polymerization become very high.
• As the polymer is formed, it precipitates out and, under the influence
of high-speed agitation, forms a slurry.
• The polymer is isolated from the slurry and washed free of adherent
reactants.
 Solid and gas phase polymerization
• Although polymerizations in liquid systems are very popular and very
widely used for industrial production, the same can also be carried out in
solid and gaseous phases.
• Solid phase polymerization is mostly restricted to chain polymerization.
 Limitations of SPP
SGP polymerization has the following limitations

1. restricted to low temperatures,

2. thermal activation of the reaction is quite difficult
3. the photo or radiation-activation technique is resorted.
4. Since molecular mobility in the solid state is completely restricted,
the polymer-building process becomes quite slow.
 SPP-Example 01
A good example of solid-state polymerization is the preparation of poly-formaldehyde
by the radiation polymerization of solid trioxane.

o Single crystals of trioxane, on irradiation, polymerise to form highly crystalline and

fibrous polyformaldehyde:
o Solid-state polymerisation of trioxane can also be brought about by conventional
cationic initiators such as BF,.
 SGPP-Example 01
• In this case, the monomer crystal is kept dipped in the catalyst
medium and the polymerisation proceeds with the diffusion of the
catalyst and the counter-ion into the monomer crystal.
 SPP-Example 02
o Photo-polymerisation of diacetylene derivatives is another example of solid-state
polymerization.
o The polymer formed is highly crystal-line and also conducts electricity:

diacetylene
derivatives
 Gas phase polymerization
• Gas phase polymerization is known in the case of very few olefinic
monomers.
• The disadvantage of the system is that it has a very poor heat transfer.
• The two methods used in the gas-phase polymerization are:
(i) spraying the catalyst (usually Zeigler-Natta type) into the gaseous
monomer
(ii) feeding the gaseous monomer into a fluidized bed made up of the
catalyst particles.
Note:
In both cases, the polymer is obtained as a free-flowing powder.
The polymerisation of ethylene and p-xylene can be cited as examples of
gas-phase polymerization.
 Spraying the catalyst into the gaseous
monomer
• In the first case, ethylene gas is passed through a fluidized bed
column filled with the Zeigler catalyst (made by mixing titanium
chloride and alkyl aluminum in a pentane medium, spray
drying, and powdering).
• The gaseous monomer is passed at room temperature at a
pressure of 4-5 atmospheres and the polymer formed is
collected as a free-flowing powder.
 Feeding the gaseous monomer into a
fluidized bed
• The polymerization of p-xylene is done in a different mode.
• First p-xylene is dehydrogenated to form its dimer (di-p-xylylene)
using superheated steam at 950°C.
• The dimer, which is a crystalline solid at room temperature, is then
heated to 600°C at I mm pressure when it sublimes forming an
equilibrium mixture of a diradical and a quinonoid.
• When this vapor is quenched to 50°C over metal surfaces, a linear
polymer called poly-p-xylylene is formed on the metal surface
quinonoid-diradical

Poly p xylylene

P xylylene
Bulk Polymerisation

Solution polymerisation , Suspension polymerisation, Emulsion

polymerisation, Melt polycondensation, Solution Polycondensation

Polymerization types differences

Bulk Polymerisation Solution, Suspension , Emulsion, Melt, Polycondensation

Polymerization types differences

Polymerization types differences
Solution polymerisation , Suspension polymerisation, Emulsion polymerisation,
Meltcondensation, Solution Polycondensation