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Styrene Butadiene Rubber

SBR (styrene-butadiene rubber) is a synthetic rubber produced by polymerizing styrene and butadiene. It exists in both emulsion polymerization and solution polymerization forms, which leads to differences in properties. Emulsion SBR has lower molar mass, higher styrene content, and higher glass transition temperature than solution SBR. It also has a broader molar mass distribution and different microstructure ratios of butadiene linkages. These differences impact properties such as strength and flexibility.

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456 views27 pages

Styrene Butadiene Rubber

SBR (styrene-butadiene rubber) is a synthetic rubber produced by polymerizing styrene and butadiene. It exists in both emulsion polymerization and solution polymerization forms, which leads to differences in properties. Emulsion SBR has lower molar mass, higher styrene content, and higher glass transition temperature than solution SBR. It also has a broader molar mass distribution and different microstructure ratios of butadiene linkages. These differences impact properties such as strength and flexibility.

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abdulqadir
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STYRENE BUTADIENE RUBBER

SBS BLOCK POLYMER

Its backbone chain is made up of three


segments. The first is a long chain of polystyrene
, the middle is a long chain of polybutadiene,
and the last segment is another long section of
polystyrene.
SBR

• Polystyrene is a tough hard plastic, and this gives SBS its


durability.
• Polybutadiene is rubbery, and this gives SBS its rubber-like
properties.
• Polystyrene chains tend to bundle together. When one
styrene group of one SBS molecule joins one bundle, and
the other polystyrene chain of the same SBS molecule joins
another bundle, the different bundles become tied together
with rubbery polybutadiene chains.
• This gives the material the ability to retain its shape after
being stretched.
SBR

• Four different basic construction units in SBR.


Three of them originate from butadiene and
one from styrene

Cis-1,4-form Trans-1,4-form

1,2-form Styrene
COMPARISON
BETWEEN THE PROPERTIES OF SBR AND NR.
Styrene Butadiene
Physical Properties Natural Rubber
Rubber
Specific Gravity g/cm3 0.93 0.94
Suitability for coloring Good Good
Tensile strength (MPa) 7-24 7-28
Hardness (Shore A) 20-100 20-100
Tear strength very good good
Abrasion resistance very good good
Electrical insulation
Good Fair
properties
RESISTANCE TO WEATHERING
sunlight fair fair
Resistance to ozone poor fair to poor
HEAT RESISTANCE poor fair
RESISTANCE TO:
mineral oils poor poor
polar substances fair fair
(Alcohols, ketones, glycols, phosphoric to poor to poor
acid esters etc.)
animal and vegetable oils poor poor
acids fair to good fair to good
swelling in water good good
Advantages of SBR
• Random copolymer of butadiene (67-85%) and styrene (15-33%)
• Tg of typical 75/25 blend is –60°C (NR has Tg -70)
• This type of rubber is usually very weak unless reinforcing fillers are
incorporated. With suitable fillers, this becomes a strong rubber
• One of the least expensive rubbers and generally processes easily.
• Inferior to natural rubber in mechanical properties
• Superior to natural rubber in wear, heat aging, ozone resistance,
and resistance to oils.
• good abrasion and aging resistance
• good elasticity
• low price
• Heat resistance is better than natural rubber
Disadvantages of SBR
• inferior mechanical properties (require
reinforcements)
• adhesion properties
• poor oil resistance
• poor ozone resistance
• do not resist aromatic, aliphatic or
halogenated solvents
• low elongation at break
Application
• More than half of the world’s synthetic rubber is SBR
• car tires (blended with BR, and NR)
• footwear 
• conveyor belts  
• hoses
• toys
• molded rubber goods
• sponge and foamed products
• waterproof materials
• belting
• adhesives
• cable insulation, industrial rubber products, adhesives, paints (latex or
emulsion)
• World usage of SBR equals natural rubber. 50% of car tires are made
from SBR
Types of SBR

Based on the manufacturing process adopted


there are two major types of SBR:
1. Emulsion SBR (e-SBR);
Hot Emulsion or Cold Emulsion
2. Solution SBR (s-SBR).

Each process produces SBR grades with different


properties.
Basics of solution polymerization

• s-SBR is made by termination-free, anionic (living)


polymerization initiated usually by alkyl-lithium compounds.
• The chemicals used are:
1. The monomers (styrene and butadiene);
2. The catalyst (usually n- or s-butyl lithium )
3. The solvent (commonly cyclohexane, hexane,
heptane, toluene, cyclopentane, isopentane or
mixtures thereof); and
4. Process additives like coupling agents, structure
modifiers, extender oil, killing agents and product
stabilizers.
Basics of solution polymerization

Chemicals interfere with catalyst & hence to be


strictly avoided

1. Carbon dioxide,
2. water,
3. oxygen,
4. alcohols,
5. mercaptans and
6. primary/secondary amines
Processing Steps
1. Make a chain of living polystyrene. This is
done by polymerizing the monomer styrene
with an anionic initiator like butyl lithium.
Processing Steps

2. This polystyrene chain is living, so if we add a


second monomer to it, it'll add to the polymer.
So we'll add some of the monomer butadiene.
That gives us a living styrene-butadiene
block copolymer.
Processing Steps
3.The next step is just to add more styrene
monomer, and get a styrene-butadiene-
styrene triblock copolymer.
Styrene monomer won't add to the anion at
the end of a living polybutadiene chain.

To add styrene we're going to react it with a


compound called dichlorodimethylsilane
Now our polymer is no longer living
Processing Steps

4. Living polystyrene homopolymer reacts with


chlorosilane end-capped polymer to give
triblock SBS polymer
Basics of emulsion polymerization

• Styrene and butadiene monomers polymerize in the


presence of
1. an emulsifier (fatty or rosin acid soaps), 2. an
initiator system,
3. a modifier (mercaptan) and
4. water.
Initiator agent in case of cold polymerization is the redox
reaction between chelated iron/organic peroxide and
sodium formaldehyde sulphoxylate as reducing agent.
For hot emulsion polymerization potassium
peroxydisulfate is used as an initiator.
Advantages of Emulsion Polymerization
• It is normally used under mild reaction conditions that are tolerant
to water and requires only the absence of oxygen.
• The process is relatively robust to impurities and amenable to
using a range of functionalized and non-functionalized monomers.
• Additional benefits include the fact that emulsion polymerization
gives high solids contents with low reaction viscosity and is a cost-
effective process.
• The physical state of the emulsion (colloidal) system makes it easy
to control the process.
• Thermal and viscosity problems are much less significant than in
bulk polymerization.
Reactions in Cold Emulsion Polymerization

• Fe(II)EDTA + ROOH → Fe(III)EDTA + RO + OH (1)

• Fe(III)EDTA + SFS → Fe(II)EDTA (2)


Processing Parameters
1. Temperature, flow rate and agitation are controlled to get the
right conversion.
2. Polymerization is normally allowed to proceed to about 60%
conversion in cold polymerization and 70% in hot polymerization
before it is stopped with a shortstop agent that reacts rapidly with
the free radicals.
3. The short stopping agent terminate the growing chain and initiate
a new one.
P + RSH → P-H + RS (3)

Some of the common shortstopping agents are sodium


dimethyldithiocarbamate and diethyl hydroxylamine.
Processing Parameters

4. The RS formed will continue to initiate the


growth of a new chain

RS + M → RS-M (4)
The thiol prevents gel formation and improves
the process ability of rubber.
Processing Parameters
3. After shortstopping, the unreacted monomers
are stripped off the latex.
– Butadiene is stripped by degassing the latex by
means of flash distillation and reduction of system
pressure.
– Styrene is removed by steam stripping the latex in
a column.

The latex is then stabilized with the appropriate


antioxidant and transferred to blend tanks.
Processing Parameters
4. The polymer is then coagulated with sulfuric acid, sulfuric
acid/sodium chloride, glue/sulfuric acid, aluminum sulfate,
or amine coagulation aid.

- Sulfuric acid/sodium chloride is used for general


purpose.
- Glue/sulfuric acid is used for electrical grade and low
water sensitivity SBR.
- Sulfuric acid is used for coagulations where low- ash-
polymer is required.
- Amine coagulating aids are used to improve coagulation
efficiency and reduce production plant pollution.
PROPERTIES OF EMULSION POLYMERIZATION AND SOLVENT POLYMERIZATION.

Emulsion - SBR Solvent-SBR


Molar mass Mn, g/mol 145000 200000
Molar mass Mw, g/mol 651000 420000
Mw / Mn 4.5 2.1
Styrene content, % 23.5 18
Cis-1,4-content, % 18 35
Trans-1,4-content, % 65 54
1,2-content, % 17 11
Glass transition temperature
- 50.6 - 69.7
Tg, °C

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