Polymers expectations, introduction, and structures. Dr.

Breinan, chemistry v11

At the conclusion of the polymers unit, you should be able to:

p. 1

1. Define monomer and polymer; explain how monomers can be used to make addition or condensation
polymers.
2. Explain the structure, including diagrams, of linear, cross-linked, and branched polymers; describe several
ways in which the structure can affect polymer function including discussion of polarity and
intermolecular forces.
3. Identify some of the most commonly used polymers and their uses, including high density polyethylene,
low density polyethylene, polyester, and polystyrene.
4. Describe the properties of thermoplastic and thermosetting polymers.
5. Define the following terms: copolymer; dimer, elastomer, macromolecule, oligomer, viscosity, and
vulcanization
6. Discuss issues related to the recycling of plastic materials
7. Define important properties of plastics such as abrasion resistance, puncture resistance, tensile strength,
and strain.

Intro to polymers
Polymers are long chain molecules, sometimes called macromolecules. They are formed by linking
together (polymerizing) many small molecules called monomers. Polyethylene, for example, is formed by
polymerizing ethylene molecules. n represents a large number of units attached together in a long chain,
normally in the hundreds or thousands or even millions!

If we let E represent ethylene, the chain looks like:

-E-E-E-E-E-E-E-E-
The arrows mean the structure keeps going and going!
Some polymers, called copolymers, are made from more than one type of monomer. Let C represent
another monomer, chloroethene, or CH2=CHCl. A copolymer of ethylene and choroethene might look like:
-E-E-C-E-E-C-C-E-C-E-E-E-C-C-
Oligomers are small polymers made from a small number of monomer units, normally between 2 and 100.
Dimers, as their name suggests are made from two units. In some cases, the units themselves are large
polymers (as opposed to most monomer units which are quite small). A common example is nucleic acids,
which you will learn about in biology. DNA is a dimer of two large copolymers where the monomer units
are sugar molecules, phosphate ions, and bases!
Structure-function:
All polymers are different from one another because of two main factors: First, the type of monomer that
makes it up. Second, the ways in which polymer chains are either bonded to, or interact with, one another.
The great variety of different types of polymers and their incredible wide range of properties are due to the
wide variety of monomers that compose the polymers, as well as the different interactions between polymer
chains. Aspects of polymer structure that affect properties are the chemical makeup of the monomer, polarity
of the monomer, length of chains, chain structure, and physical or chemical mixing with other materials.
Even the same polymer can be created in different forms with different structures to create different
properties. Some such forms include foams, plastics, sheets, and gels. Different manufacturing techniques
are used to create these different forms to develop materials with desired properties.

Linear, Branched, and Cross-linked Polymers

Polyethylene is called a linear or straight-chain polymer because it consists of a long string of carboncarbon bonds. These terms are misleading because the geometry around each carbon atom is tetrahedral and
the chain is neither linear nor straight, as shown in the figure below.

Polymers expectations, introduction, and structures.

Dr. Breinan, chemistry v11

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As the polymer chain grows, it folds back on itself in a random fashion to form structures such as the one
shown in the figure below on the left. Straight chains can sometimes fold tightly enough to make crystal
structures (on the right below) even though the molecules are very long!

Randomly oriented
straight chains can
be pretty messy

Neatly packed
straight chains can
make crystals!

Separate polymer chains are close to each other, but do not chemically combine. These polymer chains are
generally packed tightly together but often remain very flexible, as adjacent polymer chains can slide past
one another. However, intermolecular forces between the different chains may make this sliding and
flexibility more difficult. These forces can be greatly affected by the structures of the chains and monomers
mentioned in the previous section.
Polymers with branches at irregular intervals along the
polymer chain are called branched polymers (see figure to the
right). These branches make it difficult for the polymer
molecules to pack in a regular array, and
Therefore make the polymer less crystalline and less dense. The amount and
type of branching also affects physical properties such as viscosity and
elasticity (see below). Branches often prevent chains from getting close enough together for intermolecular
forces to work effectively.
A perfect example of this effect is seen in polyethylene. Although PE is a relatively simple polymer, there
are two common forms of it (high and low-density,) each with unique properties. Depending on the length of
the polymer chains, individual chains will begin to curl and try to fold back onto one another. The longer the
chain length, the more curling a chain will undergo, which leads to a decreased ability to pack together. The
degree to which polymer chains pack together will determine the rigidity of it. The greater the packing, the
more rigid and durable the polymer. This flexibility in PE products (no pun intended) leads to a wide
variety of common household products made from the different types of PE, like trash bags, plastic kitchen
wrap, and sandwich bags.
Cross-linked polymers contain short side chains (cross
links) that connect
different polymer chains into a network as shown in
the

Cross links
between chains

Polymers expectations, introduction, and structures.

figure to the right. At first, adding cross-links between

Dr. Breinan, chemistry v11

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polymer chains makes the polymer more elastic (they can

stretch and return to their original form.) The links can pull the chains back together when they are
stretched! The vulcanization of rubber, for example, results from the introduction of short chains of sulfur
atoms that link the polymer chains in natural rubber. Cross-linking also decreases the viscosity (the
resistance to flow) of polymers. In order for polymers to flow, the chains must move past each other and
cross-linking prevents this. Elastomers are elastic polymers created by limited cross-linking. As the
number of cross-links increases, however, the polymer becomes more rigid and cannot stretch as much; the
polymer will become less viscous and less elastic and might even become brittle.
The decision to classify a polymer as cross-linked is based on the extent to which the main chains or sidechains on the polymer backbone link covalently to adjacent polymer chains. This is not always easy to
determine because stronger intermolecular forces may mimic cross-linking. Polymers chains may have a
geometry or contain chemical groups that increase the intermolecular forces between chains. While these are
not considered cross-linking, they do affect physical properties such as elasticity and viscosity just like crosslinking does. The easiest way to distinguish between these categories is to study the effect of various
solvents (dissolving solutions) on the polymer. Cross-linked polymers are usually insoluble (dont dissolve)
in solvents because the polymer chains are tied together by strong covalent bonds. Other polymers are
usually soluble (they dissolve) in one or more solvents because it is possible to separate the polymer chains
which are not covalently linked. (As is often the case in chemistry, you might find exceptions because under
certain conditions some solvents can chemically react to break covalent cross-linking bonds.)
Linear, branched, or lightly cross-linked polymers form a class of materials known as thermoplastics.
Plastic means capable of being shaped or formed. When heated, these materials soften and can be
molded into a variety of shapes which they retain when they cool. The process is reversible, so the plastic can
be reheated and reshaped. The polypropylene used in the plastic chairs that fill many classrooms and
cafeterias is a thermoplastic. Like many thermoplastics, they are somewhat elastomeric even when too cool
to flow- at room temperature these chairs dont reshape, but they can flex so as you lean back on the chair
you can feel it give.
Heavy cross-linking after shaping a plastic produces materials known as thermoset plastics. Once the crosslinks form, the polymers shape cannot be changed again without destroying the plastic. Unlike thermoplastic
polymers, the process cannot be undone by reheating; thermoset plastics will start to decompose rather than
becoming moldable and pliable. The plastic case in which early radios were placed is an example of a
thermoset plastic; it had a tendency to shatter rather than bend if the radio was dropped on the floor.

Addition vs. Condensation reactions and polymers. The two primary methods by which polymers
form are called addition and condensation. The two processes differ significantly (see the two
examples below.) In addition reactions, double bonds are converted to single bonds to allow extra
bonds to be made, allowing a chain to extend or branch out. No atoms are lost in the process. In
condensation reactions, a small molecule, usually water, is formed and removed from two separate
molecules; in the process the two molecules are linked together. Condensations that remove water
are sometimes called dehydrations.
Addition example:
Addition polymers are created from monomers with a double bond between carbons. The double
bond includes two pairs of electrons, but only one is needed to connect the carbons. If each carbon
takes back one electron from the bond, the double bond turns back to a single bond and allows each
carbon to make an additional bond on the opposite side of the carbon atom from where the double
bond used to be (see middle pane below). If this happens in two monomers, they can bond together,
making a longer carbon chain. The formation of polyethylene is demonstrated here:

Polymers expectations, introduction, and structures.

H H

H H

C=C
+
H H

+ C=C
H

Two ethylene molecules are

reacted

H H

H H

Dr. Breinan, chemistry v11

e- freed from
double bond

CC + CC
H

H H

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H H

C C -- C C

H H
The double bonds break, allowing
each C to make an extra bond!
Note how the carbons reach out
to both sides with the electrons
freed by breaking the double bond.

H H H H
Two carbons bond together to extend
the chain. Note that both ends are still
reaching out this process can repeat
over and over!
NOTE: addition polymers usually
have main chains made only of C. Do
you see that here?

Condensation example:
In condensation reactions that release water, one end of one monomer contains a H atom and one
end of the other atom contains a hydroxyl group- an oxygen bonded to a hydrogen, shown as O-H.
These two ends combine to make water, which exits as a separate molecule and allows the
remaining parts of the monomers to join together. This example illustrates how polyamides such as
nylon or biological proteins can be formed.
H H

O H

H H

-CNH +
H

HO-CC CCH H H
Water
forming

The H end of one monomer and the OH

(hydroxyl) end of another monomer come
together allowing water to form (see circle).

H H

O H

H H

- C N C C C C H
H H H
+ H2O
Water has separated and the two monomers are
linked together. If the other ends of the
monomers create similar links, the chain can
keep extending and make a polymer.
NOTE: condensation polymers contain O or N
in the main chain. Do you see that here?