Unit 3 Polymers

UNIT LEARNING OUTCOMES

TLO 6: Apply appropriate concepts of polymerization and nanotechnology for
engineering materials.

ENGAGE
Giant molecules called polymers are made up by the linkage of simpler molecules
(monomers) by a polymerization reaction into essentially endless chain structures. Polymers
occur naturally, but the majority which are used commercially are manufactured from
simple monomers.

The most well known natural polymers are proteins (polymers of amino acids), nucleic acids
(polymers of ribose or deoxyribose sugars with attached purine or pyrimidine bases), and
the polymers of glucose (starch, glycogen, cellulose). Synthetic polymers were originally
derived from these natural polymers. The first commercially successful synthetic polymer
was cellulose nitrate (Celluloid, 1869) which was first practically molded as a substitute for
ivory in billiard balls. Nitration of cellulose, [C6H7O2(OH)3].xH2O, produces mixtures of
cellulose trinitrate, called guncotton, and cellulose dinitrate, called pyroxylin. John Wesley
Hyatt discovered that pyroxylin, when mixed with camphor, becomes a thermoplastic, a
substance which can be molded when heated. Unfortunately, cellulose nitrate is also an
explosive and its use in motion picture film and in billiard balls occasionally produced
spectacularly inflammable incidents. Cellulose acetate, discussed in a following section,
soon replaced it.

The second development was that of casein-formaldehyde plastics (A. Spitteler, 1899)
made using formaldehyde (H2C=O) and casein obtained from milk. These polymers are no
longer of industrial significance. Phenol (C 6H5OH)-formaldehyde resins (Bakelite, 1909) were
developed in the United States by the Belgian-born chemist Leo Baeckeland while
searching for a substitute for varnish shellac. Heating these resins under pressure gave soft
solids which could be molded and then hardened; they were both safe and economical.
These early polymers have now been replaced by others based on simpler monomers.

The polymer industry is normally divided into three areas on the basis of the type of product
manufactured: synthetic plastics, man-made textile fibers, and synthetic rubber. Some
polymers have properties which permit their use in more than one of these areas.

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 EXPLORE

What are Polymers?

 Polymer is a molecule, made from joining together many small molecules called
monomers.
 Polymer can be broken down into “poly”, which means “many”, and “mer”, which
means “unit”.

A polymer is a large molecule or a macromolecule which essentially is a combination of

many subunits. The term polymer in Greek means „many parts‟. Polymers can be found all
around us. From the strand of our DNA which is a naturally occurring biopolymer to
polypropylene which is used throughout the world as plastic.

Polymers may be naturally found in plants and animals (natural polymers) or may be man-
made (synthetic polymers). Different polymers have a number of unique physical and
chemical properties due to which they find usage in everyday life.

Polymers are all created by the process of polymerization wherein their constituent
elements called monomers, are reacted together to form polymer chains i.e 3-dimensional
networks forming the polymer bonds.

The type of polymerization mechanism used depends on the type of functional groups
attached to the reactants. In biological contexts, almost all macromolecules are either
completely polymeric or are made up of large polymeric chains.

Classification of Polymers:
Polymers cannot be classified under one category because of their complex structures,
different behaviours, and vast applications. We can, therefore, classify polymers based on
the following considerations.

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 A. Classification of Polymers based on origin
1. Natural Polymers: They occur naturally and are found in plants and animals. For
example proteins, starch, cellulose, and rubber. To add up, we also have
biodegradable polymers which are called biopolymers.

2. Synthetic Polymers: These are man-made polymers. Plastic is the most common and
widely used synthetic polymer. It is used in industries and various dairy products. For
example, nylon-6, 6, polyether‟s etc.

B. Classification of Polymers based on chemical structure

1. Homopolymer – polymer which consists of one type of monomer

Examples: polyethelyne, polystyrene, etc.

2. Copolymer – a polymer which is derived from more than one type of monomer.
Examples: polyethelyne-vinyl acetate (PEVA), Acrylonitrile Butadiene Styrene (ABS)

C. Classification of Polymers based on polymeric structure

1. Linear Polymers: The structure of polymers containing long and straight chains fall
into this category. PVC, i.e. poly-vinyl chloride is largely used for making pipes and
electric cables is an example of a linear polymer.

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 2. Branched-chain Polymers: When linear chains of a polymer form branches, then,
such polymers are categorized as branched chain polymers. For example, Low-
density polythene.

3. Cross-linked Polymers: They are composed of bifunctional and trifunctional

monomers. They have a stronger covalent bond in comparison to other linear
polymers. Bakelite and melamine are examples in this category.

D. Classification of Polymers based on arrangement of monomers

1. Block polymer – consists of relatively long sequences of identical monomer units

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 2. Graft polymer – branched polymer whose backbone is formed from one type of
monomer and branches are formed from other type of monomer

E. Classification of Polymers based on tacticity

Tacticity – it is the orientation of monomer units in a polymer molecule with respect
to the main chain
1. Isotactic polymer – side groups of the polymer lie on the same side of the chain

2. Syndiotactic polymer – side groups of the polymer are arranged in an alternate

manner

3. Atactic polymer – side groups are arranged in an irregular or random manner

around the main chain

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 F. Classification of Polymers based on thermal behavior
1. Thermoplastics – polymers which are easily softened upon heating
Examples: Acrylic, PVC, Polypropylene, Polystyrene, Teflon

2. Thermosets – polymers which change irreversibly into hard and rigid materials on
heating and cannot be reshaped
Examples: Melamine Formaldehyde, Bakelite, Epoxy Resin

G. Classification of Polymers based on molecular forces

1. Elastomers – polymers which can be easily stretched by applying small stress

Examples: Natural rubber (Polyisoprene), Synthetic rubbers

2. Fibers – polymers which have strong intermolecular forces between the polymer
chains
Examples: wool, cashmere, cotton, rayon, polyester, nylon

H. Classification of Polymers based on modes of synthesis

1. Addition polymers – these polymers are formed when same monomers are added –
these monomers are usually alkenes (hydrocarbons that contain double bonds)

2. Condensation polymers – these polymers are formed when two monomers react
with the elimination of smaller molecule (usually water, ammonia, methanol, or
hydrogen chloride)

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 How Can We Differentiate Natural Polymers from Synthetic Polymers?

NATURAL POLYMERS

Sources of natural polymers

 Plants
 Cellulose – polymer made up of long strands of glucose, which is also called
the “polysaccharide”. It is abundantly found in plants which give plants
their sturdy structure.

 Starch – another polymer made up of glucose monomer units. Starch is made

up by plants for them to store energy. It is a combination of “amylose” and
”amylopectin”.

 Rubber – natural rubber is a polymer that is obtained as a milky white fluid

known as latex from a tropical rubber tree. It is made up of Isoprene
monomer units.

 Animals
 DNA (Deoxyribonucleic Acid) – Polymer made up of monomer units called
“nucleotides”. DNA is found in nearly all living cells.

4 Nucleotides (nucleic acid) that form our DNA

(a) Thymine
(b) Cytosine
(c) Guanine
(d) Adenine

Genes – section of the DNA that codes for a protein is called the
genes
− Genes make all the enzymes needed to carry out the
reaction in our bodies

 Proteins – polymers made up of amino acids bonded together to create a

long chain. Proteins make up our hair and muscles.

10 Essential Amino Acids

(a) Arginine (f) Methionine
(b) Histidine (g) Phenylalanine
(c) Isoleucine (h) Threonine
(d) Leucine (i) Tryptophan
(e) Lysine (j) Valine

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 Silk – a kind of protein produced by silkworms to make their cocoon.
− it is used for the production of the silk cloth.

Other Natural Polymers

 Lignin – a polymer found in trees, together with cellulose, makes trees rigid.

 Chitin – a polymer which composes the exoskeleton of crustaceans such as crabs

and shrimps.
− It is also found in the cell wall of fungi like mushrooms.

SYNTHETIC POLYMERS

- These polymers are mostly derived from petroleum/crude oil, and manufactured in
factories. Synthetic polymers include fibers, elastomers, and the most commonly
encountered are PLASTICS.

 PLASTICS – comes from the Greek word “plastikos”, which means “to grow or form”.

7 Types of Plastics
(1) Polyethylene Terephthalate (PET or PETE)
Use: Containers of beverages

(2) High-Density Polyethylene (HDPE)

Use: Detergent bottles, Household cleaners for bottles

(3) Polyvinyl Chloride (PVC)

Use: Pipings, Wiring cables

(4) Low-Density Polyethylene (LDPE)

Use: Plastic bags, Packaging for computer hardware, plastic wraps

(5) Polypropylene (PP)

Use: Food containers

(6) Polystyrene (PS)

Use: Styrocups, styrofoam

(7) Other (e.g. Polycarbonate (PC), and other plastics not included in 1-6)
Use: Polycarbonate – alternative roofing, spectacle lenses

Other Synthetic Polymers

 Polyvinyl Acetate (PVA) – used in regular glue

 Ethylcyanoacrylic – used in superglue (stronger than PVA)

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  Polyactic Acid (PLA) – used to make a biodegradable plastic, also termed as
“bioplastic”

Structure of Polymers
Most of the polymers around us are made up of a hydrocarbon backbone. A Hydrocarbon
backbone being a long chain of linked carbon and hydrogen atoms, possible due to the
tetravalent nature of carbon.

Hydrogen
Carbon

Many common classes of polymers are composed of hydrocarbons, compounds of

carbon and hydrogen. These polymers are specifically made of carbon atoms bonded
together, one to the next, into long chains that are called the backbone of the polymer.
Because of the nature of carbon, one or more other atoms can be attached to each
carbon atom in the backbone. There are polymers that contain only carbon and
hydrogen atoms. Polyethylene, polypropylene, polybutylene, polystyrene and
polymethylpentene are examples of these. Polyvinyl chloride (PVC) has chlorine attached
to the all-carbon backbone. Teflon has fluorine attached to the all-carbon backbone.

Other common manufactured polymers have backbones that include elements other
than carbon. Nylons contain nitrogen atoms in the repeat unit backbone. Polyesters and
polycarbonates contain oxygen in the backbone. There are also some polymers that,
instead of having a carbon backbone, have a silicon or phosphorous backbone. These are
considered inorganic polymers. One of the more famous silicon-based polymers is Silly
Putty®.

Properties of Polymers

Physical Properties
▪ As chain length and cross-linking increases the tensile strength of the polymer
increases.
▪ Polymers do not melt, they change state from crystalline to semi-crystalline.

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 Chemical Properties
▪ Compared to conventional molecules with different side molecules, the polymer is
enabled with hydrogen bonding and ionic bonding resulting in better cross-linking
strength.
▪ Dipole-dipole bonding side chains enable the polymer for high flexibility.
▪ Polymers with Van der Waals forces linking chains are known to be weak, but give the
polymer a low melting point.

Optical Properties
▪ Due to their ability to change their refractive index with temperature as in the case of
PMMA and HEMA: MMA, they are used in lasers for applications in spectroscopy and
analytical applications.

Some Polymers and their Monomers

▪ Polypropene, also known as polypropylene, is made up of monomer propene.
▪ Polystyrene is an aromatic polymer, naturally transparent, made up of monomer
styrene.
▪ Polyvinyl chloride (PVC) is a plastic polymer made of monomer vinyl chloride.
▪ The urea-formaldehyde resin is a non-transparent plastic obtained by heating
formaldehyde and urea.
▪ Glyptal is made up of monomers ethylene glycol and phthalic acid.
▪ Bakelite or polyoxybenzylmethylenglycolanhydride is a plastic which is made up of
monomers phenol and aldehyde.

Types of Polymerization Reactions

The process of combining a large number of small molecules to form a single
macromolecule is known as polymerization. The small molecules that act as the building
blocks of polymers are called monomers. Based on the kinds of reactions involved,
polymerisation is divided into two groups known as addition polymerization and
condensation polymerization. Addition polymerization is the process of repeated addition
of monomers that possess double or triple bonds to form polymers. Condensation
polymerization is a process that involves repeated condensation reactions between two
different bi-functional or tri-functional monomers. Give below in a tabular column is the
difference between addition and condensation polymerization.
Addition Polymerization
This is also called as chain growth polymerization. In this, small monomer units joined to form
a giant polymer. In each step length of chain increases. For example, Polymerization of
ethane in the presence of Peroxides

Condensation Polymerization
In this type small molecules like H 2O, CO, NH3 are eliminated during polymerization (step
growth polymerization). Generally, organic compounds containing bifunctional groups
such as idols, -dials, diamines, dicarboxylic acids undergo this type of polymerization
reaction. For example, Preparation of nylon -6, 6.

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 Addition Polymerization Condensation Polymerization
Monomers must have either a double Monomers must have two similar or
bond or triple bond different functional groups
Produces no by-products By-products such as ammonia, water
and HCl are produced
The molecular weight of the resultant The molecular weight of the resultant
polymers is a multiple of monomer‟s polymer is not a multiple of
molecular weight monomer‟s molecular weight
Lewis acids or bases, radical initiators The catalysts in condensation
are catalysts in addition polymerization are catalysts in
polymerization condensation polymerization.
Common examples of addition Common examples of condensation
polymerization are PVC, polyethene, polymerization are nylon, bakelite,
Teflon etc. silicon, etc.

What is Copolymerization?
In this process, two different monomers joined to form a polymer. Synthetic rubbers are
prepared by this polymerization. For example, BUNA – S.

Uses of Polymers
Here we will list some of the important uses of polymers in our everyday life.
▪ Polypropene finds usage in a broad range of industries such as textiles, packaging,
stationery, plastics, aircraft, construction, rope, toys, etc.
▪ Polystyrene is one of the most common plastic, actively used in the packaging industry.
Bottles, toys, containers, trays, disposable glasses and plates, tv cabinets and lids are
some of the daily-used products made up of polystyrene. It is also used as an insulator.
▪ The most important use of polyvinyl chloride is the manufacture of sewage pipes. It is
also used as an insulator in the electric cables.
▪ Polyvinyl chloride is used in clothing and furniture and has recently become popular for
the construction of doors and windows as well. It is also used in vinyl flooring.
▪ Urea-formaldehyde resins are used for making adhesives, moulds, laminated sheets,
unbreakable containers, etc.
▪ Glyptal is used for making paints, coatings, and lacquers.
▪ Bakelite is used for making electrical switches, kitchen products, toys, jewellery,
firearms, insulators, computer discs, etc.

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 Commercial Uses of Polymers
Polymer Monomer Uses of Polymer
Isoprene (1, 2-methyl 1 – 1, 3- Making tyres, elastic
Rubber
butadiene) materials
BUNA – S (a) 1, 3-butadiene (b) Styrene Synthetic rubber
(a) 1, 3-butadiene (b) Vinyl
BUNA – N Synthetic rubber
Cyanide
Non-stick cookware –
Teflon Tetra Flouro Ethane
plastics
(a) Ethylene glycol (b)
Terylene Fabric
Terephthalic acid
(a) Ethylene glycol (b) Phthalic
Glyptal Fabric
acid
Plastic switches, Mugs,
Bakelite (a) Phenol (b) Formaldehyde
buckets
PVC Vinyl Cyanide Tubes, Pipes
Melamine Formaldehyde
(a) Melamine (b) Formaldehyde Ceramic plastic material
Resin
Nylon-6 Caprolactum Fabric

EXPLAIN
To be able to translate your understanding of metals, do the following activity.

Activity 1: Polymers in the Engineering Field

Self-Assessment No. 1

Based on your field of interest (e.g. mechanical engineering, civil engineering, chemical
engineering, etc.), what are the commonly used polymers and what are their uses?

To be submitted in Google classroom on:

ELABORATE & EVALUATE

Activity 2: Materials Selection: Polymers Vs. Metals

Self-Assessment No. 3

Compare and contrast polymers and metals, and come up with different scenarios where
polymers are most likely used than metals or scenarios polymers may substitute metals.

To be submitted in Google classroom on:

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