Chemistry in Action (Polymers)

Polymers
• Polymers are macromolecules formed by repeated joining of many
small molecules.

• Polymerisation is the process of joining together many small molecules

repeatedly to form very large molecules like polymers.

• Monomers are compounds that join together repeatedly to form a

polymer in the process of polymerisation.

Polymers can be natural or synthetic. The natural polymers covered include

proteins, polysaccharides and nucleic acids

The most important naturally occurring polymers are:

 Proteins
 Polysaccharides (e.g. cellulose, starch)
 Nucleic acids (e.g. DNA, RNA)
 Rubber

Synthetic polymers are produced commercially on a very large scale.

They have a wide range of properties and uses.
Plastics are all synthetic polymers

Synthetic polymers can be made from monomers by two basic polymerisation

processes:

(a) addition polymerisation which produces addition polymers

(b) condensation polymerisation which produces condensation polymers

Well-known examples of synthetic polymers are:

 Polyethene (PE)
 Polystyrene (PS)
 Polyvinyl chloride (PVC)
 Nylon
 Urea-methanal

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Chemistry in Action (Polymers)

Natural Polymers
Amino acids and protein
Introduction
Amino acid are bifunctional compounds containing both the amino (-NH2) and
carboxylic (-COOH) groups.

NH2 COOH

Classification of amino acids

1. Neutral amino acids:
Number of amino groups = number of carboxylic groups
E.g. Glysine NH2CH2COOH
2. Basic amino acids
Number of amino groups > number of carboxylic groups
E.g. Lysin
H2N NH2

COOH

3. Acidic amino acids

Number of amino groups < number of carboxylic groups
E.g. Aspartic acid
HOOC
COOH
H2N

Stereochemistry of Amino Acids

All amino acids except aminoethanoic acid contain an asymmetric atom and
exhibit optical isomerism.
Example: Alanine

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They are optical isomers, but optical inactive, since they are racemic mixture.
Laboratory synthesized amino acids are ONLY optically inactive because of
the formation of race mixture.

Physical properties of Amino Acids

The dipole moments of the amino acids are very large. For example,
+
NH3CH2COO- CH3CH2COOH CH3(CH2)2CH2NH2
Dipole Moment 14D 1.7D 1.4D
Ionic Acid Base
Compound

In fact, in the solid state and in solution, amino cids exist as internal ionic
salts, called Zwitterions.

So,
 Amino acids are high melting point solids.
 e.g. Glycine melts at 235℃
 They are very soluble in water, but they only dissolove slightly in organic
solvents.
 They have a very large dipole moment.

Chemical properties of Amino Acids

Amphoteric nature of amino acids

At some intermediate pH value, a dipolar (zwitterions) form is produced.

The hydrogen ion from the carboxyl

group is trasnsferred to the basic
amino group within the molecule.

+ OH− + OH−
H3N – CH – COOH H3N – CH – COO− H2N – CH – COO−
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| H+ | H+ |
R R R
Chemistry in Action (Polymers)

The existence of the zwitterionic form can be explained in terms of acid-base

theory:
1. –NH2 is a stronger base than –COO-
2. –COOH is a stronger acid than –NH3+
Further evidence for zwitterions formation is electrophoresis.

Methods to separate a mixture of amino acids.

Paper chromatography will be used to separate amino acids.

There is a thin film of water on the chromatography paper.
The amino acids distribute themselves between the stationary phase (water
on the paper) and the moving phase (the solvent/eluent)
To make the amino acid spots visible to naked eyes, spray chromatography
paper with ninhydrin solution which reacts with amino acids to give purple
coloured compounds.
(also accept using UV radiation/ iodine vapour to detect the amino acid spots.)

Reactions of Amino acids

Two main types reaction of the Amino Acids

1. reaction of the carboxyl group

2. reactions of the amino group

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Dil. NaOH(aq) H
NH2 CCOO-Na+
R
HO
SOCl2 or PCl5
NH2 C-C-Cl
Showing acidic R
Properties H
Fusing with soda lime NH2-C-H
R

HO
CH3OH/H+ +
H NH3 C-C-OCH3
NH2 CCOOH R
R
H
Dil HCl - +
Cl NH3 CCOOH
Showing basic
Properties R

OHH
CH3COCl
CH3-C-N-C-COOH
R

Peptides, Polypeptides and protein

Dipeptide

The (-NH2) group of one amino acid can react with the (-COOH) group of
another to form an amide.
The resultion molecule is a dimmer containing two amino acid units which is
describes as a dipeptide.
In the process, the two amino acid molecules are joined by the condensation
reaction. A water molecule is eliminated.

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Amino acids are linked together by peptide linkage.

Polypeptide
Amino acids undergo condensation polymerization to form long-chain
polyamide molecules.
dipeptide

Further
reaction
of each
end

Polypeptide/protein

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(1) If n< about 50, the product is a polypeptide.

(2) If n> about 50, the product is a protein.

Structure of proteins
Protein structure is describe at 4 levels: 1∘, 2∘, 3∘ & quaternary.

Being polyamides, both proteins and nylon can be hydrolysed and are thus
broken down to their constituent amino acids.

For example,

Polypeptide

Dipeptide

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Amino acids

The peptide linkages in a protein molecule can be broken by hydrolysis using

mineral acids or some enzymes.

On complete hydrolysis, the protein is broken down into amino acids. By

analyzing the resulting amino acids, the composition of the protein molecule
may be deduced.

Carbohydrates
Monosaccharide, disaccharide and polysaccharide

Sugar, starch and cellulose are carbohydrates. Carbohydrates are important

in the diet as a source of energy. They are compounds containing carbon,
hydrogen and oxygen with the general formula CxHyOz.

Carbohydrates may be divided into three groups,

 Monosaccharides
 Disaccharides
 Polysaccharides

The simplest carbohydrates are the sugars. (glucose, fructose and ribose)

Monosaccharides

The monosaccharides consist of a single polyhydroxyaldehyde or

polyhydroxyketone.

Monosaccharides are a group of sweet, soluble crystalline molecules with

relatively low molecular masses. They cannot be hydrolyzed into simpler
compounds. The monosaccharides commonly found in food have the general
formula C6H12O6. Two most important examples are glucose and fructose.
They are found in many fruits and in honey. Glucose is also found in the blood

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of animals (including humans)

Each monosaccharides molecule contains one carbonyl group. All the other
carbon atoms are bonded to hydroxyl groups. There are aldose and ketose,
for which the carbonyl group is and is NOT terminal respectively.

aldehyde

ketone

Open chain and ring structures of glucose and fructose

Glucose can exist in acyclic and cyclic forms:

0.02%

36% 64%

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Glucose contains an aldehyde group in its acyclic form. Glucose is an

aldohexose

Most of the reactions of glucose in aqueous solutions are due to presence of

the free aldehyde group of the acyclic form.These reactions include its
reducing action

Fructose can exist as acyclic form, as well as cyclic forms of 6-membered

rings and 5-membered rings

Fructose contains a keto group in its acyclic form

 fructose is an ketohexose

Most of the reactions of fructose in aqueous solutions are due to:

 presence of the free keto group of the acyclic form

Disaccharides

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Disaccharides are sweet, soluble and crystalline.

They have the general formula: C12H22O11
Disaccharides can be formed from the condensation reaction of two
monosaccharide molecules a water molecule is eliminated

Common disaccharides include Sucrose (Source: sugar cane), Maltose

(Source: malt) and Lactose (Source: milk)

Glycosidic Linkage in Carbohydrates

Common disaccharides are formed from the condensation reaction between
two monosaccharide molecules and a water molecule is eliminated
The bond formed between two monosaccharides is called a glycosidic linkage

A sucrose molecule is formed by the condensation reaction of a glucose

molecule and a fructose molecule

A maltose molecule is formed by the condensation reaction of two glucose

molecules

Polysaccharides
Polysaccharides are polymers of monosaccharides
General formula: (C6H10O5)n where n is a large number (up to thousands)
Examples of polysaccharides: starch and cellulose
Starch is commonly found in rice, bread and potatoes
Cellulose is found in fruits, vegetables, cotton and wood

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The condensation process can be repeated to build up giant molecules of

polysaccharides
e.g. Starch

Cellulose

Adjacent chains of cellulose molecules are linked up by hydrogen bonds.

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These cellulose chains intertwine into fibrils of considerable strength.

DNA as Nucleic acid

Nucleic acids are the molecules that preserve hereditary information,
transcribe and translate it in a way that allows the synthesis of all the various
proteins of a cell

Nucleic acid molecules are long polymers of small monomeric units called
nucleotides.
The monomers of nucleic acids, called nucleotides, are formed from the
following units:
1. A phosphate unit
2. A five carbon sugar
3. A nitrogen – containing organic base.

Two kinds of nucleic acids: deoxyribonucleic acid (DNA) and ribonucleic acid
(RNA)

The sugar component of RNA is ribose, whereas that in DNA is deoxyribose.

Deoxyribos
Ribose e

The following nitrogen bases are found in DNA and RNA:

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(in DNA)

(in RNA)

 DNA is the nucleic acid that most genes are made of

 DNAs have four different kinds of nucleotides as the building blocks
 All the four kinds of nucleotides have deoxyribose as their sugar
component
They differ in their nitrogen-containing bases
Adenine (A) and guanine (G)
 have double-ring structures
 known as purines
Cytosine (C) and thymine (T)
 have single-ring structures
 known as pyrimidines

Formation of the nucleotide of a DNA molecule

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The nucleotides within a DNA molecule

are joined together through condensation
reactions between the sugar of a
nucleotide and the phosphate group of
the next nucleotide in the sequence long
chain (i.e. a polymer) of alternating sugar
and phosphate groups is formed

Two hydrogen bonds are formed between

A in one chain and T in the other
Three hydrogen bonds are formed
between G in one chain and C in the
other

Hydrogen bonding between

complementary base pairs. The hydrogen
bonds are responsible for formation of the
double stranded helical structure of DNA.

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DNA replication
The original DNA double helix partially
unwinds, and new nucleotides line up on
each strand in a complementary manner.
Hydrogen bonds help align the new
nucleotides with the original DNA chain.
When the new nucleotides are joined by
condensation reactions, two identical double
helix DNA molecules result.

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Synthetic Polymers
Addition Polymers
Formation and Uses of Addition Polymer
Addition polymerization is a chemical process in which monomer molecules
are joined together to form a polymer without elimination of small molecules.

The resulting polymer will therefore have the same percentage composition
as the reactant monomers.

1. Polyethene, or Polyethylene [PE]

Polyethene has many useful properties:

– it is easily moulded;
– it is an excellent electrical insulator;
– it does not corrode;
– it is tough;
– it is not affected by the weather;
– it is durable.

Ethene is the monomer that is used to synthesize polyethene

Depending on the manufacturing conditions, two kinds of polyethene can be
made
 low density polyethene (LDPE)

• Molecular mass between 50 000 and 3 000 000

• Light, flexible
• Low melting point
• Used to make soft items (e.g. wash bottles, plastic bags and food
wraps)

 high density polyethene (HDPE)

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• Molecular mass up to 3 000 000

• Tougher
• Higher melting point
• Used to make more rigid items
(e.g. milk bottles and water buckets)

Polyethene is a thermoplastic
It softens at a high temperature

Uses of polyethene
Insulate telephone line
Its unique electrical properties were essential during the development of
radar.
Plastic bags
It used in supermarket for packing various food product.
milk bottles and water buckets
Hard and rigid, not poisonous

Mechanism for the addition polymerization: Free Radical Addition

Polymerization of Ethene

The reaction mechanism consists of three stages:

 chain initiation
 chain propagation
 chain termination
diacyl peroxide molecule as a initiator
Chain initiation

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Chain propagation

Chain termination steps

Addition polymers formed from these substituted ethenes (H2C=CHX) have a

range of properties predictable based on the structure of –X (non polar
substituent). –X group like –CH3 or –C6H5 are soluble in organic solvents like
acetone or propanone.

2. Polypropene (PP)
With the use of Ziegler-Natta catalyst, propene can be polymerized to

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polypropene

Polypropene can exist in different configurations depending upon the

orientation of the methyl groups in the polymer.
The properties of polypropene can be modified by adjusting the manufacturing
conditions
In isotactic polypropene, all methyl groups are on the same side of the carbon
chain.
Using Ziegler Natta Catalyst, the methyl groups all arrganged on one side of
the carbon chain.

In atactic polypropene the methyl groups are randomly arranged

Isotactic Polypropene Atactic polypropene

More symmetrical Less symmetrical
Molecules pack together closely. Poor packing
High melting point Low melting point
Greater strength sticky

 It is more rigid than HDPE and used for moulded furniture

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Chemistry in Action (Polymers)

 High mechanical strength and strong resistance to abrasion. It is used for

making crates, kitchenware and food containers
 Spun into fibres for making ropes and carpets especially useful for
making athletic wear. They do not absorb water from sweating as cotton
does

3. Polystyrene (PS)
Styrene is made from the reaction of benzene with ethane, followed by
dehydrogenation.

The styrene produced is polymerized by a free radical mechanism into

polystyrene at 85 – 100°C using dibenzoyl peroxide as the initiator

Mechanism:

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Polystyrene is transparent, brittle and chemically inert. It used to make toys,

specimen, containers and cassette cases

By heating polystyrene with a foaming agent,expanded polystyrene can be

made.

Expanded polystyrene is extremely light, white solid foam. It mainly used to

make light-weight ceiling tiles in buildings, and food boxes and shock
absorbers for packaging

4. Polyvinyl Chloride (PVC)

PVC is produced by addition polymerization of the choroethene monomers in
the presence of a peroxide catalyst (e.g. hydrogen peroxide at about 60°C)

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Chemistry in Action (Polymers)

(a) (b)
Presence of the polar C – Cl bond is considerable
dipole-dipole interactions exist between the polymer chains makes PVC a
fairly strong material
The large size of Cl atom means the chains cannot easily be moved over one
another. This result in the polymer being rigid and brittle.
PVC is hard and brittle and used to make pipes and bottles

Products made
of PVC without
plasticizers
When plasticizers are added, the effectiveness of the dipole- dipole
interactions is reduced. PVC becomes more flexible
• Used to make shower curtains, raincoats and artificial leather
• Used as the insulating coating of electrical wires

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Chemistry in Action (Polymers)

Products made
of PVC with
plasticizers

Despite its extensive uses, one problem with the use of PVC is its disposal.
PVC is non-biodegradable, normally not disposed of by land-filling.
Incineration of PVC produces HCl (g)
This HCl (g) produced is usually absorbed by the wet scrubber filled with an
alkali such as Na2CO3 (aq).

Also, monomer of PVC is a carcinogen.

5. Polytetrafluoroethene (PTFE)
PTFE is produced through addition polymerization of the tetrafluoroethene
monomers under high pressure and in the presence of a catalyst

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C—F bonds are exceptionally strong & resistant to heat and chemicals
PTFE has a relatively high melting point and is chemically inert
Its non-stick properties make it an ideal material for the coating of frying pans
⇒Since fluorine is highly electronegative atom an evenly distributed layer of
negative charge is developed on the surface of PTFE
⇒ Layers of negative F atoms repel almost all other materials
⇒ Thus preventing them from adhering to PTFE
⇒ PTFE has very slippery surface

To make Teflon stick to the surface of a newly made cooking pan,

Teflon is heated to a very high temperature
pressed firmly onto the surface of the item.
This film pressing increases the area of contact between Teflon and the
surface of the pan
Increasing the strength of van der Waals’ force
Another technique:
Teflon with oxygen-containing group is polar
This helps strengthening the attraction between Teflon and the surface.
Other polarized group: methyl methacrylate can also be incorporated into the
Teflon polymer chains to achieve the above purpose.

Whatever the technique, there is still the chance of Teflon peeling off from
cooking ware after extended use, because
⇒Teflon decompose at high temperature
⇒Its coefficient of expsion is different from that of the material of the cooking
surface

6. Polymethyl Methacrylate (Perspex) (PMMA)

PMMA is formed by the free radical addition polymerization of methyl
methacrylate in the presence of an organic peroxide at about 60°C

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Chemistry in Action (Polymers)

PMMA is a dense, transparent and tough solid makes it a good material for
making safety goggles, advertising sign boards and vehicle light protectors
However, it has poor scrtching resistance and can be dissolved by a number
of organic solvents.

Condensation Polymers
Formation and Uses of Condensation Polymer
Condensation polymerization is a chemical process in which monomer
molecules are joined together to form a polymer with elimination of small
molecules such as water, ammonia and hydrogen chloride

Ethanoic Ethanol Ethyl ethanoate

acid (An ester)
Each monomer molecule must have at least two functional groups

1. Polyamide
1. Nylon
Nylon 6,6

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Chemistry in Action (Polymers)

faster

When a solution of hexane-1,6-dioyl dichloride in hexane

is poured gently onto a solution of 1,6-diaminohexane in
water, a white film of nylon is formed at the interface
between the two layers. The film can be pulled up as a
string and wound onto a stirring rod.
Used for making carpets, thread, cords and various kinds
of clothing from stockings to jackets
Advantages:
 drips dry easily
 not easily attacked by insects
 resists creasing

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There are interchain hydrogen bond so Nylon6, 10 is expected to have a

lower tensile strength than nylon6,6. There is decrease in the number of
hydrogen bond per unit length, as a result of the longer carbon chain in nylon
6,10

3. Kevlar
Aramid is a synthetic poly amide
Aliphatic hydrocarbon unit within the polmer chain has been replaced by an
aromatic unit in Aramid
• Kevlar is an aromatic polyamide
• The structure of Kevlar is similar to nylon-6,6
• The two monomers of Kevlar are benzene-1,4-dicarboxylic acid and
1,4-diaminobenzene
Both monomers are bifunctional

In Kevlar, the starting material was modified to create straighter chains in the

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polymer. A polyamide was produced with the heat resistance of asbestos.

Strength was much greater than steel.

In Kevlar the aliphatic hydrocarbon chain parts of the poly amide are replaced
by benzene rings. These parts of the polymer chain make the chains inflexible
due to delocalized bonding.
Some of this delocalization extends beyond the benzene rings and onto part
of the amide link resulting in long, rigid molecules that do not easily flex or
twist.

This extended delocalization also leads to enhanced intermolecular hydrogen

bonging between the adjacent Kevlay polymer chains.
This hydrogen bonding network causes the chains to interlock each other,
forming a sheet structure.

All the C = O and – N – H groups in the polymer chains are on opposite sides.
This makes the chains highly symmetrical. The regular structure of the
polymer chains allows them to interlock with each other.

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Applications:
(a) Kevlar is an unusual polymer with fire resistant properties and also
great strength. It is found in the crash helmets of Formula I racing
drivers as well as in the suits of racing motorcyclists.
(b) The hull of this offshore racing craft is also reinforced with Kevlar.
(c) Kevlar is used in making bullet proof vests. A more recent innovation is
to use carbonanotubes to make fibres for these bullet proof vests.
These new bullet proof vests can be made 30 % lighter, but 1.5 times
more bullet resistant than conventional Kevlar vests.

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Chemistry in Action (Polymers)

(b)

(a)
(c)

2. Dacron
Formed by repeated condensation reactions of benzene-1,4-dicarboxylic acid
(also called terephthalic acid) and ethane-1,2-diol (also called ethylene glycol)
in the presence of a catalyst and at a low pressure and moderate temperature
(about 250°C)

The two monomers of Dacron are:

The polymerization begins with the formation of an ester

A water molecule is eliminated

Due to polarization of the carbonyl groups C=O, Dacron chains are cross-

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linked by strong dipole-dipole attractions

⋅ ⋅ ⋅ ⋅
⋅⋅ ⋅⋅ ⋅⋅ ⋅⋅
⋅⋅ ⋅⋅ ⋅⋅ ⋅⋅
⋅ ⋅ ⋅ ⋅

Properties of Dacron:
 High tensile strength
 High resistance to stretching
 Low absorption of moisture
Garments made of Dacron:
 are tough
 can resist wrinkling
 can be washed and dried easily and quickly
Excellent for making trousers and skirts, sheets and boat sails
Can be used alone or blended with cotton to make it absorb sweat better

3. Urea-methanal
Produced by the condensation polymerization of urea and methanal under
heat and pressure
When an urea molecule joins up with a methanal molecule, water molecule is
eliminated
In the presence of excess methanal, further condensation reactions between
the polymer chains and methanal occur.Cross-linkages between the polymer
chains are formed. A rigid structure of urea-methanal is produced

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• Urea-methanal is a thermosetting plastic and cannot be softened or

melted again by heating once they have been set hard
• Excellent electrical insulator
• Resistant to chemical attack

Effect of Structure on Properties of Polymers

• Polymers are long-chain giant molecules
• The final form and the properties of the polymers depend on how these
long polymer chains are packed together
• If the polymer chains do not have a specific arrangement but are
loosely packed together the polymer is said to be amorphous
• Amorphous polymers are generally transparent, flexible and less dense
• When the polymer chains are regularly packed together, the polymer is
said to be crystalline
• Polymers with a high degree of crystallinity are translucent or opaque,
harder and denser
• The attractive forces holding polymer chains together also affect the
properties of polymers

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• Polymer chains containing carbon and hydrogen atoms only are held
together by weak van der Waals’ force
• slow melting points
• low mechanical strength
• If polymer chains are held together by stronger van der Waals’ forces
or hydrogen bonds, the mechanical strength of the polymers would be
stronger
• If cross-linkages are present between polymer chains, the polymers
would be mechanically stronger, more elastic or more rigid ,depending
on the extent of cross- linkages in the polymer

Low Density Polyethene and High Density Polyethene

High Density Polyethene
• When Ziegler-Natta catalysts are used, the
polymer chains produced are long
molecules with very little branching. The
polymer chains can pack closely together
into a largely crystalline structure
Thus, the polymer has a higher density

• Compared with LDPE, HDPE

 is harder and stiffer
 has a higher melting point
 has greater tensile strength
 has strong resistance to chemical attack
 has low permeability to gases

blow-molded objects: bottles for milk, soft drinks, shampoos, bleaches and so
on

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Low Density Polyethene

• When ethene is polymerized at 200°C and 1000 atm using peroxide as

the catalyst, low density polyethene (LDPE) is made
• Under these reaction conditions, highly branched polymer chains are
formed
• The branches prevent the polymer chains from getting close to each
other. The polymer chains do not pack together well and creates a
significant proportion of amorphous regions in the structure
• Thus, the polyethene made has a low density

Low density polyethene is a

 Waxy
 Semirigid
 Translucent material
 Low melting point

Nylon and Kevlar

• Nylon is a group of polyamides
• It contains a relatively large number of crystalline regions arranged in a

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random manner
• When nylon is spun into fibres and is drawn
• the crystalline regions are aligned
• leads to an increase in the tensile strength

Non-aligned
crystalline region

Aligned
crystalline
region
In the stretched or drawn nylon, the polymer chains line up and are parallel to
each other. The amide groups on adjacent chains form strong hydrogen
bonds with each other
These hydrogen bonds hold the adjacent chains together making nylon thread
strong

The structure of Kevlar is basically the same as nylon-6,6

When molten Kevlar is spun into fibres, the polymer has a crystalline
arrangement and the polymer chains oriented parallel to each other

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• Kevlar is much stronger than nylon

• The difference in their strength is due to
the orientation of the amide groups along the polymer chains
• In nylon, between the amide groups are the carbon chains the  C = O
and  N  H groups can be on opposite sides or on the same side
• When the  C = O and  N  H groups are on the same side, the
polymer chain would not be straight and the number of hydrogen bonds
formed between adjacent chains would be less
• Kevlar has a regular structure
the polymer chains interlock with each other
Kevlar fibres are very strong
used for making reinforced rubbers and bullet-proof vests

Vulcanization of Polymers
Natural rubber is a polymer of the monomer
2-methylbuta-1,3-diene (isoprene)

2-Methylbuta-1,3-diene

• Poly(2-methylbuta-1,3-diene) or polyisoprene can exist in two isomeric

forms
• Natural rubber is the cis-form

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Part of a polymer chain of natural rubber

Natural rubber is not a useful polymer because it is too soft and too
chemically reactive. The long chain molecules can be coiled twisted and
interwined with one another

Vulcanization of natural rubber is the chemical process that confers cross-

linkage among the polymer chains of rubber, turning natural rubber into a
flexible elastic material.

• In the process of vulcanization,1–3 % by mass of sulphur is added

to natural rubber and the mixture is heated
• Short chains of sulphur atoms (i.e. cross-linkages) are formed between
the polymer chains
• The sulphur changes rubber into a thermosetting polymer by cross
linking the polymer chains through reaction at some of the double
bonds as shown:

This makes the rubber harder and reduces its susceptibility to oxidation or
other chemical attrack.
• When vulcanized rubber gets hot, the polymer chains cannot slip
across one another since they are still held together by short chains of
sulphur atoms
• That is why vulcanized rubber does not melt when heated and does not
become brittle when cooled

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The extent of the cross-linkages formed between the polymer chains affects
the properties of vulcanized rubber
• If the rubber has few cross-linkages, the rubber is softer, more flexible
and more elastic
• If the rubber has many cross-linkages, it is stiffer, less flexible and less
elastic
• Car tyres are made of vulcanized rubber
• Because of the presence of cross-linkages among the polymer chains,
the rubber does not melt when it gets hot
• That is the reason why car tyres do not melt when drivers drive really
fast

Car tyres are made of vulcanized

rubber

Degradable Plastics
• Natural polymers (e.g. wood and paper) are
biodegradable Micro-organisms in water and in the
soil use them as food
• Synthetic polymers (e.g. plastics) are non-
biodegradable can remain in the environment for a
very long time
• Nowadays, plastic waste constitutes about 7 % of
household waste
• In Hong Kong, plastic waste is buried in landfill sites
it remains unchanged for decades
more and more landfill sites have to be found
Uses of plastics in Hong Kong (an approximation)
(a) Hong Kong is a highly densely populated city
(b) The volume of domestic waste generated daily is very great.
(c) Plastic waste contributes to the main bulk of our domestic waste.
(d) Few sites are left to be used for landfill
(e) The building / operation cost of incineration plants is high and recycling
of plastics also involves very tedious procedures.

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Chemistry in Action (Polymers)

In order to tackle the pollution problems caused by the disposal of plastic

waste, degradable plastics have been invented

Several types of degradable plastics:

• biopolymers
• photodegradable plastics
• synthetic biodegradable plastics

1. Biopolymers
• Polymers made by living micro-organisms (e.g. paracoccus, bacillus
and spirullum)
• e.g. The biopolymer poly(3-hydroxybutanoic acid) (PHB) is made by
certain bacteria from glucose
• When PHB is disposed, the micro-organisms found in the soil and
natural water sources are able to break it down within 9 months
• However, PHB is 15 times more expensive than polyethene

(a) Paracoccus (b) Bacillus

(c) Spirullum

2. Photodegradable Plastics
• Photodegradable plastics have light-sensitive functional groups (e.g.
carbonyl groups) incorporated into their polymer chains
• These groups will absorb sunlight use the energy to break the chemical
bonds in the polymer to form small fragments

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Chemistry in Action (Polymers)

3. Synthetic Biodegradable Plastics

• Made by incorporating starch or cellulose into the polymers during
production
Micro-organisms consume starch or cellulose and the plastics are broken
down into small pieces
• The very small pieces left have a large surface area greatly speeds up
their biodegradation

• Drawbacks of this method:

• the products of biodegradation may cause water pollution
• the rate of biodegradation is still too low for the large quantity of
plastic waste generated
• They are much more expensive than ordinary materials.
• When buried in landfill, they will not be exposed to sunlight light
and may therefore remain unchanged for many years.
• Their long term effects on the environment are unknown of any
residues.
• They may encourage a ‘throwaway is OK’ culture.
• They interfere with the present recycle program.

END

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