Synthetic Rubbers

By Dr. Suranga M. Rajapaksha

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 Introduction
 Natural Rubber, the material obtained from the rubber tree Hevea Brasiliensis.
 Rubber trees are basically found in tropical & semitropical countries. Indonesia, Malaysia, Sri Lanka,
South America and India have abundant resource of natural rubber.
(1).
 Natural Rubber is a polymer of Isoprene.
 Isoprene polymerizes to give Polyisoprene polymer, a simple alkene
having each unit still containing one double bond.

(2).
 Polymerization of Isoprene may follow either of the two pathways; either of cis-
polymerization or trans-polymerization.
 Isoprene (2-Methyl -1, 3-butadiene) undergoes cis-polymerization to form natural rubber.

(3).

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 Use of Rubber in Industry
∞ The rubber products can be based on NR or SR or on blends of these rubbers depending on the end use
applications of the products.

∞ The synthetic rubbers are very important class of rubbers that are used to produce number of products that
find uses in variety of applications. Some synthetic rubbers mix with NR or between synthetic rubbers to
yield blends that are capable of offering compromise of properties.

Global Rubber Production and

Consumption

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 History of Synthetic Rubber
∞ A war-born material, synthetic rubber became one of the most important creations of man when the
progress of modern civilization was still dependent on the volatility of global natural rubber supply.

∞ In 1906, worldwide natural rubber output was 60,000 ton, already an inadequate amount for the
rising demand created by the burgeoning automobile industry.

∞ That same year, managers of the German company Bayer decided to offer a price of 20,000 gold
marks - an equivalent back then of $5,000 (Rs ~ 750000 /=) - for a chemist in their company to
invent within three years a satisfactory rubber substitute.

∞ In 1909, Fritz Hofmann, chief chemist in the Bayer pharmaceutical division, presented the first
sample of synthetically produced polyisoprene.

∞ After 1910, lower natural rubber prices reduced the attractiveness of developing synthetic rubber.

∞ World war II catalyzed the production of synthetic rubbers.

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 Polymerization Reactions

Chain Growth Step Growth

‡ Free radical ‡ Polycondensation
‡ Cationic ‡ Polyaddition
‡ Anionic
‡ Group Transfer
‡ Coordination

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 Polymerization techniques

1. Bulk polymerization 2. Solution polymerization

3. Suspension polymerization

4. Emulsion polymerization

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 Bulk polymerization
∞ Simplest process.

Advantages Disadvantages
∞ High rate of polymerization ∞ Auto acceleration
∞ High degree of polymerization ∞ Poor reproducibility
∞ Minimum contamination by
impurities
∞ Higher molar mass

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 Solution polymerization
∞ Many difficulties associated with bulk polymerization can be overcome.

Challenges
∞ Selecting a suitable solvent
∞ Low polymerization rate compared to bulk polymerization
∞ Low degree of polymerization compared to bulk polymerization
∞ Isolation of the polymer requires,
∞ Evaporation of the solvent,
∞ Precipitation of the polymer

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 Suspension polymerization
∞ Many difficulties associated with bulk polymerization can be overcome.
∞ Low viscosity
∞ High thermal conductivity
∞ Controlled auto acceleration
∞ Reaction mixture is suspended as tiny droplets in an inert medium.
∞ Initiator, monomer, and polymer must be insoluble in suspension medium.
∞ Droplets of organic phase are formed and maintained in suspension by
vigorous agitation
∞ Widely used in industrial scale to produce Polystyrene, MMA, PVC, etc.

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 Emulsion polymerization
∞ Great industrial importance
∞ Heterogeneous
∞ System prior to initiation contains,
∞ Water phase
∞ Large monomer droplets
∞ Emulsifier micelles containing
solubilized monomer
∞ Dissolved emulsifier
∞ Monomer-free micelles

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 Distinguish Features of Synthetic Rubber Latex

Ω Particle shape
Ω Spherical in shape

Ω Particle size
Ω Particle size smaller than many in ammonia-preserved
natural rubber latex.

Ω Particle size distribution

Ω Size distribution is narrow compared to NR

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 Kinetic Stability of Colloidal Suspensions
Ω The stability of colloids is very important in the conception of many products used every
day such as paints.

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 Interactions in Synthetic Latex
Ω The different interactions between dispersed (particles) and
dispersion (medium) phases are one of the critical points determining
the behavior and stability of colloids.

Ω These interactions that control the properties of the colloid depend on

the number of particles and their distance. The physical and chemical
properties will impact those interactions.

Ω The interaction between two bodies is dominated by two forces,

1. An attractive van der Waals forces.
2. A repulsive electrostatic forces.
3. Steric.

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Interactions in Colloidal suspensions

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Interactions in Colloidal suspensions

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Agglomeration of Synthetic Rubber Latex

Ω For most applications of rubber latexes must have high solids content. To
achieve this, with reasonable fluidity, the latex particles must be large.
Limitations in the kinetics of emulsion polymerization make it desirable to
polymerize a small particle latex.

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 Agglomeration and Concentration

Chemical Methods Physical Methods

Ω By addition of solvents Ω By freezing and
Ω By addition of electrolytes thawing
Ω By partial destruction of surface- Ω By mechanical
activity of colloid stabilizers agitation
Ω By addition of surface-active
substances

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 Agglomeration by Addition of Solvents
Ω Partial agglomeration can be effected by adding a solvent , and then
subjecting the mixture to heating and agitation.

Ω Solvents which can be used with SBR latices include Benzene, Toluene,
and Styrene.

Ω The effect of the added solvent is to swell the latex particles as the
solvent is absorbed into the particles. Polymer-aqueous interface
increases reduction in the surface concentration of the colloid
stabilizers in the latex.

Ω If the amount of colloid stabilizer present in the initial latex is

inadequate, then some bulk coagulation may occur during heating and
agitation.
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 Agglomeration by Addition of Electrolytes
Ω Colloidal particles are neutralized by the oppositely charged electrolyte
ions.
Ω The destabilization of colloid occurs at the electrolyte concentrations
exceeding the value of the critical coagulation concentration.
Ω The critical coagulation concentration is strongly dependent on the
valence of the electrolyte ions. The higher the valence the lower the
critical concentration of the electrolyte required for the coagulation of the
colloid.

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Agglomeration by Addition of Electrolytes

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 Agglomeration by Partial Destruction of
Surface-Activity of Colloid Stabilizers
Ω Partial destruction of surface activity of the colloid stabilizers are achieved by
partial soap neutralization.

Ω Partial soap neutralization is done by lowering the pH.

Ω As the pH degreases, so partial agglomeration of latex particles occurs. After

desired degree of agglomeration has been achieved, the pH is raised again by
addition of alkali.

Ω Suitable volatile bases (alkali) include, ammonia, methylamine, diethylamine,

and triethyl amine.

Ω Suitable acids, benzoic acid, chloroacetic acid, HCl, and fumaric acid etc.

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 Agglomeration by Freezing and Thawing
Ω Controlled partial agglomeration in the synthetic lattices can be induced by
subjecting the latex to freezing and then subsequent thawing.

Advantages
Ω Ease of control.
Ω Absence of any additives.
Ω Rapid rate of agglomeration occurs once the appropriate destabilizative
conditions have been established.

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 Rubber

General purpose Rubbers Special purpose Rubbers

Rubber used in bulk (NR/ BR/ SBR) Rubbers used in products that require
• Tyres and tubes specialized properties
• Conveyer belt • EPDM – Resistance to Ozone and UV
• Tubings and Hoses • NBR – Oil resistance
• Mats and florings • PU – Resistance to ink and oil, good
• Footware abrasion resistance
• Bumpers and fenders • Silicone – high flexibility, high
• Rubber bands temperature supplications, insulation
• Latex products properties, inert rubber.
• IIR – Resistance to air permeation,
Resistance to Ozone and UV

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STYRENE BUTADIENE RUBBER
SBR
∞ 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.

∞ These programs were expanded when the United States entered World War
II.

∞ The synthetic rubber efforts were initially focused on a hot polymerized (41°
C) E-SBR.

∞ Production of a 23.5% styrene and 76.5% butadiene copolymer began in

1942.

∞ Cold polymerized E-SBR (5°C),that has significantly better physical

properties than hot polymerized SBR, was developed in 1947.

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 SBR Monomers

Styrene
1,3-Butadiene
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 Construction units of SBR
∞ Construction unit from styrene

Styrene

Ethylene Polyethylene 26
 Construction units of SBR

1,3-Butadiene

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4 Basic construction units of SBR

Vinyl form

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 SBR There are NO double
bonds on the backbone of
the polymer chain.

Double bonds are on the Double bond is on the

backbone of the polymer pendent group of the
chain. polymer chain.

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 Manufacture of E-SBR Cont.
∞ Cold E-SBR
∞ Polymerization at 5-10 ˚C is called the cold process, and the product is
called cold SBR

∞ Hot E-SBR
∞ Polymerization at 50 ˚C is called the hot process and the product is
called hot SBR

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 Cold vs Hot E-SBR
Hot emulsion SBR has more of a branching polymer than cold emulsion SBR, which
makes it better for extrusion, more stable, and less shrinkable.

Cold emulsion SBR is more abrasion resistant and has more tensile strength.

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 S-SBR
Solution polymerization
∞ Solution-SBR is produced by an anionic polymerization process.

∞ Water is strictly excluded. The process is homogeneous (all components are dissolved),
which provides greater control over the Emulsion process, allowing tailoring of the
polymer.

∞ Relative to E-SBR, S-SBR is increasingly favored because it offers improved wet grip and
low rolling resistance, which translate to greater safety and better fuel economy,
respectively.

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 S-SBR Advantages
Due to living anionic
polymerization reaction
Few Advantages of S-SBR over E-SBR
∞ Molecular weight can be controlled easily No side reaction or branching
with anionic polymerization
∞ Narrow distribution of molecular weight
∞ Higher concentration of pure polymer Due to Solution polymerization

∞ More control over the structural details technique

Due to anionic polymerization

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 E-SBR vs S-SBR
E-SBR – Emulsion Polymerization
• Broad molecular weight distribution Overall, emulsion SBR has good abrasion resistance while
functioning better at lower temperatures. It also has low
• Chain branching resulting in gel formation resilience, tensile strength, and tear strength.
• As styrene and 1,2 addition increases the Tg
increases

Solution-SBR – Solvent polymerized block co-polymer

• High Molecular weight
• Narrow molecular weight distribution
Solution SBR has better flexibility and tensile strength
• Mostly linear chains with out branching with lower rolling resistance than emulsion SBR. But it is
• Poor processability more expensive than E-SBR.

• Good absorption of Silica fillers

• Can easily control properties of SBR

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 Property control in SBR

∞ Styrene/butadiene composition
∞ Proportions of vinyl/cis/trans in the butadiene units
∞ Sequence distribution of the monomer units
∞ Molecular weight
∞ Molecular distribution
∞ Branching

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 SBR Advantages and Disadvantages vs NR
Advantages:
- Good Processability
- Blends with NR,BR readily
- Can be sulfur cured
- Can fill with heavy loading of filler
- Better ageing resistance than NR
- Wet skid resistance can be improved with increase in styrene content
- Good tear resistance
- Good resistance to water and chemical( Not oxidizing chemicals)

Disadvantages:

- Poor Tensile properties compared to NR

- Tackiness poor compared to NR
- Needs more accelerators to cure

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 Compounding and Processing of SBR
∞ The compounding and processing of SBR is similar to Natural Rubber and other
unsaturated hydrocarbon rubber.
∞ Processing of SBR depend on,
∞ Molecular weight
∞ Molecular weight distribution
∞ Branching

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 SBR Curing
~ Styrene-butadiene rubber can be cured using sulfur, sulfur donor systems and also cured
by peroxides.

~ SBR has less unsaturation compared to NR.

~ SBR is slow curing compared to NR.

~ Require more accelerators than NR and supported by secondary accelerator such as DPG
(Diphenyl guanidine) or Thiurum accelerator.

~ Comparatively needs less sulfur than NR.

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 Tg of polymers

A glass transition temperature (Tg) is

the temperature at which a polymer turns from a
ductile material to a hard, brittle material. Each
polymer with an amorphous structure has its own
unique glass transition temperature, which makes a
given polymer better suited for some applications
over others

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 The use of SBR in Tires
Varying the monomer content in SBR copolymer, used in tire tread blends, can modify the
properties of tires.

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The effect of monomer content and Tg
on properties of tires

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 Properties
SBR vs NR
Properties NR SBR
Tensile strength Excellent Good
Elongation at tear Very good Good
Compression set Good Good
Heat resistance Fair Good
Resilience Excellent Good
Temperature range ˚C -55 to100 -45 to100

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 Properties
SBR vs NR
Properties NR SBR
Resistance
-weather and ozone Poor Fair
-Acids and Alkali Fair Fair
- Aliphatic and aromatic Poor Poor
oils
-Abrasion Excellent Excellent
-Tear Excellent Fair
-Flame Poor Poor
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 SBR Suppliers & Grades
Hot Polymerized SBR – grades 1009 – clariflex s 100 - grade 1018 - Polysar S 1018, Ameripol
Cold Polymerized SBR - 1500,1502,1505, 1509 – Buna SB ,Europrene
Clariflex, plioflex, Krylene, Kuhmo, Nippon
Oil Extended SBR - 1720NS, 1778NS 1712 HA, DSM,Goodyear,
Shell, Good Year, Bayer, ENI chem
Carbon Black /Oil SBR – 1609 N 110/40,1805 N330/75
DSM ( Carbomix), Ameripol, ENI chem
Solution Polymerized SBR – Bayer, ENIchem

SBR- solution vinyl –Butadiene – Styrene Rubber- Bayer, ENIchem

SBR latex – Nitriflex, ENI chem

High Styrene Resin – Pliolite, Nippol, Nitriflex

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Applications & Uses of SBR

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 HSR (high styrene resin)
HSR is used for rubber compound reinforcement. By substituting fillers (such as carbon black, clay,
calcium carbonate) in part or entirely, it achieves more attractive physical properties and eliminates
problems in process due to high filler content. The high bound styrene content makes it very useful
for rubber compounds that require a high degree of reinforcement and hardness, combined with
excellent tear strength and flex resistance.

High styrene resin is used in rubber products that require high hardness, abrasion resistance,
flex and tear resistance in SBR, IR, NR, EPDM, EVA, and CR.

Appearance ............................................................................White Crumbs

Styrene Content (%) ................................................:60%,63%,65%,68%,80%,83%,85%

HSR can be used in a variety of rubber compounding applications such as: molded mechanical
goods, extrusions, shoe soling, electrical insulation, flooring, etc. It can be used to increase
tensile, resist
flex fatigue, abrasion, and reinforce rubber compounds to the desired hardness and strength.

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 High Impact Polystyrene (HIPS)
 High Impact Polystyrene (HIPS) is a form of polystyrene (PS) that carries with it a higher
impact strength.

 Homopolymer PS can often be brittle, and can be made more impact resistant if
combined with other materials.

 This form of PS typically is produced by adding around 5-10% rubber or butadiene

copolymer.

 This increases the toughness and impact strength of the polymer and results in a very stiff
product ideal for packaging applications.

 Good dimensional stability even at low temperature and high impact strength than
the general purpose polystyrene, good toughness, ease of processing, higher
resistance to stress cracking, high elongation at break, less resistance to ageing than
GPPS, lower hardness and rigidity than GPPS and dissolved by alcohols, ketones, 50
Common Uses of HIPS:
Consumer products: Appliance components, toy, TV and audio-visual
equipment parts, recording tape cassettes, bicycle trailer, toys

Automotive industry: Instrument panels and fittings, gasoline tanks

Food Services: Hot and cold drinking cups

Office Products: Computer Housings

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