Polymers

A large molecule consisting of (at least five)

repeated chemical units (“mers”) joined together,
like beads on a string

Polymer molecules are very large macromolecules

consisting of long and flexible chains with a string
of C atoms as a backbone
 Side-bonding of C atoms to H atoms or radicals
 Double bonds possible in both chain and side
bonds
 Repeat unit in a polymer chain (“unit cell”) is a
mer
 A single mer is called a monomer

A mer unit of PVC A mer unit of polypropylene

Most polymers are organic, and formed from
hydrocarbon molecules such as :
 Saturated (single bonds) hydrocarbon molecules

 Unsaturated hydrocarbons (double or triple bonds)

 Other hydrocarbons
 Polymerization
(the process of how polymers are made)

 Polymerization is the chemical reaction in which

high molecular mass polymer molecules are formed
from monomers.
 There are two basic types of polymerization :
1.) Addition (or chain-reaction) polymerization
2.) Condensation (or step-reaction) polymerization
1.) Addition (or chain-reaction) Polymerization
To illustrate, polymerization of ethylene to polyethylene is
used as example.
This type of polymerization is a three step process involving
two chemical entities. These 2 chemical entities are :

 A monomer : ethylene

 A catalyst – an organic peroxide, R – O – O – R which

form into free peroxide radicals :
R – O – O - R  R – O* + R – O*
* represent free electron
Step 1 : Initiation – free radical catalyst
react with the monomer

Step 2 : Propagation - a repetitive operation in which the physical chain of the

polymer is formed.

Step 3 : Termination - occurs when the left over free radical (R-O) from the original
splitting of the organic peroxide meets the end of the growing chain. This reaction
produces a complete polymer chain.
2.) Condensation (or step-reaction) Polymerization
 produces polymers of lower molecular weight than chain reactions and
requires higher temperatures to occur.
 step-wise reactions involve two different types of di-functional
monomers
 produces a small molecular by-product (water, HCl, etc.).
 Example of the formation of Nylon 66, a common polymeric clothing
material, involving one each of two monomers, hexamethylene diamine
and adipic acid, reacting to form a dimer of Nylon 66.
 Structure of Polymers Molecules
 Linear polymers are made up of one long
continous chain, Van derWaals bonding
between chains. Examples: polyethylene,
nylon.

 Branched polymers have a chain structure that

consists of one main chain of molecules with
smaller molecular chains branching from it.

 Cross-linked polymers - chains are

connected by covalent bonds. Many rubbers
have this structure

 Network polymers - 3D networks made

from trifunctional mers. Examples:
epoxies, phenolformaldehyde
 Structure of Polymers Molecules
 When all the mers are the same, the molecule is called a homopolymer
 When there is more than one type of mer present, the molecule is a
copolymer, which can have several configurations or arrangements of the
monomers along the chain. The four main configurations are depicted
below :

 Mer units that have 2 active bonds to connect with other

mers are called bifunctional

 Mer units that have 3 active bonds to

connect with other mers are called tri-
functional. They form 3-dimensional
molecular network structures.
 Polymer Molecular Shape
 The angle between the singly bonded carbon
atoms is ~ 109o -- carbon atoms form a
zigzag pattern in a polymer molecule

 Random kinks and coils lead to entanglement,

like in the spaghetti structure. Molecular
chains may thus bend, coil and kink

 Moreover, while maintaining the 109o angle

between bonds polymer chains can rotate
around single C-C bonds (double and triple
bonds are very rigid).

 Neighboring chains may intertwine and entangle.

 Large elastic extensions of rubbers correspond to unraveling of these
coiled chains
 Mechanical / thermal characteristics depend onthe ability of chain
segments to rotate.
 Isomerism
 Isomerism - Hydrocarbon compounds with
same composition may have different atomic
arrangements. Physical properties may
depend on isomeric state (e.g. boiling
temperature of normal butane is -0.5 oC, of
isobutane -12.3 oC). Two types of isomerism
are possible :

1. Stereoisomerism - atoms are linked

together in the same order, but can have
different spatial arrangement :

 Isotactic configuration: all side groups R

are on the same side of the chain.
 Syndiotactic configuration: side groups R
alternate sides of the chain.
 Atactic configuration: random
orientations of groups R along the chain.
 Isomerism
 Geometrical Isomerism - consider two carbon atoms
bonded by a double bond in a chain. H atom or radical R bonded
to these two atoms can be on the same side of the chain :
(cis- structure)

or on opposite sides of the chain

(trans- structure) :
 Polymer Molecular Weight
Macromolecules of different chain lengths and molecular weights
are formed during polymerization.
Final molecular weight (chain length) is controlled by relative rates
of initiation, propagation, termination steps of polymerization.

The average molecular weight can be

obtained by averaging the masses with
the fraction of times they appear
(number-average molecular weight) xi is number fraction of chains
of length i

or with the mass fraction of the

molecules (weight-average molecular
weight).
wi is weight fraction of chains
of length i
Alternative way to express average polymer chain
size is the degree of polymerization :

 Degree of
polymerization-average
number

 or, Degree of
polymerization-average
weight

where : m is the mer molecular weight

Example : Compute a.) the number-ave. Mol. Wt, b.) the weight-ave. Mol. Wt.,
c.) the deg of polymerization of PVC using the tabulated data shown below :

Data for Number Average Data for Weight Average

Molecular Weight Calculation Molecular Weight Calculation
Mol. Weight mean Mi number Mol. Weight mean Mi weight
Range (g/mole) (g/mole) fraction, (xi) xi Mi Range (g/mole) (g/mole) fraction, (wi) wi Mi
5,000-10,000 7,500 0.05 375 5,000-10,000 7,500 0.02 150
10,000-15,000 12,500 0.16 2,000 10,000-15,000 12,500 0.10 1,250
15,000-20,000 17,500 0.22 3,850 15,000-20,000 17,500 0.18 3,150
20,000-25,000 22,500 0.27 6,075 20,000-25,000 22,500 0.29 6,525
25,000-30,000 27,500 0.20 5,500 25,000-30,000 27,500 0.26 7,150
30,000-35,000 32,500 0.08 2,600 30,000-35,000 32,500 0.13 4,225
35,000-40,000 37,500 0.02 750 35,000-40,000 37,500 0.02 750
a.) = 21,150 b.) = 23,200

c.) = molecular weight of a PVC mer

= 2 carbon atoms + 3 hydrogen atoms + 1 chlorine atom
= 2(12.01) + 3(1.01) + 35.45
= 62.5 g/mole

degree of polymerization-number average : degree of polymerization-weight average:

= 21,150 / 62.5 = 338 = 23,200 / 62.5 = 371

Sept. 22, 2015 nended

At room temperature,
1. Short chain polymers
(molecular weight ~ 100 g/mol)
are liquids or gases,
2. Intermediate length polymers
(~ 1000 g/mol) are waxy solids,
3. Solid polymers have molecular
weights of 104 - 107 g/mol
 Summary of Polymer Molecular Characteristics
(Chemistry, Shape, Size, Structure)

Molecular Characteristics

Chemistry Size Shape Structure

(mer composition) (mol. Weight) (chain twisting,
entanglement)

Linear Branched Cross-linked Network

Isomeric States

Stereoisomers Geometric isomers

Isotactic Syndiotactic Atactic Cis Trans

 Polymer Crystallinity

Atomic arrangement in
polymer crystals is more
complex than in metals or
ceramics (unit cells are
typically large and
complex)

Polymer molecules are

often partially crystalline
(semi-crystalline), with
crystalline regions
dispersed within
amorphous material.
Degree of crystallinity is determined by:
 Rate of cooling during solidification: slow cooling  more
crystalline
 Mer complexity: simple polymers, (like polyethylene), crystallize
relatively easily than more complex ones.
 Chain configuration: linear polymers crystallize relatively easily,
branches inhibit crystallization, network polymers almost completely
amorphous, crosslinked polymers can be both crystalline and
amorphous
 Isomerism: isotactic, syndiotactic polymers crystallize relatively
easily - geometrical regularity allows chains to fit together, atactic
difficult to crystallize
 Copolymerism: easier to crystallize if mer arrangements are more
regular - alternating, block can crystallize more easily as compared
to random and graft

 More crystallinity: higher density, more strength, higher resistance

to dissolution and softening by heating
Crystallization, Melting, Glass Transition
Melting behavior of semi-crystalline polymers is intermediate between that of
crystalline materials (sharp density change at a melting temperature) and that
of a pure amorphous material (melting can be only defined from viscosity).

The glass transition temperature is between

0.5 and 0.8 of the melting temperature.
Melting involves breaking of the inter-chain
bonds, therefore the glass and melting
temperatures depend on:
 chain stiffness (e.g., single vs. double
bonds) - rigid
 chains have higher melting
temperatures
 size/weight of molecule - increasing
molecular weight
 increases Tm (range of M produces
range of Tm)
 size, shape of side groups, side
branches, crosslinking, defects, etc.
Polymer Classification According to How they
Behave When Heated
 Thermoplastic polymers (thermoplasts) - soften reversibly
when heated (harden when cooled). At high temperatures,
the inter-chain bonding is weakened allowing deformation at
low stresses. Most thermoplasts are linear polymers and
some branched structures. They can be semi-crystalline or
amorphous.
 Thermosetting polymers (thermosets) - harden permanently
when heated. Covalent crosslinks (~ 10 -50% of mers)
formed during heating. Cross-linking hinder bending and
rotations. Thermosets are harder, more dimensionally stable,
and more brittle than thermoplasts. Examples: vulcanized
rubber, epoxies, resins.They cannot be remolded or recycled.
They must be re-machined, used as fillers, or incinerated to
remove them from the environment.
Polymer Processing
There are five basic processes to form polymer products or
parts. These include;
 Injection molding,
 Compression molding,
 Transfer molding,
 Blow molding,
 Extrusion.
Compression molding and transfer molding are used mainly for
thermosetting plastics.
Injection molding, extrusion and blow molding are used
primarily with thermoplastics
Thermoplastics are formed above their glass
transition temperature if amorphous, or above their
melting temperature if crystalline. An applied
pressure must be maintained as the piece is cooled so
that the formed article will retain its shape.

Thermosetting polymers are accomplished in two

stages :
 Preparation of linear polymer as a liquid (called
prepolymer),
 Curing occur during heating and/or by addition of
catalyst often under pressure.
During curing, chemical and structural changes on
molecular level occurs.
 Injection Molding
This very common process for forming plastics involves four steps:

1. Powder or pelletized 3. The pressurized material is held

polymer is heated to in the mold until it solidifies.
the liquid state.
4. The mold is opened and the part
2. Under pressure, the removed by ejector pins.
liquid polymer is
forced into a mold
through an opening,
called a sprue. Gates
control the flow of
material.
 Compression Molding
This type of molding was among the first to be used to form
plastics. It involves four steps:
1. Pre-formed blanks, powders or
pellets are placed in the bottom
section of a heated mold or die.
2. The other half of the mold is
lowered and is pressure applied.
3. The material softens under heat
and pressure, flowing to fill the
mold. Excess is squeezed from
the mold. If a thermoset, cross-
linking occurs in the mold.
4. The mold is opened and the part
is removed.
Transfer Molding
This process is a modification of compression molding. It is used
primarily to produce thermosetting plastics. Its steps are :
1. A partially polymerized material is
placed in a heated chamber.
2. A plunger forces the flowing
material into molds.
3. The material flows through
sprues, runners and gates.
4. The temperature and pressure
inside the mold are higher than in
the heated chamber, which
induces cross-linking.
5. The plastic cures, is hardened,
the mold opened, and the part
removed.
Blow Molding
Blow molding produces bottles, globe light fixtures, tubs,
automobile gasoline tanks, and drums. It involves :
1. A softened plastic tube is extruded
2. The tube is clamped at one end and inflated to fill a mold.
3. Solid shell plastics are removed from the mold.
This process is rapid and relatively inexpensive.
Extrusion
This process makes parts of constant cross section like pipes and
rods. Molten polymer goes through a die to produce a final
shape. It involves four steps:
1. Pellets of the polymer are mixed with coloring and additives.
2. The material is heated to its proper plasticity.
3. The material is forced through a die.
4. The material is cooled.
 Other Polymer Processing Methods
Rotational molding - Fluidized bed coating –
powder or liquid is loaded air flow upward thru a bed
into the empty mold, of polymer particles,
moves to the furnace and creating a fluid-like
heated while it rotates in particle cloud. When a
two perpendicular axis, to heated object is dipped
ensure that it is evenly into the bed, particles
coated by the polymer, fused into the exposed
Rotation continue while surface coating the
cooling ouside the object. The coat thickess
furnace. Mold opens and depends on time the
the finished item drops. object stays in the bed.
Fiber spinning – a liquid
polymer is extruded thru
small holes in the
spinnerets to form thin
filaments, which solidify
upon leaving the spinneret.
After solidification, the
filaments are combined to
make threads, and/or
drawn to change the thread
properties, then spun in
spools
 End of Presentation
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