Presented by Iwan Susanto, Ph.

Mechanical Engineering Department

Politeknik Negeri Jakarta Created by Dr. Vika Rizkia
 Polymers are compounds which consist of very large
Polymers… molecules formed by repeated joining of many small
molecules

Poly- means "many" and -mer means "part" or "segment". Mono means "one". So,
monomers are those molecules that can join together to make a long polymer chain.

Many many many MONOmers make a POLYmer! usually a single polymer molecule is made
out of hundreds of thousands (or even millions!) of monomers!

Sometimes polymers are called "macromolecules" - "macro"

means "large"  polymers must be very large molecules

The chemical reactions which monomers joined together to form

polymer are called polymerization reactions

n momomer units polymerization Polymer

 Differences between
molecule and monomer…
Hydrocarbons (many organic materials) = composed of hydrogen and
carbon

H
H-C-H Similarly

H
Ethylene
Methane
Covalent Bonding
 Consider again the hydrocarbon ethylene (C2H4), which is a gas at ambient temperature
and pressure

If the ethylene gas is subjected catalytically to appropriate conditions of

temperature and pressure, it will transform to polyethylene (PE), which is a
solid polymeric material

Catalyst bonding unsatisfied for this C atom

bonding satisfied for C atom

Angle =109o
 Unpaired electron

Methyl group
Polymer consisting of multiples of
the same repeating units as
Polyethylene

Resulted products from two

different monomers (e,g A and B)
polymerized together

Polymers obtained from three

different monomers (e.g. A, B
and C)
 Naturally occurring polymers are
Natural Polymers macromolecules derived from living
things

e.g. wool, paper, cotton, starch, silk and

rubber

1. Proteins
Vital activity Example of proteins Functions
Nutrition Digestive enzymes
e.g. trypsin, • Catalyzes the hydrolysis of
proteins to polypeptides
amylase • Catalyzes the hydrolysis of
starch to maltose
lipase • Catalyzes the hydrolysis of fats
to fatty acids and glycerol
 Vital activity Example of proteins Functions

Respiration and Haemoglobin • Responsible for the

transport transport of O2/CO2
throughout the body
Immune Antibodies • Essential to the
response defence of the body
(e.g. against bacterial
invasion)
Growth Hormones • Controls growth and
(e.g. tyrosine) metabolism
 Vital activity Example of proteins Functions
Support and Actin and myosin • Responsible for
movement muscle contraction
Collagen • Gives strength with
flexibility in tendons and
cartilage
Sensitivity and Hormones • Controls blood sugar level
coordination (e.g. insulin)
Amino Acids as the Basic Unit of Proteins
Amino acids are the basic structural units of proteins

The various amino acids differ only in their side

chains (i.e. R groups)

the various R groups give each amino acid

distinctive characteristics

influence the properties of the proteins

consisting of them
2. Carbohydrates
Dextro-lemon powder and
grapes contain D-glucose

Carbohydrates are divided into three groups:

a. Monosaccharides C6H12O6
• Two most important examples: glucose and fructose
• Found in many fruits and in honey
• Glucose is also found in the blood of animals (including humans)

Fruits contain fructose 2. Disaccharides C12H22O11

• Disaccharides are sweet, soluble and crystalline
• Disaccharides can be formed from the condensation
reaction of two monosaccharide molecules

Sucrose Maltose Lactose

Source sugar cane malt milk

Constituent mono- a glucose unit and a two glucose units a glucose unit and a
saccharides fructose unit galactose unit
3. polysaccharides
• Polysaccharides are polymers of monosaccharides (C6H12O6)
• General formula: (C6H10O5)n
where n is a large number (up to thousands)
• Examples of polysaccharides: starch and cellulose
• Starch is commonly found in rice, bread and potatoes
• Cellulose is found in fruits, vegetables, cotton and wood

Food containing sucrose and maltose

3. Deoxyribonucleic Acid (DNA)
They differ in their nitrogen-containing
bases

Adenine (A) and guanine (G) :

- have double-ring structures
- known as purines

Cytosine (C) and thymine (T)

- have single-ring structures
- known as pyrimidines
Synthetic polymers can be made from monomers by TWO basic polymerization processes:
1. Addition polymerization (produces addition polymers)
2. Condensation polymerization (produces condensation polymers)

Addition Polymerization
Addition polymerization is a chemical process in which monomer molecules are joined
together to form a polymer without elimination of small molecules
Sometimes called chain-growth polymerization (many monomer molecules add to give a
polymer)

Alkenes and their derivatives are common starting materials

Usually starts with the generation of free radicals which initiate a chain reaction

A catalyst is often required to initiate the generation of free radicals

 Involves a simple addition of monomer molecules to each other
without the loss of any atoms from the original molecule

NOTES:
It is possible to
produce a saturated
long chain polymer
from unsaturated
monomer
Examples of addition polymers:
 Polyethene (PE)
 Polypropene (PP)
 Polystyrene (PS)
 Polyvinyl chloride (PVC)
 Polytetrafluoroethene (PTFE)
 Polymethyl methacrylate (PMMA)
1. Polyethene/Polyethylene (PE)
Ethene is the monomer that is used to
synthesize polyethene
a. low density polyethene (LDPE)
Depending on the manufacturing conditions, two
kinds of polyethene can be made
- low density polyethene (LDPE)
- high density polyethene (HDPE)
Free radical
mechanism
a. low density polyethene (LDPE)

- Molecular mass between 50 000 and 3 000 000

- Light, flexible
- Low melting point
- Used to make soft items (e.g. wash bottles, plastic bags and food wraps)
a. high density polyethene (HDPE)

Ziegler Natta catalyst : TiCl4 + Al(C2H5)3

Karl Ziegler and Giulio
Natta : Nobel
Laureate in Chemistry,
1963

• Molecular mass up to 3 000 000

• Tougher
• Higher melting point
• Used to make more rigid items
(e.g. milk bottles and water buckets)
a. high density polyethene (HDPE)
Reaction Mechanism: (optional)
Free Radical Addition Polymerization of Ethene
The reaction mechanism
consists of three stages: 1. Chain initiation
- chain initiation
- chain propagation The radical (R•) produced then reacts with an ethene
- chain termination molecule  form a new radical
2. Chain propagation
The resulting radical is electron-deficient and is very reactive
 able to attack another ethene molecule
 give a radical with a longer carbon chain

By repeating the step

 the carbon chain of the radical grows in length

chain-growth polymerization
3. Chain termination
- The radicals react to give a stable molecule
- The reaction stops
2. Polypropene/Polypropylene (PP)
With the use of Ziegler-Natta catalyst TiCl4 + Al(C2H5)3, propene can be polymerized
to isotactic polypropene (ionic mechanism)

H H H H H
CH3 CH3 CH3 CH3 CH3
C C C C C
C C C C
H2 H2 H2 H2

- More rigid than HDPE (used for moulded furniture)

All methyl groups are arranged on the
same(iso) side of the polymer chain.
- close packing
- high-density, rigid, tough, high
melting point.
(Used to make sheets and films for
packaging and as fibres in the
manufacture of carpets)
- High mechanical strength and strong resistance to
abrasion (used for making crates, kitchenware and food
containers)
- Spun into fibres for making ropes and carpets
(especially useful for making athletic wear)
- They do not absorb water from sweating as cotton
does
2. Polypropene/Polypropylene (PP)
3. Polystyrene (PS)
Styrene is made from the reaction of benzene with ethene, followed by dehydrogenation

The styrene produced is polymerized by a free radical mechanism into polystyrene

 at 85 – 100°C O

 using dibenzoyl peroxide as the initiator C O

O C

O
PS is more rigid than HDPE due to the induced dipole-induced dipole interaction between benzene rings
of adjacent polymer chains.

Polystyrene is transparent, brittle and chemically inert (used to make toys, specimen containers and
cassette cases)
By heating polystyrene with a foaming agent (e.g. pentane + steam),
 expanded polystyrene can be made
Expanded polystyrene is
- an extremely light, white solid foam
- mainly used to make light-weight ceiling tiles in buildings, and food boxes and
shock absorbers for packaging
4. Polyvinyl Chloride (PVC)
PVC is produced by addition polymerization of the choroethene(vinyl chloride) monomers
 in the presence of a peroxide catalyst (e.g. hydrogen peroxide at about 60°C)

Presence of the polar C  Cl bond

 considerable dipole-dipole interactions exist
between the polymer chains
 makes PVC a fairly strong material

PVC is hard and brittle (used to make pipes and

bottles)
When plasticizers O
are added  the effectiveness of the dipole-dipole
C
interactions is reduced
R
 PVC becomes more flexible
e.g.
DEHP
R
C

- Used to make shower curtains, raincoats and artificial

O
leather
- Used as the insulating coating of electrical wires
Products made of PVC with plasticizers Products made of PVC without plasticizers
5. Polytetrafluoroethene (PTFE)
PTFE is produced through addition polymerization of the tetrafluoroethene monomers under
high pressure and in the presence of a catalyst (Commonly known as Teflon or Fluon)

Fluorine is larger than hydrogen

- the molecular mass of PTFE > PE
- leads to greater van der Waals’forces
between the polymer chains

- PTFE has a relatively high melting

point and is chemically inert
- Its non-stick properties make it an
ideal material for the coating of
frying pans
- As the insulating coating of electrical
wires
- As sealing tapes for plumbing joints
- For making valves and bearings
6. Polymethyl Methacrylate (PMMA)
More commonly known as perspex

PMMA is formed by the free radical

addition polymerization of methyl
methacrylate in the presence of an
organic peroxide at about 60°C

Unlike PP, it is easily scratched

PMMA is a dense, transparent and tough solid makes it a good material for making
safety goggles, advertising sign boards and vehicle light protectors
Condensation Polymerization
Condensation polymerization is a chemical process in which monomer molecules are joined
together to form a polymer with elimination of small molecules such as water, ammonia
and hydrogen chloride
In condensation polymerization, each monomer molecule must have at least two
functional groups (bifunctional)
Examples of naturally occurring
condensation polymers are:
Proteins, Polysaccharides, DNA

Examples of synthetic
condensation polymers are:
- Nylon (a polyamide)
- Kevlar (a polyamide)
- Dacron (a polyester)
- Urea-methanal
Polyamide : Polymer with repeating units held by amide
linkages
1. Nylon
A group of condensation polymers formed by the condensation polymerization between a
diamine and a dicarboxylic acid
One of the most important nylon is nylon-6,6, made from the condensation polymerization
between hexane-1,6-diamine and hexanedioic acid

The condensation polymerization

begins with the formation of a
dimer, and a water molecule is
eliminated
2. Kevlar
Kevlar is an aromatic polyamide The structure of Kevlar is similar to nylon-6,6
The two monomers of Kevlar are benzene-1,4-dicarboxylic acid and 1,4-diaminobenzene

water molecules are eliminated

Part of a polymer chain of Kevlar is shown below :

2. Kevlar
The repeating unit of Kevlar is:

Kevlar is a very strong material (used for reinforcing car tyres)

Used to make ropes 20 times as strong as steel ropes of the same weight
Used for making reinforced aircraft wings and bullet-proof vests

Kevlar undergoes alkaline hydrolysis

3. Dacron
Dacron is the DuPont trade mark for the polyester :
Polyethylene terephthalate (PET, PETE, PETP)
Sometimes called Terylene
PET is a condensation polymer formed between a dioic acid and a diol.
terephthalic acid ethane-1,2-diol
Esterification
(condensation)
the ester molecule formed still has unreacted functional groups at both ends

Repeated condensations

(Polyester)
  strong
 tough
 smooth
 resistant to water and chemicals

resistant to wrinkle Clothes made of 100% cotton.

can be dried easily soft, comfortable, absorb sweat

Clothes made of 100% polyester. quickly
Clothes made of 35% polyester and 65%
cotton
Strong and comfortable to
wear
4. UREA METHANAL
Urea-methanal is a polyamide, which is a condensation polymer formed from the following
two monomers:

Polymer: Repeating unit:

Stage One : repeated condensations

Conc. H2SO4 −H2O repeated

as catalyst condensations
Stage Two :
Formation of cross-
links
For cross-links to
form, one of the
monomers must
have more than two
reactive sites further
−H2O
condensations
- white in colour
- hard and rigid
- excellent electrical and heat insulator
- resistant to chemical attack
- insoluble in any solvent
- upon heating, it does not change in shape
or melt
- under strong heating, it decomposes

Urea-methanal is a thermosetting plastic

 once set hard cannot be softened or melted
again by heating
1. LINEAR POLYMERS
Linear polymers are those in which the mer
units are joined together end to end in single
chains
These long chains are flexible and may be
thought of as a mass of spaghetti, where each
circle represents a mer unit
For linear polymers, there may be extensive van
der Waals and hydrogen bonding between the
chains
polyethylene, polyvinyl chloride, polystyrene,
polymethyl methacrylate, nylon, and the
fluorocarbons
1. BRANCH POLYMERS
Polymers may be synthesized in which side-
branch chains are connected to the main
ones, these are fittingly called branched
polymers
The branches, considered to be part of the main-
chain molecule, result
from side reactions that occur during the
synthesis of the polymer
The chain packing efficiency is reduced with the
formation of side branches, which results in a
lowering of the polymer density
Those polymers that form linear structures may
also be branched
3. CROSSLINKED POLYMERS 4. NETWORK POLYMERS
In crosslinked polymers, adjacent linear chains Trifunctional mer units, having three active
are joined one to another at various covalent bonds, form three-dimensional
positions by covalent bonds Networks and are termed network polymers

The process of crosslinking is achieved either
during synthesis or by a nonreversible chemical
reaction that is usually carried out at an
elevated temperature.
Often, this crosslinking is accomplished by
additive atoms or molecules that are covalently
bonded to the chains
a polymer that is highly crosslinked may be
classified as a network polymer
These materials have distinctive mechanical and
thermal properties; the epoxies and phenol-
formaldehyde belong to this group

Many of the rubber elastic materials are

crosslinked; in rubbers, this is called
vulcanization

It should be pointed out that polymers are not usually of only one distinctive structural type. For
example, a predominantly linear polymer might have some limited branching and crosslinking
Thermoplasts soften when heated (and eventually liquefy) and harden when cooled—
processes that are totally reversible and may be repeated.
On a molecular level, as the temperature is raised, secondary bonding forces are diminished
(by increased molecular motion) so that the relative movement of adjacent
chains is facilitated when a stress is applied.
Irreversible degradation results whenthe temperature of a molten thermoplastic polymer is
raised to the point at which molecular vibrations become violent enough to break the
primary covalent bonds. In addition, thermoplasts are relatively soft.
Most linear polymers and those having some branched structures with exible chains are
thermoplastic
Polyethylene (PE), Polystyrene (PS) and PVC consist of entangled or branched
macromolecules held together by intermolecular forces
Thermosetting polymers become permanently hard when heat is applied and do not
soften upon subsequent heating

During the initial heat treatment, covalent crosslinks are formed between adjacent
molecular chains; these bonds anchor the chains together to resist the vibrational and
rotational chain motions at high temperatures.

Crosslinking is usually extensive, in that 10 to 50% of the chain mer units are crosslinked

Only heating to excessive temperatures will cause severance of these crosslink bonds
and polymer degradation

Thermoset polymers are generally harder and stronger than thermoplastics, and have
better dimensional stability.
What’s Your Message?