POLYMERS

Group Members
Seda KOCA
Bengi AYDLEK
Didem Bra KABAKI
Gzde ERGN

11.11.2009
Hacettepe University

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
Polymers 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

Chain-growth polymerization

Growth throughout matrix

Growth by addition of monomer

only at one end of chain

Rapid loss of monomer early in

the reaction

Some monomer remains even at

long reaction times

Same mechanism throughout

Different mechanisms operate at

different stages of reaction (i.e.
Initiation, propagation and
termination)

Average molecular weight

increases slowly at low
conversion and high extents of
reaction are required to obtain
high chain length

Molar mass of backbone chain

increases rapidly at early stage
and remains approximately the
same throughout the
polymerization

Ends remain active (no

termination)

Chains not active after

termination

No initiator necessary

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

consumed.

until

all

monomer

is

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

Disadvantages

High yield per reactor

volume

Difficult of removing the lost

traces of monomer

Easy polymer recovery

Dissipating heat produced

during the polimerization

Final product form

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 polymerization)

Disadvantages

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
Chanda

Salil K. Roy)

(Plastic Technology Handbook-Manas

Molecular configuration of polymers

Side groups atoms or molecules with free bonds, called freeradicals, 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: IsotacticSyndiotactic 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=cc/
density of entire sample
c density of the crystalline fraction.
c 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 .

amorphous portions

Figure 9. Arrangement of crystalline and

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 polymers 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 wont 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 100-150C)

POLYCARBONATE
NYLON(POLYAMIDE)
POLYETHYLEN TEREPHATALATE-PET

High Performance Polymers (have a thermal resistance

>150C)

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 CO 2
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 (900915 kg/m 3),

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 ice cream and margarine tubs,
meat trays, microwave containers, sandwich
packs etc.

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 thermosets hardening is a consequence of
polymerization reaction

REFERENCES
Franois 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 reuse 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

Mechanical recycling

Chemolysis
Glycolysis
Methanolysis
Hydrolysis

Chemical recycling

Thermolysis
Pyrolysis
Hydrogenation

Energy recycling

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 adults 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
Franois Carderelli, Materials Handbook: A Concise Desktop

Reference,2nded.,Springer
Donald Hudgin, Plastics Technology Handbook, 4 th 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