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A Project Report on

PRODUCTION OF STYRENE BUTADIENE RUBBER

SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIRMENTS FOR THE


AWARD OF THE DEGREE OF

BACHELOR OF TECHNOLOGY

IN

CHEMICAL ENGINEERING
Submitted By

Meenakshi Josyula (146142)


Spandana Langoju (146119)
Swathi Muthyam Bollapally (146242)

Akhil Nambiar (146202)

Under the Guidance of

Dr. A. Seshagiri Rao

Associate Professor

DEPARTMENT OF CHEMICAL ENGINEERING


NATIONAL INSTITUTE OF TECHNOLOGY
WARANGAL-506004 (TELANGANA)
November 2017
DEPARTMENT OF CHEMICAL ENGINEERING NATIONAL
INSTITUTE OF TECHNOLOGY WARANGAL-506004

CERTIFICATE

This is to certify that the project entitled “Production of Styrene Butadiene Rubber”
carried out by Ms. Meenakshi Josyula (146142), Ms. Spandana Langoju (146119), Ms.
Swathi Muthyam Bollapally(146242) and Mr. Akhil Nambiar (146202) of final year B.Tech
Chemical Engineering during the 7th semester of the year 2017-2018 is a bonafide work
submitted to the National Institute of Technology, Warangal in partial fulfillment of
requirements for the award of degree of Bachelor of Technology.

Project Guide Head of the Department

Dr. A. Seshagiri Rao Dr. A. Sarath Babu


Associate Professor Associate Professor
Dept. of Chemical Engineering Dept. Of Chemical Engineering
NIT-Warangal NIT-Warangal
ACKNOWLEDGEMENT

We consider it as a great privilege to express our deep gratitude to many respected


personalities who guided, inspired and helped us in the successful completion of our
project.

First, we would like to express our deepest gratitude to our guide, Dr. A. Seshagiri Rao,
Associate Professor, Department of Chemical Engineering, National Institute of
Technology, Warangal, for his constant supervision, guidance, suggestions and invaluable
encouragement during the project.

We take this opportunity to express our gratitude to Dr. A. Sarath Babu, Head of the
Chemical Engineering Department, for his dedication towards our academics, and for his
valuable suggestions and encouragement.

We wish to thank all the faculty members in the department for their kind cooperation and
support given throughout our project work.

We are also thankful to all of our friends who have given valuable suggestions and help in
all stage of development of the project.

Finally, we would like to dedicate this work to our parents who has provided support and
encouragement during every part of our life.

Meenakshi Josyula
Spandana Langoju
Swathi Muthyam Bollapally

Akhil Nambiar
CONTENTS

CHAPTER 1

Introduction………………………………………………………………….....1

CHAPTER 2

Market Analysis………………………………………………………………...4

CHAPTER 3

Properties of Styrene Butadiene Rubber…………………………………....10


3.1. Mechanical Properties………………………………………………….....10

3.2. Electrical Properties………………………………………………………10

3.3. Resistance to Fluids…………………………………………………….....10

3.4. Cure Properties……………………………………………………………10

3.5. Effect of Processing Parameters on Material Properties …………….…..13

3.5.1. Background…………………………………………………………….13

3.5.2. Effect of Viscosity on Properties of SBR……………………………...13

3.5.3. Effect of Molecular Weight on Properties of SBR…………………….14

3.5.4. Effect of Polymerization Temperature on Properties of SBR…….……14

3.5.5. Effect of Styrene Content on Properties of SBR……………………….14

3.5.6. Effect of Glass Transition Temperature on Properties of SBR………...14

3.5.7. Effect of Emulsifiers On Properties Of SBR…………………………..15

CHAPTER 4

Applications of Styrene Butadiene Rubber………………………………………..16


4.1. Background……………………………………………………………….16

4.2. Applications of Polymerized Styrene Butadiene Rubber…………………16

4.2.1. Tyre Manufacturing……………………………………………………16

4.2.2. SBR Waterproof Bonding……………………………………………...16

4.2.3. Shoe Industry...................................................................................…...17


CHAPTER 5

Production of Styrene Butadiene…………………………………………….19

5.1.Methods of Polymerization…………………………………………….19

5.1.1. Emulsion Polymerization………………………………………………19

5.1.2. Solution Polymerization………………………………………………...21

5.2. Selection of Polymerization……………………………………………..22

5.3. Methods of Production…….................................................................23

5.4. Process Description………………………………………………….23

5.4.1.Production………………………………………………………………23

5.4.2.Monomer recovery……………………………………………………..24

5.4.3.Coagulation and drying………………………………………………...24

5.4.4.Process Flow description………………………………..……………...26


CHAPTER 6

Material Balance………………………………………………………………27
6.1. Assumptions for Material Balance………………………………………27

6.2. Typical Recipe for Cold Emulsion Polymerization……………………...27

6.3. Calculation of Inlet Flow Rates………………………………………….28

6.4. Material Balance across Each Equipment………………………………..30

6.4.1. Mixer…………………………………………………………………...30

6.4.2. Feed Cooler…………………………………………………………….31

6.4.3. SBR Reactor……………………………………………………………32

6.4.4. Butadiene Separation…………………………………………………..33

6.4.5. Styrene Separation……………………………………………………..35

6.4.6. Coagulation, Filter, Dryer……………………………………………...36

6.4.7. Overall Balance ………………………………………………………...38


REFERENCES……………………………………………………………....39
Chapter 1

INTRODUCTION

Rubber, any solid substance that upon vulcanization becomes elastic; the term includes
natural rubber (caoutchouc) and synthetic rubber. The term elastomer is sometimes used to
designate synthetic rubber only and is sometimes extended to include caoutchouc as well.

Natural Rubber, also called India Rubber or caoutchouc, is a thicksotropic visco-elastic


Non-Newtonian material. It's a mixture of organic compound polyisoprene and small amounts
of other organic compounds as well as water. This polymer is the main component. This
material is classified as anelastomer (an elastic polymer). It is derived from latex, a milky
colloid produced by some plants. The plants are ‘tapped’, that is, an incision made into the
bark of the tree and the sticky, milk colored latex sap collected and refined into a usable
rubber. Polyisoprene can also be produced synthetically. Natural rubber is used extensively in
many applications and products, as is synthetic rubber. It is normally very stretchy and
flexible and extremely waterproof.

Synthetic Rubber is any type of artificial elastomer, invariably a polymer. An elastomer is a


material with the mechanical (or material) property that it can undergo much more elastic
deformation under stress than most materials and still return to its previous size without
permanent deformation. About 15 billion kilograms of rubbers are produced annually, and of
that amount two thirds is synthetic.

The more than one dozen major classes of synthetic rubber are made of raw material derived
from petroleum, coal, oil, natural gas, and acetylene. Many of them are copolymers, i.e.,
polymers consisting of more than one monomer. By changing the composition it is possible to
achieve specific properties desired for special applications. The earliest synthetic rubbers were
the styrene-butadiene copolymers, Buna S and SBR, whose properties are closest to those of
natural rubber. SBR is the most commonly used elastomer because of its low cost and good
properties; it is used mainly for tires. Other general purpose elastomers are cis-polybutadiene
and cis-polyisoprene, whose properties are also close to that of natural rubber.

There were a number of reasons responsible for the development of an alternative or


substitute for natural rubber. These included volatile or rising prices for natural rubber on the

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world market in response to the general state of the economy, political events which cut
customers off from the suppliers of raw materials, long transport distances, regional
constraints with respect to establishing rubber plantations and the increase in global demand
for rubber.

Styrene-Butadiene Rubber (SBR), a general-purpose synthetic rubber, produced from a


copolymer of styrene and butadiene. Exceeding all other synthetic in consumption, SBR is
used in great quantities in automobile and truck tires, generally as an abrasion-resistant
replacement for natural rubber (produced from polyisoprene).

SBR is a mixture of approximately 75 percent butadiene (CH 2=CH-CH=CH2) and 25 percent


styrene (CH2=CHC6H5). In most cases these two compounds are copolymerized (their single-
unit molecules linked to form long, multiple-unit molecules) in an emulsion process, in which
a soap like surface-acting agent disperses, or emulsifies, the materials in a water solution.
Other materials in the solution include free-radical initiators, which begin

the polymerization process, and stabilizers, which prevent deterioration of the final product.
Upon polymerization, the styrene and butadiene repeating units are arranged in a random
manner along the polymer chain. The polymer chains are cross-linked in the vulcanization
process.

For many purposes SBR directly replaces natural rubber, the choice depending simply on
economics. Its particular advantages include excellent abrasion resistance, crack resistance,
and generally better aging characteristics. Like natural rubber, SBR is swollen and weakened
by hydrocarbon oils and is degraded over time by atmospheric oxygen and ozone. In SBR,
however, the main effect of oxidation is increased interlinking of the polymer chains, so,
unlike natural rubber, it tends to harden with age instead of softening. The most important
limitations of SBR are poor strength without reinforcement by fillers such as carbon black
(although with carbon black it is quite strong and abrasion-resistant), low resilience, low tear
strength (particularly at high temperatures), and poor tack (i.e., it is not tacky or sticky to the
touch). These characteristics determine the use of the rubber in tire treads; essentially, its
proportions decrease as the need for heat resistance increases until 100 percent natural rubber
is reached in the heaviest and most severe uses, such as tires for buses and aircraft.

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A large amount of SBR is produced in latex form as a rubbery adhesive for use in applications
such as carpet backing. Other applications are in belting, flooring, wire and cable insulation,
and footwear.

SBR is a product of synthetic rubber research that took place in Europe and the United States
under the impetus of natural rubber shortages during World Wars I and II. By 1929 German
chemists IG Farben had developed a series of synthetic elastomers by copolymerizing two
compounds in the presence of a catalyst. This series was called Buna, after butadiene, one of
the copolymers, and sodium (natrium), the polymerization catalyst. During World War II the
United States, cut off from its East Asian supplies of natural rubber, developed a number of
synthetics, including a copolymer of butadiene and styrene. This general-purpose rubber,
which had been called Buna S by German chemists Eduard Tschunkur and Walter Bock, who
had patented it in 1933, was given the wartime designation GR-S (Government Rubber-
Styrene) by the Americans, who improved upon its production. Subsequently known as SBR,
this copolymer soon became the most important synthetic rubber, representing about one-half
of the total world production.

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Chapter 2
MARKET ANALYSIS

Styrene-butadiene elastomers (SBR) are the largest-volume synthetic rubber, accounting for
about 32% of world consumption of synthetic rubber in 2009, according to the International
Institute of Synthetic Rubber Producers. SBR is produced through the copolymerization of
butadiene with styrene at a ratio of about 3:1. In addition, there are two major types of SBR—
emulsion and solution. Emulsion grade continues to lose ground to solution grade, which is
better able to meet the increasingly stringent specifications of high-performance tires. There is
a need worldwide for more solution SBR capacity as demand is outpacing demand for
emulsion-grade.

The tire industry is the dominant consumer of SBR, accounting for 70% of output. Apart from
this, SBR is also used in conveyor belts, industrial hoses, various molded and extruded rubber
goods, footwear and other consumer goods. Some grades of SBR—those that are waterproof
and free from impurities—are also utilized in the cable industry. Protective rubbers resistant
to y-radiation are also SBR-based.

Fig.1 World Consumption of SBR

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As with most of the chemical industry, the market for SBR was hit by the global economic
crisis/recession during 2008/2009. In consequence, demand for essentially all end uses
suffered from the impact of the crisis. Currently, recovery is fastest in China and a few other
Asian countries.

The world’s largest SBR consuming regions were China, the United States, Western Europe,
and Central and Eastern Europe, accounting for two-thirds of total world consumption. China
became the world leader in SBR consumption in 2009, overtaking North America. China’s
vast capacity additions, linked with increased demand in the domestic automobile industry
and high demand for tires, raised its consumption of SBR to the highest in the world. This will
remain true in the forecast period from 2009 to 2014. The world average annual growth rate
for SBR consumption during 2009–2014 is expected to be about 5% as a result of high
demand in regions such as China, India, Central and South America, Central and Eastern
Europe (including Russia), and other Asian countries.

China is expected to drive much of the SBR demand and is the fastest-growing market (based
on volume), at roughly 6% per year during the forecast period. From 2007 to the end of 2009,
China added nearly 400 thousand metric tons of SBR capacity. From 2010 to 2014, China
plans to add another 400 thousand metric tons of SBR capacity. Other countries planning SBR
capacity additions during 2010–2014 include Russia and India. Saudi Arabia has a few
developments that may introduce SBR capacity beyond 2014.

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Fig.2 SBR End Use Consumption

Table1. Capacity of SBR Production

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Table2. Demand and Supply of SBR in INDIA

Fig.3 Global Styrenic Polymers Consumption Growth

Styrene butadiene rubber (SBR) has been growing at similar rates to GDP over the past 10
years. The geographical development however reflects increasing car usage in developing
countries and flat growth in North America and Western Europe. The scale of growth in
developing regions will however overweigh the slowdown in mature markets, and
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consumption will grow at faster rates over 2008-2015 than it has over the past decade. The
popularity of bio fuels has increased the competition for agricultural land, and impacted on
the rubber industry by restricting the availability of land for natural rubber production. SBR
consumption is further supported by increasing usage of energy saving tyres and the trend of
“Radicalization”, both of which favor a higher proportion of synthetic rubber in tyre
compounds.

From the following two pie charts (Fig.4 & Fig.5) it can be noticed that the largest portion of
the monomers, styrene and butadiene goes into the production of Styrene-Butadiene Rubber.
This itself is a proof of the astronomical demand of this rubber in the world market.

About 40% of world styrene production and 32% of world butadiene production goes into the
production of Styrene Butadiene Rubber. This is more than any of their other uses.

Fig.4 Styrene Derivative Demand

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Fig.5 Global Butadiene Consumption Volumes by Application

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Chapter 3

PROPERTIES OF STYRENE BUTADIENE RUBBER

3.1 Mechanical Properties

Since styrene- butadiene rubber lacks the self- reinforcing qualities of natural rubber due to
stress induced crystallization, gum vulcanize of styrene- butadiene rubber have lower tensile
properties. The tensile property of Emulsion polymerized styrene- butadiene rubber
vulcanizates depends in great measure on the type and amount of filler in the compound.
Cured gum stocks have only 2.8 to 4.2 MPa tensile strength, while fine particle carbon black
loadings can produce tensile strength of 27.6 MPa. Though the compression set of some of the
common emulsion polymerized styrene- butadiene rubber compounds is high, by proper
compounding and blending, it is possible to obtain emulsion styrene- butadiene rubber
vulcanizates with a low compression set.

3.2 Electrical Properties

Styrene- butadiene rubber is a non- polar polymer and its vulcanizates are poor conductors of
electricity. The electrical properties of emulsion polymerized styrene- butadiene rubber
depend to a large extent on the amount and type of emulsifier and coagulating agent(s) used.

3.3 Resistance to Fluids

While emulsion polymerized styrene- butadiene rubber vulcanizates are resistant to many
polar solvents such as dilute acids and bases, they will swell considerably when in contact
with gasoline, oils, or fats. Due to this limitation, styrene- butadiene rubber cannot be used in
applications that require resistance to swelling in contact with hydrocarbon solvents.

3.4 Cure Properties

Styrene- butadiene rubber can be cured with a variety of cure systems including sulfur
(accelerators and sulfur), peroxides and phenolic resins. Processing of styrene- butadiene
rubber compounds can be performed in a mill, internal mixers or mixing extruders. Styrene-
butadiene rubber compounds are cured in a variety of ways by compression, injection

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mounding, hot air or steam autoclaves, hot air ovens, microwave ovens and combinations of
these techniques.

SBR or Styrene Butadiene


 Abbreviation SBR
 Chemical Definition Styrene Butadiene

♦ Physical & Mechanical Properties


 Hardness Range 30 – 95 Shore A
 Tensile Strength Range 500 – 3,000 PSI
 Elongation (Range %) 450 % – 600 %
 Abrasion Resistance Excellent
 Adhesion to Metal Excellent
 Adhesion to Rigid Materials Excellent
 Compression Set Good to Excellent
 Flex Cracking Resistance Good
 Impact Resistance Excellent
 Resilience / Rebound Good
 Tear Resistance Fair to Excellent
 Vibration Dampening Fair to Good

♦ Chemical Resistance
 Acids, Dilute Fair to Good
 Acids, Concentrated Poor to Fair
 Acids, Organic (Dilute) Good
 Acids, Organic (Concentrated) Poor to Good
 Acids, Inorganic Fair to Good
 Alcohol’s Good
 Aldehydes Poor to Fair
 Alkalis, Dilute Fair to Good
 Alkalis, Concentrated Fair to Good
 Amines Poor to Good

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 Animal & Vegetable Oils Poor to Good
 Brake Fluids, Non-Petroleum Based Poor to Good
 Diester Oils Poor
 Esters, Alkyl Phosphate Poor
 Esters, Aryl Phosphate Poor
 Ethers Poor
 Fuel, Aliphatic Hydrocarbon Poor
 Fuel, Aromatic Hydrocarbon Poor
 Fuel, Extended (Oxygenated) Poor
 Halogenated Solvents Poor
 Hydrocarbon, Halogenated Poor
 Ketones Poor to Good
 Lacquer Solvents Poor
 LP Gases & Fuel Oils Poor
 Mineral Oils Poor
 Oil Resistance Poor
 Petroleum Aromatic Poor
 Petroleum Non-Aromatic Poor
 Refrigerant Ammonia Good
 Refrigerant Halo fluorocarbons R-12, R-13
 Refrigerant Halo fluorocarbons w/ Oil Poor
 Silicone Oil Poor
 Solvent Resistance Poor

♦ Thermal Properties
 Low Temperature Range - 60º F to - 30º F
 Minimum for Continuous Use (Static) - 60º F
 Brittle Point - 80º F
 High Temperature Range + 210º F to + 250º F
 Maximum for Continuous Use (Static) + 225º F

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♦ Environmental Performance
 Colorability Good
 Flame Resistance Poor
 Gas Permeability Fair
 Odor Good
 Ozone Resistance Poor
 Oxidation Resistance Fair to Excellent
 Radiation Resistance Poor to Good
 Steam Resistance Fair to Good
 Sunlight Resistance Poor
 Taste Retention Fair to Good
 Weather Resistance Fair to Good
 Water Resistance Good to Excellent

3.5 Effect of Processing Parameters on Material Properties

3.5.1 Background

Emulsion polymerized styrene- butadiene rubber (E- SBR) is one of the most widely us
polymers in the world today. Emulsion polymerized styrene- butadiene rubber is employed in
many demanding applications, which enhance the quality of life and contribute significantly
to our economy and standards of living.

3.5.2 Effect of Viscosity on Properties of SBR

Emulsion polymerized styrene- butadiene rubber is commercially available in Mooney


viscosities ranging from 30 to about 120 (ML1+ 4@ 125C). Lower Mooney viscosity
emulsion polymerized styrene- butadiene rubber grades band more easily on the mill,
incorporate fillers and oil more readily, show less heat generation during mixing, are
calendared more easily, shrink less, give higher extrusion rates and have superior extrudate
appearance than the higher Mooney viscosity grades. On the other hand, the high Mooney
viscosity styrene- butadiene rubber’s have better green strength, less porosity in the
vulcanizate, and accept higher filler and oil loadings.

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3.5.3 Effect of Molecular Weight on Properties of SBR

As the molecular weight of the styrene- butadiene rubber increases, the vulcanizate resilience
and the mechanical properties, particularly tensile strength and compression set, improve. The
processability of styrene- butadiene rubber improves as its molecular weight distribution
broadens. Formation of high molecular weight fractions with the increase in the average
molecular weight can however, prevent improvements in the processability. This is due to the
fact that the tendency for gel formation also increases at higher molecular weights.

3.5.4 Effect of Polymerization Temperature on Properties of SBR

In addition to the polymer viscosity, polymerization temperature also plays an important role
in shaping the processability. Emulsion styrene- butadiene rubbers produced at low
polymerization temperatures have less chain branching than those produced at higher
temperature. At an equivalent viscosity, cold polymerized emulsion polymerized styrene-
butadiene rubber is normally easier to process than hot polymerized emulsion polymerized
styrene- butadiene rubber, and this applies particularly to a better banding on mills, less
shrinkage after calendering, and a superior surface of green tire compounds. Hot rubbers give
better green strength because they have more chain branching.

3.5.5 Effect of Styrene Content on Properties of SBR

The styrene content of most emulsion styrene- butadiene rubber varies from 0% to 50%. The
percent styrene of most commercially available grades of emulsion polymerized styrene-
butadiene rubber is 23.5%. In vulcanizates of styrene- butadiene rubber, as styrene content
increases, dynamic properties and abrasion resistance decrease while traction and hardness
increase.

3.5.6 Effect of Glass Transition Temperature (Tg) on Properties of SBR

Polymerization temperature also affects the microstructure of emulsion polymerized styrene-


butadiene rubber. In the cold polymerized emulsion polymerized styrene- butadiene rubbers,
the butadiene component has, on average, about 9% cis- 1.4, 54.5% trans- 1.4, and 13% of
vinyl- 1.2 structure. At a 23.5% bound styrene level, the glass transition temperature, Tg, of
styrene- butadiene rubber is about –50° C. As the styrene content in the styrene- butadiene
rubber increases, the glass transition temperature also increases. Rubbers with very low Tg
values are characterized by a high resilience and good abrasion resistance, but have poor wet

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traction. By contrast, those rubbers with high Tg, as, for instance, styrene- butadiene rubber
1721, exhibit a low resilience and poor abrasion resistance with an excellent wet traction.

3.5.7 Effect of Emulsifiers on Properties of SBR

The emulsifier remains in the rubber after coagulation can also have an influence on the
processability. Rosin acid emulsifiers impart better knitting, tack and adhesion to the styrene-
butadiene rubber polymer. Generally, polymers emulsified with rosin acid have better
extrusion rates, slower cure rates, poorer heat resistance and can cause mould fouling and
polymer discoloration. Fatty acid emulsified styrene- butadiene rubber polymers generally
have less tack, faster curing, and high tensile properties. A compromise of the above
properties is obtained by using a mixed rosin acid/ fatty acid emulsifier system.

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Chapter 4
APPLICATIONS OF STYRENE BUTADIENE RUBBER

4.1 Background

Emulsion polymerized styrene- butadiene rubber (E- SBR) is one of the most widely used
polymers in the world today. Emulsion polymerized styrene- butadiene rubber is employed in
many demanding applications, which enhance the quality of life and contribute significantly
to our economy and standards of living.

4.2 Applications of Polymerized Styrene Butadiene Rubber

E- SBR is predominantly used for the production of car and light truck tires and truck tire
retread compounds. A complete list of the uses of SBR includes houseware mats, drain board
trays, shoe sole and heels, chewing gum, food container sealants, tires, conveyor belts, sponge
articles, adhesives and caulks, automobile mats, brake and

clutch pads, hose, V- belts, flooring, military tank pads, hard rubber battery box cases,
extruded gaskets, rubber toys, moulded rubber goods, shoe soling, cable insulation and
jacketing, pharmaceutical, surgical, and sanitary products, food packaging, etc.

4.2.1 Tyre Manufacturing

Styrene Butadiene Rubbers are uniquely suited for use in tire compounds, from tread to
sidewall to inner body. These synthetic rubbers are used extensively in tire tread compounds,
where inherent hysteresis and abrasion resistance benefits contribute to improved tire
performance. This performance is possible by controlling the polymers' glass transition
temperature through styrene and vinyl adjustments to meet specific tire applications

4.2.2 SBR Waterproof Bonding

SBR is a specially compounded latex mix designed for use with cement based mixes. It is
ideal for producing high abrasion resistant floors and renders, and patching and bonding onto
backgrounds with low suction. When dry the finished mortars or concrete show a vastly
improved resistance to water. It can be used internally or externally where improvements in
the physical properties of Portland cements systems are required.

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4.2.3 Shoe Industry

Styrene-butadiene rubber (SBR) has large applications in the shoe industry, especially as
expanded sheets used to produce insoles and inner soles. According to TG analysis, the rubber
content in SBR residues (SBR-r) was found to be around 26-wt%. Based on that data, a cost-
effective technique for the reuse of SBR-r in Nitrile rubber (NBR) was developed. Later, the
effect of SBR-r on the cure behavior, mechanical performance, swelling, and crosslink density
of reused rubber was investigated, with more emphasis placed on the effect of both particle
size and loading of waste filler. Cure characteristics such as optimum cure time and scorch
time were then reduced by the increasing amount of SBR-r filler. Owing to the reinforced
nature of the largest particle size SBR-r, the best results for the mechanical properties of NBR
were those in which SBR-r was added at the end of the cure process. The study has thus
shown that SBR residue (SBR-r) can be used as an economical alternative filler in NBR.

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Table3. Typical applications of emulsion polymerized styrene butadiene rubber.

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Chapter 5
PRODUCTION OF STYRENE BUTADIENE RUBBER

5.1 Methods of Polymerization

5.1.1 Emulsion Polymerization

Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion
incorporating water, monomer, and surfactant. The most common type of emulsion
polymerization is an oil-in-water emulsion, in which droplets of monomer (the oil) are
emulsified (with surfactants) in a continuous phase of water. Water-soluble polymers, such as
certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as
emulsifiers/stabilizers. The name "emulsion polymerization" is a misnomer that arises from a
historical misconception. Rather than occurring in emulsion droplets, polymerization takes place
in the latex particles that form spontaneously in the first few minutes of the process. These latex
particles are typically 100 nm in size, and are made of many individual polymer chains. The
particles are stopped from coagulating with each other because each particle is surrounded by the
surfactant ('soap'); the charge on the surfactant repels other particles electro statically. When
water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles
arises because these water-soluble polymers form a 'hairy layer' around a particle that repels
other particles, because pushing particles together would involve compressing these chains.

Emulsion polymerization is used to manufacture several commercially important polymers.


Many of these polymers are used as solid materials and must be isolated from the aqueous
dispersion after polymerization. In other cases the dispersion itself is the end product. A
dispersion resulting from emulsion polymerization is often called a latex (especially if derived
from a synthetic rubber) or an emulsion (even though "emulsion" strictly speaking refers to a
dispersion of an immiscible liquid in water). These emulsions find applications in adhesives,
paints, paper coating and textile coatings. They are finding increasing acceptance and are
preferred over solvent-based products in these applications as a result of their eco-friendly
characteristics due to the absence of VOCs (Volatile Organic Compounds) in them.

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5.1.2 Solution Polymerization

Solution polymerization is used to create polymers and copolymers by dissolving a monomer


and a catalyst in a non-reactive solvent. During this process, the solvent liquid absorbs the
heat generated by the chemical reaction which controls the reaction rate. The liquid solvent
used in the solution polymerization procedure usually remains a solvent for the resulting
polymer or copolymer. This process is only suitable for the creation of wet polymer types, as
the removal of excess solvent is difficult. While removal of excess solvent is possible using
distillation, it is usually not considered economically possible in an industrial situation.

The process of solution polymerization offers a few advantages as well as one major
disadvantage. The advantages include precise control of the chemical reaction, control of the
resulting heat and viscosity, and control over auto acceleration of the process. The
Disadvantage of the process is the difficulty involved in the removal of excess solvent from
the finished product.

The solvents used in the solution polymerization procedure must be chosen carefully. A
solvent that is non-reactive to the monomer is essential to the process. If a reactive solvent is
used, dangerous chain reaction processes or other undesirable effects can occur as a result of
auto acceleration. Auto acceleration is a reaction that occurs when the heat produced by
polymerization does not dissipated quickly enough by the solvent. As the heat builds up, the
viscosity of the solution increases, causing the polymerization process to accelerate beyond
safe control.

Industrial solution polymerization processes are commonly used to produce polymers with
special characteristics. The chemical reaction that takes place between the monomer and
catalyst can lend unique properties to the end product. One example of this type of polymer is
sodium polyacrylate, the exceptionally absorbent polymer used in disposable diapers.

While this process is not generally feasible for dry polymers, it works well for wet polymer
types. The process of industrial solution polymerization is used to create polymers and
copolymers that can be used in their solution form. Examples of this usage include industrial
glues and surface coatings.

Synthetic elastomers can also be produced using the solution polymerization process. This
method produces a more precise polymer than emulsion polymerization methods.
20
By controlling the addition of refined monomers to the catalyst-solvent solution, the resulting
polymers can be carefully designed for specific properties. These synthetic elastomers are
commonly found in products such as latex gloves, neoprene wetsuits and floor covering
materials
5.2 Selection of Polymerization Process
Most often Emulsion Polymerization is chosen over Solution Polymerization. It is because of
the following advantages:
 High molecular weight polymers can be made at fast polymerization rates. By contrast, in
bulk and solution free radical polymerization, there is a tradeoff between molecular
weight and polymerization rate.

 The continuous water phase is an excellent conductor of heat and allows the heat to be
removed from the system, allowing many reaction methods to increase their rate.

 Since polymer molecules are contained within the particles, the viscosity of the reaction
medium remains close to that of water and are not dependent on molecular weight.

The final product can be used as is and does not generally need to be altered or processed.
Moreover some of the disadvantages of solution polymerization are:

 Chain transfer to solvent occurs, leading to low molecular weights.

 Difficult to remove solvent from final form, causing degradation of bulk properties.

 Environmental pollution due to solvent release.

Hence, EMULSION POLYMERISATION is chosen for the production process.

5.3 Methods of Production

According to the temperature two processes have been developed, the hot process(52
Celcius) and the cold process(5-10 celcius). At present time about 75% of the world production
is carried out by 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
or sodium persulphate is used. To control the temperature, a soap in water emulsion is added
because most heat is liberated during the process.At lower temperature chain length can be
controlled more efficiently than in hot process. Hence cold process is more efficient than hot
process.

It should be noted that the hot process and the cold process differ in the preparation of latex
only. Compounding and vulcanizing are done as in the case of natural rubber; it is mixed with
reinforcing fillers such as carbon black. In cold process the chain length is less than that in the
hot process. Hence rubber obtained from cold process is more elastic, less hard and more resilient.
5.4 Process Description

5.4.1 Production

The copolymers of styrene and butadiene which contain over 50% percent butadiene are
known as SBR. The usual monomer ratio is 70 to 75 parts of butadiene to 30 to 25 parts of
styrene. As the styrene content is increased above 50%, the product becomes increasingly
plastic and is used in latex paint. The polymerization is carried out in an emulsion at about 50
degree centigrade and requires 5 to 15 hours. A series of reactors is used in the process. The
heat of polymerization is at given operating conditions is usually 1280kJ/kg of rubber
produced and removed by internal coils. The molecular weight of polymer is regulated by the
use of a modifier, such as a tertiary C-12 mercaptan, which regulates chain growth. The
reaction is terminated at 60 to 75 percent of completion because usually higher conversion
gives polymers with inferior properties due to cross-linking and branching. Sodium nitrite and
sodium dimethlydithiocarbamate are added to terminate the reaction. The unreacted butadiene
is flashed off, and the styrene is discovered by steam distillation.

The emulsion, in effect latex, is accumulated in holding tanks and blended to the proper
specifications for the grade of rubber required. It is coagulated and extensively washed and
dewatered prior to the drying operations. Much of the SBR is extended with oil before it is
vulcanized. The softening effects of oil are counterbalanced by the addition of carbon black.
Much of the SBR sold is in the form of master batches, to which oil and carbon have already
been added.

Emulsion produces a random distribution of polymer units. A typical distribution of SBR


produced by emulsion polymerization contains 23% of styrene units, and butadiene units
(77% of the total) have the configuration of 65% trans-1, 4, 18% cis-1, 4 and 17% vinly-1, 2.

SBR doesn’t crystallize when stretched, as natural rubber does, and thus is very weak unless
reinforced with carbon black or other materials. It is even then, less strong than natural rubber.
Its vulcanization properties are good and the ageing characteristics are satisfactory. Over 70%
of the SBR produced is used for the tire and tread rubber, over 15 percent for mechanical
goods and 10 percent is sold as latex.

23
5.4.2 Monomer recovery

· The rubber quality and the rate of reaction both fall off as the polymerisation proceeds,
and it is customary to stop the reaction short of complete conversion to rubber.

· Recovery of the unreacted monomers and purification of is an essential step in


economical synthetic-rubber production.

· Methods of recovery by steam stripping of aqueous lattices or by distillation from


solvents systems are employed.

· In some cases, recovery of the monomer can be accomplished during the step in a
devolatilizing extruder dryer.

· Water or solvent is removed by a combination of mechanical squeezing and by


passage through a vacuum section.

· The space and maintenance and labor requirements of such dryers are sufficiently less
than for the multipass apron dryer, so that has been installed in several new rubber
plants.

5.4.3 Coagulation and Drying

· The finishing process usually consists of precipitating the rubber from the latex
emulsion or from the solvent solution in crumb form; it is then dried and compressed
into a bale.

· Ordinary lattices may be easily coagulated by the addition of sodium chloride and
dilute sulphuric acid, alum, or virtually any combination of electrolyte and dilute acid.

· The rubbers which result from solution polymerisation will result into a crumb form
by adding the solution into a tank of hot water under violent agitation, with or without
the addition of wetting agents, to control crumb size and prevent reagglomeration.

· The coagulated crumb is separated from the scrum and washed on vibrating screens or
rotating filters and dried at appropriate temperatures.

· Rubber is a difficult material to dry, and care must be taken not to overheat it or
otherwise cause deterioration. Drying-times in conventional hot-air drying aprons may
take as long as several hours

24
Block Flow Diagram
BUTADIENE
butane
Charge Houdry Compression CAA shipping
Quench
Heater Reactors And absorption and extraction

STYRENE

ethylene ethylbenzene
catalytic distillation and
ethylbenzene dehydrogenation BTX Distillation styrene
n
concentration

COPOLYMER

monomer tank
form

pigment copolymer
preparation reactions recovery latex storage coagulation

soaps
activators
catalysts

raw materials

drying boiling shipment


shortstops
modifiers
inhibitors

Fig.6 Block diagram for SBR production

Process Flow Diagram

Fig7. Process Flow Diagram

25
5.4.4 Description of Process Flow Diagram

Styrene and Butadiene along with potassium Resin acid soap, Tert-Dodecyl Mercaptan,
Potassium PyroPhosphate, Ferrous Sulphate and water is fed to the mixer where it is mixed
with the recycle streams. The mixed feed is fed to the reactor where the polymerization of
styrene and butadiene to form styrene butadiene rubber takes place. Conversion obtained is
60%. Styrene and Butadiene are separated from the reactor effluents in styrene stripper and
butadiene stripper respectively. The recovered styrene and butadiene are recycled and mixed
with the fresh feed. The bottoms from the styrene stripper is fed to a coagulating, filtering and
drying unit in which the Styrene Butadiene Rubber is separated from remaining Styrene,
Butadiene, Resin acid soap, Tert-Dodecyl Mercaptan, Potassium PyroPhosphate, Ferrous
Sulphate and water. These are discharged as effluent and the SBR is obtained as product.

26
Chapter 6

MATERIAL BALANCE

6.1 Assumptions for Material Balance

 There is no material loss from any equipment along any flow line by any means

 There is no accumulation of material in any equipment, Steady state exists.

The production of SBR is done via cold polymerization of Styrene and Butadiene. Styrene
conversion of about 60% is achieved in the reactor. SBR is produced by the following
reaction.

nCH2 = CH – CH = CH2 + xC6H5 – CH = CH2 


Butadiene Styrene

-( CH2 – CH = CH – CH2)n – ( CH2 – CH(C6H5) )x –


Styrene Butadiene Rubber

Basis: We assume that plant produces 50,000 metric tons of Styrene Butadiene rubber every
year and number of days of observation of the plant is taken as 315 days in a year after taking
into account the maintenance and cleaning operations.

Also the conversion based on Styrene, from literature is about 60%.

6.2 Typical Recipe for Cold Emulsion Polymerization

Table4. The typical recipe for cold emulsion polymerization of SBR is given below:

Components Parts by Weight Function

(per 100 parts of SBR)

Styrene 25 Monomer

Butadiene 75 Monomer

27
Potassium Resin acid soap 4.0 Emulsifier

D-Isopropyl Benzene 0.08 Initiator


Peroxide

Chain
Tert-Dodecyl Mercaptan 0.2 Modifier

Potassium PyroPhosphate 0.18 Buffer

Ferrous Sulphate 0.14 Activator

Water 180

*The consumption of Catalyst, Modifier, Buffer, Activator and Emulsion in the production is
negligible, but the recovery being uneconomical, we let go these feed components in the
effluents.

6.3 Calculation of Inlet Flow Rates

We have assumed 50,000 metric tons of SBR being produced per year.

Therefore, SBR production per hour

= 50,000 / (24*315)

= 6.61375 metric tons of SBR


= 6613.75 kg/hr of SBR

SBR contains only 25 parts of Styrene and 75 parts of Butadiene.

So, Styrene required for production is

= (0.25* 6613.75) Kg/hr


= 1653.4375 Kg/hr

28
Butadiene required for production,

= (0.75* 6613.75) Kg/hr


= 4960.3125 Kg/hr

*This is theoretical requirement of styrene and butadiene. Practically 100% recovery of


styrene and butadiene is not possible. So, actual requirement of styrene and butadiene will
be more than this.

Requirement of other feed components in the mixed feed at steady state.

Tert-Dodecyl Mercaptan required for production

= (0.002* 6613.75) Kg/hr


= 13.2275 Kg/hr

Potassium PyroPhosphate required for production

= (0.0018* 6613.75) Kg/hr


= 11.905 Kg/hr

Ferrous Sulphate required for production

= (0.0014* 6613.75) Kg/hr


= 9.26 Kg/hr

Water required for production

= (1.8* 6613.75) Kg/hr


= 11898.21 Kg/hr

Resin acid soap required for production

= (0.04* 6613.75) Kg/hr


= 264.55 Kg/hr

29
6.4 Material Balance across Each Equipment

6.4.1 Mixer

Fig8. Mixer

The feed and recycle streams are mixed in the mixer.

Table5. Detailed material balance for mixer is:

Feed Recycle Net Input Output

(Stream 1) (Stream 7&8) (Stream 2)

Total Flow (kg/hr) 18817.4125 3835.9795 22652.05 22652.05

Component Flow (kg/hr)

Styrene 1748.232 1007.498 2755.73 2755.73

Butadiene 5060.3147 2633.6853 7694 7694

Water 11888.282 9.928 11898.21 11898.21

Styrene Butadiene - 5.15 5.15 5.15


Rubber

Tert-Dodecyl 13.21646 0.01104 13.2275 13.2275


Mercaptan

Potassium 11.89508 0.00992 11.905 11.905


PyroPhosphate

Ferrous Sulphate 9.25228 0.00772 9.26 9.26

Resin acid soap 264.229 0.321 264.55 264.55

30
6.4.2 Feed Cooler

Fig9. Feed Cooler

The output of Fuel mixer is directly fed to feed cooler. The mass balance across the feed
cooler is given by

Table6. Detailed material balance across feed cooler

Input Output

(Stream 2) (Stream 3)

Total Flow (kg/hr) 22652.05 22652.05

Component Flow (kg/hr)

Styrene 2755.73 2755.73

Butadiene 7694 7694

Water 11818.21 11818.21

Styrene Butadiene 5.15 5.15


Rubber

Tert-Dodecyl 13.2275 13.2275


Mercaptan

Potassium 11.905 11.905


PyroPhosphate

Ferrous Sulphate 9.26 9.26

Resin acid soap 264.55 264.55

31
6.4.3 SBR Reactor

Fig10. Reactor

In SBR reactor, polymerization of Styrene and Butadiene takes place to give Styrene
Butadiene Rubber.

Table7. Detailed material balance for SBR reactor is:

Input Output

(Stream 3) (Stream 4)

Total Flow (kg/hr) 22652.05 22652.05

Component Flow (kg/hr)

Styrene 2755.73 1102.292

Butadiene 7694 2733.6875

Water 11898.21 11898.21

Styrene Butadiene 5.15 6618.9


Rubber

Tert-Dodecyl 13.2275 13.2275


Mercaptan

Potassium 11.905 11.905


PyroPhosphate

Ferrous Sulphate 9.26 9.26

Resin acid soap 264.55 264.55

32
6.4.4 Butadiene Separation

Fig11. Butadiene Stripper

In the Butadiene separation, Butadiene is taken as light key while all other components
are taken as heavy key.

Let F, D, W be Feed, top product and bottom product flow rate respectively.

F = 22652.032 kg/hr

Now, as we know

F=D+W (1)

And Fxy = Dxd + Wxw . (2)

Where xf, xd and xw are mass fractions of Styrene in feed, distillate and bottoms.

xf = 0.12067

Now fixing xd = 0.995 and xw = 0.005.

We get from equation 1 and 2.

D + W = 22652.0322 (3)

(0.995*D) + (0.005*W) = 2733.6875 (4)

Solving 3 and 4 simultaneously, we get

D = 2645.5 Kg/hr

W = 20006.532 Kg/hr

Amount of Butadiene in Top Product

= 2646.89 * 0.995 = 2633.66 Kg/hr.

33
Table8. Detailed material balance for Butadiene separation

Feed Top Product Bottom Ptoduct

(Stream 4) (Stream 7) (Stream 5)

Total Flow (kg/hr) 22652.05 2645 20007.05

Component Flow (kg/hr)

Styrene 1102.292 0.641 1101.651

Butadiene 2733.6875 2633.66 100.0275

Water 11898.21 6.92 11891.29

Styrene Butadiene 6618.9 3.48 6615.42


Rubber

Tert-Dodecyl 13.2275 0.0077 13.2198


Mercaptan

Potassium 11.905 0.00692 11.898


PyroPhosphate

Ferrous Sulphate 9.26 0.00538 9.25462

Resin acid soap 264.55 0.254 264.296

34
6.4.5 Styrene Separation.

Fig12. Styrene Stripper

The bottoms from Butadiene separation are fed to Styrene separation.

In Styrene separation, Styrene is taken as light key while all other components are taken
as heavy key.

Let F, D, W be feed, distillate and bottoms flow rate respectively.

F = 20006.53 Kg/hr

Now, as we know

F = D+W (5)

Fxf = Dxd + Wxw. (6)

Where xf, xd, xw are mass fractions of Styrene in Feed, Distillate, Bottoms.

xf = 0.05506

Now fixing, xd = 0.995 and xw = 0.005.

We get from equation 5 and 6,

D + W = 20066.53 (7)

(0.995*D) + (0.005*W) = 1101.651 (8)

Solving 7 and 8 simultaneously, we get,

D = 1011.7357

F = 18994.7963.
35
Amount of Styrene in Distillate = 1011.7357*0.995 = 1006.857 Kg/hr.

Table9. Detailed Material balance for Styrene separation

Feed Distillate Bottoms

(Stream 5) (Stream 8) (Stream 6)

Total Flow (kg/hr) 20007.05 1011.7 18995.35

Component Flow (kg/hr)

Styrene 1101.651 1006.857 94.794

Butadiene 100.0275 0.0253 100.0022

Water 11891.29 3.008 11888.282

Styrene Butadiene 6615.42 1.67 6613.75


Rubber

Tert-Dodecyl 13.2198 0.00334 13.21646


Mercaptan

Potassium 11.898 0.003 11.895


PyroPhosphate

Ferrous Sulphate 9.25462 0.00234 9.25228

Resin acid soap 264.296 0.067 264.229

6.4.6 Coagulation, Filter, Drier

Fig13. Coagulating, Filtering & Drying Unit


36
SBR is coagulated, washed, filtered and dried so as to get separated from unrecovered styrene
& butadiene as well as from unwanted effluents including water, Tert-Dodecyl Mercaptan,
Potassium PyroPhosphate, Ferrous Sulphate and Resin acid soap.

Table10. Detailed material balance for Coagulator, Filter & Drier

Input Output 1 Output 2 Net Output

(Stream 6) (Stream 9) (Stream 10)

Total Flow (kg/hr) 18995.35 6613.75 12381.6 18995.35

Component Flow (kg/hr)

Styrene 94.794 - 94.794 94.794

Butadiene 100.0022 - 100.0022 100.0022

Water 11888.282 - 11888.282 11888.282

Styrene Butadiene 6613.75 6613.75 - 6613.75


Rubber

Tert-Dodecyl 13.21646 - 13.21646 13.21646


Mercaptan

Potassium 11.895 - 11.985 11.985


PyroPhosphate

Ferrous Sulphate 9.25228 - 9.25228 9.25228

Resin acid soap 264.229 - 264.229 264.229

37
6.4.7 Overall Balance

Table11. Overall Balance

Feed Product Effluent

Total Flow (kg/hr) 18995.35 6613.75 12381.6

Component Flow (kg/hr)

Styrene 1748.232 - 94.794

Butadiene 5060.3147 - 100.0022

Water 11888.282 - 11888.282

Styrene Butadiene - 6613.75 -


Rubber

Tert-Dodecyl 13.21646 - 13.21646


Mercaptan

Potassium 11.895 - 11.895


PyroPhosphate

Ferrous Sulphate 9.25228 - 9.25228

Resin acid soap 264.229 - 264.229

38
REFERENCES

(1) M. Gopala Rao and Marshall Sittig, “Dryden’s Outlines of Chemical Technology”,
2nd Ed., East-West press.

(2) R. H. Perry and Don W. Green, “Perry’s Chemical Engineers’ Hand Book”, 6th and
7th Ed., McGraw Hill International edition.

(3) R. K. Sinnott, “Coulson and Richardson’s Chemical Engineering Series, volume-6,


Chemical Equipment Design” 3rd Ed., Butter Worth-Heinemann.

(4) Max S. Peters and Klaus Timmerhaus, “Process Plant Design and Economics For
Chemical Engineers”, 3rd Ed., McGraw Hill Book Company.

(5) L.E. Brownell and E.H. Young, “Process Equipment Design”, John Wiley & Sons
Inc. New York.

(6) Reid Sherwood, “Properties of gases and liquids”.

(7) Nicholas P. Chopey, “Handbook of Chemical Engineering”, 3rd Ed., McGraw Hill
Book Company.

(8) McCabe, Warren L. Smith, “Unit Operations of Chemical Engineering”, McGraw Hill
Book Company.

(9) Robert E. Treybal, “Mass- transfer Operations”, 3rd Ed., McGraw Hill Book Company.

(10) J. M. Smith, H. C. Van Ness and M. M. Abbot, “Introduction to Chemical


engineering Thermodynamics”, 6th Ed., McGraw Hill Book Company

39

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