Rubber

Natural Rubber Synthetic Rubber

Classification of rubbers:
According to sources, there are two types of rubber, i.e.
natural and synthetic rubbers.
The process of vulcanization can divide rubber into two
types:
➢ Vulcanizable Rubber: i. Diene rubbers and ii. Nondiene
rubbers
➢ Non-vulcanizable Rubber.
 Monomers, polymers and coplymers of rubbers

H2C CH 2 CH 2 CH 2 CH 2
CH 2 C CH CH 2 C C C C
H3C HH3C H n
CH 3
NR, RI
Isprene, Hevea Latex
H2C CH 2 CH 2 CH 2
CH 2 CH CH CH 2 C C C C n
Butadiene H H H H
BR
CH CH 2
CH 2 C CH CH 2 +
H H
CH 2 C C CH 2 CH 2 C
H H
Styrene + butadiene
SBR
 C H H
C H 2 C H C H C H 2
+ H 2 C C H 2 C C C H 2 C H 2 C
H H
B u ta d ie n e + a c r y lo n itr ile C N N B R C N

H H 2
C H 2
C C H C H 2 C H 2 C C C
H
C l C l C R
C h lo r o p r e n e

H 3 C
H 2 H 2 H 2
C C H 2 + C H 2
C C H C H 2 C C C C C H C
H 3 C I I R
I s o b u ty le n e + is o p r e n e C H 3
C H 3

H 2
H C C H + N a S 4 C H 2 C S S T h io k o l A

C l C l S S
E th y le n e d ic h lo r id e + s o d iu m te tr a s u lf id e

O H S i O S i O H O H S i O S i O S i O

D im e th y ls ilo x a n e S ilic o n e r u b b e r
Properties and importance of rubber:
Rubber has certain properties, which make it very useful.
• First and the foremost is elasticity or rubberiness. On an
account of this property a rubber band can be stretched to
nine to ten times its original length.
• Flexibility, which gives rubber a great importance. Rubber
sheet is almost flexible as a piece of cloth.
• Rubber is highly impermeable to both water and air. So it
can be used to hold water or to keep water out. It can also
be used to contain air and other gases or to keep these out.
• Rubber shows a great resistance to cutting, tearing and
abrasion over a wide range of temperature (-50oF to
250oF)
• Atmosphere and many chemicals also have no corrosive
effect on rubber. No changes are noted with addition of
alcohol, ether, ketones, esters and hydrocarbon oils, all
of that are inactive with rubber.
• Another great quality of rubber is that all its important
properties such as hardness, strength, abrasion,
resistance etc can be modified to the desired extent by
compounding techniques.
• The plasticity of rubber makes it pliable and amiable to all the
manufacturing process. The plasticity increases with temperature,
so the rubber stock can be sheeted on a calendar, extruded through
a tube machine or molded in mould.

• Another unique quality of uncured natural rubber is its tackiness,

that is, when two fresh surfaces of milled rubber are pressed
together they coalesce to form a single piece. This tack makes the
manufacturing of composite articles, such as tire, from separate
pieces very simple.

• When rubber is stretched or otherwise deformed and held in this

condition, it becomes warm and heat is evolved. This heat comes
from two sources: The Joule effect and Hysteresis.
The Joule effect is simply an entropy effect similar to the
compression and release of gas. When the rubber stretched the
molecules change from a condition of complete disorder due to
thermal vibration to one of partial order that is they line up beside
one another and the energy present in the thermal vibrations escapes
in the form of heat.
Hysteresis is a frictional effect caused by rubber molecules rubbing
against one another, which causes an irreversible loss of mechanical
energy in the form of heat. Frictional heat causes the temperature
rise in tire or in rubber.
Collection of latex:
➢ Rubber is found in the rubber tree as an aqueous milky juice called latex.
Preparation of rubber:
➢ Latex from tree contains 30 to 35% of rubber particles.
➢ Sodium bi-sulphate may be added to prevent discoloration by
enzymatic action and oxidation products.
➢ As the particles carry negative charges, which keep them from
coalescing, it is necessary to add dilute formic or acetic acid to
bring about coagulation.
➢ It is then passed through three or four sets of rollers and the
sheets are hung up to dry in well ventilated corrugated iron sheets
for 10 to 12 days.
➢ The dried sheet has a crinkled surface a pale yellow color and is
sold as pale creep.
Chemical composition of natural rubber latex:
The dry rubber content is determined by coagulating a
weighted amount of latex with acetic acid, warming the
mixture, gently washing the coagulum, drying and
weighting it. The chemical composition of natural rubber
latex are as follows:

Contents % Contents %

Water 55 Liqids, Amino acids 0.2

Rubber Hydrocarbon 35 Quebrachitol 1.0

Proteins 4.5 Inorganic salts 0.4

Acetone extracts 3.9

Chemical constitution of Natural Rubber:
The unit which is repeating in the rubber is C5H8 group. The
constitution of this repeating unit is cis-1,4-isoprene. So the empirical
formula of rubber is (C5H8). The molecular formula of rubber is (C5H8)
x, where x may vary from 10000-20000. The molecular weight of
natural rubber varies over 250000 to about 750000.
Chemical Reaction of Natural Rubber:
Rubber can be hydrogenated at high temperature and pressure using
platinum blacks catalyst. Hydrogenated rubber is transparent material
which is non-elastic.
Rubber reacts with halogen. Chlorinated rubber is produced by the
reaction of chlorine with rubber. Chlorinated rubber is used widely in
acid and alkali resistant paints and varnished adhesives. It is inelastic
amorphous white powder. Hydrochloric acid reacts with rubber to
yield rubber hydrochloride ((C5H8.HC1)x.
Oxidizing agents such as nitric acid, peroxybenzoic acid, other
peroxides and permangate oxidize Rubber: By the oxidation of rubber,
first unstable peroxide of rubber is formed which is transformed into a
stable oxide.
By heating rubber with 1% of an organic sulphonychloride or an
organic sulphonic acid at 125-130 oC, it is converted into a tough
thermoplastic resin.
Vulcanization:
Vulcanization is the process of combining rubber and sulfur under
the influence of heat and pressure to change the rubber to elastic,
strong, non-plastic and non-tacky material. The change of properties
by vulcanization are due to the physico-chemical change of raw
rubber resulting from the cross linking of unsaturated hydrocarbon
chain of rubber with sulfur.
Natural rubber is a cis-1, 4-poly isoprene. The long chain poly
isoprene molecules have some free atom of rotation about the single
carbon-carbon bonds and can assume many conformations. The
chains may be coiled, twisted, intertwined. Rubber can be extended
as much as 500 to 1000%. The extensibility is due to straightening of
coiled chains as shown in the following scratches.
When rubber is vulcanized some of the sulfur atoms react with poly
isoprene chains to produce across linked structure. These cross
links reduce the extensibility of rubber and make it harder. So the
hardness of vulcanized rubber depends upon the % of sulfur
incorporated with rubber. The amount of incorporated sulfur vary 1-
5% of rubber for ordinary soft rubber and 40-50% for hard rubber. The
chemical reagents that are used for vulcanizing are: sulfur, sulfur
mono chloride, selenium, Tellurium, thorium disulfides, poly sulfide
polymers, Alkyl phenol sulfides.
Inert Fillers:
Large amount of inert fillings materials may be added to rubber. Some merely
serve to harden or to dilute the mixture. Clays, Calcium carbonate, Crushed coal,
almost any finely divided solid-can be added to rubber, usually with a reduction in
all tensile properties but with a desirable cost reduction.
Reinforcing agents:
Some finely divided amorphous materials, notably carbon blacks and silica
unexpectedly greatly increase the strength, resilience, abrasion, resistance and
other desirable properties are known as reinforcing agents.
Pigments:
Pigments are finely divided powders which are used in rubber to improve
properties, to lower the cost. There are many colour pigments which are used
solely for color. The important pigments are: carbon black, zinc oxide, calcium
carbonate, titanium oxide (white), ferric oxide (red), antimony sulfide (crimson),
chromium trioxide (green), lead chromate (yellow), zinc sulfide (white), the effect
of the pigments depend on size of the particle, the shape of the particle, the
chemical nature of the surface and the degree of the dispersion in the rubber.
Types and uses of Synthetic Rubber
Various types of rubbers have been synthesized since the invention of
synthetic rubber. Given below are some of the common types of synthetic
rubbers that are used in different industries.

•Polychloroprene (CR): It is also commonly known as ‘neoprene’ and

shows a greater resistance to heat along with better chemical stability.
Owing to these properties, it is used in laptop sleeves, gaskets, fan belts
of automobiles, and hoses.

•Styrene-Butadiene (SBR): This rubber shows better resistance to

abrasion as well as wear and tear, and is hence used in tires, mainly of
buses and aircraft. It is also used in conveyor belts and the soles of
shoes.
▪ Ethylene Propylene Diene Monomer (EPDM): Along with heat and
weather, this rubber shows good resistance to various chemicals. It is
used in the heat collectors present in solar panels, mechanical
vibrators, electrical insulation, and radiators.

▪ Acrylonitrile Butadiene (NBR): It shows better resistance to

chemicals. This makes it useful in the production of lab gloves and oil
seals. It is also used in synthetic leather, V belts, and O rings.

▪ Polysiloxane (SI): It provides electrical insulation, and has low

chemical and thermal conductivity. Also known as silicone rubber, it is
used in coatings, as a sealant, and to make molds like the ones used
in dentistry.
▪ Chloro Isobutylene Isoprene (CIIR): It has good physical properties,
and shows resistance to heat and weathering. It is used as an
additive in oils and fuels. It is also used in the manufacturing of
various sports goods, and chewing gum as well.
▪ Chlorosulphonated Polyethylene (CSM): Along with resistance to
chemicals and temperature, this rubber also is resistant to UV light. It
is used in coating as well roofing materials, and foldable kayaks.

▪ Perfluoroelastomer (FFKM): This rubber has good resistance to

chemicals and temperature. It is used in the fabrication of silicon
wafers. It is also used in chemical processing and high-pressure
seals.
▪ Thermoplastic Polyether-ester (YBPO): This rubber has high
flexibility, and shows good resistance to chemicals. It is used as
buffers, and in the production of belts and moldings.
Silicone rubber
Silicone rubber is a durable & highly-resistant elastomer (rubber-like
material) composed of silicone (polymer) containing silicon together with
other molecule like carbon, hydrogen and oxygen. Its structure always
comprises siloxane backbone (silicon-oxygen chain) and an organic
moiety bound to the silicon.
Hence, the properties of silicone rubber can vary greatly depending on
the:
Organic groups (methyl, vinyl, phenyl, trifluoropropyl or other groups)
•Chemical structure
•As compared to organic rubber, silicone rubber has Si-O bond in its structure, and
hence, it has better:
Heat resistance
•Chemical stability
•Electrical insulation
•Abrasion resistance
•Weather ability as well as Ozone resistance

Silicone rubbers can withstand temperature ranging from -50°C to 350°C (depends in
duration of exposure). Parts made of silicone rubber when exposed to wind, rain and
UV rays for long periods result in virtually no change in physical properties. Unlike
most organic rubbers, silicone rubber is not affected by ozone as well.

Silicone Rubber’s special features, are hence, originated from its unique
molecular structure that they can carry both inorganic and organic properties
With these unique characteristics, silicone rubber is widely used in
industries such as aerospace, automotive, construction, medical, food
processing etc.

Overall silicone rubbers are used various applications as elastomers,

adhesives & sealants, potting, and encapsulating compounds as well as in
coatings, lubricants etc.

Commercial grade Silicone rubbers were first introduced by Dow Corning

(now 100% Dow subsidiary) in 1943. Today, silicone rubbers are
manufactured by several companies.
Different Types & Method Used to Synthesize Silicone Rubbers
•
The organic groups in silicone rubbers may be methyl, vinyl, phenyl or
other groups. According to ASTM D1418 standard, which covers a
system of general classification or nomenclature for rubber and rubber
lattices, silicone rubbers are classified as:

Methyl Group – Also known as dimethylsilicone elastomer/rubber or

simply methyl silicone rubber. It is also referred by MQ.
•Methyl and Phenyl Groups – Also known as methyl-phenylsilicone
elastomer/rubber or phenylsilicone rubber. It is referred as PMQ and it
has excellent low temperature performance
•Methyl and Vinyl Groups – Also known as methylvinylsilicone
elastomer/rubber. It is referred as VMQ as well.
•Methyl, Phenyl and Vinyl Groups – It is referred as PVMQ as well and
known for its excellent low temperature performance.

•Fluoro, Vinyl and Methyl Groups – Also known as fluorinated rubber

or Fluorosilicone rubber. It is referred as FVMQ and they are highly
resistant to chemical attach (fuel, oil, solvent…)

•Apart from its molecular structure, another factor for classifying silicone
rubber are viscosity and method employed for their processing. Silicone
rubber is available in three main forms:

Solid Silicone Rubber or High Temperature Vulcanized, HTV - Solid

silicone rubber contains polymers with a high molecular weight and
relatively long polymer chains. They are available in uncured form and
required traditional rubber processing techniques.
Liquid Silicone Rubber, LSR - Liquid silicone rubber contains
polymers of lower molecular weight and hence shorter chains. It has
better flow properties. It is processed on specially designed injection
molding and extrusion equipment.

Room Temperature Vulcanized, RTV – RTV silicone rubber is a type of

silicone rubber made from one-part (RTV-1) or two-component (RTV-2)
systems where their hardness range of very soft to medium. They are
available for potting, encapsulations, sealants etc.

Liquid Silicone Rubber maintains mechanical properties over a wide

range of temperatures (from -50°C to 250°C). This heat-cured elastomer
provides excellent optical clarity, durability and design freedom. This
innovative transparent material serves diverse applications such as high-
power LED lighting, electronics, automotive lighting and many others.
Method of Synthesis

Overall, silicone rubbers synthesis majorly involves three steps i.e.

preparation of chlorosilanes followed by hydrolysis and then
polymerization yielding silicone elastomers.

Today, silicones are obtained commercially from chlorosilanes prepared

following the direct process of Rochow. The reaction giving chlorosilanes
takes place in a fluidised bed of silicon metal powder in which flows a
stream of methylchloride, usually at temperatures of 250 to 350°C and at
pressures of 1 to 5 bars. A copper-based catalyst is used.