POLYMER

PROCESS
 The Outline

Reactions of polymers
Addition Polymerization
Step Growth Polymerization

Kinetic Of Polymerization

Polymerization Processes
Bulk Polymerization
Solvent Polymerization
Suspention Polymerization
Emulsion Polymerization
Special Processes
 The Outline

Chemical and Physical Structures of Polymers

Polymer’s molecular structures

Confriguration and conformation of polymers
Chain structures of polymers

Physical Structures of Polymers

Polymer crystallinity
Crystallinity and amorphousness of polymers
 Outline

Types of Polymers and Polymer Processing

Members of Polymers

Definition of Thermosets & Thermoplastics

Common products and their properties

Forming Techniques of Polymers

Extrusion of polymers
Injection Molding
Blow Molding
Thermoforming
Compression Molding
Casting
 The Outline

Recycling of Polymers

Definiton of Recycling
Why is recycling important?
Benefits
Recycling of polymers
Addition Polymerization (Chain Growth)
Step Growth Polymerization (Condensation)
Differences between step-growth polymerization and
chain-growth polymerization
Step-growth polymerization
Growth throughout matrix
Rapid loss of monomer early in the
reaction
Same mechanism throughout
Average molecular weight increases
slowly at low conversion and high
extents of reaction are required to
obtain high chain length
Ends remain active (no termination)
No initiator necessary
Chain-growth polymerization
Growth by addition of monomer only at
one end of chain
Some monomer remains even at long
reaction times
Different mechanisms operate at
different stages of reaction (i.e.
Initiation, propagation and
termination)
Molar mass of backbone chain increases
rapidly at early stage and remains
approximately the same throughout the
polymerization
Chains not active after termination
Initiator required
Step of Radical Chain Polymerization

Initiation

Propagation

Termination
INITIATION
PROPAGATION
 TERMINATION
Dead Polymer
i.) Coupling or Combination;

ii.) Disproportionation
CHAIN TRANSFER REACTIONS
Transfer to monomer reaction

Transfer to initiator reaction

Transfer to solvent reaction

 IONIC CHAIN POLYMERIZATION

Using catalyst, not initiator

Highest reaction rate

Termination step is just disproportionation

Environment must be pure

Reaction occurs in the cold

Anionic Polymerization=Living Polymerization

If the starting reagents are pure and the

polimerization reactor is purged of all oxygen and

traces of water, polimerization can proceed until

all monomer is consumed.

CONDENSATION POLYMERIZATION

Using catalyst

Minumum two functional groups required

Usually linear

Molecular weight increases slowly at low conversion

High extents of reaction are required to obtain high

chain length
KINETICS OF POLYMERIZATION

Reaction rate of ionic polimerization more than
radicalic polimerization

So kinetics of ionic polimerization are not calculated

But kinetics of radicalic polimerization can be

analysed
 Kinetic of Radicalic Polymerization
Initiation;

Propagation;

Termination;
Kinetic of Radicalic Polymerization

Ro = overall rate of
polimerization

Rp = rate of chain
propagation

Ri = rate of initiation
step

Rt = rate of termination
step
Kinetic of Condensation
Polymerization

Equivalent reactivity
of functional groups.

It may be first, second

or third order by
depending upon.
 Kinetic of Condensation
Polymerization

Assumption = a stoichiometry balance of monomer concentration

POLYMERIZATION PROCESSES

Bulk Polymerization

Solvent Polymerization

Suspention Polymerization

Emulsion Polymerization

Special Processes

Electrochemical Polymerization

Radiation Polymerization

Grow-discharge (Plasma)
 Bulk Polymerization

The simplest technique

It gives the highest-purity polymer

Ingredients : monomer,

monomer-soluble initiator,

perhaps a chain transfer agent

Advantages
High yield per reactor volume
Easy polymer recovery
Final product form
Disadvantages
Difficult of removing the lost
traces of monomer
Dissipating heat produced during
the polimerization
 Solution Polymerization

Heat can be removed by conducting the polymerization in an organic solvent or
water

Initiator or monomer must be soluble in solvent

Solvents have acceptable chain-transfer characteristics

Solvents have suitable melting or boiling points for the conditions of

polymerization

Ingredients : monomer

initiator

solvent

Advantages Disadvantages
Temperature control is easy Small yield per reactor volume
Easy removed Solvent recovery
 Suspention Polymerization

Coalescense of sticky droplets is prevented by PVA

Near the end of polymerization, the particles harder and they can be

removed by filtration, then washing

Ingredients : water-insoluble monomer,
water-insoluble initiator,
sometimes chain transfer agent
suspention medium (water-usually)

Advantages (according to bulk Disadvantages

polymerization)
Forming process not using Polymer purity is low

Stirring is easy Reactor capital costs are higher

than for solution polymerization

Separation process is easy

 Emulsion Polymerization

Particles are formed monosize with emulsion polymerization

Polymerization is initiated when the water-soluble radical enters

a monomer-containing micelles.

Ingredients : water-insoluble monomer,

water-soluble initiator,
chain transfer agent,
dispersing medium (water),
fatty acid,
surfactant such as sodium salt of a long chain
Molecular structure of polymers

Typical structures are :

linear (end-to-end, flexible, like PVC, nylon)

branched

cross-linked (due to radiation, vulcanization)

network (similar to highly cross-linked structures,termosetting
polymers)

Figure1. Schematic representation of (a) linear, (b and c) branched, and (d and e) cross-linked polymers.

The branch points and junction points are indicated by heavy dots (Plastic Technology Handbook-Manas Chanda Salil K. Roy)
 Chemical Structure of Polymers
Molecular configuration of polymers

Side groups atoms or molecules with free bonds, called free-radicals, like H, O,
methyl affects polymer properties.

Stereoregularity describes the configuration of polymer chains :

Isotactic is an arrangement where all substituents are on the same side of the
polymer chain.

Syndiotactic polymer chain is composed of alternating groups

Atactic the radical groups are positioned at random

Figure 2: Isotactic Syndiotactic and Atactic combinations of a stereoisomers of polymer chain

(http://www.microscopy-uk.org.uk/mag/imgsep07/atactic.png)
 Molecular configuration of polymers

FIGURE.3. Diagrams of (a) isotactic, (b) syndiotactic, and (c) atactic configuration in a vinyl polymer.
The corresponding Fischer projections are shown on the right.
(Plastic Technolgoy Handbook)
Table 1. Properties of Polypropylene Stereoisomers
(Plastic Technology Handbook)
Molecular configuration of polymers
Geometrical isomerism:

The two types of polymer configurations are cis and trans. These structures
can not be changed by physical means (e.g. rotation).

The cis configuration  substituent groups are on the same side of a carbon-
carbon double bond.

Trans  the substituents on opposite sides of the double bond.

Figure4.cis trans configurations of polyisoprene

( http://openlearn.open.ac.uk/file.php/2937/T838_1_019i.jpg )
 Conformations of a Polymer Molecule

Conformation The two atoms have other atoms or groups attached

to them configurations which vary in torsional angle are known as
conformations (torsional angle:The rotation about a single bond which
joins two atoms )

Polymer molecule can take on many conformations.

Different conformation different potential energies of the

moleculeSome conformations: Anti (Trans), Eclipsed (Cis), and Gauche (+
or -)
 Other Chain Structures

Copolymers polymers that incorporate more than one kind of

monomer into their chain (nylon)

Three important types of copolymers:

Random copolymer contains a random arrangement of the multiple
monomers.

Block copolymer contains blocks of monomers of the same type

Graft copolymer contains a main chain polymer consisting of one type
of monomer with branches made up of other monomers.

Figure 5 :Block Copolymer Graft Copolymer Random Copolymer

http://plc.cwru.edu/tutorial/enhanced/FILES/Polymers/struct/struct.htm
 Physical Characteristics of Polymers

The melting or softening temperature ↑ molecular weight ↑

The molecular shape of the polymer has influence on the elastic

properties. ↑ coils the ↑ elasticity of the polymer

The structure of the molecular chains has an effect on the strength

and thermal stability. ↑ crosslink and network structure within the
molecule ↑ the strength and thermal stability.
 Polymer Crystallinity

Crystallinity is indication of amount of crystalline region in polymer

with respect to amorphous content

X-ray scattering and electron microscopy have shown that the

crystallites are made up of lamellae which,in turn, are built-up of
folded polymer chains

Figure.6 Schematic representation of (a) fold plane showing regular chain folding, (b) ideal stacking oflamellar
crystals, (c) interlamellar amorphous model, and (d) fringed micelle model of randomly distributed crystallites

(Plastic Technology Handbook)
 Polymer crystallinity

Crystallinity occurs when linear polymer chains are structurally

oriented in a uniform three dimensional matrix. Three factors that
influence the degree of crystallinity are:

i) Chain length
ii) Chain branching
iii) Interchain bonding

Figure 7: Crystalline chain

http://plc.cwru.edu/tutorial/enhanced/FILES/Polymers/orient/Orient.htm
 Polymer cristallinity
Crystallinity influences:
Hardness,modulus tensile, stiffness, crease, melting point of polymers.

Most crystalline polymers are not entirely crystalline. The chains, or
parts of chains, that aren't in the crystals have no order to the
arrangement of their chains

Crystallinity makes a polymers strong, but also lowers their impact
resistance

Crystalline polymers are denser than amorphous polymers, so the
degree of crystallinity can be obtained from the measurement of
density  Wc=Φcρc/ ρ
ρ  density of entire sample
ρc  density of the crystalline fraction.
Φc volume fraction
Wc mass fraction
 Determinants of Polymer Crystallinity

The degree of crystallinity of a polymer depends on the rate of cooling

during solidification as well as on the chain configuration.

In most polymers, the combination of crystalline and amorphous

structures forms a material with advantageous properties of strength
and stiffness.

Figure 8: Mixed amorphous crystalline macromolecular polymer structure

(http://web.utk.edu/~mse/Textiles/Polymer%20Crystallinity.htm)
 Polymer cristallinity

Polymer molecules are very large so it might seem that they could not
pack together regularly and form a crystal. Regular polymers may form
lamellar crystals with parallel chains that are perpendicular to the face
of the crystals.

A crystalline polymer consists of the crystalline portion and the

amorphous portion. The crystalline portion is in the lamellae, and the
amorphous portion is outside the lamellae .

Figure 9. Arrangement of crystalline and amorphous portions

http://pslc.ws/mactest/crystal.htm#structure
 Cristillanity and amorphousness

An amorphous solid is formed when the chains have little orientation

throughout the bulk polymer. The glass transition temperature is the point
at which the polymer hardens into an amorphous solid.

In between the crystalline lamellae,regions with no order to the
arrangement of the polymer chains  amorphous regions

Polyethylene can be crystalline or amorphous. Linear polyethylene is nearly
100% crystalline. But the branched polyethylene is highly amorphous.

Figure 10.Linear and Branched Polyethylene

(http://pslc.ws/macrog/kidsmac/images/pe03.gif )
Examples...

Highly crystalline polymers:
Polypropylene, Nylon, Syndiotactic polystyrene..

Highly amorphous polymers:
Polycarbonate, polyisoprene, polybutadiene

Polymer structure and intermolecular forces has a major role of a
polymer’s crystallinity.
Classification of Polymers
…with regard to their thermal processing behavior ;

Thermoplastic Polymers (Thermoplastics)

soften when heated and harden when cooled

Thermosetting Polymers (Thermosets)

once having formed won’t soften upon heating
Thermoplastics

have linear or branched structure
chains are flexible and can slide past each other

have strong covalent bonds and weak intermolecular van
der Waals bonds

elastic and flexible above glass transition temperature

can be heat softened, remolded into different forms

reversible physical changes without a change in the

chemical structure
Thermosets

chains chemically linked by covalent bonds

hardening involves a chemical reaction which
connects the linear molecules together to form a
single macromolecule.
Thermosets

once polymerization is complete, cannot be softened, melted
or molded non-destructively.

have higher thermal, chemical and creep resistance than

thermoplastics

Thermosets suitable materials for

Composites
Coatings
Adhesive applications
Common thermoplastics
Commodity Polymers
POLYETHYLENES
POLYPROPYLENE
POLYSTYRENE
POLYVINYLCHLORIDE-PVC
POLYMETHYLMETHACRYLATE-PMMA
Engineering Polymers(have a thermal resistance 100-150°C)
POLYCARBONATE
NYLON(POLYAMIDE)
POLYETHYLEN TEREPHATALATE-PET
High Performance Polymers (have a thermal resistance >150°C)
POLYTETRAFLUOROETHYLENE-teflon
POLYARYLETHERKETONES-PEEK
POLYETHYLENE

prepared directly from the polymerization of ethylene (C2H4).

two main types are; low-density (LDPE) and high-density

polyethylene (HDPE)

Advantages
cheap
good chemical resistance
high impact strength

Limitations
low heat resistance (upper temperature limit is 60°)
degrade under UV irradiation.
high gas permeability, particularly CO2

Applications
extensively for piping and packaging
chemically resistant fittings, garbage bags
containers, cable covering
POLYPROPLYLENE

improved mechanical properties compared to polyethylene;
has a low density (900–915 kg/m3), harder, and has a higher
strength
Good chemical and fatigue resistance

Disadvantages
Oxidative degradation, high thermal expansion, high creep
poor UV resistance

Applications
medical components, films for packaging (e.g. cigarette
packets)reusable containers, laboratory equipment
POLYSTYRENE

a light amorphous thermoplastic

Advantages
low cost, easy to mould, rigid, transparent
no taste, odor, or toxicity, good electrical insulation

Disadvantages
sensitive to UV irradiation (e.g. sunlight exposure)
chemical resistance is poor, brittle

Applications
CD-DVD cases, electronic housings, food packaging, foam
drink cups and egg boxes
POLYVINYLCHLORIDE-PVC

was the first thermoplastic used in industrial applications

very resistant to strong mineral acid and bases, good electrical

insulators, flame-retardant

Two grades of the PVC material are available:

rigid PVC is used in the construction industry for piping
cold water and chemicals
flexible PVC is used in wire and cable coating, paints, signs
Common thermosets

EPOXIES

UNSATURATED POLYESTERS

PHENOL FORMALDEHYDE (PHENOLIC)

POLYURETHANES
EPOXIES

Advantage
mechanically strong, highly adhesive
good chemical and heat resistance
electrical insulators

Disadvantage
expensive

Applications
as industrial adhesives, coatings or as matrices in advanced
reinforced plastics and also as encapsulation media
UNSATURATED POLYSTERS

Advantage
hard, high strength
cheap compared to Epoxy
good electrical insulator
high heat resistance

Disadvantage
poor solvent resistance compared to other thermosets

Applications
molding or casting materials for a variety of electrical
applications, matrix for composites such as fiberglass
boats, fences, helmets, auto body components
PHENOLICS

most commonly used thermosets

high hardness, excellent thermal stability; low

tendency to creep

Applications
wiring devices, bottle caps, automotive parts, plugs
and switches, as adhesives coatings and molded
components for electrical applications
POLYURETHANES

depending on the degree of cross-linking they behave as
thermosets or thermoplastics

low cost, high impact strength, high adhesion properties

be processed into coatings, adhesives, binders, fibers and

foams
Methods of polymer fabrication

 Extrusion of polymers
 Injection Molding
 Blow Molding
 Thermoforming
 Compression Molding
 Casting
Extrusion of polymers

method used mainly for thermoplastics

is a continuous process as long as raw pellets are supplied

is a process of manufacturing mostly long products of constant

cross-section;
i.e.. rods, sheets, pipes, films, wire insulation coating
… extrusion

pelletized material is successively compacted, melted and

formed into a continuous charge of viscous fluid

temperature of the material is controlled by thermocouples

forcing soften polymer through a die with an opening

the product going out of the die is cooled by blown air or in

water bath
extruder
Injection Molding

most widely used technique for thermoplastics

highly productive method, profitable in mass production of
large number of identical parts

polymer in form of pellets is fed into machine and is pushed

forward into a heating chamber then the molten plastic is
forced through a nozzle into the enclosed mold cavity

pressure is maintained until solidification and then the mold
opens and the part is removed
Blow Molding

is a process in which a heated hollow thermoplastic tube
(parison) is inflated into a closed mold

disposable containers, recyclable bottles, automotive fuel
tanks, tubs are produced

involves manufacture of parison by extrusion, injection or
stretching

parison in a semi molten state is placed in a two piece mold
having the desired shape

parison is inflated by air blown, taking a shape conforming that

of the mold cavity

parison is then cut on the top, mold cools down, its halves
open, and the final part is removed
Thermoforming

is a process of shaping flat thermoplastic sheet

softening the sheet by heat, followed by forming it in the mold
cavity

Thermosets can not be formed by the thermoforming because
of their cross linked structure

widely used in the food packaging industry; manufacturing of
Thermoforming methods
three thermoforming methods, differing in the forming stage:

1. Vacuum Thermoforming; shaping a preheated thermoplastic

sheet by means of vacuum produced in the mold cavity

2. Pressure Thermoforming;... by means of air pressure.

3. Mechanical Thermoforming;... by direct mechanical force

Thermoforming by vacuum and mechanical force
Compression Molding
used mostly for molding thermoset resins

pre-weighed amount of a polymer mixed with additives is

placed into the lower half of the mold

polymer is preheated prior to placement into heated mold
cavity ,half of the mold moves down, pressing on the polymer
charge and forcing it to fill the mold cavity

suitable for molding large flat or moderately curved parts; side

panels for automotive, electric housings etc.
Casting

both thermosets and thermoplastics may be cast.

molten polymer is poured into a mold and allowed to solidify

for thermoplastics solidification occurs upon cooling

while thermoset’s hardening is a consequence of
polymerization reaction
REFERENCES
 François Carderelli, Materials Handbook: A Concise Desktop
Reference,2nded.,Springer
 Donald Hudgin, Plastics Technology Handbook, 4th ed., Taylor & Francis
Group
 J. A.Brydson, Plastics Materials, 7thed., Heinemann
 William D. Callister ,Materials Science and Engineering,7th ed., Wiley
 http://www.substech.com
 http://www.azom.com
 http://en.wikipedia.org
 Recycling:
A Sector of Solid
Waste Management

http://environment.utk.edu/policy.html
What is Recycling?

Recycling refers to the process of collecting used materials

which is usually considered as ‘waste’ and reprocessing
them. Recycling varies from ‘re-use’ in the sense that while
re-use just means using old products repeatedly, recycling
means using the core elements of an old product as raw
material to manufacture new goods.
Why Recycling is Important?

Recycling Saves Energy

Recycling Saves Environmental Conditions and Reduces

Pollution

Recycling Saves Natural Resources

Economic Benefits

Recycling Saves Space for Waste Disposal

Benefits

• Conserves Resources
• Prevents emissions of greenhouse gasses &
water pollutants
• Supplies valuable raw materials to industry
• Saves tax-payer dollars
• Creates jobs
• Stimulates development of greener technologies
• Reduces the need for new landfills and
incinerators
Recycling of polymers
Recycling of Polymers

Chemical recycling
Mechanical recycling Energy recycling

Chemolysis
Thermolysis
Glycolysis
Pyrolysis
Methanolysis
Hydrogenation
Hydrolysis
 Why do we use mechanical, chemical and
energy recycling?

Hence mechanical recycling is realy best suited to clean plastic
waste,such as packaging material.
•Chemical recycling of waste plastics is important issue.

We have applied reaction in water or organic solvent in

sub- or supercritical condition to convert polymers into its monomers.
Condensed polymers such as polyethylene terephthalate or
nylon 6 were depolymerized to its monomers by hydrolysis of
alcoholysis in supercritical water or alcohol.
Conclusive Facts
1 t = 20,000 plastic bottles

25,000 t of bottles recycled in the UK in 2003 saved approximately

25 million kWh of energy

25 recycled PET bottles can be used to make an adult’s fleece jacket

Recycling a single plastic bottle can conserve enough energy to light

a 60 W lightbulb for up to 6 h
SOME PHOTOS
We have done it!!!

Ref: http://www.container-recycling.org/ assets/ppt/1PlasticDebrisConference9.ppt

 Look at the changes you could
make with recycling...

http://environment.utk.edu/policy.html
 REFERENCES

http://www.buzzle.com/articles/why-is-recycling-important.html

http://www.chevroncars.com/learn/wondrous-world/recycling-process

www.container-recycling.org/ assets/ppt/1PlasticDebrisConference9.ppt

 François Carderelli, Materials Handbook: A Concise Desktop

Reference,2nded.,Springer

 Donald Hudgin, Plastics Technology Handbook, 4th ed., Taylor & Francis
Group
 REFERENCES

 J. A.Brydson, Plastics Materials, 7thed., Heinemann

 William D. Callister ,Materials Science and Engineering,7th ed., Wiley

 http://www.substech.com

 http://www.azom.com

 http://en.wikipedia.org
 REFERANCES

Plastic Technology Handbook, 4th Edition, Authors: Manas Chanda,Salil K.
Roy

http://pslc.ws/mactest/crystal.htm#structure

http://plc.cwru.edu/tutorial/enhanced/FILES/Polymers/struct/struct.htm