Gazi University Faculty of

Engineering Department of
Chemical Engineering

CHE462
POLYMER TECHNOLOGY
 INTRODUCTION

Today, a large part of the field of organic chemistry is made up of polymer

chemistry. Polymer chemistry is very important for industry.

Polymers are used in the production of many materials that are utilized in
everyday life, from nylon bags, plastic cups, gloves, car tires, varnishes, to paint
and Teflon production.

Polymers are lightweight, inexpensive, have sufficient mechanical properties,

are easy to shape, and are resistant to chemicals.

Besides chemistry, polymers are also used in mechanical, textile, industrial, and
physics engineering fields. They are also of great importance in biochemistry,
biophysics, and the medical field.
Polymer and plastic are closely related terms, but they have different meanings.
1. Polymer:
•Definition: A polymer is a large molecule made up of smaller, repeating molecular units
called monomers, which form long chains. Polymers can be either natural or synthetic.
•Examples: Natural polymers include DNA, proteins, rubber, and cellulose, while synthetic
polymers include nylon, polyester, and polyethylene.
•Scope: Plastic is a subset of polymers, meaning all plastics are polymers, but not all
polymers are plastics.
2. Plastic:
•Definition: Plastic refers to synthetic materials made from polymers that can usually be
easily molded and shaped. Plastics often include chemical additives to enhance their
properties.
•Characteristics: Plastics are lightweight, durable, and inexpensive. A key feature of plastics
is their ability to be molded or shaped into various forms using different manufacturing
techniques.
•Examples: Common synthetic plastics include polyethylene (PE), polypropylene (PP),
polyvinyl chloride (PVC), polystyrene (PS), and Teflon.
 Vulcanization is a chemical process that
enhances the durability and elasticity of
rubber by heating it with sulfur or other
vulcanizing agents. This treatment
strengthens the rubber, making it more kauçuk
resilient and flexible. It is widely used in
industries, especially for producing tires and
other rubber products.
In short, vulcanization improves the
mechanical properties of rubber through a
heat and chemical process.

Ebonite, also known as hard rubber, is a material

made by vulcanizing natural rubber with a high
amount of sulfur (typically 30-40%). This process
gives the rubber a hard, rigid structure, making it
durable and resistant to chemicals.

Cellulose nitrate (also known as

nitrocellulose) is used in the
production of plastics (such as
celluloid), varnishes, adhesives, and
explosives (like smokeless powder
and dynamite).
 MONOMER, POLYMER

MONOMER: A MONOMER IS A SINGLE ATOM, SMALL MOLECULE, OR MOLECULAR

FRAGMENT THAT, WHEN BONDED TOGETHER WITH IDENTICAL AND SIMILAR TYPES OF
MONOMERS, FORM A LARGER, MACROMOLECULE KNOWN AS A POLYMER.
MONOMERS BOND TOGETHER TO FORM POLYMERS DURING A CHEMICAL
REACTION CALLED POLYMERIZATION AS THE MOLECULES LINK TOGETHER BY
SHARING ELECTRONS.

THE WORD MONOMER COMES FROM THE GREEK WORD “MONO,” MEANING “ONE,”
AND “MEROS,” MEANING “PART.” AS THE PREFIX IN MONOMER IMPLIES, THINK OF
MONOMERS AS A SINGLE, SIMPLER BASIC UNIT THAT OF AND IN ITSELF IS OF LESSER
IMPORTANCE, BUT COMBINED, THEY ARE THE BUILDING BLOCKS THAT FORM INTO A
GREATER COMPLEX STRUCTURE.
Polymer: A polymer is a large molecule, or macromolecule,
composed of small repeating singular molecular structural
units called monomers. The repeating molecular units are
joined together chemically through covalent bonds.

The word polymer comes from the Greek “poly” (many)

and “meros” (part).

All are found in a wide range of both consumer

and industrial products:
•Nylons in textiles and fabrics
•Teflon in non-stick pans
•Polyvinyl chloride (PVC) in pipes
•Tires
•Electrical switches
•Rubber
•Styrofoam cups
•Disposable PET bottles
• THE MAJOR DIFFERENCES BETWEEN SMALLER MOLECULES
AND POLYMERS LIE NOT WITH THEIR CHEMICAL PROPERTIES
BUT WITH THEIR PHYSICAL ONES. THEIR LARGER SIZES LEAD
TO MUCH STRONGER INTERMOLECULAR FORCES LEADING
IN TURN TO MUCH HIGHER MELTING POINTS, AND THE
CHARACTERISTIC PROPERTIES OF HARDNESS AND
FLEXIBILITY.

1) van der Waals forces

2) covelant bonds
Polymerization
3) dipole/dipole attractions;
4) hydrogen bonds
 Repeating Unit and Polymer
IN THE CHEMICAL REPRESENTATION
REPEATİNG UNİT:
OF POLYSTYRENE, THE STRUCTURE GIVEN IN
PARENTHESES IS CALLED A REPEATING UNIT
(OR MER).

IN POLYMER SCIENCE, THE POLYMER CHAIN OR

SIMPLY BACKBONE OF A POLYMER IS THE
MAIN CHAIN OF A POLYMER.
Main chain, Side group: The series of atoms that form the skeleton
of the polymer molecule by connecting to each other along the
chain is called the main chain. Some chemical units called side
groups are also attached to the atoms in the polymer main chain.

For example; Carbon atoms form the main chain of polyethylene, and
all of its side groups are hydrogen atoms.

In polytetrafluoroethylene (PTFE, teflon), there are carbon atoms in

the main chain, and the side groups are fluorine atoms.
Most polymers are synthesized from monomers with different side groups.

Phenyl with hydrogen in polystyrene

Chlorine along with hydrogen in poly(vinylchloride),

Methyl with hydrogen in polypropylene It has

side groups.
 Different types of polymer chain

THERE ARE FOUR BASIC POLYMER STRUCTURES WHICH ARE SHOWN IN

THE FIGURE BELOW.
⚫ SOME POLYMERS MIGHT CONTAIN A MIXTURE OF THE VARIOUS BASIC
STRUCTURES. THE FOUR BASIC POLYMER STRUCTURES ARE LINEAR,
BRANCHED, CROSSLINKED, AND NETWORKED.

Thermoset
Thermoplastics
Elastomer
⚫ LINEAR POLYMERS RESEMBLE ‘SPAGHETTI’ WITH LONG CHAINS. THE
LONG CHAINS ARE TYPICALLY HELD TOGETHER BY THE WEAKER VAN
DER WAALS OR HYDROGEN BONDING. SINCE THESE BONDING TYPES
ARE RELATIVELY EASY TO BREAK WITH HEAT, LINEAR POLYMERS ARE
TYPICALLY THERMOPLASTIC.
⚫ BRANCHED POLYMERS RESEMBLE LINEAR POLYMERS WITH THE
ADDITION OF SHORTER CHAINS HANGING FROM THE SPAGHETTI
BACKBONE.

⚫ SINCE THESE SHORTER CHAINS CAN INTERFERE WITH EFFICIENT PACKING

OF THE POLYMERS, BRANCHED POLYMERS TEND TO BE LESS DENSE THAN
SIMILAR LINEAR POLYMERS.
⚫ CROSSLINKED POLYMERS RESEMBLE LADDERS. THE CHAINS LINK FROM
ONE BACKBONE TO ANOTHER. SO, UNLIKE LINEAR POLYMERS WHICH
ARE HELD TOGETHER BY WEAKER VAN DER WAALS FORCES,
CROSSLINKED POLYMERS ARE TIED TOGETHER VIA COVALENT BONDING.
⚫ NETWORKED POLYMERS ARE COMPLEX POLYMERS THAT ARE HEAVILY
LINKED TO FORM A COMPLEX NETWORK OF THREE-DIMENSIONAL
LINKAGES.

⚫ THESE POLYMERS ARE NEARLY IMPOSSIBLE TO SOFTEN WHEN HEATING

WITHOUT DEGRADING THE UNDERLYING POLYMER STRUCTURE AND ARE
THUS THERMOSETTING POLYMERS.
 HOMOPOLYMERS ARE A TYPE OF POLYMER COMPOSED OF A SINGLE
TYPE OF MONOMER. THEY CONSIST OF UNIFORM, REPEATING
MOLECULAR CHAINS. THE RESULT IS A RELATIVELY SIMPLE STRUCTURE
MADE OF THE REPEATING UNIT. HOMOPOLYMERS ARE USUALLY FORMED
THROUGH ADDITION POLYMERIZATION.

⚫ EXAMPLES OF HOMOPOLYMERS INCLUDE:

⚫ POLYETHYLENE
⚫ POLYSTYRENE
⚫ POLYPROPYLENE
⚫ POLYMETHYL METHACRYLATE (ACRYLIC)
⚫ A COPOLYMER IS A POLYMER THAT IS MADE UP OF TWO OR MORE
MONOMER SPECIES.

⚫ MANY COMMERCIALLY IMPORTANT POLYMERS ARE COPOLYMERS.

EXAMPLES INCLUDE POLYETHYLENE-VINYL ACETATE (PEVA), NITRILE
RUBBER, AND ACRYLONITRILE BUTADIENE STYRENE (ABS).

⚫ THE PROCESS IN WHICH A COPOLYMER IS FORMED FROM MULTIPLE

SPECIES OF MONOMERS IS KNOWN AS COPOLYMERIZATION. IT IS
OFTEN USED TO IMPROVE OR MODIFY CERTAIN PROPERTIES OF
PLASTICS.
⚫ BLOCK COPOLYMERS
WHEN MORE THAN ONE HOMOPOLYMER UNITS ARE LINKED
TOGETHER VIA COVALENT BONDS, THE RESULTING SINGLE-CHAIN
MACROMOLECULE IS CALLED A BLOCK COPOLYMER.

⚫ AN EXAMPLE OF SUCH A POLYMER IS ACRYLONITRILE BUTADIENE

STYRENE, COMMONLY REFERRED TO AS SBS RUBBER.
⚫ AN ILLUSTRATION DESCRIBING THE STRUCTURE OF AStyrene
Acrylonitrile Butadiene BLOCK (ABS) is a synthesized by the
polymerization of acrylonitrile and styrene monomers alongside
COPOLYMER WHICH IS MADE UP OF polybutadiene.
THE MONOMERS ‘A’ AND
Acrylonitrile provides ‘B’ ISheat and chemical
hardness,
resistance to the product. Styrene monomer imparts good
PROVIDED BELOW. processability to ABS, while butadiene makes the product harder
and more resistant even at low temperatures.
⚫ ALTERNATE COPOLYMERS ARE THE POLYMERS IN WHICH TWO OR MORE
MONOMERS ARE ARRANGED IN A SEQUENCE THAT FOLLOWS SOME STATISTICAL
RULE.

⚫ AN EXAMPLE OF A THIS POLYMER IS THE MADE FROM THE COPOLYMERS OF STYRENE

AND BUTADIENE.

⚫ AN ILLUSTRATION DESCRIBING THE STRUCTURE OF A STATISTICAL COPOLYMER IS

PROVIDED BELOW.
MONOMERS ARRANGED RANDOMLY THROUGHOUT THE POLYMER
(ABAAABBABBBBA).
⚫ BRANCHED COPOLYMERS FEATURING DIFFERENTLY STRUCTURED
MAIN CHAINS AND SIDE CHAINS ARE KNOWN AS GRAFT
COPOLYMERS.

⚫ AN ILLUSTRATION DETAILING THE STRUCTURE OF A GRAFT COPOLYMER

MADE UP OF MONOMERS A AND B IS PROVIDED BELOW.
 MOLECULAR WEIGHT
• Molecular weight, M: Mass of a mole of chains.

Low M

high M

Not all chains in a polymer are of the same length

— i.e., there is a distribution of molecular weights

26
 MOLECULAR WEIGHT DISTRIBUTION
Adapted from Fig. 14.4, Callister & Rethwisch 8e.
total wt of polymer
Mn =
total # of molecules

M n = xi Mi
M w = wi Mi

Mi = mean (middle) molecular weight of size range i

xi = number fraction of chains in size range i
wi = weight fraction of chains in size range i
27
 MOLECULAR WEIGHT CALCULATION

Example: average mass of a class

Student Weight
mass (lb) What is the average
1 104 weight of the students in
2 116 this class:
3 140 a) Based on the number
4 143
fraction of students in
5 180
each mass range?
6 182
b) Based on the weight
fraction of students in
7 191
each mass range?
8 220
28
9 225
10 380
 MOLECULAR WEIGHT CALCULATION (CONT.)
Solution: The first step is to sort the students into weight ranges. Using
40 lb ranges gives the following table:
Calculate the number and weight
weight number of mean number weight
range students weight
fraction
fraction
of students in each weight
fraction
Ni Wi xirange as follows:
wi
m as s (lb) m as s (lb) Ni NiWi
xi = wi =
81-120 2 110 0.2 0.117
Ni  NiWi
121-160 2 142 0.2 0.150
161-200 3 184 0.3 0.294
For example: for the 81-120 lb range
201-240 2 223 0.2 0.237
  2
241-280 0 - 0 =
x81−1200.000 = 0.2
281-320 0 - 0 0.00010
321-360 0 - 0 0.0002 x 110
361-400 1 380 0.1 w 81−120 =
0.202 = 0.117
1881
total Ni NiWi  total
number 10 1881 weight 29
 MOLECULAR WEIGHT CALCULATION (CONT.)
weight mean number weight
range weight fraction fraction
Wi xi wi
mass (lb) mass (lb)
81-120 110 0.2 0.117
121-160 142 0.2 0.150
161-200 184 0.3 0.294
201-240 223 0.2 0.237
241-280 - 0 0.000
281-320 - 0 0.000
321-360 - 0 0.000
361-400 380 0.1 0.202
Mn = x M
i i = (0.2 x 110 + 0.2 x 142 + 0.3 x 184 + 0.2 x 223 + 0.1 x 380) = 188 lb

Mw = w M i i = (0.117 x 110 + 0.150 x 142 + 0.294 x 184

+ 0.237 x 223 + 0.202 x 380) = 218 lb
Mw =  wi Mi = 218 lb
30
WHAT DID WE LEARN LAST WEEK? ☺
 4. Networked
Polymers
CLASSIFICATION OF POLYMERS BASED
ON INTER PARTICLE FORCES:

• On the basis of the magnitude of intermolecular forces, the polymers

have been classified into the following four categories:
• (A) ELASTOMERS
• (B) FIBERS
• (C) THERMOPLASTICS
• (D) THERMOSETTING POLYMERS
ELASTOMERS
 PROPERTIES OF ELASTOMERS

• Elastomers are generally very viscous, making them slow-flowing under force.
• Elasticity is the ability of an object to return to its original shape after stretching or
compressing it under force. A simple example is a rubber (lastik) band — if you
stretch a rubber band, it snaps back to its original form.
• Elastomeric polymers tend to exhibit a high level of elasticity, making them more
resistant to breaking or cracking. In fact, elastomers can reversibly extend up to
700% depending on the specific material.
 Thermoplastic and Thermosetting Plastic
The differences between thermoplastic and thermosetting plastic, the main distinguishing factor
between the two is that thermoplastic materials typically have low melting points due to which
they can further be remoulded or recycled easily.

On the other hand, thermosetting plastic is quite the

opposite. They can withstand high temperatures and
once hardened these cannot be reformed or
recycled even with the application of heat. In any
case, let’s have a look at some of the important
differences between these two compounds below.
Polymers with a high crosslinking ratio and reaching a certain value do not
pass into a liquid state if heated, they do not soften and degrade by
disintegrating with increasing temperature. Such polymers are also called
thermosets. Since thermosets are cured or cross-linked compounds, they are
long-lasting and heat-resistant. It is not possible to reprocess or shape the
materials in this group.
Most of the polymers in cross-linked and network structure, such as vulcanized
rubber, epoxy, phenolic and some polyester resins, are thermosetting.
AS WITH POLYESTER, SOME POLYMERS CAN BE BOTH THERMOPLASTIC
AND THERMOSETTING
 THERMOPLASTICS: ADVANTAGES AND
DISADVANTAGES
• Thermoplastics are ideal for injection molding because they can be heated, cooled,
reheated and reused. During the molding process, solid resin pellets are heated to their
melting point.

Liquid material enters the mold, where it cools and eventually hardens. Excess
thermoplastic material from the runner, a channel in the mold that allows plastic to flow
into the cavity, can be recycled into the batch for greater material utilization.
Thermoplastics are also relatively easy to surface finish. This supports their use not just
with injection molding, but also with CNC machining and 3D printing.

• Another advantage of thermoplastic materials is that they can be recycled and reused.
With injection molding, thermoplastics can be ground into pellets that are then re-melted.
A thermoplastic can be reused varies by the specific material.
 THERMOSETS: ADVANTAGES AND DISADVANTAGES
• The processing differences between thermosets and thermoplastics are significant, and
thermoset materials cannot be reshaped or reformed once they have “set”.

• Thermosets resist higher levels of heat, however, and thermosets provide stronger
corrosion resistance than thermoplastics. Thermosetting polymers also provide greater
resistance to creep, the tendency of a solid material to deform permanently under
mechanical stress.

• Thermosets’ physical and mechanical strength makes them a good choice for many
applications.

• The biggest disadvantage of thermosets is that they can’t be reheated for reprocessing.
They also tend to be more rigid than thermoplastics, less resistant to impact and more
prone to shattering.

• Disposing of thermosets is more challenging, but some materials can be ground into filler
materials.
• Thermoset plastics are used in consumer goods such as cooking utensils and
billiard balls, but they’re also used in commercial and industrial applications
with higher temperatures.

Examples Of Thermoset Products Include:

• Electronic Components
• High Voltage Insulators
• Heat Shields
• Motor Components And Covers
• Lighting Components
• Energy Equipment
 COMPARING THERMOPLASTIC AND
ELASTOMERS

There are differences between thermoplastic and elastomer materials due to the
existing bond structures.

This difference in mechanical properties ensures that the tensile and yield strengths are
different. To give an example; when elastomer materials are subjected to A tensile
force, they immediately begin to elongate and return to their previous shape when this
force is removed.

However, this is not the case for thermoplastics. When A tensile force acts on
thermoplastic materials, they do not suddenly start to elongate. The force needs to be
increased up to A certain point. In elastomers, elongation will occur as soon as force is
applied.
 HDPE

polietilen tereftalat (PET) or

polipropilen (PP)