Basics of Polymers

Solid Materials

M t l
Metals P l
Polymer C
Ceramics
i

Thermo -settings Thermoplastics Elastomers

Commodityy Engineering
g g Specialty
p y

Amorphous
p Crystalline
y Semi- Crystalline
y
 ADVANTAGES OF PLASTICS

„ Properties can be altered to
suit the needs
„ Good strength/weight ratio
„ Tough & durable
„ Non toxic
„ Easy Processability
„ Chemical/Moisture Resistant
„ Fire retardant
„ Do not rust/corrode.
„ Resistant to microbes
„ Attractive colours
„ Good weatherability
„ Practically maintenance free
„ Reusable / Recyclable

At Much Cheaper Price !!!

 POLYMERS:
O S INTRODUCTION
O UC O

• Polymer:
y High
g molecular weight
g molecule made up
p of a
small repeat unit (monomer).
– A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A
• Monomer: Low molecular weight compound that can be
connected together to give a polymer
• Oligomer: Short polymer chain
• Copolymer: polymer made up of 2 or more monomers
– Random copolymer:
p y A-B-B-A-A-B-A-B-A-B-B-B-A-A-B
– Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B
– Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B
 COMMON POLYOLEFINS

Monomer Polymer
CH3
H3C
Polyethylene n
Ethylene Repeat unit

CH3
CH3 n
Polypropylene CH3 CH3 CH3 CH3 CH3 CH3 CH3
Propylene

CH3
Ph n
Polystyrene Ph Ph Ph Ph Ph Ph Ph
Styrene

CH3
Cl n
Poly(vinyl chloride) Cl Cl Cl Cl Cl Cl Cl
Vinyl Chloride
F2 F2 F2 F2 F2 F2
F2C CF2 C C C C C C CF3
F3C C C C C C C
F2 F2 F2 nF F2 F2
Tetrafluoroethylene Poly(tetrafluoroethylene): Teflon 2
 Polyesters,
o yeste s, Amides,
des, a
and
dUUrethanes
et a es
Monomer Polymer
O O
H2 H2
HO2C CO2H OH HO O C C O H
HO
Ethylene Poly(ethylene terephthalate n
Terephthalic
acid glycol Ester

O O O O
H
HO 4
OH H2N 4
NH2 HO N 4 N
4
Adipic Acid 1,6-Diaminohexane Nylon 6,6 H H n
Amide
O O
H H
HO2C CO2H H2N NH2 HO N N H
Kevlar n
Terephthalic 1,4-Diamino
acid benzene

H2
OCN C NCO OH
HO
Ethylene Spandex
4,4-diisocyantophenylmethane
glycol
g y
O O
H H2 H H2 H2
HO N C N O C C O H Urethane linkage
n
 What Makes Polymers
y Unique?
q
•Really big molecules (macromolecules) like polymers have
veryy different p
properties
p than small molecules
–Chain entanglement: Long polymer
chains get entangled with each other.
• When the polymer is melted, the
chains can flow past each other.
• Below
B l th melting
the lti point,
i t the
th chains
h i
can move, but only slowly. Thus
the plastic is flexible, but cannot be
easily stretched.
• Below the glass transition point,
the chains become locked and the
polymer is rigid
 Physical
y Properties
p
Linear Polymer

Stretch

The chains can be stretched, which causes

them to flow past each other. When released,
C
Cross-Linked
Li k d Polymer
P l the polymer will not return to its original form.

Stretch

Relax
The cross-links hold the chains together.
When released, the polymer will return to it's
original form.
 Polymer Microstructure

Polyolefins with side chains have stereocenters on every other carbon

CH3
n
CH3 CH3 CH3 CH3 CH3 CH3 CH3

With so many stereocenters, the stereochemistry can be complex.

There are three main stereochemical classifications for polymers.
Atactic: random orientation

Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

 Why is this important?

• Tacticity affects the physical properties

– Atactic polymers will generally be amorphous, soft,
flexible materials
– Isotactic
I t ti and d syndiotactic
di t ti polymers
l will
ill b
be more
crystalline, thus harder and less flexible
 Polymer
y Synthesis
y

• There are two major classes of polymer formation mechanisms

– Addition polymerization: The polymer grows by sequential
addition of monomers to a reactive site
• Chain growth is linear
• Maximum molecular weight is obtained early in the
reaction
– Step-Growth polymerization: Monomers react together to
make small oligomers. Small oligomers make bigger ones,
and big oligomers react to give polymers
polymers.
• Chain growth is exponential
• Maximum molecular weight is obtained late in the
reaction
 Addition
dd t o Polymerization
o y e at o
A nA
In* In A A A A* In A A A A A*
Initiation Propagation n

*A A A A A
A *A A A A A m
m

In A A A A A In A A A A A In A A A A A A A A A A
n n m
n
A* Combination
B A A A A
m
Chain
Ch i Transfer
T f Disproportionation
New reactive site
is produced
Termination
Reactive site is consumed
MW

k propagation
MW ∝
k ter mination

0 100
% conversion
 Step-Growth
Step G o t Polymerization
o y e at o
Stage 1
n n
Consumption
of monomer

Stage 2

Combination
of small fragments

Stage 3

Reaction off
oligomers to give
high molecular
weight polymer
 TERMINOLOGY

Thermoplastics Polymers
Thermoplastics are resins that repeatedly soften when
heated and harden when cooled
Thermosetting Polymers
Thermosets are resins that undergo chemical changes
during processing to become permanently insoluble and
infusible due to they formed three-dimensional
three dimensional cross
linked network structure when heat is applied.
 Various Thermoplastics
p

PI
Specialty
PSU PTFE
Polymers LCP
PES
PPSU HPPA

Engineering PA
Polymers PC POM
PET
PPO PBT
TPE
ABS PMMA
Commodities PP--GF
PP PE--UHMW
PE
PS PVC
PP PE--HD
PE
SAN PE--LD
PE

AMORPHOUS CRYSTALLINE
CODE FOR RECYLCING
POLYMER PROPERTIES
 Amorphous vs. Crystalline Thermoplastics

• Amorphous (a-morphous = without shape) - The

polymer chains are in random arrangement. Molecular
structure is incapable of forming regular order
(crystallizing) with molecules or portions of molecules
regularly stacked in crystal-like fashion. Molecular
arrangement is randomly twisted, kinked and coiled.

• Crystalline - The polymer chains form a regular pattern.

Molecular structure forms regular order (crystals) with
molecules or portions of molecules regularly stacked in
crystal-like fashion. Molecular arrangement is arranged
in an ordered fashion.
fashion
 Amorphous vs. Crystalline Thermoplastics

Properties Crystalline Amorphous

Transparent NO Yes
Chemical Resistance Excel Poor
Stress-craze No Yes
S i
Shrinkage High
i Low
Tensile Strength and
High Low (exception in PC)
modulus
Viscosity Low High
Melt Temperature Yes No
Critical
Yes No
Temperature/Time
Specific Gravity Higher Lower
Ductility and elongation Lower Higher
Resistance to creep Higher Lower
Max. Usage Temperature Higher Lower
Flow Higher Lower
Effect of Crystallinity on Properties
 Glass Transition Temperature (Tg)

The temperature below, which a polymer is hard and above

which
hi h it is
i soft,
ft is
i called
ll d the
th glass
l t
transition
iti temperature
t t (Tg).
The hard, brittle state is known as the glassy state and the
soft flexible state as rubberyy or viscous state.
Or
The molecular mobility is just starts at that temperature called
Glass Transition Temperature.
Temperature
THANK YOU