Unit 5 - Ch 10 Chem30 12/21/06 11:33 AM Page 445

Polymerization Reactions—
Monomers and Polymers 10.5
If you take a look around you, you will likely find that you are surrounded by plastic
products of many shapes and sizes. They may include pens, buttons, buckles, and parts + EXTENSION
of your shoes, chair, and lamp. There are plastic components in your calculator, tele-
phone, computer, sporting equipment, and even the building in which you live. What are
plastics and what makes them such desirable and versatile materials?
Plastics belong to a group of substances called polymers: large molecules made by Plastics Under Pressure
Most plastics need to be heated
linking together many smaller molecules, called monomers, much like paper clips in a and melted during recycling, but
long chain. Different types of small molecules form links in different ways, by either that same heat is damaging to the
addition or condensation reactions. The types of small units and linkages can be manip- plastic, and degrades it into a less
ulated to produce materials with desired properties such as strength, flexibility, high or useful material. Researchers may
low density, transparency, and chemical stability. As consumer needs change, new poly- have a solution to the problem: a
new plastic that can be reformed
mers are designed and manufactured.
under pressure instead of heat,
Plastics are synthetic polymers, but many natural polymers have similar properties and can be recycled many times.
recognized since early times. Amber from tree sap, and tortoise shell, for example, can This technology could make
be processed and fashioned into jewellery or ornaments. Rubber and cotton are plant poly- recycling cheaper and much more
mers, and wool and silk are animal polymers that have been shaped and spun into useful environmentally friendly.
forms. In fact, our own cells manufacture several types of polymers—molecules so large www.science.nelson.com GO
and varied that they make us the unique individuals we are. Proteins and carbohydrates
are all very different natural polymers.
Polymerization is the formation of polymers from the reaction of monomer sub-
units. These compounds have long existed in nature but were only synthesized by tech-
nological processes in the 20th century. They have molar masses up to millions of grams
per mole.
1 5
Addition Polymers
Many plastics are produced by the polymerization of alkenes. For example, polyethene
(polyethylene) is made by polymerizing ethene molecules in a reaction known as PETE PP
addition polymerization. Polyethylene is used to make plastic insulation for wires, and
containers such as plastic milk bottles (Figure 1), refrigerator dishes, and laboratory 4
wash bottles. Addition polymers are formed when monomer units join each other in a
process that involves the rearranging of electrons in double or triple bonds in the
monomer. The polymer is the only product formed. LDPE
Figure 1
H H H H H H H H H H H H H H H H H H
For recycling purposes, plastics
C C + C C + C C → C C + C C + C C → C C C C C C (especially containers) are coded
with a symbol for the type of plastic
H H H H H H H H H H H H H H H H H H incorporated.
1. polyethylene terephthalate (PETE)
ethene (ethylene) part of polyethene
2. high-density polyethylene (HDPE)
(polyethylene) 3. polyvinyl chloride (PVC)
4. low-density polyethylene (LDPE)
The monomers form dimers (from two monomers) and trimers (from three 5. polypropylene (PP)
monomers), and continue reacting to form polymers (from many monomers, dimers, 6. polystyrene (PS)
7. other or mixtures
and trimers).
Look for these symbols on plastic
Polypropylene, polyvinyl chloride (PVC), Plexiglas, polystyrene (Styrofoam®), and
products and, of course, recycle
natural rubber are also addition polymers. The production process for polypropylene is the product when you are finished
illustrated in Figure 2. with it.

NEL Hydrocarbon Derivatives, Organic Reactions, and Petrochemicals 445

Unit 5 - Ch 10 Chem30 12/21/06 11:33 AM Page 446

crude oil

polypropylene
powder is
purified
purified
naphtha
propylene
fraction
monomer
from oil extrusion
into pellets

polymerization: chain
formation is assisted polypropylene pellets
by catalyst shipped to processor
Figure 2
The production of polypropylene from crude oil

Other Addition Polymers: Carpets, Raincoats, and Insulated

Cups
There are hundreds of different industrial polymers, all with different properties, and
formed from different reactants.

Polypropene
Figure 3
Propene also undergoes addition polymerization, producing polypropene, commonly
Polypropylene rope is one of
many petrochemical products. called polypropylene. You may have used polypropylene rope (Figure 3), or walked on
polypropylene carpet.

H H H H H H H H H H H H H H

C C + C C + C C + C C C C C C or C C

H CH3 H CH3 H CH3 H CH3 H CH3 H CH3 H CH3 n

propene monomers polypropene (polypropylene)

The polymerization reaction in the formation of polypropene is very similar to that of

polyethene. The propene molecule can be considered as an ethene molecule with the
substitution of a methyl group in place of a hydrogen atom. The polymer formed con-
tains a long carbon chain, with methyl groups attached to every other carbon atom in
the chain.

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Section 10.5

Polyvinyl Chloride
Ethene molecules with other substituted groups produce other polymers. For example,
polyvinyl chloride, commonly known as PVC, is an addition polymer of chloroethene.
A common name for chloroethene is vinyl chloride. PVC is used as insulation for elec-
trical wires and as a coating on fabrics used for raincoats and upholstery materials
(Figure 4).
H H H H H H H H H H H H H H

C C + C C + C C + C C C C C C or C C

Cl H Cl H Cl H Cl H Cl H Cl H Cl H n
vinyl chloride monomers polyvinyl chloride (PVC) Figure 4
Polychloroethene or polyvinyl
Polystyrene chloride is used for upholstery.
When a benzene ring is attached to an ethene molecule, the molecule is vinyl benzene,
commonly called styrene. An addition polymer of styrene is polystyrene, often used to
make cups and containers. Look for the recycle symbol with a 6 and PS.

H H H H H H H H H H H H H H

C C + C C + C C + C C C C C C or C C

H H H H H H H

n
styrene monomers polystyrene

Teflon
Teflon® is the common name for an addition polymer with nonstick properties that are
much desired in cookware (Figure 5).
The monomer used to synthesize Teflon is the simple molecule tetrafluoroethene,
CF2=CF2, an ethene molecule in which all hydrogen atoms are replaced with fluorine
atoms. The absence of carbon–hydrogen bonds and the presence of the very strong
carbon–fluorine bonds make Teflon highly unreactive with almost all reagents. It is this
unreactivity that allows it to be in contact with foods at relatively high temperatures
Figure 5
without “sticking.” The inert (unreactive) nature of Teflon makes it a very useful polymer The invention of Teflon has made life
in a wide variety of applications. There is, however, some controversy about its safety, as easier in many ways.
you will discover in the following Web Activity.

F F F F F F F F F F F F F F

C C + C C + C C + C C C C C C or C C

F F F F F F F F F F F F F F n
tetrafluoroethene polytetrafluoroethene (Teflon)

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DID YOU KNOW ? WEB Activity

Addition Monomers
Ethene and its double-bonded Web Quest—Teflon: Healthy or Hazardous?
derivatives are monomers for
Cooks used to coat pots and pans with butter or oil to keep food from sticking, but the result
polymers with a wide variety of
was greasy high-fat food. The invention of Teflon®, a non-stick cooking surface, changed all
properties. Some of these
this. Recently, concern has been growing regarding the possibility that Teflon® releases toxic
monomers include:
chemicals if it gets too hot. Research the pros and cons of Teflon®, and decide for yourself if
H H the risks are worth the benefits.

www.science.nelson.com GO
C C

H CI
Practice
monomer of PVC
1. Draw a structural formula of three repeating units of
(a) a polymer of but-1-ene
H Cl
(b) a polymer of vinyl fluoride
(c) a polymer of 1-chloro-1,2,2-trifluoroethene
C C
(d) Predict the properties of the polymer in (c) in terms of solubility in organic
solvents, rigidity, and resistance to heating.
H Cl
2. Draw a structural formula of the monomer of the following polymer:
monomer of Saran™ wrap
H F H F H F
H H
C C C C C C
C C
H CH3 H CH3 H CH3
H CN 3. What monomer could be used to produce each of these polymers?
monomer of acrylic (a) CH CH CH CH CH CH

H COOCH3 CH3 CH3 CH3 CH3 CH3 CH3

C C F F F F
(b) F F
H CN C C C C C C
monomer of instant glue
CH3 Cl CH3 Cl CH3 Cl

4. What functional group(s), if any, must be present in a monomer that undergoes an

addition polymerization reaction?
5. Addition polymers may be produced from two different monomers, called
co-monomers. Saran™, the polymer used in a brand of food wrap, is made from the
monomers vinyl chloride and 1,1-dichloroethene. Draw structural formulas for each
monomer, and for three repeating units of the polymer, with alternating co-monomers.
6. (a) What are the typical properties of a plastic?
(b) What types of bonding would you expect to find within and between the long
polymer molecules?
(c) Explain the properties of plastics by referring to their bonding.
7. Polymerization is a term used for a crude-oil refining process that converts small
alkenes into gasoline-sized molecules. The polymerization process is controlled to
produce dimers and trimers only (not large polymers), using phosphoric acid as a
catalyst. Provide a structural formula equation for the reaction of
(a) three molecules of ethene
(b) propene and but-1-ene
(c) but-1-ene and but-2-ene
8. Find out from your community recycling facility what types of plastic products are
accepted for recycling in your area. If there are some plastics that are not accepted,
find out the reason. Summarize your findings in a well-organized table.

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Section 10.5

WEB Activity DID YOU KNOW ?

Photodegradable Polymers
Case Study—Recycling Plastics James Guillet (1927–2005), a
Canadian green-chemist, used his
Much of the plastic we use today is collected. We sometimes think of collecting as "recycling,"
fascination with photosynthesis to
but true recycling only happens if the plastic is used to make a product similar to the original
inspire his study of the
one. How is recycling done? Investigate several Web sites and gather information to write a
photochemistry of synthetic
procedure for processing recycled plastic. Also, collect some pros and cons from multiple
systems. While on holidays in the
perspectives concerning the use of plastics.
Bahamas, he was disturbed by the
www.science.nelson.com GO quantity of plastic litter and
realized that, with his knowledge,
he could “make it disappear.”
Guillet registered three patents for
Condensation Polymers photodegradable polymers in 1970.
Some polymers, including the synthetic fibres nylon and polyester, and natural polymers Unfortunately, his invention was
like proteins and DNA, are produced by condensation polymerization reactions. These not widely embraced. Self-
interests lobbied against his
reactions involve the formation of a small molecule (such as H2O, NH3, or HCl) from “human-made plastics.”
the functional groups of two different monomer molecules. The small molecule is said to
be “condensed out” of the reaction. The monomer molecules bond at the site where atoms
are removed from their functional groups. To form a condensation polymer, the monomer
molecules must each have at least two functional groups, one on each end.

Comparing Natural with Synthetic Polymers

Research chemists have found that Nature has many well-designed molecular structures
that are polymers. Many synthetic condensation polymers are structural analogs of the
DID YOU KNOW ?
nutrient molecules found in foods: they have structures similar to those of lipids (fats Aboriginal Technologies
and oils), proteins, and carbohydrates. Over the next few pages, there is a classification Aboriginal peoples used many
natural materials to create useful
and description of some of these natural polymers: proteins and carbohydrate poly- technologies. For example,
mers. Most of us recognize these classes of compounds as categories of foodstuffs. Food Aboriginal peoples invented the
labels usually list the mass of fat, protein, and carbohydrate per serving. birch-bark canoe, seal-skin kayak,
A synthetic compound that has a similar chemical structure to a naturally occurring rawhide and willow snowshoes,
substance is called a structural analog. For example, nylon is a structural analog of pro- and animal skin tipis. The natural
polymers, such as cellulose and
tein, but not a functional analog (Figure 6). Functional analogs are synthetic compounds
protein, in these Aboriginal
that perform the same function as a naturally occurring substance but do not neces- technologies have, in some cases,
sarily have similarities in chemical structure. For example, synthetic sweeteners are func- been replaced by synthetic
tional analogs of sweet carbohydrates: sugars. Chemists who study natural chemicals in polymers.
order to prepare synthetic copies are called natural-product chemists.
Natural Product Lipids Proteins Carbohydrates Figure 6
(food nutrient molecules) ↓ ↓ ↓ Food nutrients and their synthetic
structural analogs are an example
Structural Analog Polyesters Nylon Cellulose Polymers
of natural product chemistry, where
(synthetic polymers)
chemists copy and modify the
structure of chemicals found in
nature.
Lipids and Polyesters
Lipids (fats and oils) are formed by esterification reactions between glycerol (propane-
1,2,3-triol) and fatty acids (long-chain carboxylic acids). Since glycerol has three hydroxyl
(–OH) groups, three molecules of fatty acid can react with each glycerol molecule to
form a tri-ester. This reaction is a condensation reaction that is not, strictly speaking, a
polymerization reaction: The largest molecule formed is a tri-ester.

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Learning Tip glycerol  saturated fatty acid 0 saturated fat  water

You are not required to learn H O
the names of carboxylic acids
beyond ten carbons. You also
H
H C O C C17H35
do not have to name the
triesters representing fats and H C OH O
oils. You should, however, learn O
the general structures of H C OH + 3 C17H35 C H C O C C17H35 + 3 O H
• polyalcohols (especially OH O
propane-1,2,3-triol), H C OH H
• saturated and unsaturated octadecanoic acid H C O C C17H35
fatty acids, and H or stearic acid
• triester fats and oils.
(fatty acid) H
propane-1,2,3-triol glyceryltrioctadecanoate or
(glycerol) tristearin or glyceryltristearate
(saturated fat present in butter and lard )

BIOLOGY CONNECTION
glycerol  unsaturated fatty acid 0 unsaturated oil  water
Correlation versus Cause
and Effect H
Many biochemistry studies related
to food are correlational studies. H C OH H H
These studies look for a correlation O
(relationship) between two H C OH + 3 CH3 (CH2)7 C C (CH2)7 C
variables (without being able to OH
control all other variables—as a H C OH
cause–effect study would). For 9-octadecenoic acid
example, scientists found a strong H (oleic acid)
correlation between saturated fats
(and transfats), and artery and propane-1,2,3-triol
heart diseases. Chemists
(glycerol)
responded with creative solutions H O H H
(Figure 7).
H C O C (CH2)7 C C (CH2)7 CH3
O H H

H C O C (CH2)7 C C (CH2)7 CH3 + 3 O H

O H H
H
H C O C (CH2)7 C C (CH2)7 CH3
Figure 7
Butter and margarine are H
examples of saturated and glyceryltri (9-octadecenoate)
unsaturated fats (lipids). There are (triolein, an unsaturated
many criteria that can be used to cis fat present in olive oil )
evaluate which is the best product.
www.science.nelson.com GO
At one time, unsaturated fats were considered to be healthier in the diet than saturated
fats and oils. Unsaturated oils are generally liquids at room temperature. To change the
oil into a solid (such as margarine), the unsaturated fat is partially hydrogenated to
remove some of the double bonds and increase the melting point. Subsequent research
showed that, although unsaturated fats were healthier, the hydrogenation process created
unhealthy transformed fats.

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Section 10.5

Practice DID YOU KNOW ?

9. Unsaturated lipids are generally more liquid (i.e., oils), and saturated lipids are Transfat
generally more solid (i.e., fats). Create a hypothesis to explain the difference between A transfat has a double bond
the melting points of unsaturated versus saturated lipids. where the hydrogen atoms are on
the opposite side of the double
10. The fatty acid C19H39COOH reacts with glycerol, C3H5(OH)3, to produce peanut oil.
bond. Trans means across, so the
Write a structural formula equation to communicate this reaction.
hydrogen atoms are across the
11. The fatty acid CH3—(CH2)7—CH— — CH—(CH2)7—COOH is hydrogenated. Write a double bond from one another.
structural formula equation for this chemical reaction.
H H
C C

Polyesters
cis
When a carboxylic acid reacts with an alcohol in an esterification reaction, a water mol- orientation
ecule is eliminated and a single ester molecule is formed. The two reactant molecules are
linked together into a single ester molecule. This esterification reaction can be repeated H
to form not just one ester molecule, but many esters joined in a long chain, a polyester. C C
This is accomplished using a dicarboxylic acid (an acid with a carboxyl group at each end
of the molecule), and a diol (an alcohol with a hydroxyl group at each end of the mol- H
trans
ecule). Ester linkages can then be formed end to end between alternating acid mole- orientation
cules and alcohol molecules.

HO OC
CH2
CH2
CO OH  H O
CH2
CH2
O H  HO OC
CH2
CH2
CO OH  →

ethane-1,2-dicarboxylic acid ethane-1,2-diol

OC
CH2
CH2
CO
OCH2
CH2O
OC
CH2
CH2
CO
 H2O(l)

If we were to depict the acid with the symbol 
 , the alcohol with o
o, and the
ester linkage with o, we could represent the polymerization reaction like this:

  o
o  
  o
o →

o
o
o
o
 water
polyester

Dacron®, another polyester, is made from p-phthalic acid (p-dibenzoic acid) and
ethane-1,2-diol (ethylene glycol). Note the two carboxyl groups in the dicarboxylic acid
and the two hydroxyl groups in the polyalcohol that start the chain reaction.

O O O O

HO C C OH + H O CH2 CH2 O H + HO C C OH + H O CH2 CH2 OH +

ethylene glycol
p-phthalic acid ethylene glycol p-phthalic acid

( (
O O

O C C O CH2 CH2 + H O H
n
a polyester (Dacron®)

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DID YOU KNOW ? Practice

Amines and Amides 12. Draw a structural formula equation to show a repeating unit of a condensation
Two classes of organic compounds polymer formed from the following compounds:
that are not studied in detail in this
HOOC CH2 CH2 COOH and HO CH2 CH2 CH2 CH2 OH
textbook are amines and amides.
The simplest amines have the —NH2 13. What functional groups must be present to form a polyester?
(amino) functional group, as in
R—NH2. The simplest amides have 14. How are the reactions to form fats and to form polyesters similar and different?
the —CONH2 functional group in a
molecule of R—CONH2. A polyamide
may be formed naturally or
technologically by repeatedly
reacting a carboxyl group with an WEB Activity
amino group. The —CONH— group is
called an amide (or peptide) linkage. Simulation—Molecular Modelling
Proteins and nylon are polymers
Molecular modelling has become more of a computer activity than a physical activity. Chemists
that are called polyamides. Protein
routinely use interactive models to better understand how the shapes of compounds affect their
polymers are specifically called
properties. Check out some of the molecular modelling Web sites.
polypeptides.
www.science.nelson.com GO

Proteins and Nylon

Proteins are a fundamental structural material in plants and animals. Scientists estimate
that there are more than ten billion different proteins in living organisms on Earth.
Remarkably, all of these proteins are constructed from only about 20 amino acids.
Through a reaction that involves the carboxyl group and the amine (–NH2) group,
amino acids polymerize into peptides (short chains of amino acids) or proteins (long
chains of amino acids). The condensation reaction of the amino acids glycine and ala-
nine illustrates the formation of a dipeptide. Condensation polymerization produces a
protein, with a molar mass tens of thousands to millions of grams per mole—thou-
sands of monomers long.

H O H O
N CH2 C + N CH C →
H O H H O H
CH3

H O
N CH2 C O + O H
H N CH C
H
H O H
CH3

glycine + alanine → a dipeptide + water

The dipeptide reacts with itself or with more glycine and/or alanine. Of course, other
amino acids may be present to produce an even more complex peptide. The polypeptide
produced by polymerization is a protein with peptide (–CONH–) linkages. The fol-
lowing general equation illustrates the formation of a protein from amino acids.

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Section 10.5

peptide
linkage
H H O H H O H O H O
N C C ON C C OH N C C N C C  H O
H R H H R H R H R n H

amino acid 1 amino acid 2 polypeptide segment

DID YOU KNOW ?
Nylon
Many synthetic polymers, such as nylon, form in similar ways to proteins. Nylon is a
Nylon was designed in 1935 by
synthetic condensation polymer. For both the natural polymer (protein) and the synthetic Wallace Carothers, a chemist who
polymer (nylon), the polymer forms by the reaction of a carboxyl group (–COOH) with worked for DuPont; the name
a –NH2 group with amide linkages (–CONH–). Polymers with amide linkages are called nylon is a contraction of New York
polyamides. Amide linkages in proteins are called peptide linkages and the polymers are and London.
called polypeptides.

() ()
H H
O O H H
C C C + N C N →
H O O H H H
H 4 H 6

amide linkage

() ()
H
O O H
C C C
N C N + O H
H 4
H H
H 6 n H

hexane-1,6-dioic acid + 1,6-diaminohexane → part of the nylon 6,6 polymer chain + water

INVESTIGATION 10.5 Introduction Report Checklist

Preparing Nylon 6,10 (Demonstration) Purpose Design Analysis

Problem Materials Evaluation
Nylon was considered the “miracle” fibre when it was discovered Hypothesis Procedure
in 1935. At the time, nylon was unique because it was the first Prediction Evidence
synthetic fibre produced from petrochemicals. It initiated an entire
new world of manufactured fibres. In this demonstration, sebacoyl
chloride, COCl(CH2)8COCl(l), reacts with 1,6-diaminohexane to
Problem
produce one type of nylon. For the prediction, write a condensed How does the combination of sebacoyl chloride and
or line structural formula equation showing the formation of the 1,6-diaminohexane form the polymer known as nylon 6,10?
polymer. Design
Purpose A solution of 1,6-diaminohexane is carefully poured on top of an
The purpose of this demonstration is to use your knowledge of aqueous solution of sebacoyl chloride. The nylon that forms at the
condensation polymerization to explain the formation of a nylon interface of the two layers is slowly pulled out of the mixture
polymer. using forceps.

To perform this investigation, turn to page 464.

Nylon was synthesized as a substitute for silk, a natural polyamide whose structure nylon
mimics. The onset of the Second World War speeded up nylon production to make
parachutes, ropes, cords for aircraft tires, and even shoelaces for army boots. It is the
–CONH groups that make nylon such a strong fibre. When spun, the long polymer

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DID YOU KNOW ? chains line up parallel to each other, and the –CONH groups form hydrogen bonds with
–CONH groups on adjacent chains.
Pulling Fibres
When a polymer is to be made into O O O O
a fibre, the polymer is first heated
and melted. The molten polymer is N C C N N C C N nylon polymer chain
then placed in a pressurized
container and forced through a
H H H H
small hole, producing a long strand, hydrogen bonding between chains
which is then stretched (Figure 8).
The process, called extrusion, O O O O
causes the polymer chains to orient
themselves lengthwise along the C N N C C N N C nylon polymer chain
direction of the stretch. Covalent or
hydrogen bonds form between the H H H
chains, giving the fibres added
strength. Kevlar
To illustrate the effect of hydrogen bonding in polyamides, consider a polymer with very
hopper
special properties. It is stronger than steel and heat resistant, yet is lightweight enough to
pellets of polymer
wear. This material is called Kevlar® (Figure 9) and is used to make products such as air-
hole
craft, sports equipment, protective clothing for firefighters, and bulletproof vests for
police officers. What gives Kevlar these special properties? The polymer chains form a
molten polymer strong network of hydrogen bonds holding adjacent chains together in a sheet-like struc-
bobbin
ture. The sheets are in turn stacked together to form extraordinarily strong fibres. When
Figure 8 woven together, these fibres are resistant to damage, even that caused by a speeding bullet.
Making a polymer
Figure 9
The chemical structure of Kevlar, N H
with hydrogen bonding between N H
the shaded polymer chains N H

H N
H N
H N C O
C O
C O

O C
O C
DID YOU KNOW ? O C
N H
N H

Paintball: A Canadian N H
Invention
The sport of paintball was invented
in Windsor, Ontario. Paintballs were H N
first used to mark cattle for H N
slaughter and trees for harvesting, H N C O
using oil-based paints in a gelatin
shell. When recreational paintball C O
use demanded a water-based paint, C O
the water-soluble gelatin shell was
modified by adjusting the ratio of
the synthetic and natural polymers O C
used. O C
O C

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Section 10.5

Practice
15. What kind of polymerization does the formation of a polyamide (natural or synthetic)
involve?
16. Provide one example each of a natural and of a similar synthetic condensation
polymer.
17. Draw a structural formula representation of the nylon 6,8 repeating unit, formed by
reacting H2N(CH2)6NH2 and HOOC(CH2)6COOH.

EXPLORE an issue Issue Checklist

Issue Design Analysis
Natural or Artificial Polymers? Resolution Evidence Evaluation

From the time your grandparents were babies to the time you
were born, diapers have been made entirely of polymers.
Cotton cloth diapers were, and still are, made of cellulose, a
• Polyurethane, rubber, and Lycra: Any or all of these stretchy
substances may be used in the leg cuffs and the waist-
natural polymer. Nowadays, disposable diapers, made mainly band.
of synthetic polymers, are a popular choice. Which is better for
the baby? How do they affect our environment? The typical • Cellulose: Basically processed wood pulp, this natural
polymer is obtained from pine trees. It forms the fluffy
disposable diaper has many components, mostly synthetic
filling of a diaper, absorbing liquids into the capillaries
plastics, that are designed with properties particularly
between the fibres.
desirable for its function.
• Polyethylene film: The outer surface is impermeable to • Polymethylacrylate: This crystalline polymer of sodium
methylacrylate absorbs water through osmosis and
liquids, to prevent leakage. It is treated with heat and
hydrogen bonding. The presence of sodium ions in the
pressure to appear cloth-like for consumer appeal.
polymer chains draws water that is held between the
• Hot melts: Different types of glue are used to hold chains. The presence of water results in attractions
components together. Some glues are designed to bond between the chains and causes the formation of a gel
elastic materials. (Figure 10).
• Polypropylene sheet: The inner surface at the leg cuffs is Manufacturers claim that grains of sodium
designed to be impermeable to liquids and soft to the polymethylacrylate can absorb up to 400 times their own mass
touch. The main inner surface is designed to be porous, to in water. If sodium ions are present in the liquid, they act as
allow liquids to flow through and be absorbed by the bulk contaminants, reducing absorbency because the attraction of
of the diaper. water to the polymer chains is diminished. Urine always
contains sodium ions, so the absorbency of diapers for urine is
actually less than the advertised maximum.

dry in water












H


Figure 10
C Polymethylacrylate
O
Na

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Proponents of natural products argue that disposable diapers Issue

pose a long-term threat to our environment, filling waste Do cloth diapers pose less of a threat to the environment than
disposal sites with non-biodegradable plastics for future disposable diapers?
centuries. The industry has developed some new
“biodegradable” materials—a combination of cellulose and Resolution
synthetic polymers, for example. Some of these materials have Consumers should return to using cloth diapers in order to
proven too unstable to be practical, while others appear to protect the environment.
biodegrade in several years, which gives the diapers a
reasonable shelf life. The energy and raw materials needed to Design
manufacture the huge quantity of disposable diapers used is Within small groups, research the pros and cons of using cloth
also of concern. Diaper manufacturers and their supporters diapers. Gather information from a wide variety of perspectives.
argue, however, that using the natural alternative—cloth
diapers—consumes comparable amounts of energy in the www.science.nelson.com GO

laundry. In addition, the detergents used in the cleaning

process are themselves non-biodegradable synthetic
compounds made from petroleum products.

Carbohydrates and Cellulose Acetate

The monomers of carbohydrates—compounds with the general formula Cx(H2O)y—are
simple sugar molecules. The sugar monomers undergo a condensation polymerization
reaction in which a water molecule is formed, and the monomers join together to form
a larger molecule. For example, the sugar monomers glucose and fructose can form
sucrose (table sugar) and water. Both starch and cellulose consist of long chains of glu-
cose molecules. Simple sugar monomers are sometimes called monosaccharides; dimers
are called disaccharides; and polymers are called polysaccharides.

CH2OH CH2OH
O HOCH 2 O CH2OH O H
H H H HOCH 2 O CH2OH
H H
+ → + O H
OH H HO OH HH OH H
HO OH HO O OH HH H

H OH H OH H OH
H OH
glucose + fructose → sucrose + water

DID YOU KNOW ? Starch for Energy; Cellulose for Support

Starchy foods such as rice, wheat, corn, and potatoes provide us with readily available
Maple Sugar and Corn energy. They are also the main method of energy storage for the plants that produce
Canadian Aboriginal peoples
them, as seeds or tubers. Starches are polymers of glucose, in either branched or
introduced Europeans to maple
sugar. Sugar (a disaccharide) can be unbranched chains; they are, thus, polysaccharides.
obtained from sugar cane (from We have, in our digestive tracts, very specific enzymes. One breaks down starch.
South America) and sugar beets However, the human digestive system does not have an enzyme to break down the other
(from southern Alberta). The polymer of glucose: cellulose. Cellulose is a straight-chain, rigid polysaccharide with
greatest contribution of Aboriginal glucose–glucose linkages different from those in starch or glycogen. It provides structure
agriculture is corn—one of the most
and support for plants, some of which tower tens of metres in height. Wood is mainly
prolific and widespread crops in
human history—from which we cellulose; cotton fibres and hemp fibres are also cellulose. Indeed, it is because cellulose
obtain corn syrup. is indigestible that whole grains, fruits, and vegetables are good sources of dietary fibre.
It is the different glucose–glucose linkages that make cellulose different from starch.
When glucose forms a ring structure, the functional groups attached to the ring are
fixed in a certain orientation above or below the ring. Our enzymes are specific to the

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Section 10.5

orientation of the functional groups, and cannot break the glucose–glucose linkages
found in cellulose. Herbivores such as cattle, rabbits, termites, and giraffes rely on some BIOLOGY CONNECTION
friendly help to do their digesting: They have specially developed stomachs and intestines Glycogen
that house enzyme-producing bacteria or protozoa to aid in the breakdown of cellu- Animals also produce a starch-like
substance, called glycogen, that
lose.
performs an energy storage
In starch, glucose monomers are added at angles that lead to a helical structure, which function. Glycogen is stored in the
is maintained by hydrogen bonds between –OH groups on the same polymer chain muscles as a ready source of
(Figure 11(a)). The single chains are sufficiently small to be soluble in water. Thus, energy, and also in the liver, where
starch molecules are both mobile and soluble—important properties in their role as it helps to regulate blood glucose
readily available energy storage for the organism. levels.
In cellulose, glucose monomers are added to produce linear polymer chains that can www.science.nelson.com GO
align side by side, favouring interchain hydrogen bonding (Figure 11(b)). These inter-
chain links produce a rigid structure of layered sheets of cellulose. This bulky and inflex-
ible structure not only imparts exceptional strength to cellulose; it also renders it insoluble
in water. It is, of course, essential for plants that their main building material does not
readily dissolve in water.
DID YOU KNOW ?
Cotton—A Natural Polymer
North American Aboriginal
CH2OH CH2OH CH2OH CH2OH
peoples made extensive use of
H O H H O H H O H H O H cotton for clothing. This technology
H H H H was exported to Europe, where it
OH H OH H OH H OH H contributed to starting the
O O O O industrial revolution in Britain.
Cotton is a natural carbohydrate
H OH H OH H OH H OH (cellulose) polymer. There are now
(a) starch regenerated (manufactured) fibres
from cellulose, such as cellulose
CH2OH acetate and cellulose nitrate. In
1850, long-fibre cotton comprised
H O over 50% of Britain’s exports. The
CH2OH H O
mechanization and infrastructure
H O OH H developed for processing cotton,
CH2OH H O
H and the resulting capital gained,
H O OH H helped to fuel and shape the
H O H OH
H Industrial Revolution.
O OH H H OH
H
H OH
(b) cellulose

Figure 11
The difference in linkages between glucose monomers gives very different three-dimensional
structures.
(a) In starch, the polymer takes on a tightly coiled helical structure.
(b) In cellulose, the linked monomers can rotate, allowing formation of straight fibres.

mini Investigation Starch and Cellulose

Use a molecular model kit and/or a computer program to
construct and/or investigate molecular models of glucose,
sucrose, starch, and cellulose.

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NEL Hydrocarbon Derivatives, Organic Reactions, and Petrochemicals 457

Unit 5 - Ch 10 Chem30 12/21/06 11:33 AM Page 458

DID YOU KNOW ? Practice

The Centre of the Chocolate 18. Identify the functional groups present in a molecule of glucose and in a molecule of
Sucrose, a disaccharide, is slightly fructose.
sweeter than glucose but only half 19. Describe several functions of polysaccharides and how their molecular structures
as sweet as fructose. The enzyme serve these functions in plants.
sucrase, also called invertase, can
20. Compare the following pairs of compounds, referring to their structure and
break sucrose down into glucose
properties:
and fructose—a mixture that is
(a) sugars and starch
sweeter and more soluble than the
(b) starch and cellulose
original sucrose. The centres of
some chocolates are made by 21. What are the distinctive features of carbohydrate molecules that, given a structural
shaping a solid centre of sucrose formula, would allow you to classify them as carbohydrates?
and invertase, and coating it with 22. Explain in terms of molecular structure why sugars have a relatively high melting
chocolate (Figure 12). Before long, point compared with hydrocarbons of comparable size.
the enzyme transforms the sucrose 23. Describe, and then explain, the relative solubility of glucose, starch, and cellulose in
centre into the sweet syrupy mixture water.
of glucose and fructose.

Cellulose Acetates—Structural Analogs of Polysaccharides

Chemists have researched and developed polymers that are modifications of natural
polymers. These natural–synthetic polymers are called biopolymers. For example, starch
and cellulose have been made into synthetic polymers. An example is cellulose triacetate.
Cellulose, a polysaccharide, is modified by reacting it with acetic acid, CH3COOH(l), and
acetic anhydride, (CH3CO)2O(l), with sulfuric acid as a catalyst.

Figure 12 CH2OH CH2OOCH3

Invertase breaks sucrose down to
glucose and fructose in some O O
chocolates.
H catalyst H
H H
→
OH H OOCH3 H
O H O H

H OH n H OOCH3 n
cellulose → cellulose triacetate

Cellulose triacetate is a polymer that is used in fabrics such as permanently pleated gar-
ments, textured knits, and sportswear. There are other, similar, cellulose acetates.

WEB Activity

Case Study—Cellulose Acetate

This activity leads you through an exploration of the historical and current work done by
polymer chemists to use natural polymers to produce synthetic polymers with desired
characteristics and applications.

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Section 10.5

Learning Tip
SUMMARY Polymers—Plastics, Fibres, and Food
Try to equate the classification
of condensation polymers with
Polymers are a common part our everyday world and include natural polymers (lipids the three food groups when
(triesters), proteins, and carbohydrates) and synthetic polymers (e.g., nylon, cellulose organizing your knowledge of
polymers:
acetate, and polyesters). For the structural formula equations of these polymers, see pre-
vious pages. • polyesters include lipids and
polyester fabrics
• polyamides include proteins
Addition Polymers and polyamide fabrics
Synthetic Addition Polymer (e.g., polypropene) • polysaccharides include
carbohydrates and, for
H H H H example, cellulose acetate.
Chemists create classification
C C → C C systems to help them organize
their knowledge. Use the same
H CH3 H CH3 n approach to your advantage.

Condensation Polymers (Structural Analogs)

Polyesters
• Natural “Polyester” (e.g., butter):
glycerol
fatty acid → fat or oil
water
e.g., C3H5(OH)3
3 C17H35COOH → C3H5(OOCC17H35)3
3 H2O
• Synthetic Polyester (e.g., Dacron)
dicarboxylic acid
polyalcohol → polyester
water
e.g., HOOCC6H4COOH
HOCH2CH2OH →
[–OOCC6H4COOCH2CH2–]n
n H2O
Polyamides
• Natural (proteins; polypeptides):
amino acid
amino acid
… → protein
water
e.g., H2NCH2COOH
H2NCHCH3COOH →
[–NHCH2CONHCHCH3CO–]n
n H2O

• Synthetic (e.g., nylon 6,6):

dicarboxylic acid
diamine → nylon
water
e.g., HOOC(CH2)4COOH
H2N(CH2)6NH2 →
[OC(CH2)4CONH(CH2)6NH–]n
n H2O
Polysaccharides
• Natural (e.g., starch):
glucose
glucose → starch
water
glucose
glucose → cellulose
water
(The glucose molecules that polymerize to produce starch or cellulose have slightly
different stereochemical formulas.)
C6H12O6
C6H12O6 → [–C6H10O5–]n
n H2O
• Synthetic (e.g., cellulose triacetate):
cellulose
acetic acid
acetic anhydride → cellulose acetate
...
[–C6H10O5–]n
CH3COOH
(CH3CO)2O → [–C6H7O5(OCH3)3–]n
...

NEL Hydrocarbon Derivatives, Organic Reactions, and Petrochemicals 459

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Section 10.5 Questions

1. Teflon®, made from tetrafluoroethene monomer units, is 11. Starch and cellulose have the same caloric value when
a polymer that provides a non-stick surface on cooking burned, but very different food values when eaten by
utensils. Write a structural formula equation to represent humans. Explain.
the formation of polytetrafluoroethene. 12. Explain why the sugars in a maple tree dissolve in the sap
2. Polyvinyl chloride, or PVC plastic, has numerous but the wood in the tree trunk does not.
applications. Write a structural formula equation to 13. Many consumer products are available in natural or
represent the polymerization of chloroethene (vinyl synthetic materials: paper or plastic shopping bags, wood
chloride). or plastic lawn furniture, cotton or polyester clothing.
3. Using a molecular model kit, construct models of the Choose one consumer product and list the advantages and
following monomers and polymers: disadvantages of the natural and synthetic alternatives,
(a) starch (d) polypropene with particular reference to structure and properties of the
(b) polyvinyl chloride (e) a polyester material used as it relates to the function of the product.
(c) nylon (f) cellulose acetate 14. Classify the type of polymerization for each of the following
4. As with most consumer products, the use of polyethylene polymers:
has benefits and problems. What are some beneficial uses (a) polyethenes (c) polyamides
of polyethylene and what problems result from these uses? (b) polyesters (d) polysaccharides
Suggest alternative substances for each application. 15. Research or use what you know to write a combination of a
5. Use the information in this section and from your own word, molecular formula, and structural formula equation
research to continue gathering perspective statements for each of the following chemical transformations:
concerning the statement that we should be saving more (a) starch (from grain) to glucose to ethanol
fossil fuels for petrochemical use in the future. (b) cellulose (from aspen trees) to glucose to methanol
6. The first nylon product that was introduced to the public, in
1937, was a nylon toothbrush called Dr. West’s Miracle-Tuft Extension
toothbrush. Earlier toothbrush bristles were made of hair 16. Alkyd (oil-based) paint is a polyester formed by reacting
from animals such as boar. From your knowledge of the glycerol (CH2OHCHOHCH2OH) with
properties of nylon, suggest some advantages and 1,2-benzenedicarboxylic acid (C6H4(COOH)2). Communicate
drawbacks of nylon toothbrushes compared with their this reaction using a structural formula equation.
natural counterparts.
17. What functional group(s), if any, must be present in a
7. Oxalic acid is a dicarboxylic acid found in rhubarb and monomer of a condensation polymer?
spinach. Its structure is shown below.
18. In an attempt to reduce body weight, many Canadians are
O O considering low-carbohydrate or low-sugar diets. Based on
your knowledge of the chemistry of carbohydrates and
HOC COH sugars, comment on which of these diets might be more
effective.
Draw three repeating units of the condensation polymer
made from oxalic acid and ethan-1,2-diol. 19. Natural rubber is made from resin produced by the rubber
tree, Hevea brasiliensis.
8. What is the synthetic polymer analog of each of the (a) Research the history of the use of rubber by Aboriginal
following foods? peoples long before Europeans came to the Americas.
(a) pasta (b) Research the commercial invention, production, and
(b) meat use of natural rubber, and the circumstances that
(c) butter stimulated the development of synthetic rubber.
9. Suppose that two new polymers have been designed and (c) Write a brief report on your findings.
synthesized for use as potting material for plants. 20. Raymond Lemieux, from Lac La Biche, Alberta, was the first
(a) List and describe the properties of an ideal polymer to chemist to artificially synthesize sucrose (in 1953). Consult
be used to hold and supply water and nutrients for a the biographical information of Lemieux. Describe his
plant over an extended period of time. interest in science and one of his other accomplishments
(b) Design an experiment to test and compare the two (other than the synthesis of sucrose).
polymers for the properties you listed. Write a brief
description of the procedures followed, and possible www.science.nelson.com GO
interpretations of experimental results.
10. When we purchase a product, we may want to consider not 21. Check the latest Alberta Chemical Operations Directory to
only the source of its components, but also the requirements see if there are any new monomer and polymer chemical
for its use and maintenance. In your opinion, how valid is the plants in Alberta.
use of the terms “organic,” “natural,” and “chemical” in the
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promotion of consumer goods?

460 Chapter 10 NEL