NATURAL RUBBER

Rubber trees are grown in tropical and semitropical countries such as Indonesia, Malaysia, Sri
Lanka, South America and southern parts of India (Kerala, Tamil Nadu, Karnatka etc), etc. On making
a cut in the bark of the rubber tree, a white viscous fluid exudes which is known as latex. Latex is a
colloidal solution of rubber particles (30-40%). So, natural rubber can be obtained from latex by coagulation
process. For this we add some electrolyte solution to the latex. Commonly used coagulating agent is
dilute acetic acid. The solid obtained is pressed with the help of rollers to make rubber sheets.
Structure. In terms of chemistry natural rubber is a polymer of 2-methyl-1, 3-butadiene. The
monomer which is also known as isoprene undergoes 1,4-additon polymerization to give natural rubber.
The polymerization is shown below:
CH3
n CH2

CH3
CH

CH2

Polymerization

CH2

Isoprene
(2-Methyl-1,3-butadiene)

CH

CH2

Polyisoprene
(Natural rubber)

From the structure it is clear that the polymer contains double bonds capable of showing geometrical
isomerism. So, we can have more than one type of natural rubbers due to cis- or trans orientation across
the double bonds. Since each repeating unit in polyisoprene contains a double bond, it may have either all
cis or all trans or alternate cis and trans or randam cis and trans orientation. Natural rubber obtained
from rubber tree polyisoprene having cis-orientation across all double bonds. On the other hand
synthetically prepared polymer of isoprene has trans-orientation across all double bonds and is known as
gutta percha.

H2C
H3C

CH2
H

H3C

H3C

H
CH2

CH2

CH2

cisPolyisoprene
(Natural rubber)

H3C
H2C

H
C

CH2

CH2
H

transPolyisoprene
(Gutta Percha)

H2C
H3C

H2C
H3C

CH2
H

H
CH2

VULCANIZED RUBBER
Natural rubber is soft, elastic and tacky material. It has a coiled structure rather than having a
straight chain structure. On applying deforming force it gets streched like a spring and regains its
original structure when deforming forces are removed. This explains the elasticity of the natural rubber.
Other properties include a large water absorption capacity, low tensile strength, resistance to abrasion,
not-resistant to the action of organic solvents and attack by oxidising agents. The temperature range for
which it maintains its elasticity is 283-335 K. It can not be used for making articles below 283 K and
above 335 K. Because it becomes brittle below 283 K and becomes sticky above 335 K.

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B.Sc. I (IInd Semester)

Absence of polar groups/substituents in natural rubber are responsible for lowers intermolecular
forces of attraction which are weak van dar Waals interactions. Since the orientation at each double
bond is cis, this means the molecules do not fit closely so the forces of interaction are further weakened.
On the basis of above properties we can easily see that natural rubber has limited uses. In order to
improve properties of natural rubber like elasticity, tensile strength etc. many attempts were made.
Charles Goodyear in 1839 added sulphur at 373 415 K to natural rubber which improved many of its
properties. This process of adding sulphur to natural rubber for improving its properties is called
vulcanization and the rubber obtained is called vulcanized rubber.
Added sulphur forms disulphide linkages (cross-links between polymeric chains) through their
reactive allylic positions as shown below.
S

S
S

Stretched
S

S
S

Relaxed

S
S

CH3
CH

CH2

S
CH

CH3
C

CH

CH

CH3
CH

CH2

CH2

CH

CH2

CH

CH2

S
CH

CH

CH2

CH

CH

CH

C
(A) In vulcanized rubber, the polymer chains are held together by polysulphide bridges or cross links,
(B) When the strecthing force is applied, the chains can straigthen out but they cannot slip past each
other because of polysulphide bridges. When the stretching force is withdrawn, the chains tend to coil
up again and the rubber returns to its original shape, (C) Sulphur cross links at reactive allylic sites.

The vulcanization increases tensile strength, hardness, modulus of elasticity, reduces water absorption
tendency and increases resistant to the action of organic solvents and oxidising agents. The improvement
of properties depends the amount of sulphur added. For example, rubber, used for making tyres, has 5%
suphur, ebonite has 20-25% sulphur, and battery case rubber has 30% suphur. It should be noted that
vulcanization (direct addition of sulphur) is slow. Hence, now a days, we use substances like zinc oxide
(ZnO), 2-mercaptobenzothiazole, 2, 2'-dithiobisbenzothiazole, tetramethylthiuram disulphite etc. as
additives for vulcanization.

N
SH

2-mercaptobenzothiazole

n
2, 2'-dithiobisbenzothiazole

H3C

N
CH3

S
S

N
CH3

Tetramethylthiuram disulphite

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CH3