THE WORLD OF POLYMERS

CHEMISTRY FOR ENGINEERS

J D D. DELA CRUZ/TRP
TECHNOLOGICAL UNIVERSITY OF THE PHILIPPINES – TAGUIG
BASIC ARTS AND SCIENCES DEPARTMENT
CHEMISTRY SECTION

for instructional purposes only

POLYMERS
WHAT ARE POLYMERS?
▪ Greek words - poly meaning several and
meros meaning parts.
▪ Large molecule consisting of repeated
chemical units (`mers') joined together,
like beads on a string.
▪ Polymers usually contain many or more
than five monomers, and some may
contain hundreds or thousands of
monomers in each chain.
 WHAT ARE POLYMERS?
The small building-block molecules
are called monomers.
HYDROCARBON MOLECULES
ALKANES – A single
covalent bond exists
when each of the
two bonding atoms
contributes one
electron
ALKENES & ALKYNES –
Double and triple
bonds between two
carbon atoms involve
the sharing of two
and three pairs of
electrons,
respectively.
 AROMATIC
also known as arenes, are chemical
compounds that contain
conjugated planar ring systems
with delocalized pi electron clouds
instead of discrete alternating single
and double bonds.
HYDROCARBON MOLECULES
HYDROCARBON MOLECULES
 AROMATIC HYDROCARBONS
Nomenclature of Benzene Derivatives
 Nomenclature of Benzene Derivatives
• To name a benzene ring with one substituent, name the
substituent and add the word benzene.

• Many monosubstituted benzenes have common names

which you must also learn.

14
 Nomenclature of Benzene Derivatives
• There are three different ways that two groups can be
attached to a benzene ring, so a prefix—ortho, meta, or
para—can be used to designate the relative position of the
two substituents.

ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene

or or or
o-dibromobenzene m-dibromobenzene p-dibromobenzene
or 1,2-dibromobenzene or 1,3-dibromobenzene or 1,4-dibromobenzene
15
 SATURATED
hydrocarbon, all
bonds are single
ones, and no new
atoms may be joined
without the removal
of others that are
already bonded.
UNSATURATED molecules that have double and
triple covalent bonds, each carbon atom is not
bonded to the maximum (four) other atoms; as
such, it is possible for another atom or group of
atoms to become attached to the original
molecule.
UNSATURATED molecules that have double and
triple covalent bonds, each carbon atom is not
bonded to the maximum (four) other atoms; as
such, it is possible for another atom or group of
atoms to become attached to the original
molecule.
ISOMERISM – hydrocarbon compounds
with the same composition may have
different atomic arrangements.
ISOMERISM – hydrocarbon compounds
with the same composition may have
different atomic arrangements.
 STEREOISOMERISM
ISOTACTIC
Denotes the situation
in which atoms are
linked together in the SYNDIOTACTIC
same order (head-to-
tail) but differ in their
spatial arrangement. ATACTIC
all the R groups are situated on the same
side of the chain ISOTACTIC
R groups alternate sides of the chain. SYNDIOTACTIC
random orientations of groups R along the chain. ATACTIC
random orientations of groups R along the chain.
 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 MOLECULES

Macromolecules – the molecules in polymers are

gigantic in comparison to the hydrocarbon
molecules already discussed because of their size.
MONOMER refers to the small molecule from
which a polymer is synthesized.

“Mer” originates from the Greek word meros,

which means part; the term polymer was
coined to mean “many mers.”
THE CHEMISTRY OF POLYMER MOLECULES
 THE CHEMISTRY OF POLYMER MOLECULES

COVALENT ATTACHMENT
 HYDROCARBON DERIVATIVES
• Functional group: an atom or group of atoms within a
molecule that shows a characteristic set of physical and
chemical properties

• Functional groups are important for three reason; they

are
1. the units by which we divide organic compounds into
classes
2. the sites of characteristic chemical reactions
3. the basis for naming organic compounds
Functional groups
Alk is the prefix of the group (Meth, Eth, Prop, etc.)
Common
Family Structure IUPAC nomenclature
nomenclature

Alcohols R—OH Alkanol Alkyl alcohol

Carboxylic acids (Alk + 1)anoic acid -

Aldehydes Alkanal -

Alk(1)yl Alk(2)yl
Ketones Alkanone
ketone
Functional groups
Alk is the prefix of the group (Meth, Eth, Prop, etc.)
IUPAC Common
Family Structure
nomenclature nomenclature

Ethers R1—O—R2 alkoxyalkane Alk(1)yl Alk(2)yl ether

Alk(1)yl (Alk +
Esters Alk(1)yl Alk(2)anoate
1)(2)anoate

Amides (Alk + 1)anamide -

Amines R—NH2 Alkamine Alkyl amine

HYDROCARBON MOLECULES
ALCOHOL NOMENCLATURE
CARBOXYLIC ACIDS NOMENCLATURE
CLASSIFICATION OF POLYMERS

SOURCE

STRUCTURE

POLYMERIZATION

MOLECULAR FORCE
 CLASSIFICATION OF POLYMERS BY SOURCE

(1) MAN-MADE OR SYNTHETIC POLYMERS that are synthesized in the

laboratory;
Synthetic – synthesized from small organic molecules, such as nylon
or polyethylene
 CLASSIFICATION OF POLYMERS BY SOURCE

(2)NATURAL POLYMER that are found in nature.

Natural – those derived from plants and animals, such as starch,
proteins, nucleic acids (DNA), natural rubber

Polymers such as polysaccharides (starch, cellulose), proteins

and nucleic acids etc. which control various life processes are
also called biopolymers.
 CLASSIFICATION OF POLYMERS BY SOURCE
▪ Starch - It is a polymer of α-glucose. It is a chief food
reserve of plants.

▪ Cellulose- It is also a polymer of β-glucose. It is a chief

structural material of the plants and provides food,
clothing and shelter.

▪ Proteins : These are polymers of α -amino acids. They

have generally 20 to 1000 a-amino acids joined
together in a highly organized arrangement. These are
building blocks of animal body and constitute an
essential part of our food.
CLASSIFICATION OF POLYMERS BY SOURCE
 CLASSIFICATION OF POLYMERS BY SOURCE

Nucleic acids - These are polymers of various nucleotides.

For example, RNA and DNA are common nucleotides. These
control heredity at molecular level.

Natural rubber - It is a polymer of unsaturated hydrocarbon,

2-methyl-l, 3-butadiene also called isoprene. It is obtained
from latex of rubber trees. In natural rubber 10,000 to 20,000
isoprene units are linked together.
 CLASSIFICATION OF POLYMERS BY SOURCE

(3) SEMI – SYNTHESIS POLYMERS cellulose and derivatives of cellulose.

 CLASSIFICATION OF POLYMERS BY SOURCE

(3) SEMI – SYNTHESIS POLYMERS cellulose and derivatives of cellulose.

These polymers are mostly derived from naturally occurring polymers

by chemical modifications like vulcanized rubber.
CLASSIFICATION OF POLYMERS

SOURCE

STRUCTURE

POLYMERIZATION

MOLECULAR FORCE
CLASSIFICATION OF POLYMERS BY STRUCTURE

(1) LINEAR POLYMERS – Long and straight chains.

CLASSIFICATION OF POLYMERS BY STRUCTURE

(2) BRANCHED CHAIN POLYMERS – Linear

and having some branches. (Low density
polymers)
CLASSIFICATION OF POLYMERS BY STRUCTURE

(3) CROSS-LINKED POLYMERS – Formed from

bifunctional and trifunctional monomers and
contains strong covalent bonds. (Bakelite,
Melamine)
CLASSIFICATION OF POLYMERS

SOURCE

STRUCTURE

POLYMERIZATION

MOLECULAR FORCE
 CLASSIFICATION OF POLYMERS BY
POLYMERIZATION
(1)ADDITION POLYMERS – Formed by repeated
addition of monomer molecules possessing double
or triple bond.
 CLASSIFICATION OF POLYMERS BY
POLYMERIZATION

(2)CONDENSATION POLYMERS – Formed by repeated condensation

reaction between two different bi-functional or tri-functional
monomeric units
CLASSIFICATION OF POLYMERS BY
POLYMERIZATION
 POLYMERIZATION

(1)INITIATION REACTION:
 POLYMERIZATION

(1)INITIATION REACTION:

Homolysis –the cleavage of the chlorine-chorine

bond in a symmetrical way
Odd electron – not paired and does not have a
partner of opposite spin
 POLYMERIZATION

(1)INITIATION REACTION:

An atom or group of atoms possessing an odd

(unpaired) electron is called a free radical
 POLYMERIZATION

(1)INITIATION REACTION:
 POLYMERIZATION
(2)RAPID PROPAGATION
~1000 MER UNITS IN 1-10 MS:
POLYMERIZATION
 POLYMERIZATION
(3)TERMINATION:
When two active chain ends meet each
other or active chain ends meet with initiator
or other species with single active bond:
 POLYMERIZATION

TERMINATION:
 POLYMERIZATION

Chain-initiating step - in which energy is

absorbed and a reactive particle generated.
Chain-propagating steps - each of which
consumes a reactive particle and generates
another.
Chain-terminating steps - in which reactive
particles are consumed but not generated;
 POLYMERIZATION
INITIATION, PROPAGATION, TERMINATION

______________- each of which consumes a

reactive particle and generates
______________- in which reactive particles are
consumed but not generated;
______________- in which energy is
absorbed and a reactive particle generated.
another.
H2C=CHCl polyvinyl chloride
H2C=CHC6H5 polystyrene
F2C=CF2 Teflon
The tetrafluoroethylene monomer, can
polymerize to form polytetrafluoroethylene
(PTFE)
The vinyl chloride (CH2“CHCl) monomer is a slight
variant of that for ethylene, in which one of the four
H atoms is replaced with a Cl atom.

Polytetrafluoroethylene (having the trade name

TeflonTM) belongs to a family of polymers called
the fluorocarbons.
 CLASSIFICATION OF POLYMERS BY
POLYMERIZATION

(2)CONDENSATION POLYMERS – Formed by repeated condensation

reaction between two different bi-functional or tri-functional
monomeric units
 The compounds having reactive functional groups
like -OH, -NH2, -COOH etc. on the extreme ends of
the chain behave as bifunctional monomers.
For example: HO-{CH2)2-OH,
HOOC-{CH2)2-COOH,
H2N-{CH2)s-NH2
A polymer formed by the condensation of two or more
than two monomers with the elimination of simple
molecules like water, ammonia, hydrogen chloride,
alcohol etc. is called condensation polymer.
 Difference Between Addition and Condensation
Polymerization
Addition Polymerization Condensation
▪ It requires the Polymerization
presence of a multiple • It requires two reactive
bond in the monomer. functional groups to be
▪ present at both ends of
the monomer.
 Difference Between Addition and Condensation
Polymerization
2. There can be one or 2. There should be at least
two monomers having two different monomers
multiple bond or bonds. having functional group
which can react with each
other.

73
 Difference Between Addition and Condensation
Polymerization
3. No by product is 3. Generally a by-product
formed i.e., no simple is formed i.e., a simple
molecule is eliminated. molecule such as H20,
NH3 etc. is eliminated

74
 Difference Between Addition and Condensation
Polymerization
4. A homo-chain polymer, 4. Hetero-chain polymer,
generally a thermoplastic which may be either
is obtained. These thermoplastic or thermo-
polymers have only C setting is obtained.
atoms in the polymer These polymers have
chain some atom than C atoms
in the polymer chain.

75
 Difference Between Addition and Condensation
Polymerization
5. The growth of chain 5. The growth of chain is
in at one active centre at minimum two active
only. centres.

76
 Some polymers may be
represented using the
following generalized form,
where the “R” depicts
either an atom [i.e., H or Cl,
for polyethylene or
poly(vinyl chloride),
respectively], or an organic
group such as CH3, C2H5,
and C6H5 (methyl, ethyl,
and phenyl).
CLASSIFICATION OF POLYMERS

SOURCE

STRUCTURE

POLYMERIZATION

MOLECULAR FORCE
Thermoplastic Polymers

Thermoplastic polymers (thermoplasts):

➢ soften reversibly when heated (harden when cooled)
➢ At elevated T inter-chain bonding is weakened allowing
deformation at low stresses.
➢ Most thermoplasts are linear polymers and some
branched structures
➢ Examples: PVC, Teflon, polythene, polystyrene,ABS
(Acrylonitrile butadiene styrene).
Thermoplastic Polymers
Thermoplastic polymers (thermoplasts):
▪ Solid materials at room temperature but viscous liquids
when heated to temperatures of only a few hundred
degrees
▪ This characteristic allows them to be easily and
economically shaped into products
▪ They can be subjected to heating and cooling cycles
repeatedly without significant degradation
▪ Symbolized by TP
Thermosetting Polymers

Thermosetting polymers (thermosets):

➢ harden permanently when heated.
➢ Covalent crosslinks (10% - 50% of monommers) formed
during heating.
➢ Cross-linking hinder bending and rotations. Thermosets are
harder, more dimensionally stable, and more brittle than
thermoplasts.
➢ Examples: vulcanized rubber, epoxies, epoxy, polyurethane,
resins.
Elastomers and Fibres

▪ The polymers that have elastic character

▪ In elastomers the polymer chains are held together by
intermolecular forces.
▪ The most important example of elastomer is natural rubber.

▪ Fibres : These are the polymers which have strong intermolecular

forces between the chains. These forces are either hydrogen bonds
or dipole-dipole interactions
▪ These polymers are long and thread like and can be woven into
fabrics. Common examples are nylon-66, dacron, silk.
Thermoplastic Polymers - Thermoplastics
▪ These are the polymers which can be easily softened
when heated and hardened when cooled with little
change in their properties.
▪ The molecular forces in these polymers are intermediate
between those of elastomers and fibres.
▪ There is no cross linking between the chains.
 Thermosetting Polymers - Thermosets
• Cannot tolerate repeated heating cycles as
thermoplastics can
• When initially heated, they soften and flow for
molding
• Elevated temperatures also produce a chemical
reaction that hardens the material into an infusible
solid
• If reheated, thermosets degrade and char rather than
soften
• Symbolized by TS
 Polymer types

According to ‘end-use’
Polymer types includes:
1. Plastics
2. Elastomers (or rubbers)
3. Fibers
4. Coatings
5. Adhesives
6. Foams
7. Films
What do the recycling numbers mean?
• reference to what type of plastic the container is made of.
• use in classifying the different types of plastic and it aids
recyclers in the sorting process. Different molecules do
not mix when plastics are recycled.
1 – Polyethylene Terephthalate (PET or PETE or
Polyester)

Source: Mould and Die World Magazine

2 – High-Density Polyethylene (HDPE)
The more highly ordered structure of HDPE gives it greater density, rigidity,
strength, and a higher melting point than LDPE. The high-density form is
opaque; the low-density form tends to be transparent

HDPE and LDPE

https://www.youtube.com/watch?v=tFhLK3WYuPU
93
3 – Polyvinyl Chloride (PVC
4 – Low-Density Polyethylene (LDPE)
5 – Polypropylene (PP)
6 – Polystyrene (PS)
98
99
100
101
 1. Plastics
• are materials that have some structural rigidity under load,
and are used in general-purpose applications
• have a wide variety of combinations of properties:
✓Can be brittle or flexible
✓May have any degree of crystallinity
✓All molecular structures and configurations
possible
✓Can be either thermoplastic or
thermosetting
The stress–strain behavior for brittle (curve A), plastic (curve B), and
highly elastic (elastomeric) (curve C) polymers.
Stress is defines as internal resistance force per unit area.where as
strain is define as ratio of change in length to oringinal length.
2. Elastomers
Properties depend on degree of vulcanization
and on whether any reinforcement is used
• SBR (Styrene-Butadiene Rubber)
➢most important synthetic elastomer
➢Used predominantly in automobile tires,
reinforced with carbon black
• NBR (Nitrile-butadiene rubber or Buna-N): highly
resistant to degradation and swelling
3. Fibers
3. Fibers
• polymers capable of being
drawn into long filaments
having at least a 100:1
length-to-diameter ratio
• symmetrical and have
regular repeat units
Criteria:
✓must have a host of rather restrictive physical and
chemical properties.

✓ may be subjected to a variety of mechanical

deformations—stretching, twisting, shearing, and
abrasion

✓must have a high tensile strength (over a relatively wide

temperature range) and a high modulus of elasticity, as
well as abrasion resistance
Criteria:
✓molecular weight of fiber materials should be relatively
high or the molten material will be too weak and will
break during the drawing process.

✓fiber polymers must exhibit chemical stability to a

rather extensive variety of environments, including
acids, bases, bleaches, dry cleaning solvents, and
sunlight.

✓ must be relatively nonflammable and amenable to

drying
4. Coatings
4. Coatings
4. Coatings
• Applied to the surface of materials to serve one or more
of the following functions:

(1) to protect the item from the environment that may

produce corrosive or deteriorative reactions;
(2) to improve the item’s appearance; and
(3) to provide electrical insulation.
4. Coatings
These organic coatings fall into several different
classifications:
• Paint
• Varnish
• Enamel
• Lacquer
• Shellac
4. Coatings
• Many common coatings are latexes.
• A latex is a stable suspension of small insoluble polymer
particles dispersed in water.
• They don’t contain large quantities of organic solvents
that are emitted into the environment—that is, they
have low volatile organic compound (VOC) emissions.
5. Adhesives
• Substance used to bond together the surfaces of two
solid materials “adherends”
• Two types of bonding mechanisms
• Mechanical - actual penetration of the
adhesive into surface pores and crevices.
• Chemical - involves intermolecular forces
between the adhesive and adherend
(forces may be covalent and/or van der
Waals)
 Adhesive materials based
Natural adhesives on synthetic polymers

• animal glue • Polyurethanes

• Casein • Polysiloxanes
• Starch (silicones)
• Rosin • Epoxies,
• Polyimides
• Acrylics
• Rubber materials
POLYURETHANES ARE THERMOSETS!
Polyurethanes

A type of elastomer which is capable of experiencing

large and irreversible elastic deformations.
It’s amorphous, having molecular chains that are
naturally coiled and kinked in its unstressed state.
PU is the acronym for Polyurethane.
Who Invented it?
• The underlying chemistry
behind polyurethane was
first developed by Professor
Dr. Otto Bayer (1902-1982).

• He invented the
Diisocyanate Polyaddition
Process which is the base
patent in the polyurethane
industry.
The Forms of Polyurethane

FLEXIBLE –
Solid & Foams REBOND -
Foams
RIGID – Resins
(Table-top
covers, furniture
protection, etc)
POLYMER PROCESSING

From Natural Gas to Plastics

https://www.youtube.com/watch?v=C7EwPX7312k

AZCCruz, MatE 131. ©

POLYMER PROCESSING

AZCCruz, MatE 131. ©

POLYMER PROCESSING

AZCCruz, MatE 131. ©

 EXTRUSION
A process technique for
converting thermoplastic
materials in powdered or
regular form into a
continuous uniform melt,
shaped into items of uniform
cross area by forcing through
a die.
EXTRUSION
 COMPRESSION MOLDING
• Preweighed material
is loaded into lower
half of heated
mold/cavity
• HEAT and PRESSURE
are applied to melt
the powder and for
it to flow into all
parts of mold.
THERMOFORMING

USED FOR MODERATELY

COMPLEX SHAPED PARTS
THAT ARE NOT SUITED FOR
INJECTION MOLDING:
• TOO LARGE AND
EXPENSIVE
• VERY THIN WALLS
CASTING
LIQUID MATERIAL IS POURED INTO A MOLD AND ALLOWED TO
SOLIDIFY.
RESIN IS MIXED WITH HARDENER, CATALYST, OR ACCELERATOR
BEFORE POURING INTO MOLD.
MOLD IS USUALLY COATED WITH A RELEASING AGENT SUCH AS WAX,
SILICONE OIL, ETC

AZCCruz, MatE 131. ©

 Molecular cross links in Polyurethanes
• Polyurethanes does not really formulated and mastered right away, there are
instances that polyurethanes, especially in forms have errors – molecular cells.
• Molecular cells in PU are the crosslinks between urethane monomers and could
form open or closed cells.
• OPEN CELL PU – these foams are ideal for cushioning and absorbing liquids.
• CLOSED CELL PU – foams that are ideal for insulation and exterior purposes.
Crystallinity in Polymers

• Both amorphous and crystalline structures are possible,

although the tendency to crystallize is much less than for
metals or non-glass ceramics
• Not all polymers can form crystals
• For those that can, the degree of crystallinity (the
proportion of crystallized material in the mass) is always
less than 100%
Crystalline Polymer Structure

• Crystallized regions in a polymer: (a) long molecules forming crystals

randomly mixed in with the amorphous material; and (b) folded chain
lamella, the typical form of a crystallized region
Crystallinity and Properties

• As crystallinity is increased in a polymer

• Density increases
• Stiffness, strength, and toughness increases
• Heat resistance increases
• If the polymer is transparent in the amorphous state, it
becomes opaque when partially crystallized
Low Density & High Density Polyethylene
Polyethylene type Low density High density

Degree of crystallinity 55% 92%

Specific gravity 0.92 0.96

Modulus of elasticity 140 MPa 700 MPa
(20,000 lb/in2) (100,000 lb/in2)

Melting temperature 115C 135C

(239F) (275F)
134
https://www.youtube.com/watch?v=JararyOXa0Q

135