POLYMERS

Polymer (or macromolecule)

 is a molecular compound distinguished by a high molar mass, ranging into thousands and
millions of grams, and made up of many repeating units. The physical properties of these so-
called macromolecules differ greatly from those of small, ordinary molecules, and special
techniques are required to study them.

Naturally occurring polymers include proteins, nucleic acids, cellulose (polysaccharides), and rubber
(polyisoprene).

Synthetic polymers
 mostly are organic compounds.
 Examples: nylon, poly(hexamethylene adipamide), Dacron, poly(ethylene terephthalate),
Lucite or Plexiglas, poly(methyl methacrylate)

The word polymer literally means “many parts”.

All polymers are made up of very large molecules. These large molecules are made up of many
smaller molecules linked end to end. A typical polymer molecule might contain hundreds or even
thousands of these smaller constituent molecules called monomers.

Monomer

 the small repeating unit from which a polymer molecule is made

To illustrate how the properties of a polymer can depend on its atomic composition, let us
consider three common items and look at the polymers from which they are made. The plastics bottles
in which your milk, juice, or shampoo come, are usually made of a plastic called polyethylene.

Polyethylene molecules

 are composed entirely of just two elements, carbon and hydrogen

The carbon atoms are linked together in a large chain that is called the polymer backbone of the
polymer molecule, and there are two hydrogen atoms attached to each carbon.

Polymer backbone
 the long chain of atoms – usually carbon atoms - running the length of a polymer
molecule

The molecular model at the top of the figure (refer to the figure below) shows a portion of a
polyethylene molecule. If one of the two hydrogen atoms on every other carbon is replaced with a
chlorine atom, as shown in the middle of the figure, we will have poly (vinyl chloride). This polymer is
commonly referred to as PVC. Plastic pipe made from PVC has been widely used in plumbing for many
years, so you have probably seen PVC pipe in either your house or hardware store. The PVC used for
pipes is much harder and stronger than the polyethylene in soda bottles. Yet the chemical composition
and structures of these two materials are very similar. Suppose we replace the second hydrogen on
every other carbon atom with chlorine, then we will have poly(vinylidene chloride), which is the “plastic
wrap” used in almost every kitchen to cover leftovers.
 MODELS SHOWING HOW ATOMS ARE ARRANGED IN MOLECULES OF
POLYETHYLENE, POLY(VINYL CHLORIDE) AND POLY(VINYLIDENE CHLORIDE)

Polyethylene

Poly(vinyl chloride) or PVC

Poly(vinylidene chloride)

Made from high-density Made from polystyrene Made from poly(vinyl chloride)
polyethylene
Two different kinds of synthetic polymers

1. Addition polymers

 monomer units add directly to one another; typically, only one kind of monomer is involved

2. Condensation polymers

 monomer units combine by splitting out (condensing) a simple molecule such as H₂O. Typically,
two different monomers react with one another to form a condensation polymer.

Addition Polymers

Below are some of the more familiar synthetic addition polymers. Notice that each of these is
derived from a monomer containing a carbon-carbon double bond. Upon polymerization, the double
bond is converted to a single bond and successive monomer units add to one another.

Polyethylene is the most familiar addition polymer which is a solid derived from the monomer ethylene.
We might represent the polymerization process as

where n is a very large number, of the order of 2000.

Branched and linear polyethylene

The polyethylene bottle at the left is
made of pliable, branched
polyethylene. The one at the right is
made of semirigid, linear
polyethylene.

Depending upon the condition of polymerization, the product may be branched polyethylene,
which has a structure of the type
 Here, neighboring chains are arranged in a somewhat random fashion, producing a soft, flexible
solid (figure shown above). The plastic bags at the vegetable counters of supermarkets are made of this
material.

Linear polyethylene consists almost entirely of unbranched chains.

Neighboring chains in linear polyethylene line up nearby parallel to each other. This gives a
polymer that approaches a crystalline material. It is used for bottles, toys, and other semirigid objects.

Two forms of polyethylene (differ slightly in density):

1. high-density polyethylene (HDPE)

 linear polyethylene which is represented by the symbol “HDPE #2” on the bottom of a plastic
bottle

2. low-density polyethylene (LDPE)

 branched polyethylene with the corresponding symbol “LDPE #4”

Note: The smaller the number, the easier it is to recycle.

EXAMPLE:

The addition polymer polyvinyl chloride (PVC) has the structure

(a) Draw the structure of the monomer from which PVC is made.

(b) How many monomer units are in a PVC polymer that has a molar mass of 1.33 x 105 g/mol?

Solution

(a)

(b) MM of CH2CHCl = 66.49 g/mol

No. of monomer units = (1.33 x 105)/66.49 = 2.00 x 103

Condensation Polymers

In order to produce a condensation polymer, the molecules involved must have functional groups at
both ends of the molecule. When an alcohol with two –OH groups, HO-R-OH, reacts with a dicarboxylic
acid, HOOC-R’-COOH, a polyester is formed. The first step in the process is the formation of a simple
ester that has a reactive group at both ends of the molecule.

The –COOH group at one end of the ester molecule can react with another alcohol molecule. The –OH
group at the other end can react with an acid molecule. This process can continue, leading eventually to
a long-chain polymer containing 500 or more ester groups. The general structure of the polyester can
be represented as

One of the
most familiar polyesters is Dacron, in which the monomers are ethylene glycol and terephthalic acid:
EXAMPLE

(a) Show the structure of the ester formed when one molecule of ethylene glycol reacts with one
molecule of terephthalic acid.

(b) Draw the structure of a section of the Dacron (Mylar) polymer.

In (a), split out H₂O between the alcohol and acid molecules. In (b), continue the esterification
process at both ends of the molecule obtained in (a).

Solution

Another type of condensation polymer is a polyamide formed

when a diamine reacts with a dicarboxylic acid:

Condensation can continue to form a long-chain polymer such

as nylon-66, which has the structure

Nylon can be made by the reaction between

hexamethylenediamine, H2N – (CH2)6 –
NH2, and adipic acid, HOOC – (CH2)4 –
COOH. It forms at the interface between the
two reagents.
This polymer was first made in 1935 by Wallace Carothers at
DuPont; it is readily prepared in the laboratory by bringing the
two monomers into contact with one another.
Copolymer

Nylon and Dacron are two examples of copolymers made from than one type of monomer. In
these cases, because the monomers are arranged in a regular, alternating series, they can be further
classified as alternating copolymers. These are other important types of copolymers as well. One of the
more creative ways to engineer materials is to design block copolymers.

A block copolymer has regions in the material where a single monomer unit is repeated.

Copolymers can be grown with different arrangements of monomers. The different colored
circles represent two different monomers. For the most part, the names of these types of copolymers
are self-explanatory. The different monomers alternate in an alternating copolymer or are randomly
combined in a random copolymer. In a block copolymer, each type of monomer tends to be clumped
together. Graft copolymers involve side chains of one polymer attached to a backbone of a different
polymer.

Spandex is an example of a block copolymer. In this material, some regions of the polymer are
relatively stiff, whereas others are flexible. The resulting material is both strong and flexible, leading to
widespread use in sports gear and fashion.

Another engineering material that is a copolymer is commonly called ABS (acrylonitrile,

butadiene, and styrene). This material is a graft copolymer in which both butadiene and acrylonitrile are
attached to a polystyrene backbone. The resulting polymer offers a combination of the properties of its
three constituents. Polystyrene provides ease of processing, glossiness, and rigidity. Acrylonitrile adds
chemical resistance and hardness, and butadiene provides impact resistance. The specific composition
can be tailored to a particular application. ABS is the standard material of choice for the strong plastic
cases of computers, televisions, and other household electronic goods and sometimes is used as an
alternative to PVC for pipes.
Physical Properties

There are two key reasons for the importance of polymers as engineering materials. First and
most obviously, polymers offer physical properties such as strength and elasticity that can be desirable
in a wide range of uses. Second, those properties can be controlled or tailored to a greater degree than
is usually possible in metals or other classes of materials. Through the choice of a particular polymer
and the details of its synthesis and processing, materials engineers can choose the properties they need
with striking degree of specificity.

We begin by considering the thermal properties of polymers. In choosing a polymer for a

specific design, you would obviously need to make sure that your finished object will be suitable for the
temperature range in which it will be used. But an experienced engineer will also recognize the need to
think about the way the object will be manufactured. Many plastic components are formed at high
temperatures, and different polymers respond in dramatically different ways to heat.

Polymers are often divided into two broad categories:

1. Thermoplastic polymers melt or deform on heating. This may seem like a weakness because it means
that they are not suitable for high temperature applications. But a great many plastic objects, including
children’s toys and bottles of many sorts, are generally used at ambient temperatures. Depending on
their complexity, products made from thermoplastic polymers are typically extruded or formed in molds
or presses. The fact that the material softens or melts when heated allows shaping it into the desired
form. Once cooled, the polymer solidifies and regains its structural properties.

2. Thermosetting polymers

If we were trying to design an object that might need to be used at higher temperatures,
though, the fact the thermoplastics soften and melt will make such materials a poor choice. Instead we
might turn to thermosetting polymers, which can maintain their shape and strength when heated. The
name “thermosetting” comes from the fact that these polymers must be heated to set or “lock in” their
structures. But once this has been done, the materials offer increased strength and do not lose their
shape upon further heating. Rather than being extruded, most thermosetting polymers are molded.
The molecular origin of the difference between thermoplastic and thermosetting polymers is shown in
the figure. The initial heating and setting of a thermosetting polymer produces a number of links
between sites on the carbon backbone of different molecular chains. These links are referred to as
cross-links because they cross between and link individual molecular strands of the polymer.
 The different properties of thermoplastic and thermosetting polymers result from the ways in
which the polymer chains interact with one another. Chemically, these cross-links are additional
covalent bonds that join the polymer chains to one another. Like most covalent bonds, they are strong
enough that they do not readily fail upon heating. So the cross-linked polymer keeps its shape.

An important example of the engineering importance of cross-linking in American industrial

history is the discovery of vulcanization. In vulcanization, natural rubber is heated in the presence of
sulfur. This produces cross-linking and leads to a harder material that is markedly more resistant to
heat. Until vulcanization was discovered, natural rubber was difficult to use in applications such as
automobile tires because it would become sticky when heated. Natural rubber is no longer widely used,
having been replaced by synthetic forms.

Elasticity

 another critical physical property of polymers

 the ability of many polymeric materials to be stressed and deformed but return to their original
shape. Fibers, in particular, must be elastic.
 Polymers that are particularly flexible and elastic are sometimes referred to as elastomers. The
forces between polymer molecules in an amorphous solid are not as strong as those in a more
crystalline system, so they can be deformed and restored with less force.

Polymers and Additives

Despite their wide range of useful properties, polymers alone often do not have the
characteristics needed for a particular design. Additives can be included in the material to control
polymer properties further. Pigments, for example, can be added solely to change the color of the
material and don’t influence the underlying molecular structure of a polymer. PVC alone, for example is
too brittle for many applications. To rectify this, relatively small molecules called plasticizers are added
to improve its flexibility. A plasticizer must be capable of being incorporated into the solid polymer, so
its structure should resemble the polymer being used. It must be nonvolatile, or it will escape from the
solid too quickly and no longer impart the desired flexibility. Plasticizers do escape slowly and often the
smell associated with plastic materials arises from the release of trace amounts of these additives.
Other additives that find regular use include antistatic agents, fillers, fire retardants, and light and heat
stabilizers.

Although other elements can form polymeric materials, it is the chemical characteristics of
carbon that make the modern plastic industry possible.

EXERCISES:

1. Define the following terms:

a. Polymer c. Addition polymers
b. Monomer d. Condensation polymers
2. Name at least three common polymers and give examples of their uses.
3. Distinguish between a block copolymer and a graft copolymer.
4. What is the key physical property that characterizes a thermoplastic polymer?
5. What conditions would prohibit the use of a thermoplastic polymer?
6. What happens molecularly in a thermosetting polymer when it is heated?