Rubber Materials and Processing

Technology
Historical
Historically natural rubber as a material was known to and used
by men as early as the 6th century. Rubber is a product of
American. Columbus on his voice to America found the native
of West indies playing games with rubber ball, made from the
resin of a tree and introduce it to Europe after his return in
1946. Joseph priesetly, the discoverer of oxygen, credited with
introducing the word “Rubber” as he observed the ability of
material to “rub out” a lead pencil mark. Charles Good year
hardened a mixture of rubber and sulphur by heating. It
improves the properties of rubber and made it more useful.
The term “vulcanization” was assigned to this process by
Thomas Hamcock in 1843. Dunlop in 1888 made and patented
pneumatic rubber tires which were filled with air.
The major classes of rubbers are: Natural rubber: natural
rubber is a natural product, and is found in juices of many
plants such as Goldenord , Russian dandelion, Milk wood etc,
but the principal sources is Heveabrasiliensis tree.
Synthetic rubber: various synthetic robots are produced
synthetically, viz Buna-S, Neoprene, Poly- isobutylene. Rubber
like plastics: The third category,i.e., rubber like plastic (also
known as elastomers) do have rubber like properties but the

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basic structure is different. This category includes silicones,
plasticized polyvinyl, polyethylene, flexible polyesters etc.

Rubber Plants
Natural rubber of nearly same characteristics, occurs in the
inner bark and to a lesser extend in the leaves and root of more
than 500 tropical plants, but none has proves to be as
successful as the Latex from the tree HeveaBrasilensis, a native
American. 90% of the supply is derived from the tree
HeveaBrasilensis. Sir Henry Wickham smuggled about 70,000
seeds of this tree from Brazil as its export was prohibited.
About 90% of these seeds became sterilized. A part of it was
sent to Ceylon which latter on extended to Malay, Netherlands,
East Indies, and other part of south east Asia. Forest of rubber
trees also found in Amazon Valley, Central America and Africa.
The plant yield milky suspension of crude rubber is called
"Latex". The bully tree of America gives "Balata". The
guttaparcha of south east Asia yields "Guttaparcha" and the
guayule tree of Mexico and California forms "Guaylue" rubbers.
In Russia it is known as "Kok- saghir". The improved plant has
been found to contain about 12% rubber and the yield is about
600 kg per hectare, where as Hevea rubber yield is about
450kg/hecktare.
Latex
Latex is an emulsion of polyhydrocarbon droplets in an aqueous
solution, i.e., it is a colloidal dispersion of negatively charged

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particles of rubber (about 1-2u in diameter) and looks like milk.
The charge on the rubber particles stabilizes the emulsion. The
percentage of rubber in it is 25-35%. Latex is collected by
tapping the tree in such a manner as to allow the liquid to be
accumulated in small cups, which must be collected frequently
to avoid putrefaction, or contamination. A full grown hevea
tree gives about 5gms of rubber in a day and about 1.75 kg per
year. The latex has the following average composition:
Water 60%
Rubber hydrocarbon 35%
Protiens, enzymes and nucliec 3%
acid
Fatty acids and esters 1%
Inorganic salts 1%

Coagulation of Rubbers:

Refining of crude Rubber

1. Breakdown
2. Compounding

The following compounding agents are usually employed:

Reinforcing agents
Innert Fillers

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Softeners and Extenders
Agresistore or Antioxidents
Colour and pigments
Vulcanising agents
Accelerators
Activators
Peptizers

Pure rubber is useless as pure gold. The desired properties of

plasticity, elasticity, toughness, hardness, softness, abrasion
resistance, impermeability etc achieve by the process of
compounding, which consists of the above processes.
Chemical Nature of Natural Rubber hydrocarbon

Physical Properties of Rubber

Natural rubber is an amorphous solid in soluble in water,

acetone, and methanol, but soluble in turpentine, petrol, ether,
carbon disulphide and benzene. The colour of freshly
coagulated rubber is brownish to white. It is elastic and
elasticity greatly increases after vulcanization. However, it
becomes a hard solid called ebonite, when vulcanized with
about 30-35% sulphur. Natural rubber slowly swells up by
impregnating the solvent and then form viscous and sticky
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solution. The molecular weight of rubber varies from 1.30,000 -
3,40,000.
Chemical Properties of Rubber

Natural rubber slowly oxidises on exposure to air. When heated

in air it softens and then burns to form CO2 and water. When it
destructive distillation is carried out at high temperature, it
produces the dimer of isoprene and when destructive
distillation is carried out at low temperature, the product
contains two liquids, i.e., isoprene and dimer of isoprene. On
heating the rubber at very high temperature, a liquid known as
"Oil of rubber" is obtained. The rubber powder reacts with
hydrogen gas in presence of catalyst to form fully saturated
hydrocarbon (C5H10)n known as "hydro rubber".
Rubber Reclaiming
Rubber reclaiming is a process by which vulcanized rubber is
treated to produce a plasticized vulcanizable product, retaining
the original dispersed ingredients, and capable of being mixed
and co-vulcanized with natural rubber, styrene butadiene
rubber, or polybutadiene. Reclaimed rubber has been an
effective and versatile source of rubber hydrocarbon for the
compounder for almost as long as the vulcanization process has
been known. Its characteristics have remained constant despite
the continuing change and variations that take place in the raw
materials forming the base.

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As compared to new rubber the price of reclaimed rubber is
quite low. First quality whole tyre reclaimed contains 50% oof
rubber hydrocarbon by weight and non-rubber component
consist of valuable softeners, zinc oxide, antioxidant and carbon
black.
Reclaiming process

Reclaimed rubber is produced by treating scrap vulcanized

rubber with devulcanizing agents and plasticizers under
pressure and heat, simultaneously or subsequently working the
material mechanically. Devulcanization agents or active agents
include xylylmercaptan, dixylyldisulphide, dodecyl mercaptan,
tail oil derivatives, pine tar, coal-tar, etc.

There are five important methods of processes for reclaiming

vulcanized scrap rubber:
1. Digestor
2. Heater or pan
3. High pressure steam
4. Lancaster-Banbury
5. Reclaimator
This is the main process for the manufacture of reclaimed
rubber in the present day. This is the wet process using coarsely
ground scrap, in which the fibre is chemically decomposed and
washed away. Scratch tyres or big truck tyres are cur down to
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size on a splitter which cut the tyre in half longitudinally. The
ground scrap is then passed under a magnetic separator for
removal of ferrous metal which may have been picked up in the
tyre service.

Weight scrape about (2 tons) is mixed with water and

reclaiming and defibering agents, the whole being dumped into
the digester which is a steam jacketed, agitator equipped
autoclave. If a kg/cm² (200°C) steam is used in the jacket, the
digestion time is 8-12h, during which the rubber becomes
devulcanized and the fibre becomes hydrolyzed (the
temperature range for the digester process is 170-210°C and
time is 5-24h) Reclaiming agents are naval stores, petroleum
and coal-tarbased oils and resin, as well as various chemical
softeners, defibering agents are chiefly caustic soda and zinc
and calcium chlorides.
Rubber Reclaiming
Rubber reclaiming is a process by which vulcanized rubber is
treated to produce a plasticized vulcanizable product, retaining
the original dispersed ingredients, and capable of being mixed
and co-vulcanized with natural rubber, styrene butadiene
rubber, or polybutadiene. Reclaimed rubber has been an
effective and versatile source of rubber hydrocarbon for the
compounder for almost as long as the vulcanization process has
been known. Its characteristics have remained constant despite

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the continuing change and variations that take place in the raw
materials forming the base.
Synthetic Rubber
Synthetic high polymer processing either the same or similar
physical properties as that of natural rubber are called synthetic
rubber. Usually synthetic rubber is an improvement over
natural rubber, specially with respect to its resistance to oils,
gas, solvent, etc. Synthetic Rubber has been produced by the
polymerization of a large number of conjugated dienes
resembling to that of isoprene. The polymers of butadiene in
presence of sodium is known as Buna rubber (German name
"Bu" from butadiene and "na" from the symbol of sodium, Na).
American made Styrene-Butadiene rubber (SBR) usually known
as GRS (Government Rubber Synthetic). Buna S or SBR is far
superior to Buna rubber and is made by emulsion
copolymerization of butadiene and styrene.

According to the temperature of the reaction, two process has

been developed, the hot process (50°C) and the cold process
(about 5°C). At the present time about 75% of the total
production is carried out by the cold process, because of the
formation of better and good quality rubber by lowering the
reaction temperature. In cold process, free radical catalyst,
such as benzoyl peroxide, sodium persulphate, etc is used.
Common types of rubbers are:

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1. GRS: It is a copolymer of styrene and butadiene shows
properties similar to natural rubber than any other synthetic
rubber. It has good heat and abrasion resistance but poor oil
resistance.
2. Nitrile (Buna N) rubber: This is polymer of butadiene and
acrylonitrile having excellent resistance to abrasion, oil and
solvents. This hen incorporated in phenolics (produces very
versatile rubber phenols).
3. Neoprene: This is polymer of chloro-butadiene and depends
upon polymerization rather than vulcanization for its
properties. This has excellent resistance to ozone, oils, sunlight,
heat and good mechanical properties.
4. Butyl rubber: This is a copolymer of isobutylene and isoprene
or butadiene and shows good resistance to oils. It has excellent
resistance to strong acid and is therefore used for lining acid
storage tanks.
5. Polysulphides (Thiokols): These are copolymer of sodium
polysulphides and ethylene dichloride or dichloroethyl ether).
These are resistance to wide range of solvents, ozone, sunlight
and aging.

6. Plyisobutylene (Vistanex): This is a polymer of isobutylene

which can be produced from soft sticky gums to tough elastic
solid. This product has excellent resistance to acids or alkalies.
This is mostly used along with other synthetic.
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Uses: It has a good heat, weathering, ozone, solvent and
abrasion resistance than natural rubber. It is used in the
production of tyres. It is also used flooring, belting, hose, shoe
soles, coated fabric etc.
Styrene Butadiene Rubber (SBR)
Raw materials. Styrene, butadienes, activaton, oil, antioxidant.

Reaction.

Process Description

A typical flow diagram has been shown in Fig. 5.3 for producing
butadiene- styrene rubber starting from butadiene and styrene.
Butadiene and styrene in the ratio of 75:25 with amount of
activators are fed to a polymerization reactor. The advantage of
emulsion polymerization is taken here with a vigorous stirring
of monomers inside the reactors. Temperature for hot rubber
production is maintained at 50°C. At this temperature,
conversion to polymer of 56 per cent per hour occurs. A
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sufficient time of polymerization is given to obtain the desired
degree of conversion to polymer. Short stop is then added and
the latex is charged into a blowdown tank where it is warmed
by the addition of steam and the unreacted butadiene is
flashed off. The product from butadiene flash tank is then fed
to styrene stripper where the remaining styrene is stripped off
by the addition of heat to stripper. The bottom product of the
styrene stripper is then blended with oil, coagulated, filtered,
dried and baled to get the finished SBR.

The monomer free emulsion is blended with compounding

ingredients in blending tanks. The latex is coagulated to rubber
'crumbs' which are worked to remove catalyst and emulsifying
agents and crumbs are dried by hot air in continuous belt
dryers and then pressed into bales.

For producing the cold rubber the polymerization reactors are

maintained at 5°C where 60 per cent conversion to polymer
occurs in about 12-15 hours. The use of redox catalysts more
than offsets the decrease in reaction rates (because of low
temperature). The former processes were batch but now
continuous processes are used for the purpose.

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It should be noted that cold process differ from hot process in
the preparation of latex only. Compounding and vulcanization

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are done as in the same case of natural rubber. In cold process
the chain length of the copolymer is less than in hot process.
Hence, rubber obtained from cold process is more elastic, less
hard and more resilience.

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