Activity 44

Polymer Chemistry
Why?
Polymers are large molecules that are built from repeating units called monomers. Because the
properties of polymers are extremely diverse, they have widespread and increasing applications.
They are key components in living organisms and have many applications in daily life, medicine,
technology, and industrial processes. You should know something about the properties of polymers
and how polymers are made because you encounter them daily and the jobs of many chemists
involve working with polymers.

Learning Objectives
Identify reactions that are used to synthesize polymers
Summarize information on polymer structure, properties, and uses

Success Criteria
Ability to identify polymerization reactions and properties of polymers
Ability to write the reactants and products of polymerization reactions

Prerequisites
Activity 3: Molecular Representations
Activity 4: Alkane Nomenclature
Activity 8: Some Types of Chemical Reactions: An Introduction

Contributed by Joseph Lauher, Stony Brook University

Activity 44 Polymer Chemistry

301

Information
Addition Polymers
Small molecules with multiple bonds can come together as monomers to form larger molecules
called polymers. During the polymerization process the multiple bonds are lost and new single
bonds between the monomers are formed. Each monomer is simply added to the end of a growing
chain, so these molecules are called addition polymers. The formation of polyethylene from ethylene
is an example of addition polymerization.
Figure 44.1

n
C2H4 ethylene

n
(C 2H4)n polyethylene

Key Questions
1. What is the relationship between a monomer and a polymer.
A monomer is a small molecule that reacts with itself or other monomers to form a much
larger molecule of repeating units called a polymer.

2. What are the characteristics of addition polymerization?

The monomers have a multiple bond, and during the polymerization the multiple bond is
lost, and a new single bond is formed between the monomer units.

Exercises
1. The following molecules also undergo addition polymerization via the ethylene double bond.
Draw the respective polymers.
N
a.

acrylonitrile
N

b.

c.

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styrene

propene (or propylene)

Foundations of Chemistry

2. What monomers would you use to form the following addition polymers?
FF

FF

FF

FF

a.
d.
FF
Cl

b.
e.

F F
Cl

F F
Cl

F F

teflon

Cl
polyvinylchloride (PVC)

Cl

Problems
1. When the molecule styrene is polymerized, sometimes a small amount of a compound called
divinylbenzene is added. This addition makes the resulting polymer harder and stronger via a
process called crosslinking. Explain crosslinking in terms of addition reactions involving these
two reactants. Illustrate your explanation with a drawing of the cross-linked polymer.

styrene

divinylbenzene

Divinylbenzene has two ethylene groups so it can react with two polystyrene chains and
link them together.

Activity 44 Polymer Chemistry

303

2. a) Natural rubber is a polymer of the molecule called isoprene. Polyisoprene is a linear chain
with a methyl side group next to a double bond in the chain. Draw the polymer in the box
below.
b) Charles Goodyear discovered a process called vulcanization that led to an increase in the
strength and durability of rubber by crosslinking the polymer with the element sulfur. The
double bonds in the polyisoprene chain are not affected by the cross linking. Draw the
crosslinked polymer in the second box below. (If you cant figure this out, maybe you can
find pictures in your text or other resource.)

n
rubber

isoprene

S8 plus heat

vulcanized rubber

Information
Condensation polymers
In a condensation polymer, monomers form bonds between their functional groups by eliminating a
small molecule such as water or HCl. Two common examples given below are amides and esters.
H
H

Figure 44.2

+ H

O
-H2O

H
N
O

H
N

N
H

O
n

nylon 66 - a polyamide

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Foundations of Chemistry

O H

H O

+
H O

O H
H

H
O

O
O

O
n

O
O

O
n

a polyester

a polyester

Exercises

-H2O

-H2O

Figure 44.3

3. Draw the polymers that would result from the following condensation reactions.
H

O
a)

Cl

Cl

b)

glycine

O
O

O
c)

N
H

O
H

lactic acid

4. What monomers
would give
H polymers?
O condensation
H the following
O
a)
a)

N
N
O
H

NO

H OO
O

OO H

N
O

N
H

NO

O
O

OO

b)

b)

ON
H
N

N
H

N
H

O
O

O
O

Activity 44 Polymer Chemistry

305

Key Questions
3. What structural features must a molecule have in order to form a polymer by a condensation
reaction?
In a condensation polymer, monomers form bonds between their functional groups by
eliminating a small molecule such as water or HCl. Typical functional groups are an acid
and an alcohol, an acid and an amine, or an acid chloride and an amine.

4. What structural features must a molecule have in order to form a polymer by an addition
reaction?
A double bond is eliminated and a single bond to the next monomer is formed. So for
addition polymerization monomers with multiple bonds are needed.

5. What features in the structure of a polymer would make the material very strong and rigid?
Strong bonds along the polymer chain and numerous strong cross links between chains
would make the polymer strong and rigid.

6. Why do polymers not melt and become liquid when they are heated in the same way that ice
melts and becomes water?
Crystals of small molecules, such as water, are held together by noncovalent interactions.
Crystals have a well-defined structure and definite melting temperature. Because of their
size, polymers generally do not form crystalline solids, but rather they form disordered
solids called glasses. Polymers in these disordered solids also interact with each other by
noncovalent interactions, but the polymers have different structures and interactions that
exist at the same time in different regions of the solid. As a result, these different regions
become liquid-like at different temperatures, and consequently melting and the melting
temperature are not well-defined. Also, parts of the polymer chain are tethered to each
other, so one part can not diffuse away like a small molecule on the surface of a crystal can
when it has enough energy.

Note: This question goes beyond the information presented in the model. Often the last Key
Question in a section is such a divergent question. Divergent questions are intended to relate
the material to the real world, have the students think more deeply about the material, or to
go beyond the material that is presented. One purpose of such questions is to engage fast
teams and give others time to catch up. If students have trouble with this question, assign it
as a literature research project and have teams report back at the next class meeting.

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Foundations of Chemistry