Chemistry 1040

Sex, Drugs and Organic Chemistry

Topic 4: POLYMERS
THERES A GREAT FUTURE IN PLASTICS

Introduction
MR. MCGUIRE:

Ben!

BEN:

Mr. McGuire

MR. MCGUIRE (overwhelmed with pride):

Ben.
BEN:

Mr. McGuire.

Mr. McGuire takes Ben's arm and steers him down the hall toward the back of the house and out through
the back door.
EXT. BRADDOCK BACKYARD AND POOL AREA - NIGHT

The pool is eerily lit. There are FOUR PEOPLE standing and TALKING, drinks in their hands, at the back
of the yard.
MR. MCGUIRE:

Ben - I just want to say one word to you - just one word -

BEN:

Yes, sir.

MR. MCGUIRE:

Are you listening?

BEN:

Yes I am.

MR. MCGUIRE: (gravely)

Plastics.

They look at each other for a moment.

BEN:

Exactly how do you mean?

MR. MCGUIRE:

There is a great future in plastics.

Think about it. Will you think about it?

BEN:

Yes, I will.

MR. MCGUIRE:

Okay. Enough said. That's a deal.

Excerpt from the Original Screenplay of The Graduate, by Buck Henry

The scene in The Graduate, in which the earnest family friend confides in newly graduated
Dustin Hoffman that, ...there is a great future in plastics, was a humorous comment on the
huge gap between the generation represented by Hoffmans Benjamin Braddock and that of his
parents. With the perspective of thirty+ years, the exchange is even funnier while at the same
time quite prophetic. Already in the 1960s, plastics had become ubiquitous in our society, but
even Mr. McGuire would have been surprised by the sheer diversity of products today that are a
direct outgrowth of the original plastics. High-tech camping gear, cell phones, computers and
CDs are just some of the items made of polymers (the more general name for synthetic materials
which include plastics), and new cars include nearly 400 lb of various plastics. This section will

provide a brief introduction to the chemistry of some of the most common and well-known
polymers, with an emphasis on how their molecular structure leads to the properties that make
them valuable materials.
PolymersThe Concept
A polymer is a material made up of small repeating structural units combined to give a very
large, linear structure. These ultra-large molecules are called macromolecules. The small
repeating units found within polymers come from the individual starting molecules, which are
called monomers. All commercially important polymers are made up of hundreds or thousands
of monomer units joined together to form one large molecule. Long before the first synthetic
polymer was invented, we used natural polymers, such as cotton, silk and wool, for our clothing.
Like synthetic polymers, these natural polymers consist of many of the same small molecules
joined together in a long chain to make macromolecules. Regardless of their ultimate source,
what all polymers have in common is that they are made up of very large, linear molecules
containing repeating groups within the chain. The size of the individual polymer molecules and
the nature of the groups ultimately controls what physical properties the bulk material will have.
In many cases (e.g., polyethylene, polyvinyl chloride, polystyrene) the monomer molecules
contain C=C double bonds that are broken during the polymerization process. These are
referred to as chain-growth polymers. In other cases, the monomer molecules may connect
while forming a molecule of water (e.g., nylon or polyethylene terephthalate [PET]). These are
called step-growth polymers. Generic examples of each type of process are shown below (Fig.
1).
W

W Z W Z W Z W Z

C C C C

C C
X

X Y

Monomer (alkene)

repeating
units (from
monomers)

HO C C OH
H2 H2
O

Monomers (alcohol
and carboxylic acid)

X Y n

Polymer (n is a large number)

HO C C O
H2 H2

HO C R C OH

X Y

C C C C

R C

O
O C C O
H2 H2

C R C OH
n

H2O
Polymer (n is a large number)
(a polyester)

Figure 1. Generic Examples of Polymer Formation From Monomers.

The intentional preparation of polymers began in the mid-19th century. Celluloid, formed
from a mixture of nitrocellulose and camphor, was the first moldable plastic, and was used as a
substitute for ivory in piano keys and billiard balls. Because nitrocellulose is explosive, this
created some excitement during billiard matches or particularly vigorous piano recitals. Not long
after, the first synthetic fiber, rayon, was invented and became used as a silk substitute. As
2

chemists began to discover that many small alkene molecules could be inadvertently
polymerized, and as certain specific needs arose due to shortages of natural materials, new
polymers were invented with increasing frequency. Another important milestone was the
development of synthetic rubber by the Germans during World War I. In the sections that
follow, we will consider each of the major types of polymers separately, with a discussion of the
monomers and the common uses of each.
Polyethylene
The simplest synthetic polymer is polyethylene. Recall that ethylene is the old name for
ethene, the simplest example of an alkene (Figure 2). Polyethylene is a chain-growth polymer, in
which the double bond of the alkene monomer gets broken as new bonds are formed between
monomer molecules. Can you predict the basic structure of polyethylene? As you might
imagine, it simply consists of CH2CH2- units repeated again and again. The most common type
of chain-growth polymerization uses radical initiation, in which a small amount of a compound
with only seven valence electrons (R, called a free radical) begins the polymerization by
adding to an alkene monomer and generating a new radical that then adds to another alkene, and
so on. The polymer is terminated by reaction with another radical, either another initiator or
another growing chain.
H
H

H
R C C

H
+

C C
H

ethene
(ethylene)

radical
initiator

repeating
units (from
monomers)

addition of another
molecule of monomer

H H

H H

R C C

C C

H H

H H

addition of another
molecule of monomer

H
H
new radical

H
C C

H
C C

H
C C
H
H

many
more
steps

growing chain

H H
R C C
H H

H
C C
H

H H

H H

H H

R C C

C C

C C R

H H

H H

H H
n
polymer molecule

Figure 2. Polymerization of Ethylene to Form Polyethylene.

Polyethylene is used widely in our society. In 1997, over 20 billion lb of varying grades of
polyethylene was produced in the United States. There are two main types of polyethylene, high
density polyethylene (HDPE) and low density polyethylene (LDPE). High density
polyethylene is harder and stronger than LDPE, so it is used for gas tanks, heavy duty pipes,
appliance cabinets, and in other situations requiring great strength. In contrast, LDPE tends to be
much softer and is also usually transparent. Examples of LDPE that you may have encountered
include plastic wrap, grocery bags and disposable diaper liners.
What is the difference between low- and high-density polyethylene that leads to the different
physical properties? The same starting material is used in either case. The answer lies in the
nature of the individual polymer molecules from which the material is made. Low-density
polyethylene tends to consist of relatively short chains of about 500 monomer units, with a
considerable degree of branching (Fig. 3), while HDPE chains are much longer (about 10,000
monomer units) and are not branched. Because they are long and straight, HDPE molecules are
3

able to pack together more closely, which leads to the higher density of this material. Their
strength derives from both the rigidity of this tightly-packed structure and the overall length of
the molecules. While HDPE is generally a superior material, it is more expensive to make than
LDPE. LDPE is formed by radical polymerization as discussed above, while formation of
HDPE requires the use of sophisticated and expensive catalysts. As a result, LDPE is the
polymer of choice for products that do not require a lot of strength or toughness.
H C H
H C H
H
H H

H H

C C

C C

C C

H H

H H
H
H C HH H
H C

C C

H C H

H H

H C H
LDPE: polymer molecules have
lots of branching

Molecules unable to pack

together very closely

H H

H H

H H

H H

H H

H H

C C

C C

C C C C

C C

C C

H H

H H

H H

H H

H H

H H

HDPE: polymer molecules have

little or no branching

Molecules able to arrange themselves

in very close proximity

Figure 3. Shape of Low Density and High Density Polyethylene Polymer Molecules Affects
Their Arrangement
Polypropylene
Polypropylene is quite similar in structure to polyethylene, given the close relationship
between the two monomers (Fig. 4). Propylene (or propene, as it is also called) is like ethylene,
except with a methyl group (CH3) replacing one of the hydrogens. So, once the polymer is
formed, there will be methyl groups attached to every other carbon on the long chain. You might
imagine that the arrangement of the methyl groups would be completely random, that is, some
might end up on adjacent carbons, while others would be separated by one or two CH2 groups.
However, polypropylene is made only using catalysts like the ones used for HDPE, and these
conditions lead to a very regular arrangement of the methyl groups on alternating carbon atoms
as shown.
Polypropylene is a fairly versatile polymer, used as both as a plastic (i.e., moldable material)
and as fiber (i.e., spun into long strands that can be used in textiles, etc.). In 1997, over 13
billion pounds of it was manufactured. Because it melts at a relatively high temperature, it is
4

used to make dishwasher-safe containers. Both HDPE and LDPE melt at considerably lower
temperatures, so they are seldom used in this way. (Try putting a milk jug, often made of HDPE,
in your dishwasher. On second thought, dont try it.) One of the most common uses of
polypropylene fibers is in indoor-outdoor carpeting. It is also used in thermal underwear.
H

H
vs.

C C
H

ethene
(ethylene)

CH3

polymerization

C C
H

R
catalyst

CH3 H

CH3 H

H
n

propene
(propylene)

CH3
R

polypropylene
(note CH groups on
3
every other carbon)

Monomer units come together

in regular fashion:
H
C C
H

Not in a random way:

CH3
H
CH3
H
C C
H
CH3
H
H
C C
H
H

H
C C
H

CH3
C
H3
H
H
C C
H
H
H
H

X
CH3
C C
H

irregular arrangement of CH3

groups not seen

CH3 CH3 H

CH3

Figure 4. Formation of Polypropylene from Propene.

Additional Work:
1. Although polypropylene forms only with the methyl groups on every other carbon,
there is still a possibility for different arrangements of the methyl groups. Can you
see it? (Hint: are there any chiral centers in the polymer molecule?)
2. Polyisobutylene is a useful material that is completely impermeable to gases.
Because of this property, it is used for the inner liner of tires and basketballs. It was
originally developed by the Germans as a rubber substitute, and is sometime known
as butyl rubber. Given the structure of the monomer below, can you predict what
the polymer would look like?
H

CH3
C C
CH3

isobutylene

3. Apply a similar analysis to polyisobutylene as you did to polypropylene in problem 1.

(I.e., is there more than one possible way the methyl groups can be arranged on the
polymer chain?)
5

Polyvinyl Chloride
Polyvinyl chloride (often abbreviated as PVC), as you might guess, comes from the
monomer vinyl chloride (Fig. 5). It is a commercially important product, with over 14 billion
pounds produced in 1997. Most of you are familiar with PVC as a material for making pipes,
suggesting that it is a fairly stiff material. It is also the main component of linoleum flooring and
vinyl siding,* and the material of choice for electrical insulation. However, it can also be
formulated as a highly flexible material, either opaque or transparent, to make upholstery
(vinyl covering), garden hoses and shower curtains. This is accomplished by including
additional compounds, called plasticizers, that keep it soft and flexible. However, some of the
most common plasticizers have received quite a bit of attention over the last ten years because
they are suspected of being environmental estrogens that act on the estrogen receptor and
affect sexual development in higher animals (including us). This will be discussed further in the
section on sex hormones.

Cl

radical

polymerization

C C
H

vinyl chloride

Cl

Cl

Cl

H H
n
polyvinyl chloride

Figure 5. Formation of Polyvinyl Chloride from Vinyl Chloride.

Like LDPE, PVC is generally made using a radical initiator, and like polypropylene, the
monomer units come together so that the non-hydrogen group (the chlorine atom in this case)
appears on every other carbon atom of the polymer chain. Polyvinyl chloride was originally
discovered in 1912 by a German chemist, Fritz Klatte. He had been looking for useful things to
do with excess acetylene that his company had acquired, and had converted it to vinyl chloride.
He stored it on the shelf, and later found that it had polymerized. His company patented it, but
never found a use for it and the patent expired in 1925. A year later, an American chemist,
Waldo Semon independently invented PVC. His company, B. F. Goodrich, determined that it
was waterproof and decided to market it for shower curtains. They filed a U.S. patent
(apparently Klattes company had obtained only a German patent) and made millions out of this
material.
Polystyrene
Polystyrene is found in many places in our society. It is best known as the main ingredient
of styrofoam cups and dishes, though it is also used to form the jewel case for CDs. These are
two very different types of materialhow can they come from the same polymer? It turns out
that the difference does not come from the way it is formed, as was the case with LDPE and
HDPE, but rather from the way it is fabricated after it is formed. The hard, transparent material
of jewel boxes is made by melting polystyrene and pouring it into molds. For styrofoam, small
beads of polystyrene are prepared, containing a low boiling liquid inside. Nowadays the liquid is
*

The term vinyl is well known in our culture, as in vinyl siding, vinyl tops to cars and vinyl records (remember
those?). In all cases, this is referring to a plastic material whose main component is PVC. In organic chemistry, a
vinyl group is a C=C bond with three hydrogens that is attached to something else (CH2=CH-X), hence vinyl
chloride.

usually pentane (C5H12), which boils at about 36 C (97 F), though until recently
chlorofluorocarbons (CFCs) were used. This use of CFCs was curtailed due to their role in the
destruction of stratospheric ozone. The beads are placed in a mold and heated using steam,
which causes the pentane to vaporize and greatly expand the beads. The expanded beads fuse
together to form the shape of the mold. The bubbles left behind make the material very light
weight and also a good thermal insulator.
Like LDPE and PVC, polystyrene is formed by radical polymerization (Fig. 6). The starting
monomer, styrene, consists of an ethylene molecule in which one of the hydrogen atoms has
been replaced by an aromatic ring. When these monomers come together, they do so in such a
way that the aromatic rings are attached to alternating carbon atoms of the chain.

radical
R

C C
H

polymerization

styrene

H
n
polystyrene

Figure 6. Polymerization of Styrene to Give Polystyrene.

Additional Work:
4. Polyvinyl acetate is used in wood glue, as a coating to make paper shiny, and in latex
paint. Given the structure of vinyl acetate below, suggest what polyvinyl acetate
looks like.
5. Suppose there were a polymer with the structure shown below (there is). Can you
infer the structure of the likely monomer? [By the way, this is one of the common
ingredients of superglues. Can you guess why a monomer would be used in a
glue?]

CH3
O
H
R

CH3
O O
H

CH3
O O
H

O
C

H C

H
n

Teflon
Teflon, more correctly named polytetrfluoroethylene, is a highly useful polymer due to its
unique properties. It was discovered by accident in the 1930s when a chemist at Dupont was
experimenting with tetrafluoroethylene (see Fig. 7) as a possible refrigerant. When he opened
the tank, nothing came out, yet it was heavy, as if it were full. Eventually, he sawed the tank
open and found that it was full of a white powder, which he correctly surmised to be polymerized
7

tetrafluoroethylene. Although it was not clear what caused the polymerization within the tank, it
was found that radical polymerization works well for the formation of this material.

radical

polymerization

C C
F

tetrafluoroethylene

polytetrafluoroethylene
(Teflon)
Figure 7. Formation of Teflon from Tetrafluoroethylene.
What uses do you associate with Teflon? Probably the first thing that you thought of was
nonstick pans. It is also put on carpet and fabrics to make them stain resistant (e.g., Dupont
StainmasterTM), used to seal metal pipes (Teflon tape) and in artificial body parts. The common
feature of all of these uses is the chemical resistance of this material. The fluorine atoms that
surround the carbon chain of the polymer protect it from chemical attack, and also repel most
other materials. As a result, it is very inert (i.e., chemicals wont react with it) and resistant to
anything sticking to it.
Polyethylene Terephthalate
Polyethylene terephthalate (the second word is pronounced terrathalate) is the most
important example of the class of polymers known as chain-growth or condensation
polymers. This group also includes Nylon and virtually all of the naturally occurring polymers
except rubber (e.g., cellulose, silk, etc.). As you saw in Figure 1, these polymers are not formed
from alkene monomers. Instead, two reactive groups come together to join two monomer
molecules with the simultaneous formation of a small molecule such as water. Polyethylene
terephthalate is typically abbreviated as PETE or PET, although the latter is sometimes
discouraged due to trademark infringement with a brand of condensed milk.
In the lab, PET is very easy to make by simply heating two different kinds of molecules
together: phthalic acid and ethylene glycol (Fig. 8). Each of these monomers has two of the
same functional group; phthalic acid has two carboxylic acid groups, while ethylene glycol has
two alcohol groups. Another functional group that you have seen, called esters, is usually
formed from an alcohol and a carboxylic acid, as shown in the figure. If this process is carried
out using double-barreled monomers such as phthalic acid and ethylene glycol, the product
that is left still has one carboxylic acid and one alcohol left. Therefore, each of these can react
again to form two more esters, and once again, there are still two reactive functional groups at
each end. As you can imagine, this process can continue for a very long time, giving large
polymer molecules made up of repeating ester units. That is why this particular class of
polymers is also called polyesters. Since PET is by far the most common example, you should
assume that any item of clothing that contains a certain percentage of polyester probably has
PET in it.
PET is a very important commercial product. As already noted, it can be spun into fibers for
clothing, and this form is known by the trade name Dacron. Interestingly, Dacron is also used in
a variety of medical applications, such as patching damaged blood vessels and even the septum
in the heart. The great strength of Dacron fibers is a result of the ability of the ester groups and
the aromatic rings of individual polymer molecules to line up with each other in long strands.
8

You have probably also encountered PET in other places, such as drink bottles. Interestingly, the
use of PET in bottles was invented by Nathaniel Wyeth, brother of the famous American painter,
Andrew Wyeth. Another important use is as thin ribbons, called Mylar, which are typically
coated with metal oxide for use as recording tape.
O
R

O
2

C O

H
alcohol

H
carboxylic
acid
O

terephthalic acid
(2 carboxylic acids)

HO C

H2

C OH

+ HO C C OH
H2 H2

2 H2

HO C

O C C OH
H2 H2

ester product
(1 carboxylic acid + 1 alcohol)

C OH

HO C C OH
H2 H2

H2

ethylene glycol
(2 alcohols)

C O R2
ester

HO C

O R

HO C C O C
H2 H2

O C C O C
H2 H2

HO C C O C
H2 H2

O C C O C
H2 H2
n
polyethylene terephthalate (PET or PETE)

O
C OH

O
C OH

Figure 8. Polyethylene Terephthalate from Phthalic Acid and Ethylene Glycol.

Nylon
Nylon was one of the first big success stories in the field of polymer chemistry. Nylon is an
example of a polyamide. You know what a polyester looks like from the discussion above; if
you refer to your table of functional groups, can you predict what a polyamide should look like?
Actually, the most important polyamides are the proteins, and it was from proteins that Wallace
Carrothers, a chemist at Dupont, took his inspiration. He found that mixing two monomers,
adipic acid (a molecule with two carboxylic acids as we saw with terephthalic acid) and
hexamethylene diamine (a molecule with two amine groups, similar to ethylene glycol), gave the
desired polymer (Fig. 9). As with polyesters, a molecule of water is generated each time a
monomer adds to the growing chain.
Nylons importance quickly became apparent when it was discovered how easily it could be
spun into strong, smooth fibers. It was first used in the bristles of toothbrushes. The
resemblance of this material to silk led to the notion of making stockings from Nylon, and on the
first day that Nylon stockings were offered for sale in New York City in 1940, four million pairs
were bought. Unfortunately for the avid consumers, the supply of Nylon quickly dried up after
the United States entered World War II. It found many uses, including clothing, ropes and
parachutes. It is still used for material that requires great strength and durability.
9

O
R1

O H

H
R1

N R2

C O
H

carboxylic
acid
O

H
amine

C N R2

H2O

amide
H2O

HO C C C C C C OH
H2 H2 H2 H2

H2N C C C C C C NH2
H2 H2 H2 H2 H2 H2

adipic acid
(2 carboxylic acids)
O

hexamethylene diamine
(2 amines)
O H

HO C C C C C C N C C C C C C NH2
H2 H2 H2 H2
H2 H2 H2 H2 H2 H2
amide product
(1 carboxylic acid + 1 amine)
O
HO C (CH2

)
4

O H
C

O H

H O

N (CH2)6 N C (CH2)4 C N (CH2)6 NH2 + n+1 H2O

n
6 carbons

6 carbons

Nylon 6,6
Figure 9. Nylon 6,6 from Condensation Polymerization of Adipic Acid and Hexamethylene
Diamine.
The particular type of nylon invented by Carrothers and Dupont was called nylon 6,6 due to
the number of carbons in each of the monomer pieces, and was such a commercial hit that other
chemical companies tried to develop alternative products that did not infringe on the Dupont
patent. A way around this was found with the closely related polymer, nylon 6 (Fig. 10). Unlike
nylon 6,6, nylon 6 is made from a single monomer that contains an amide functional group
within a ring. When this amide, caprolactam, reacts with water and acid (H+), it is converted
into a molecule with one carboxylic acid and one amine. This molecule can then react with more
of the caprolactam to give a new amide that has a carboxylic acid and an amine at the two ends,
and eventually a polymer that looks very much like nylon 6,6. However, since there is only one
monomer, having six carbon atoms, it is called nylon 6.
One of the main reasons for the high tensile strength of the nylons (the property that allows
very strong fibers to be made from them) is the ability of the individual polymer chains to form
connections between each other (Fig. 11). Amides such as those found in the nylons can form
what is called hydrogen bonds. These connections are weaker than a full fledged covalent
bond, but formation of several of them between two chains will hold them very tightly together.
The same principle is seen in the chemistry of proteins, which are also polymers made up of
repeating amide bonds. As we will see later this semester, hydrogen bonds between amide
10

groups hold proteins into unique shapes that are necessary for their biological activity. They also
play an important role in the binding together of two protein molecules, the attraction of a
substrate for an enzymes active site, or the affinity of a drug for a particular receptor. Hydrogen
bonds are also an important part of the chemistry of the genetic code, although in this case it
does not involve amide groups.
O
amide C

break here

H+
+ H2O

H
O
H
OH
N
= HO C (CH2)5 NH
2

caprolactam

1 carboxylic acid + 1 amine

O
C

O
HO C (CH2

)
5

NH2

H O

HO C (CH2)5 N C (CH2)5 NH2

amide product
(1 carboxylic acid + 1 amine)
O

H O

H O

HO C (CH2)5 N C (CH2)5 N C (CH2)5 NH2

6 carbons

Nylon 6

Figure 10. Formation of Nylon 6 from Caprolactam.

N
H2 (CH2)6 N C (CH2)4 C
H O

Nylon 6,6:
O

)
)
N (CH2 6 N C (CH2 4 C OH

O H

O H

H O
n

H O

O H
)

HO C (CH2)4 C N (CH2)6 N C (CH2

)
C N (CH2 6 NH2
n
hydrogen bonds holding
chains together

H2N (CH2

C N (CH2
O H
H O

HO C (CH2

N (CH2)5 C OH

O H
n

Nylon 6:
O

H O

)
N C (CH2)5 N C (CH2 5 NH2
n

Figure 11. Hydrogen Bonds Between Chains of Nylon 6,6 or Nylon 6.

11

One final point concerning polyamides such as the nylons concerns a structurally similar
polymer, Kevlar. Kevlar is an amazingly strong material when spun into fibers; in fact, its
tensile strength is greater than that of steel. Yet, it is much lighter than steel or other metals
known for their strength. As a result, it is used in bulletproof vests, Army helmets and protective
clothing worn by firefighters. One of the monomers used to make Kevlar should be familiar to
you, terephthalic acid (remember PET?). The other is a compound with two amine groups, like
the compound hexamethylene diamine used in nylon 6,6. However, in this case the two amine
groups are attached directly to an aromatic ring (Fig. 12). The two monomers come together in
the same way as we saw before with nylon 6,6, forming a long chain in which the individual
monomers are connected by amide linkages. The aromatic rings in both pieces make the
polymer molecule very rigid, but the individual polymer chains can still bind to each other with
hydrogen bonds, as we saw with the nylons. The result is a very stiff, strong material. In fact,
the biggest challenge with Kevlar is how to fabricate itit does not melt until it is heated above
500 C (912 F).
O
HO C

H2

O
C OH + H2N

NH2

HO C

1,4-diaminobenzene
(aka phenylene diamine;
2 amines)

terephthalic acid
(2 carboxylic acids)

NH2

amide product
(1 carboxylic acid + 1 amine)

H O

HO C

N C

H
N

NH2

n
Kevlar

Figure 12. Formation of Kevlar from Terephthalic Acid and 1,4-Diaminobenzene.

Other Important Polymers
There are many other important polymers aside from those described above. However, space
and time limitations prevent us from covering them in the same level of detail. They will each
be described briefly, in terms of the molecular structures of the monomers and polymers, their
properties, and their uses.
Another natural polymer that has been widely used is rubber. Rubber is obtained from the
rubber tree as latex, and can be made synthetically from a simple, five-carbon monomer called
isoprene (Fig. 13). Because of its pure hydrocarbon structure, rubber is quite waterproof. When
it is vulcanized by treatment with sulfur, rubber becomes much harder, but still flexible. This
observation was made by Charles Goodyear, and led to the modern tire industry. A close relative
of rubber, also obtained from trees, is gutta-percha. Can you tell the difference between the two
polymers? They are alkene isomers. The cis double bonds in rubber make it very elastic, while
the trans double bonds of gutta-percha make it stiffer and more brittle. Gutta percha is used for
packing root canals and as a covering for golf balls.
Additional Work:
6. Two close relatives of rubber and gutta-percha are polybutadiene and neoprene, made
from the monomers butadiene and chloroprene. Given the structures of the
monomers (next page), can you predict the structures of the polymer products?
12

Cl

butadiene

chloroprene
"cis" double bonds

H3C

H3C

H3C

isoprene

H3C

natural rubber
(polyisoprene)

"trans" double bonds

CH3

CH3

CH3

gutta-percha
Figure 13. Rubber and Gutta-Percha.
Polyurethanes arealso elastomers, like rubber and its relatives. A urethane is like a cross
between an amide and an esterit contains a carbonyl (C=O) with both a nitrogen and an
oxygen attached to the carbonyl carbon (Fig. 14). Polyurethanes are typically made from two
different monomers, one containing two isocyanate groups and one containing two alcohol
groups. There are many examples of polyurethanes, and one is shown in the figure. They are
used to make foam rubber, and also make up one of the parts of the unusual material known as
spandex (Lycra).
H O
1

N C O R2
a urethane

O C

C
H2

N C O

+ HO C C OH
H2 H2

isocyanate groups

O H

H O
O C N

C
H2

N C

O C C O C
H2 H2

H O
C
H2

N C O C C OH
H2 H2
n

a polyurethane

Figure 14. Polyurethane.

Another type of elastic polymer that you may have heard of is silicone. It is interesting to
note that the silicones (there are a number of them in use) do not have any carbon atoms in the
polymer chain. Instead, they are made up of a repeating O-Si-O-Si- pattern. Using your
knowledge of valence, you should realize that the silicon atoms need to have four bonds, just like
carbon atoms. The remaining two bonds to each Si are connected to organic pieces, such as
methyl (CH3) or phenyl (C6H5) groups (Fig. 15). The reason that silicones are so flexible is that
the polymer backbone (the O-Si chain) can easily bend. Because they are waterproof and easily
13

molded, silicones are used for caulking. They are also chemically quite inert, so they are used in
various prosthetic body parts. Finally, an interesting side note: if silicone is mixed with boric
acid (B(OH)3), the product is an extremely stetchable, yet bouncy materialsilly putty.

CH3

CH3

CH3

Si O Si O Si O
CH3

CH3

Si O

Si O

Si O

CH3
n
n

Figure 15. Structures of Typical Silicone Rubbers.

Those of you who wear glasses may be familiar with another type of polymer, the
polycarbonates. Polycarbonates are made from two pieces, a compound called bisphenol A
and phosgene, a very dangerous compound used as a chemical weapon in World War I (Fig. 16).
The two pieces combine to form a carbonate linkage in the repeating chain. Carbonates
resemble the urethane, except that they have two oxygens attached to the C=O instead of an
oxygen and a nitrogen. The polycarbonate that is used for eyeglass lenses is different. One
starts with a monomer containing a C=C bond at each end, and this is polymerized in the same
way as polyethylene or polypropylene. However, in this case the polymer chains are joined
together by carbonate links, which makes the material very strong and hard, yet lightideal for
glasses.
CH3

O
R O C O R

HO

+ Cl

OH

CH3
bisphenol A

a carbonate

CH3
O

phosgene
CH3

O C O

NaOH

C Cl

CH3

O C

CH3

n
O

O
O

O carbonates

O
O

O
alkenes

Figure 16. Two Types of Polycarbonate.

Three final polymers that we will briefly mention are polymethyl methacrylate,
polyacrylonitrile, and polyvinyl pyrrolidone (Fig. 17). These are all made by chain-growth
polymerization of alkene monomers, as we saw already with other polymers such as
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polyethylene, polypropylene, polystryene, polyvinyl chloride and teflon. Polymethyl

methacrylate is best known as Plexiglass, an extremely tough (almost unbreakable) and
transparent material, and as Lucite, which is used in bathtubs, sinks and other fixtures.
Polyacrylonitrile itself is used only as a starting material for making carbon fibers. However,
when a mixed polymer made from a mixture of acrylonitrile and methyl methacrylate is made, it
can form the fibers that we know as acrylic. Finally, polyvinyl pyrrolidone is interesting,
because it is used in hairspray (along with silicone). The B-52s would not have made it big
without this polymer.

O
C O-CH3

radical

R C C

C C
H

O
OCH3 O
OCH3 O
OCH3
H C
H C
H C

polymerization

CH3

methyl methacrylate

H CH3

radical

polymerization

C C
H

C C

H CH3
n
polymethyl methacrylate (Plexiglass, Lucite)

H CH3

H C

H C

H C

R C C

C C

C C R

H H

H H

H H

N
H

C C

n
polyacrylonitrile

acrylonitrile

N
O
OCH3
H C
H C

acrylonitrile
radical

C C

R C C

+
polymerization

H CH3

methyl methacrylate

O
OCH3 N
H C
H C
C C

H CH3 H CH3

C C

H CH3
n

"acrylate" fiber

N
H

radical

polymerization

O
N O N
H
H
R C C

C C

H H

H H

O N
H
C C R
H H
n

H
vinyl pyrrolidone

polyvinyl pyrrolidone

Figure 17. Polymethyl Methacrylate, Acrylic, and Polyvinyl Pyrrolidone.

15