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Styrene Butadiene Rubber
            (SBR)

                           Syed Mohammed Sajl
                               Semester 6
                             B Tech – PS & E

Thursday, March 07, 2013       Review Seminar - Semester 5   1
Introduction
• Styrene-butadiene or styrene-butadiene rubber
  (SBR) describe families of synthetic rubbers
  derived from styrene and butadiene.
• These materials have good abrasion resistance
  and good aging stability when protected by
  additives.
• In 1929, E Tchunkur and A Bock discovered that
  mixtures of butadiene and styrene.
• The styrene/butadiene ratio influences the
  properties of the polymer: with high styrene
  content, the rubbers are harder and less rubbery.
Thursday, March 07, 2013     Review Seminar - Semester 5   2
• In the 1930’s, the first emulsion
  polymerized SBR known as Buna S was
  prepared by I. G. Farbenindustrie in
  Germany.
• The U. S. Government in 1940 established
  the Rubber Reserve Company to start a
  stockpile of natural rubber and a synthetic
  rubber program.
• About 50% of car tires are made from
  various types of SBR

Thursday, March 07, 2013   Review Seminar - Semester 5   3
Figure: Structure of Styrene-Butadiene



Thursday, March 07, 2013              Review Seminar - Semester 5   4
Production
Thursday, March 07, 2013     Review Seminar - Semester 5   5
E-SBR (Cold Rubber)
• The Emulsifiers for the dispersion of
  monomers during polymerization are of an
  anionic nature.
• The ratio of butadiene to styrene is mostly
  76.5% to 23.5% by weight.
• The free radicals required for the initiation
  step are obtained by the reaction of Iron
  (II) salts with p-menthane hydroperoxide.

Thursday, March 07, 2013   Review Seminar - Semester 5   6
• For redox activators, one uses chelating
  agents, like Sodiun Salt of Ethylene-
  diaminetetraactic acid, together with
  Sodium formaldehyde sulfoxylate.
• The pH of the reaction medium is usually
  adjusted to about 11 to 12.
• Tertiary Dodecyl Mercaptan is mostly used
  as a chain modifier, it only terminates itslef
  when all the monomer has reacted.
• Prior to coagulation, stabilizers are added
  to the latex depending on desired
  qualitites.
Thursday, March 07, 2013   Review Seminar - Semester 5   7
OE-E-SBR Caron Black Master
               batch
• With some SBR grades, extender oils (OE-E-
  SBR) and Carbon Black Master batch are
  added at the end of polymerization stage.
• The oil extension, the rubber is usually
  produced to higher molecular weights.
• The oils is co-precipitated with rubber from
  the latex, acts as plasticizer during
  processing.
• Post dispersion in the latex, after co-
  precipitation, it is possible to incorporate
  carbon black finely dispersed in the rubber.
Thursday, March 07, 2013   Review Seminar - Semester 5   8
E-SBR (Hot Rubber)
• The Processes are very similar for both
  Hot and Cold Rubbers.
• We use soaps from fatty acids or alkylaryl
  sulfonates. The polymerization
                                                          O
  temperature is normally about 50 C or
  even higher.
• The free radicals are created from
  Potassium Persulfate and Mercaptaqn to
  initiate Polymerization.
Thursday, March 07, 2013    Review Seminar - Semester 5       9
The following parameters are important
for the production of SBRs:
• Monomer Ratio (mostly 23.5% styrene)
• Polymerization Temperature
• Chain modifiers
• Emulsifier
• Stabilizer
• Coagulant
• Oil, type and amount
• Carbon Black, type and amount

Thursday, March 07, 2013   Review Seminar - Semester 5   10
L-SBR
• Solution-SBR is produced by an anionic
  polymerization process.
• Polymerisation is initiated by alkyl lithium
  compounds. Water is strictly excluded.
• The process is homogeneous (all
  components are dissolved), which
  provides greater control over the process,
  allowing tailoring of the polymer.

Thursday, March 07, 2013   Review Seminar - Semester 5   11
• The organolithium compound adds to one
  of the monomers , generating a carbanion
  that then adds to another monomer, and
  so on.
• Relative to E-SBR, S-SBR is increasingly
  favored because it offers improved wet
  grip and rolling resistance, which translate
  to greater safety and better fuel economy,
  respectively


Thursday, March 07, 2013   Review Seminar - Semester 5   12
Properties
Thursday, March 07, 2013     Review Seminar - Semester 5   13
Properties of E-SBR
• E-SBR is commercially available in Mooney
  viscosities ranging from 30 to about 120
  (ML1+4@125 C).           O




• Lower Mooney viscosity E-SBR 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
  SBR’s have better green strength, less porosity in
  the vulcanizate, and accept higher filler and oil
Thursday, March 07, 2013       Review Seminar - Semester 5   14
• As the molecular weight of the SBR
  increases, the vulcanizate resilience and the
  mechanical properties, particularly tensile
  strength and compression set, improve.
• The processability of SBR 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.


Thursday, March 07, 2013   Review Seminar - Semester 5   15
• In addition to the polymer viscosity,
  polymerization temperature also plays an
  important role in shaping the processability.
• E-SBRs produced at low polymerization
  temperatures have less chain branching than
  those produced at higher temperature.
• The styrene content of most emulsion SBR
  varies from 0% to 50%. The percent styrene
  of most commercially available grades of E-
  SBR is 23.5%.
• In vulcanizates of SBR, as styrene content
  increases, dynamic properties and abrasion
  resistance decrease while traction and
  hardness increase.
Thursday, March 07, 2013   Review Seminar - Semester 5   16
MECHANICAL PROPERTIES:
• SBR lacks the self-reinforcing qualities of natural
  rubber due to stress induced crystallization, gum
  vulcanizates of SBR have lower tensile properties.
• The tensile property of E-SBR 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
  E-SBR compounds is high, by proper compounding
  and blending, it is possible to obtain E-SBR
  vulcanizates with a low compression set.
Thursday, March 07, 2013   Review Seminar - Semester 5   17
ELECTRICAL PROPERTIES
• SBR is a non-polar polymer and its vulcanizates
  are poor conductors of electricity. The electrical
  properties of E-SBR depend to a large extent on
  the amount and type of emulsifier and coagulating
  agent(s) used.
RESISTANCE TO FLUIDS
• While E-SBR 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, SBR
  cannot be used in applications that require
  resistance to swelling in contact with hydrocarbon
  solvents.
Thursday, March 07, 2013   Review Seminar - Semester 5   18
Properties of L-SBR
L-SBR with Random Distribution of Styrene:
• These compounds have low hysteresis, less heat
  buildup and superior abrasion resistance than E-
  SBR.
• L-SBRs are purer than E-SBR as they do not
  contain residual emulsifier.
• They have lower water absorption and particularly
  good electrical properties.
• They are odor free and light colored.
L-SBR with Blocky Monomer Distribution:
• They have good elastic properties, low water
  absorption and low electrical conductivity
Thursday, March 07, 2013    Review Seminar - Semester 5   19
L-SBR with SBS Triblocks:
• At Room Temperature, it has high elasticity and
  tensile strength.
• The SBS polymers are physical in nature and
  due to the separation of styrene into discrete
  phases, these can be used in products which
  require only a low heat resistance.
• Above 70 C, the SBS polymers lose their
                           O



  elasticity and strength.
• The resistance to organic solvents is also poor.



Thursday, March 07, 2013       Review Seminar - Semester 5   20
Application &
                     Uses
Thursday, March 07, 2013   Review Seminar - Semester 5   21
Application & Uses
E-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, moulded rubber goods, shoe
  soling, cable insulation and jacketing, pharmaceutical,
  surgical, and sanitary products, food packaging, etc.
Thursday, March 07, 2013         Review Seminar - Semester 5   22
Random L-SBR:
• It is used in blends with E-SBR to improve the
  extrudability and specifically, the sharpness of
  edges and the surface smoothness of
  extrudates.
Blocky L-SBR:
• The preferred use is in hard shoe soling, roll
  covering and special technical rubber products
Thermoplastic L-SBR:
• It is used in instances where products require
  low heat resistances have to produced in great
  quantity in roofing, shoe applications and nipples
  of babu bottles
Thursday, March 07, 2013   Review Seminar - Semester 5   23
References &
                    Acknowledgements
Thursday, March 07, 2013   Review Seminar - Semester 5   24
Acknowledgements
•Rubber Technology Handbook – Werner
 Hofmann
•www.wikipedia.com
•www.google.com




Thursday, March 07, 2013   Review Seminar - Semester 5   25
Download this Slideshow:
                           http://slidesha.re/link


Thursday, March 07, 2013           Review Seminar - Semester 5   26
Thursday, March 07, 2013   Review Seminar - Semester 5   27

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Styrene-Butadiene Rubber (SBR)

  • 1. Styrene Butadiene Rubber (SBR) Syed Mohammed Sajl Semester 6 B Tech – PS & E Thursday, March 07, 2013 Review Seminar - Semester 5 1
  • 2. Introduction • Styrene-butadiene or styrene-butadiene rubber (SBR) describe families of synthetic rubbers derived from styrene and butadiene. • These materials have good abrasion resistance and good aging stability when protected by additives. • In 1929, E Tchunkur and A Bock discovered that mixtures of butadiene and styrene. • The styrene/butadiene ratio influences the properties of the polymer: with high styrene content, the rubbers are harder and less rubbery. Thursday, March 07, 2013 Review Seminar - Semester 5 2
  • 3. • In the 1930’s, the first emulsion polymerized SBR known as Buna S was prepared by I. G. Farbenindustrie in Germany. • The U. S. Government in 1940 established the Rubber Reserve Company to start a stockpile of natural rubber and a synthetic rubber program. • About 50% of car tires are made from various types of SBR Thursday, March 07, 2013 Review Seminar - Semester 5 3
  • 4. Figure: Structure of Styrene-Butadiene Thursday, March 07, 2013 Review Seminar - Semester 5 4
  • 5. Production Thursday, March 07, 2013 Review Seminar - Semester 5 5
  • 6. E-SBR (Cold Rubber) • The Emulsifiers for the dispersion of monomers during polymerization are of an anionic nature. • The ratio of butadiene to styrene is mostly 76.5% to 23.5% by weight. • The free radicals required for the initiation step are obtained by the reaction of Iron (II) salts with p-menthane hydroperoxide. Thursday, March 07, 2013 Review Seminar - Semester 5 6
  • 7. • For redox activators, one uses chelating agents, like Sodiun Salt of Ethylene- diaminetetraactic acid, together with Sodium formaldehyde sulfoxylate. • The pH of the reaction medium is usually adjusted to about 11 to 12. • Tertiary Dodecyl Mercaptan is mostly used as a chain modifier, it only terminates itslef when all the monomer has reacted. • Prior to coagulation, stabilizers are added to the latex depending on desired qualitites. Thursday, March 07, 2013 Review Seminar - Semester 5 7
  • 8. OE-E-SBR Caron Black Master batch • With some SBR grades, extender oils (OE-E- SBR) and Carbon Black Master batch are added at the end of polymerization stage. • The oil extension, the rubber is usually produced to higher molecular weights. • The oils is co-precipitated with rubber from the latex, acts as plasticizer during processing. • Post dispersion in the latex, after co- precipitation, it is possible to incorporate carbon black finely dispersed in the rubber. Thursday, March 07, 2013 Review Seminar - Semester 5 8
  • 9. E-SBR (Hot Rubber) • The Processes are very similar for both Hot and Cold Rubbers. • We use soaps from fatty acids or alkylaryl sulfonates. The polymerization O temperature is normally about 50 C or even higher. • The free radicals are created from Potassium Persulfate and Mercaptaqn to initiate Polymerization. Thursday, March 07, 2013 Review Seminar - Semester 5 9
  • 10. The following parameters are important for the production of SBRs: • Monomer Ratio (mostly 23.5% styrene) • Polymerization Temperature • Chain modifiers • Emulsifier • Stabilizer • Coagulant • Oil, type and amount • Carbon Black, type and amount Thursday, March 07, 2013 Review Seminar - Semester 5 10
  • 11. L-SBR • Solution-SBR is produced by an anionic polymerization process. • Polymerisation is initiated by alkyl lithium compounds. Water is strictly excluded. • The process is homogeneous (all components are dissolved), which provides greater control over the process, allowing tailoring of the polymer. Thursday, March 07, 2013 Review Seminar - Semester 5 11
  • 12. • The organolithium compound adds to one of the monomers , generating a carbanion that then adds to another monomer, and so on. • Relative to E-SBR, S-SBR is increasingly favored because it offers improved wet grip and rolling resistance, which translate to greater safety and better fuel economy, respectively Thursday, March 07, 2013 Review Seminar - Semester 5 12
  • 13. Properties Thursday, March 07, 2013 Review Seminar - Semester 5 13
  • 14. Properties of E-SBR • E-SBR is commercially available in Mooney viscosities ranging from 30 to about 120 (ML1+4@125 C). O • Lower Mooney viscosity E-SBR 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 SBR’s have better green strength, less porosity in the vulcanizate, and accept higher filler and oil Thursday, March 07, 2013 Review Seminar - Semester 5 14
  • 15. • As the molecular weight of the SBR increases, the vulcanizate resilience and the mechanical properties, particularly tensile strength and compression set, improve. • The processability of SBR 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. Thursday, March 07, 2013 Review Seminar - Semester 5 15
  • 16. • In addition to the polymer viscosity, polymerization temperature also plays an important role in shaping the processability. • E-SBRs produced at low polymerization temperatures have less chain branching than those produced at higher temperature. • The styrene content of most emulsion SBR varies from 0% to 50%. The percent styrene of most commercially available grades of E- SBR is 23.5%. • In vulcanizates of SBR, as styrene content increases, dynamic properties and abrasion resistance decrease while traction and hardness increase. Thursday, March 07, 2013 Review Seminar - Semester 5 16
  • 17. MECHANICAL PROPERTIES: • SBR lacks the self-reinforcing qualities of natural rubber due to stress induced crystallization, gum vulcanizates of SBR have lower tensile properties. • The tensile property of E-SBR 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 E-SBR compounds is high, by proper compounding and blending, it is possible to obtain E-SBR vulcanizates with a low compression set. Thursday, March 07, 2013 Review Seminar - Semester 5 17
  • 18. ELECTRICAL PROPERTIES • SBR is a non-polar polymer and its vulcanizates are poor conductors of electricity. The electrical properties of E-SBR depend to a large extent on the amount and type of emulsifier and coagulating agent(s) used. RESISTANCE TO FLUIDS • While E-SBR 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, SBR cannot be used in applications that require resistance to swelling in contact with hydrocarbon solvents. Thursday, March 07, 2013 Review Seminar - Semester 5 18
  • 19. Properties of L-SBR L-SBR with Random Distribution of Styrene: • These compounds have low hysteresis, less heat buildup and superior abrasion resistance than E- SBR. • L-SBRs are purer than E-SBR as they do not contain residual emulsifier. • They have lower water absorption and particularly good electrical properties. • They are odor free and light colored. L-SBR with Blocky Monomer Distribution: • They have good elastic properties, low water absorption and low electrical conductivity Thursday, March 07, 2013 Review Seminar - Semester 5 19
  • 20. L-SBR with SBS Triblocks: • At Room Temperature, it has high elasticity and tensile strength. • The SBS polymers are physical in nature and due to the separation of styrene into discrete phases, these can be used in products which require only a low heat resistance. • Above 70 C, the SBS polymers lose their O elasticity and strength. • The resistance to organic solvents is also poor. Thursday, March 07, 2013 Review Seminar - Semester 5 20
  • 21. Application & Uses Thursday, March 07, 2013 Review Seminar - Semester 5 21
  • 22. Application & Uses E-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, moulded rubber goods, shoe soling, cable insulation and jacketing, pharmaceutical, surgical, and sanitary products, food packaging, etc. Thursday, March 07, 2013 Review Seminar - Semester 5 22
  • 23. Random L-SBR: • It is used in blends with E-SBR to improve the extrudability and specifically, the sharpness of edges and the surface smoothness of extrudates. Blocky L-SBR: • The preferred use is in hard shoe soling, roll covering and special technical rubber products Thermoplastic L-SBR: • It is used in instances where products require low heat resistances have to produced in great quantity in roofing, shoe applications and nipples of babu bottles Thursday, March 07, 2013 Review Seminar - Semester 5 23
  • 24. References & Acknowledgements Thursday, March 07, 2013 Review Seminar - Semester 5 24
  • 25. Acknowledgements •Rubber Technology Handbook – Werner Hofmann •www.wikipedia.com •www.google.com Thursday, March 07, 2013 Review Seminar - Semester 5 25
  • 26. Download this Slideshow: http://slidesha.re/link Thursday, March 07, 2013 Review Seminar - Semester 5 26
  • 27. Thursday, March 07, 2013 Review Seminar - Semester 5 27