Petrochemical Technology 2022

Rubber Materials & Processing Technology

1. Classify rubber. (19,14) 1.75

The major classes of rubbers are:
Natural rubber: Natural rubber is a natural product, and is
found in juices of many plants such as Goldenrod , Russian
dandelion, Milk wood etc, but the principal sources is
Hevea brasiliensis tree.
Synthetic rubber: Various synthetic rubbers 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 2 basic structure is different. This
category includes silicones, plasticized polyvinyl,
polyethylene, flexible polyesters etc.

2. Discuss about the compounding of rubber. (19,18,14) 3

In order to make the rubber suitable for various uses some
other ingredients are added for improving the quality of
rubber. The process of mixing other ingredients in proper
proportions is known as rubber compounding. For example
to make easy the vulcanisation processes, lime, litharge,
manganese and zinc oxides are used. By adding these
materials not only time required for vulcanization is reduced
but also the rubber quality is improved.

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The various ingredients used for rubber compounding may

be categorised as follows:
(a) Plasticizer
The use of plasticizer for compounding the rubber makes it
softer and plastic. The different plasticizers for the purpose
are: (a) bitumen (asphalt and petroleum residue can also be
used in place of bitumen); (b) stearic acid; (c) cumarone
resins.
(b) Fillers
The fillers are employed for changing the rubber properties
for useful purposes. By the use of fillers the various
properties of rubber viz., hardness, modulous, elongation
specific gravity, resistance to tearing, conductivity, electrical
properties, flammability, resistance to water, solvents and
chemical, aging etc. are improved. Example: zinc oxide, iron
oxide, lithophone, talc , graphite, carbon black etc.
(c) Extenders
The function of extenders is to enable the compound to be
loaded more without the full in the properties. Thus when
extenders are added, this gives a cheaper product with better
processing quality. The materials which are used as rubber
extenders are:

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(i) Reclaimed rubber. It is a mixture of rubber hydrocarbons and

fillers. The advantages of using reclaimed rubber as the
extenders are: low thermoplasticity. fast processing, low heat
development reduced swelling and shrinkage, high rate of care,
good ageing and being cheaper to the compound.
(ii) Factice. The factice is a kind of elastic gum which is made by
reacting certain unsaturated vegetable oils with sulphur.
(iii) Mineral rubber. The mineral rubber is another classical
rubber extender or rubber substitute. At present most mineral
rubbers are simply petroleum asphalts. It gives a product with
only moderately lower tensile and tear strength and with poor
resilience and heat build up on flexing.
(d) Colours and Pigments
In compounding of rubber, mineral colours and pigments are
also important material by the use of which the quality of
rubber is improved. The properties desired for colours and
pigments are: light fastness, resistance to dry heat, cover- ing
power, open steam vulcanisation and low cost. The often used
mineral colours and pigments for the purpose are lithophone,
zinc oxide, titanium oxide, litharge, antimony, sulphide etc.
(e) Accelerators
To get the strength, toughness and high elasticity in the rubber,
it is vulcanised. Vulcanisation is a process which changes the
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properties of rubber. Accelerators increase the rate of

vulcanization. In the different words the accelerators cut down
the cure time for rubber vulcanization. The basic types of
accelerators include:
(a) Aldehyde-amine condensates. (b) Guanidine and
thiocarbanilide.

(f) Antioxidents and Antiaging Ingredients

All rubber-like materials whether natural or synthetic are
subject to deterioration.
Commonly it is seen that rubber tyres and tubes when kept for
long become tacky and soft. Then they again become hard and
then start getting tearing off. The strong, flexible vulcanised
rubber thus becomes hard, brittle and weak and its elasticity is
decreased. This deterioration is known as aging which takes
place due to oxidation of rubber and also due to heat, sunlight,
free sulphur and the presence of some metals. Oxidation
increases the weight of rubber, it is decomposed and peroxide
is formed. The aging occurs also due to presence of some metal
salts e.g., salt of copper, cobalt and manganese.
The ingredients which are used to stop the ageing process are
known as antioxidant although some accelerators reduce aging.
Antioxidants not only stop the deterioration but also help in
other ways. Some required properties of antioxidants are:
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(a) good mixing properties with rubber, (b) Non-interference

during vulcanisa- tion, (c) No colouring of vulcanised rubber, (d)
Non-poisonous, and (e) beneficial effect on the vulcanised
rubber.
The antioxidants commonly used are: (a) wax, (b) phenols, (c)
primary amines-they are colourants and are poisonous, (d)
ammonia phenols and phenol ammonium salt, (e) aldehyde
ammonia, (f) substituted diphenyls, (g) secondary naphthalene
amine, (h) dihydroquinoline and (i) mercapto benze amidazale.
3. Discuss the synthesis of butyl rubber. (19) 4
The production of both isoprene and isobutylene is carried
out through thermal cracking of the natural gas. Or it is
even done through lighter fractions of the gas oil. Under
normal temperature and pressure conditions, physically,
isobutylene is obtained in a gaseous form while isoprene
occurs as a volatile liquid.
To convert isobutylene into butyl rubber, it is stored under
very low temperatures and is further diluted with methyl
chloride. Following this, the addition of isoprene is done in
the presence of aluminium chloride. This initiates the
reaction leading to copolymerization of these elements.
This makes isoprene gain good strength, just like natural
rubber.
Further, the presence of unsaturated groups makes it
resistant to oxidation. In the case of temperature above

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glass transition, butyl rubber exhibits an unusually slow

molecular motion rate.
Reference: https://www.vedantu.com/chemistry/butyl-
rubber
4. Classify synthetic rubbers with examples. (19’,17) 1.75

Reference: (1) (PDF) Sensor-Based Real-Time Detection in

Vulcanization Control Using Machine Learning and Pattern
Clustering (researchgate.net)
5. Mention the properties and uses of natural rubber. (19’)
3
Properties of Natural Rubber:
Some of the unique properties of natural rubber are as
follows:
 Natural rubber combines strong tensile and tears
strength with excellent fatigue resistance.

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 It has great green strength and tack, which means it

can attach to itself as well as other materials, making
fabrication easier.
 One of its disadvantages is that it has a modest
resistance to environmental degradation caused by
heat, light, and ozone.
 Natural rubber adheres well to a brass-plated steel
cable, making it perfect for use in rubber tires.
 It has a low hysteresis, which means it generates less
heat, preserving new tire service integrity and
extending retreadability.
 Natural rubber has a low rolling resistance and
improves fuel efficiency.
 Cutting, chipping, and tearing resistance is excellent.
Uses of Natural Rubber
Some of the uses of natural rubber are as given below:
 Natural rubber is a good water repellent.
 This may be the most effective defence against
infections like the AIDS virus (HIV). Latex is utilized in
surgical and medical examination gloves for this
reason.
 Natural rubber is a great material for springs.
 Catheters, balloons, medical tubes, elastic thread,
and various adhesives all include natural rubber latex.
 It is the only raw material utilized by the car industry,
other than rayon.

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 Rubberwood is a byproduct of natural rubber that is

becoming increasingly important. It serves as a
supply of charcoal for the local community's cooking.
Reference: Natural Rubber and Properties: Types & Uses
(collegedunia.com)

6. Discuss with diagram the production of styrene-

butadiene rubber. (20,19’,17,15) 4
Raw materials. Styrene, butadienes, activators, oil,
antioxidant.
Reaction.

Process Description
A typical flow diagram has been shown in the adjacent
figure 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 5-6 percent per
hour occurs. A 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
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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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Figure 1: Production of SBR

It should be noted that cold process differ from hot

process in the preparation of latex only. Compounding and
vulcanization 13 are done as in the same case of natural
rubber. In cold process the chain length of the copolymer

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is less than in hot process. Hence, rubber obtained from

cold process is more elastic, less hard and more resilience.

7. What are the compositions of Latex? How can you

prepare crude rubber from it? (18) 3
The latex has the following average composition:

Rubber is withdrawn from the plant as white milky

exudate. This is really a suspension of rubber globules in
water. The latex has tendency to coagulate and this is
enhanced by adding formic acid.The water is removed by
pressing rolls and the rubber in the form of sheets is hung
in smoke houses for drying. Thus crude natural rubber is
obtained.

8. Discuss the rubber reclaiming and its importance in

rubber applications. (18) 3
Rubber reclaiming is a process by which vulcanized rubber
is treated to produce a plasticized vulcanizable product,
retaining the original dispersed in gradients, and capable
of being mixed and covulcanized with natural rubber,
styrene butadiene rubber, or stereo regular
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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 its base. Equally
constant are the practical benefits, both technical and
economic, that reclaimed rubber imparts to rubber
compounds of all kinds. These include improved process
efficiencies with re- sultant economic savings beyond
those derived from lower material costs.
Importance of rubber reclaiming in rubber application:
I. Reclaimed Rubber is Sustainable
II. Reclaimed Rubber has Many Uses
Here are just a few out of the hundreds of things
you can do with reused rubber:
 Landscaping companies can use it for mulch.
 Construction crews can minimize the tracking of
debris with trackout control mats.
 Create playgrounds so that children have a safe place
to play.
 Urban planners can use rubber to make parking lots
safer.
 Shoe manufacturers can create more high-quality
shoes.
III. Vulcanized Rubber is Stronger than Standard
Rubber

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IV. Reclaimed Rubber is Cheaper

V. Products you can trust
Reference: Benefits of Reclaimed Rubber - RubberForm Recycled Products
9. Mention the uses of Buna S rubber. (17) 2
Uses of Buna-S rubber:
It is used widely in pneumatic tires in shoe
heels and soles, gaskets and even chewing
gum
It is a commodity material which competes
with natural rubber
It is extensively used in coated papers,
being one of the most cost-effective resins
to bind pigmented coatings.
It is also used in building applications, as a
sealing and binding agent behind renders
as an alternative to PVA,.
Additionally, it is used in some rubber
cutting boards.
Reference: https://blog.oureducation.in/proporties-
and-uses-of-buna-s
10. What is Latex? How can you prepare crude rubber
from it?(16) 2.5
Latex, colloidal suspension, either the milky
white liquid emulsion found in the cells of
certain flowering plants such as the rubber tree (Hevea
brasiliensis) or any of various manufactured water
emulsions consisting of synthetic rubber or plastic.

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Reference: Latex | Definition, Types, & Facts |

Britannica

11. Discuss in detail the refining of crude rubber. (16,14)

3.25
12. Discuss the production of neoprene rubber. (16) 3
Polychloroprene rubber is the first commercial synthetic
made available in the marker in 1935. The commercial
elastomeric polymers and copolymers of chloprene, i.e., 2-
chloro-1,3-butadience, are known in the trade by the
generic term neoprene. Polychloroprene is commercially
produced by emulsion polymerization of chloroprene.

Polychloroprene is produced from chloroprene.

Industrially, chloroprene is manufactured by the addition
of hydrogen chloride to vinyl acetylene. Vinyl acetylene
can be produced by dimerization of acetylene in presence
of cuprous chloride.

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The emulsion polymerization of chloroprene at ordinary

temperature gives neoprene. The polymerization which is
very rapid and follows free radial mechanism.
The liquid chloroprene is mixed with small amount of
pyrogallol in order to stabilized it. The chloroprene is
polymerized at 40°C to form neoprene. The mixture
contains chloroprene 100 parts, wood rosin 4 parts,
sulphur 0.6 parts, NaOH 0.8 parts, potassium persulphate
0.2-1.0 parts, sodium salts of naphthalene sulphonic acid-
formaldehyde condensate 0.7 parts and water 150 parts.
The polymer product is stabilized with tetraethyl thiurium
disulphide. The latex is demulsified by adding acetic acid.
The film is removed, washed with water and dried at
120°C. The spontaneous transformation of linear
neoprene into highly branched and cross-linked is checked
by adding initiotors.
Applications: Oil resistant, insulating coating to wire and
cables, shoe soles, tyres, gloves & industrial hoses.

13. What do you mean by natural and synthetic rubber?

Give examples. (15,20) 2
14. Write a note on the properties and uses of rubber.
(15,20) 2
Properties of rubber:
1. It is elastic; because of this property a rubber band
can be stretched to 9 or 10 times its original length

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and when the load is removed it regains its original

length.
2. It is strong and tough. Because of this property it
can be put to use even under abnormal conditions.
3. It is highly impermeable to both water and air and
therefore, it can be used to retain water as in rubber
bottles, hoses etc.
4. It exhibits a great resistance to abrasion, tearing
and cutting over a wide range of temperature—7 to
115°C.
5. It is a bad conductor of heat.
6. It can contain liquids and gases.
7. The synthetic rubber offers great resistance to
acids, petroleum products etc.
8. Its properties such as hardness, strength, abrasion,
resistance etc., can be modified to the desired extent
by compounding techniques.

Uses of Rubber:
The following are some of the uses of rubber:
1. Thermal insulation
2. Lining of reservoir
3. Rain water and flexible tubing
4. Belting of all types
5. Tyres and tubes
6. Adhesive
7. Hose pipes, printing roller etc.
8. Mounting material
9. As a buffer
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10. Gasketina material.

Reference: Rubber: Properties, Uses and Types |

Engineering (engineeringenotes.com)

15. Discuss vulcanizations of rubbers. (18) 2.75

Vulcanization is the transformation of rubber from a
predominantly plastic state into a predominantly elastic
state. The process of vulcanization consists of intro-
duction of cross links in rubber matrix. It is also defined as
process to harden rubber by the use of sulphur or a
process of treating crude rubber, rubber latex, gutta
percha etc. chemically to improve its strength, hardness
and elasticity etc.

Vulcanization changes compounded rubber from a sticky

plastic mass that melts and freezes easily to a dry elastic
materials with a rather wide tolerance for temperature
changes. Vulcanisation increases the strength
tremendously, decreases the solubility in solvents and
increases the resistance to oxidation. All the changes that
occur during vulcanization can be seen by following
equation:

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Low Tensile High tensible

High retentivity Vulcanization

Low retentivity

Thermoplasticity Non-thermoplastic

Tacky Non-tacky

Unvulcanized Vulcanized

When a mixture of 100 parts of rubber with 5 to 8 parts of

sulphur is heated at 140°C for 3 to 4 hours the vulcanization is
complete.
For reducing the curing time some suitable accelerators are
added. When rubber is mixed with 14 to 18 parts of sulphur
and the mixture is vulcanized a low tensile strength results. If
sulphur content is increased to 30 to 50 percent the rubber
becomes hard with a low elongation and high tensile strength.
The product thus obtained is known as ebonite. Part of the
sulphur which combines with the rubber is known as fixed
sulphur and which does not combine is known as free sulphur.
For producing ebonite the rubber should be mixed with 32 per
cent of sulphur.

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