Styrene Butadiene Rubber

Introduction

1. STYRENE-BUTADIENE RUBBER PRESENTED BY SHAUKAT ALI ZHCET, AMU

2. CONTENTS INTRODUCTION RAW MATERIALS TYPES APPLICATION COMMERCIAL ASPECTS REFERENCES

3. INTRODUCTION The introduction of automobiles in the early 1900s gave added impetus to find a substitute for natural rubber, the price of which tripled from $2.16/kg in 1900 to $6.73/kg in 1910. The advent of World War I gave Germany incentive to start a crash program on an alternative to natural rubber . In the late 1920s Bayer & Company began reevaluating the emulsion polymerization process of polybutadiene as an improvement over their Buna technology, which was based on sodium as a catalyst.

4. INTRODUCTION Styrene-butadiene or styrene-butadiene rubber (SBR) is a synthetic rubber copolymer consisting of styrene and butadiene. It has good abrasion resistance and good aging stability when protected by additives, and is widely used in car tyres , where it may be blended with natural rubber. Its common physical characteristics are - black in color, other colors can be compounded upon volume special request, 70 +/- 5 Durometer (hardness rating), excellent tensile strength and abrasion resistance at higher temperatures.

5. INTRODUCTION STRUCTURE OF STYRENE BUTADIENE RUBBER

6. RAW MATERIALS STYRENE Commercial manufacture of this commodity monomer depends on ethylbenzene, which is converted by several means to a low purity styrene, subsequently distilled to the pure form. A small percentage of styrene is made from the oxidative process, whereby ethylbenzene is oxidized to a hydroperoxide or alcohol and then dehydrated to styrene. A popular commercial route has been the alkylation of benzene to ethylbenzene, with ethylene , after which the crude ethylbenzene is distilled to give high purity ethylbenzene. The ethylbenzene is directly dehydrogenated to styrene monomer in the vapor phase with steam and appropriate catalysts A variety of catalyst systems are used, based on ferric oxide with other components, including potassium salts, which improve the catalytic activity

7. RAW MATERIALS BUTADIENE Economic considerations in the 1990s favor recovering butadiene from by-products in the manufacture of ethylene Butadiene is a by-product in the C4 streams from the cracking process. Depending on the feedstock's used in the production of ethylene, the yield of butadiene varies For use in polymerization, the butadiene must be purified to 99 +% Crude butadiene is separated from C3 and C5 components by distillation. Separation of butadiene from other C4 constituents is accomplished by salt complexing/solvent extraction

8. RAW MATERIALS SOAPS Critical ingredient for emulsion polymerization is the soap Performs a number of key roles, including production of oil (monomer) in water emulsion, provision of the loci for polymerization (micelle ), stabilization of the latex particle, and impartation of characteristics to the finished polymer Rosin acid soaps gave the added benefit of tack to the finished polymer

9. TYPES SBR is derived from two monomers, styrene and  butadiene. The mixture of these two monomers is polymerized by two processes: from solution (S-SBR) or as an emulsion (E-SBR ) ESBR and SSBR are made from two different addition polymerization techniques: one radical and one ionic. ESBR polymerization is based on free radicals that attack the unsaturation of the monomers, causing addition of monomer units to the end of the polymer chain, whereas the basis for SSBR is by use of ionic initiators.

10. FLOWSHEET OF EMULSION SBR

11. TYPES EMULSION POLYMERISATION Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant . This process overcomes the difficulty of heat control and low degree of polymerization The main product of Emulsion Polymerization is latex, which forms the basis of the popular latex paints By coagulating the latex with ionic salts and acids, solid rubber may also be obtained

12. TYPES ADVANTAGES OF EMULSION POLYMERISATION High molecular weight polymers can be made at fast polymerization rates The continuous water phase is an excellent conductor of heat, enabling fast polymerization rates without loss of temperature control Since polymer molecules are contained within the particles, the viscosity of the reaction medium remains close to that of water The final product can be used as is and does not generally need to be altered or processed This process overcomes the difficulty of heat control and low degree of polymerization

13. TYPES DISADVANTAGES OF EMULSION POLYMERISATION Surfactants and other polymerization adjuvants remain in the polymer or are difficult to remove For dry (isolated) polymers, water removal is an energy-intensive process Emulsion polymerizations are usually designed to operate at high conversion of monomer to polymer. This can result in significant chain transfer to polymer. Can not be used for condensation, ionic or Ziegler-Natta polymerization, although some exceptions are known .

14. FLOWSHEET OF SOLUTION SBR

15. TYPES SOLUTION POLYMERISATION Solution polymerization of monomers is carried out with dissolved monomers and initiators in solvent Typical solvents include aromatic and aliphatic hydrocarbons, esters, ethers, alcohol or water The solvent acts as diluent and aids in transfer of the heat of polymerization In presence of solvent the stirring becomes easier since the viscosity of the reaction mixture is decreased Consequently controlling of process temperature is much easier in solution polymerization compared to bulk polymerization

16. TYPES ADVANTAGES OF SOLUTION POLYMERISATION Solvent acts as a diluent and aids in removal of heat of polymerization Solvent reduces viscosity, making processing easier Thermal control is easier than in the bulk DISADVANTAGES OF SOLUTION POLYMERISATION 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

17. APPLICATIONS EMULSION SBR 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 housewares 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, molded rubber goods, shoe soling , cable insulation and jacketing, pharmaceutical, surgical , and sanitary products, food packaging, etc.

18. APPLICATIONS SOLUTION SBR For use in high-performance tires, S-SBR products provide an excellent balance between wet grip, low rolling resistance, and abrasion resistance in silica and carbon black compounds They are also used for the manufacture of high-quality industrial rubber goods

19. COMMERCIAL ASPECTS SBR: India Demand Supply   Actual Actual Actual Actual Actual Projected   2011-12 2012-13 2013-14 2014-15 2015-16 2016-17 (kt)   Capacity 20 20 40 140 290 290 Production 20 20 40 70 143 213 Dom Sales 16 18 25 60 115 180 Imports 181 212 245 230 191 133 Exports 4 4 15 10 28 33 Consumption 197 230 270 290 306 313   13.20% 16.80% 17.40% 7.40% 5.50% 2.30%

20. COMMERCIAL ASPECTS Capacity (kt) Actual Actual Actual Actual Actual Projected 2011-12 2012-13 2013-14 2014-15 2015-16 2016-17 RIL 150 150 IOCL 20 120 120 120 Eliokem 10 10 10 10 10 10 Apcotex 10 10 10 10 10 10 Total 20 20 40 140 290 290

21. COMMERCIAL ASPECTS Global capacity of SBR (emulsion) in 2015 was around 5.6 MMT while SBR (solution) was 1.7 MMT The global styrene butadiene rubber (SBR) market size was valued at USD 7.84 billion in 2015 Global solution styrene butadiene rubber (S-SBR) market size was valued at USD 2.51 billion in 2016 GLOBAL PLAYERS Asahi Kasei, Lanxess , LG Chem , Polimeri Europa, Sinopec, Bridgestone and Lion Elastomers etc.

22. COMMERCIAL ASPECTS India’s first large-scale styrene butadiene rubber (SBR) plant was built at Panipat by Indian Synthetic Rubber – a joint venture between Indian Oil & Taiwan’s TSRC Reliance Industries Ltd. began production at its new 150 KTA SBR plant at Hazira in 2015-16, which is the largest in India. The plant has capability to produce entire range of dry as well as oil extended grades of emulsion SBR In 2011 SBR capacity in India was 20 KTA and is expected to touch 290 KTA in 2016-17. The demand for SBR in India is projected at 313 KTA for 2016-17

23. COMMERCIAL ASPECTS Crude oil prices directly impact the prices of raw materials Crude oil prices were at an all-time high in 2011, which clearly reflected in butadiene prices that touched USD 3.0/kilo during the same period However , the recent dip in the prices of crude oil has brought butadiene and styrene prices to record lows These factors have led to a significant impact on the styrene butadiene rubber prices over the past few years

24. REFERENCES [1] Steven Di Pilla (2 June 2004),  Slip and Fall Prevention: A Practical Handbook , CRC, p. 82, ISBN  978-0-203-49672-5 [2] http :// cpmaindia.com/sbr_about.php [3 ] Odian , G,  Principles of Polymerization , Wiley, New York [4] https:// nptel.ac.in/courses/103103026/module4/lec38/3.html [5] https:// nptel.ac.in/courses/103103029/pdf/mod7.pdf [6] https://www.chemarc.com/content/product-profile-sbr- - styrene-butadiene-rubber/59db1f20903c8c57d2a36c03