CHEMISTRY FOR ENGINEERS
Module 9: Polymers
MODULE 9
POLYMERS
ENGR, MA. JEANNETTE U. OBIAS
Module Author
Biological Sciences Department
College of Science and Computer Studies
De La Salle University-Dasmariñas
Dasmariñas City, Cavite
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CHEMISTRY FOR ENGINEERS
Module 9: Polymers
Motivating Activity
Below are some words that you will encounter during our discussion. Arrange the scramble
words. Write your answers on the blank provided.
1. SPLYREMO ___ ___ ___ ___ ___ ___ ___ ___
2. TOESSALERM ___ ___ ___ ___ ___ ___ ___ ___ ___ ___
3. SCARDOBOHYRN ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___
4. OROMMEN ___ ___ ___ ___ ___ ___ ___
5. CRABEHDN ___ ___ ___ ___ ___ ___ ___ ___
6. SLSKRINDEC ___ ___ ___ ___ ___ ___ ___ ___ ___ ___
7. REANIL ___ ___ ___ ___ ___ ___
8. LULLOCESE ___ ___ ___ ___ ___ ___ ___ ___ ___
9. WORTKEN ___ ___ ___ ___ ___ ___ ___
10. REMTHOSTALICP ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ __
“Nature uses human imagination to lift her work of creation to even higher levels” by Luigi
Pirandello
Remember Iron age? During those times people used more on metals. Through industrial
revolution, things changed so fast the we replaced metals and started on using plastics. So
instead of depending too much on nature, man started using their imagination to make
plastics. In chemistry, the term we used for plastics is polymers. Let us discuss and
understand more on polymers. Polymers is a large molecules or macromolecules with
repeated subunits (monomer) connected with each other by chemical bonds. Monomer is a
molecule with low molecular weight that can bond with another low molecular weight molecule
to form polymer.
Historically, polymer is not new. During the 1800, scientists had discovered this already. British
chemist Alexander Parkes treated cellulose with nitric acid and a solvent which produced
nitrocellulose. When nitrocellulose is added with camphor it produced celluloid that can be
used for film industry and a replacement for ivory. Hence, when nitrocellulose is added with
ether and alcohol it produced a polymer that can be used for surgical dressing. Another
polymer that has been achieved during this time is vulcanization of rubber which was
discovered independently by German chemist Friedrich Ludersdorf and American inventor
Nathaniel Hayward. Vulcanization process was done when natural rubber is treated with
sulfur and applying heat according to British engineer Thomas Hancock (UK patent) and
American chemist Charles Goodyear.
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Module 9: Polymers
CLASSIFICATION OF POLYMERS
Polymers can be classified as natural, semi-synthetic and man-made (synthetic) polymers
based from source. Natural polymers occur naturally which can be found in plants and
animals. It is common for natural polymers to have one type of monomer. Some examples of
natural polymers are proteins (can be found both on plants and animals), cellulose and starch
(from plants), and natural rubber (harvest from the latex of tropical plants). Cellulose which is
part of plants is composed of sugar molecules (as monomers) and as polymers it is known as
polysaccharide. Natural polymers that has been chemically modified are called semi-synthetic
polymers such as cellulose nitrate (example: rayon textile and use in modern gunpowder) and
cellulose acetate (example: use in automotive industry). Man-made (synthetic) polymers can
be done in a laboratory or produced by industrial factories. Some examples are nylon (used in
our clothes), Teflon (to coat non-stick cooking utensils) and epoxy resins (used as the binder in
countertops or coatings for floors).
There are several parameters for classifications of polymers based on:
1. Chemical Structures
2. Polymeric Structures
3. Tacticity
4. Thermal behavior
5. Molecular forces
6. Methods of synthesis
Let us discussed each classification. We will start with its (1) chemical structures. There are
two types of chemical structures namely: homopolymers and co-polymers. From the name
itself, “homo” means the same. Therefore, it means that the monomer of the polymers is the
same (A-A-A). While co-polymer means combination of two types of monomers (A-B-A-B). The
arrangement of copolymers can be divided into two namely: block and graft copolymer. Block
polymer has of relatively long sequences of identical monomeric units The
identical monomers are arranged linearly. While the graft polymers, the long sequence of
monomers is attached as branched from the long chain of polymers.
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Module 9: Polymers
Table 7.1 Comparison of homopolymers and co-polymers
HOMOPOLYMERS CO-POLYMERS
Formed by addition polymerization Formed by condensation polymerization
Single type of monomer Two types of monomers
Often has simple structure Usually has more complex structure
Has one variety Has several varieties
1. random copolymer
2. triblock copolymer
3. triblock copolymer
4. diblock copolymer
5. graft copolymer
Examples: PVC, polyethylene, polypropylene Examples: polyvinyl acetate, saran,
and polystyrene butadiene rubber and polyethylene oxide
Table 7.2 There are three type of polymers based on (2) polymeric structures:
Type of Definition Structure
Polymers
1. Linear It has a long and straight chain. So,
when combined with several
monomers it can form a long chain
which has great strength in term of
density and melting points.
2. Branched It has linear polymers with some
polymers branched out from it. This is
quite fascinating since it can have
random arrangement and not closely
packed. With this arrangement, it does
not have a solid structure which makes
it less density and low melting point.
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Module 9: Polymers
3. Cross- It is a chemical bond that links between
linked one polymer chain to another polymer
chain forming one monomeric unit. It
has a strong chemical bond which
makes it much stronger and stable. It is
very hard for this material to be
recycled.
The stereochemistry of the arrangement of atoms in polymers is called (3) tacticity. There are
three types of tacticity such as isotactic, syndiotactic and atactic or heterotactic. When the
substituents are placed on the same side of the backbone of the polymers, it is called isotactic.
When the substituents are placed on alternate position along the backbone of the polymers, it
is called syndiotactic. And the last one is atactic or heterotactic, in which the substituents are
placed on random position along the backbone of the polymer. The tacticity of the polymers
can be linked with the physical properties of the polymers. By the way, backbone of the
polymers consists of hydrocarbons.
Figure 7.1 Sample structure of different type of tacticity
On the basis on (4) thermal behavior, it can be classified into two types:
1. thermoplastics – like any other polymers materials it is bonded by intermolecular force (Van
der Waal’s forces) that can form either linear or branched structures. These materials when
heated are soften and hardened when it cools down. Since it has no interlinking bond, it can
still be remolded or reshaped. For example, ABS (acrylonitrile butadiene styrene) which is
used in musical instruments, Lego brick toys, and safety hats.
2. thermoset – unlike with thermoplastics materials, while heated it formed cross-linked with
other polymer materials such that the reaction is irreversible. Hence, it cannot be remolded or
reshaped but it can retain its strength and structure at high temperature. For examples,
bakelite which is use in toasters, handle of pans and pots, dishes, electrical outlet and billard
balls.
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Module 9: Polymers
Chemical bond holds the atoms together. One type of chemical bond is intermolecular forces
which is quite strong so that polymers can have strong physical properties. Based on (5)
molecular forces, it has two classifications.
1. elastomers - are “elastic polymers”. So, when we say elastic, it can be stretched because it
has a rubbery characteristic, and it can return to its original shape. Elastomers is composed of
long chain polymers with weak intermolecular forces.
2. fibers – is the opposite of elastomers since it has less elasticity, high tensile strength and
high melting point. It is woven in a thread - like manner that it has strong intermolecular forces
such as hydrogen bond and dipole-dipole interaction. Silk, nylon, polyester and cotton are
examples of fibers.
(6) Polymerization is the process of making monomers into polymers by addition or
condensation polymerization. From the word addition, it simply means that it has repeated
addition of monomer molecules to form polymers with removing some small molecules like
water or alcohol. While condensation polymerization, group of small molecules have to be
removed or eliminated so that the monomers can attached to the backbone of the polymers.
Figure 7.2 Some functional groups of monomers and polymers
Figure 3 Chemical equation for addition polymerization
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Module 9: Polymers
Electrophile (E+) is an atom or molecule that accepts an electron pair to make a covalent
bond. Examples of electrophiles are hydronium ion (H3O +), halogens (X), aluminum chloride
(AlCl3) and boron trifluoride (BF3).
Nucleophile (N -) is an atom or molecule that seeks a proton to make a covalent bond. Some
examples of nucleophile are halogens ions (X -), hydroxides (OH -), ammonia (NH3) and water.
Figure 4 Chemical equation for addition polymerization
PROPERTIES OF POLYMERS
There are different variables needed to create the polymer according to your requirements or
desired. Such as the monomers to be used and reagent or solvents for polymerization reaction
or cross-linking the polymer chains. The arrangement of polymers in terms of structures,
stereochemistry of the arrangement of atoms, and polymerization can also affect the properties
of polymers such as average molecular weight, density, thermal behavior and tensile strength.
Furthermore, there are two additives that can be added in polymers. One of these is
stabilizers which can be used to improve the properties of polymers to resist oxidation, less
sensitive with heat or light or flame retardants. Another one is plasticizers, to increase the
flexibility, extensibility and processability of polymers without altering the chemical
characteristics. It is often used for the manufacturing of polyvinyl chloride (PVC).
Now, we know that we just need several monomers and put them together so that we can
have a polymer. But the question is how many monomers do we need? Well, by computing the
degree of polymerization, we will be able to know how many units of monomer you need. Now
let us represent degree of polymerization with small letter n. It should be equal to the
molecular weight of polymer (M) per molecular weight of a unit of monomer (Mo).
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Mathematically;
M
degree of polymerization (n) = Mo
Sample no. 1: Calculate the degree of polymerization of a sample of polystyrene (C8H8)n
which has a molecular weight of 131,000 g/mol. (C=12.0 g/mole , H= 1.01 g/ mole).
Strategy: Calculate the molecular weight of the monomer and input in the given formula for
degree of polymerization.
Solution:
Mo = number of C atoms (atomic mass of C) + number of H atoms (atomic mass of H)
= 8 (12.0 g/mol) + 8 (1.01 g/mol) = 104.08 g/ mol
M 131000 𝑔/𝑚𝑜𝑙
degree of polymerization (n) = Mo n= = 1249
104.08 𝑔/𝑚𝑜𝑙
Sample no. 2: Calculate the average molecular weight of polymethacrylamide (C4H6O2)n
polymer with the given degree of polymerization of 725. (C=12.0 g/mole, H= 1.01 g/ mole,
O = 16.0 g/mole).
Strategy: Calculate the molecular weight of the monomer and input in the given formula
for degree of polymerization to compute for the average molecular weight of the polymer.
Solution:
Mo = number of C atoms (atomic mass of C) + number of H atoms (atomic mass of H) +
number of O atoms (atomic of O)
= 4 (12.0 g/mol) + 6 (1.01 g/mol) + 2 (16.0 g/mol) = 86.1 g/ mol
M
degree of polymerization (n) = Mo M = n x Mo
M = 725 x 86.1 = 62422.5 g/mol
The strands of polymer molecule can be arranged into two different fashion such as crystalline
and amorphous arrangement. Imagine when you arranged uncooked spaghetti noodles orderly
and compact in one container. Then you try breaking it. What happened? It is very hard to
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Module 9: Polymers
break it, right? Similarly, polymer chains in crystalline arrangement will also be strong and with
high resistance to stress. Polymers with crystalline structure can fold and formed lamellar form.
Examples of crystalline polymers are polyethylene and PET polyester. While amorphous
structure of polymer chains has disordered arrangement and it makes the polymer elastic in
property like thermoplastic materials. Examples of amorphous polymers are polystyrene and
polymethyl methacrylate. Although, thermoplastic materials can have both crystalline and
amorphous arrangement. If the materials have more crystalline arrangement then the polymer
will be quite strong and less elastic. On the other hand, if the thermoplastic materials have
more amorphous arrangement then it will be more elastic and it can easily break with greater
quantity of loads.
Figure 2 Arrangement of Polymers
Table 7.3. Comparison of Crystalline and Amorphous Polymers
Crystalline Polymer Amorphous Polymer
Ordered structure Random structure
Polymer chains can have syndiotactic and Polymer chains has atactic polymer chains.
isotactic polymer chains.
High density Low density
High chemical resistance Low chemical resistance
Higher mechanical properties Lower mechanical properties
Strong molecular forces between polymer Weak molecular forces between polymer chains
chains
Remember that when molecules absorbed heat it vibrates. Polymer molecules when heated
vibrates and their molecules move outward. For polymers, thermal properties describe the
absorption of energy in the form of heat. There are three thermal properties that can describe
the response of polymer materials namely; heat capacity, thermal expansion and thermal
conductivity. Heat capacity is the amount of heat that can be absorbed by polymer materials.
Thermal expansion describes the extent a polymer material will expand or contact when
heated or cooled. For thermal conductivity, polymer materials act as an insulators so electrical
conductivity is not possible.
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Module 9: Polymers
When amorphous polymer absorbed heat, it turns into viscous liquid or rubbery state and the
temperature at this state is called glass transition temperature (Tg). At this temperature,
amorphous polymers are hard, brittle and rigid in which it has the same characteristics of
glass. If the polymer continually absorbed thermal energy, then transition of temperature from
glass transition temperature to melting point temperature (Tm) will occur. Temperature of the
polymer can assist to identify the chemical structure of polymers since amorphous polymers
exhibit only glass transition temperature. In addition, with the presence of double bond,
aromatic groups or bulky or large side groups are present the melting point temperature of
polymers will increase since they restrict the flexibility of the carbon chain. But with the
presence of branching, the melting point temperature will decrease because of the
imperfection of the crystallites formed.
There are several factors which affect the glass transition temperature.
1. Intermolecular forces – Polymers with strong molecular forces such as hydrogen bonds
will cause Tg to increase. Examples are urea and polyurethane and natural polymer
cellulose.
2. Chain stiffness – Polymers that contains small group of molecules such as amide,
sulfone carbonyl and p-phenylene and others can increase Tg since it reduces the
flexibility of the polymer chain.
3. Cross-linking – Polymer with cross-linked structure will increase the Tg value because of
restricted rotational motion. Hence, polymer with more cross-linked structure will have
higher Tg than polymer with lesser cross-linked structure.
4. Molecular weight – The glass transition temperature also increases with large molecular
weight of the polymer. Polymers with high molecular weight have less free volume than
polymers with low molecular weight.
ECONOMICAL USES
Listed below are some examples of Polymers:
MONOMER POLYMER
NAME FORMULA NAME USES
ethene H2C = CH2 polyethylene bags, bottles, tubing,
packaging film
propene CH2 = CH-CH3 polypropylene laboratory and
household ware,
artificial turf, surgical
casts, toys
chloroethene (vinyl CH2 = CH-Cl polyvinyl chloride (PVC) bottles, floor tile, food
chloride) wrap, piping, hoses
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tetrafluoroethene CF2 = CF2 polytetrafluoroethylene bearings, insulation,
(Teflon) nonstick surfaces,
gaskets, industrial
ware
vinyl benzene (styrene) polystyrene packaging, refrigerator
doors, cups, ice
buckets, and coolers
(as foam)
ethylene glycol and HO - CH2CH2 - OH and polyethylene glycol textile fabric, twine,
terephthalic acid terephthalate (Dacron) and rope, fire hoses,
plastic containers
hexamethylenediamine H2N -(CH2)6 - NH2 and polyhexamethyleneadipamide hosiery, rope, tire
and adipic acid HOOC - (CH2)4 - COOH (Nylon 6,6) cord, parachutes,
artificial blood vessels
diisocyanate and diol OCN - (CH2)6 -NCO and polyurethane Spandex, fibers,
HO - (CH2)4 -OH bristles for brushes,
and cushions and
mattresses (as foam)
As you have seen on the table, polymers are quite useful as our household materials and to our
industries. We can say that polymers cover different areas such automotive, aerospace, medical
devices, buildings, electronics, consumer goods and packaging. Most people now use
lightweight materials which is also applicable with automotive industries and aerospace.
Economically, consumers prefer fuel efficient and fast cars so automotive industries and
aerospace shifted from using metal to polymers materials. Polymers are resistant to chemicals
or any harsh effect of the environment (corrosion) which is cost saving for repairs. Transparent
polymers have high resistance on impact which increase safety. In the field of medicine,
polymers had been increasingly very useful especially with medical devices. Most medical
devices are made of polymers. Before, they used glass syringe but now they shifted into plastic
disposable syringe. Even the thread used for suture are made of polymers; it is biodegradable.
For construction of building, adhesives, foams, sealants, fiber glass, wires, pipes and paints are
some examples of polymers. Most of the electronic materials are made of lightweight polymers
since consumers want to bring it with them for convenience. Consumer products and packaging
have high demand in the market usually because its low cost and durability. It covers a large
area in our economic growth. Nevertheless, the disposal of plastics has been our concern since
some plastics are non-biodegradable or cannot be recycled which affects our environment. Our
government recommends to recycle polymers and use biodegradable polymers. Although, some
polymers have disadvantages. With regards to thermal behavior, not all polymers can withstand
a very high temperature and heat capacity is less in comparison with metals. Some polymers
also cannot be used for heavy structure because its rigidity is very less.
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