STYRENE – BUTADIENE RUBBER ( SBR)

SBR, A CO-POLYMER OF STYRENE AND

BUTADIENE IS THE MOST IMPORTANT AND
MOST WIDELY USED SYNTHETIC RUBBER IN
THE WHOLE WORLD.

THE FIRST CO-POLYMER FROM AN EMULSION

SYSTEM WAS PREPARED AT THE RESEARCH
LABORATORIES OF I.G. FARBENINDUSTRIE AND
IT WAS NAMED BUNAS.

IN RECENT YEARS, SOLUTION METHODS OF

POLYMERISATION HAVE BECOME POPULAR.
THE RESULTING NEW RUBBERS ARE
COMPETING IN COST AND QUALITY WITH
EMULSION SBR.
 RAW MATERIAL:
BUTADIENE AND STYRENE ARE CHIEF RAW MATERIALS
REQUIRED TO MANUFACTURE SBR. OTHERS REQUIRED
IN SMALL AMOUNTS ARE THE VARIOUS EMULSIFIERS,
MODIFIERS, CATALYSTS, SHORT STOPS, CO-AGULATING
AGENTS AND ANTIOZONANTS.

BUTADIENE:
ABOUT 80% OF THE WORLD’S PRODUCTION OF
BUTADIENE IS USED TO MAKE SYNTHETIC RUBBERS.
OVER HALF OF THE BUTADIENE IS DERIVED FROM
BUTENES, ABOUT 37% FROM BUTANES AND THE
REMAINDER FROM MISC. REFINERY STREAMS. IN BOTH
EUROPE AND JAPAN, THE C4 BY-PRODUCT STREAM OF
NAPTHA IS A MAJOR SOURCE OF BUTADIENE. TWO
PROCESSES ARE POPULAR TO MAKE BUTADIENE:
 PHILLIPS PROCESS:
THE BUTENES ARE OBTAINED FROM A C3-C4
STREAM. THE PROPANE AND ISOBUTANE ARE
REMOVED BY FRACTIONATION AND THE
ISOBUTYLENE BY ABSORPTION IN SULPHURIC ACID.
THE REMAINDER IS A MIXTURE OF C4 STRAIGHT
CHAIN HYDROCARBONS INCLUDING ABOUT 30% OF A
MIXTURE OF 1-BUTENE AND 2- BUTENE. THIS IS FED
TO A CATALYTIC DEHDROGENATOR AFTER
PREHEATING TO ABOUT 550 C AND DILUTING WITH
SUPERHEATED STEAM. THE CRUDE BUTADIENE
OBTAINED IS PURIFIED BEFORE BECOMING SUITABLE
FOR POLYMERISATION.
 HOUDRY PROCESS
BUTANE IS DEHYDROGENATED IN A SINGLE STEP TO
FORM BUTADIENE USING CHROMIA –ALUMINA CATALYST.

EMULSION POLYMERISATION MAY TOLERATE THE

PRESENCE OF AS MUCH AS 5000 PPM OF ACETYLENIC
IMPURITIES IN THE POLYMERISATION RECIPE BUT
SOLUTION SBR CAN NOT ALLOW MORE THAN 50 PPM.

STYRENE: ABOUT 22% OF WORLD PRODUCTION OF STYRENE

IS USED IN SBR MANUFACTURE.

STYRENE IS MADE BY DEHYDROGENATING ETHYL BENZENE,

THE REACTION PRODUCT OF BENZENE AND ETHYLENE.

ETHYL BENZENE IS PREPARED BY ALKYLATING BENZENE

WITH ETHYLENE IN THE PRESENCE OF ALUMINIUM
CHLORIDE IN THE TYPICAL FRIEDAL CRAFTS REACTION.
 POLYMERISATION:
POLYMERISATION OF BUTADIENE CH2 = CH-CH=CH2
OCCURS BY ADDITION OF ONE UNIT TO ANOTHER
REPEATED SEVERAL THOUSAND TIMES OVER. BECAUSE
THERE ARE DOUBLE BONDS IN THE MONOMER,
ADDITIONS MAY BE OF THREE VARIETIES, KNOWN AS CIS-
1,4 , TRANS-1,4 AND VINYL(ALSO CALLED 1,2). IN A
POLYMER CHAIN THESE MAY BE ALL PRESENT TOGETHER
RANDOMLY.

SBR MADE BY EMULSION USUALLY CONTAINS 23%

STYRENE RANDOMLY DISPERSED WITH BUTADIENE IN
THE POLYMER CHAINS. THE STRUCTURE OF BUTADIENE
CHAIN IS ABOUT 18% CIS, 65% TRANS AND 17% VINYL.
INTRINSIC VISCOSITY IS 2.0 DL/G., GEL CONTENT IS
NEGLIGIBLE. MOONEY VISCOSITY (ML 1+4 AT 100 C) IS 50
AND SPECIFIC GRAVITY IS 0.94.
SBR MADE IN SOLUTION CONTAINS ABOUT SAME
PERCENT OF STYRENE BUT BOTH RANDOM AND BLOCK
CO-POLYMERS HAVE BEEN MADE. THEY HAVE LOWER
TRANS, VINYL BUT HIGHER CIS CONTENT THAN EMULSION
SBR.

THE MAIN DIFFERENCES BETWEEN EMULSION AND

SOLUTION SBR IS DUE TO LINEARITY AND MOLECULAR
WEIGHT DISTRIBUTION OF THE MOLECULAR CHAINS
RATHER THAN IN THEIR MICROSTRUCTURES.
 EMULSION POLYMERISATION:

A TYPICAL EMULSION SYSTEM CONTAINS WATER,

MONOMERS, INITIATOR AND AN EMULSIFIER(SOAP).

THERE ARE TWO EMULSION PROCESSES : HOT PROCESS

AND COLD PROCESS.

A TYPICAL RECIPE FOR INDUSTRIAL USE IS AS FOLLOWS :

BUTADIENE : 75.0
STYRENE : 25.0
N-DODECYL MERCAPTAN : 0.5 (MODIFIER)
POT. PEROXYDISULPHATE : 0.3 (INITIATOR)
SOAP FLAKES : 5.0(EMULSIFIER)
WATER : 180.0
IN THE HOT PROCESS, REACTION TAKES PLACE AT 50 C
AND THE CONVERSION TO POLYMER OCCURS AT 5-6%
PER HOUR. POLYMERISATION IS STOPPED AT 70-75%
CONVERSION LEVEL.
IN THE COLD PROCESS, REACTION TAKES PLACE AT 5 C
AND CONVERSION TO POLYMER OCCURS IN ABOUT 12
HOURS.

THE SUCCESSFUL DEVELOPMENT OF COLD

POLYMERISATION PROCESS MADE IT POSSIBLE TO
PRODUCE HIGHER MOLECULAR WEIGHT POLYMERS
WHICH COULD BE OIL EXTENDED.

THE AFFINITY OF DIFFERENT TYPES OF OILS TO SBR AND

IN GENERAL TO DIENE ELASTOMERS, DIMINISHES IN THE
ORDER AROMATIC – NAPHTHINIC – PARAFFINIC.
PARAFFIIC OILS CAN NOT BE USED WITH DIENE
ELASTOMERS AS THEY ARE INCOMPATIBLE.
 HIGH STYRENE POLYMERS:
ONLY A FEW GRADES WITH LESS THAN 23% STYRENE
ARE MADE TO OBTAIN IMPROVED LOW
TEMPERATURE SERVICE PROPERTIES.

GRADES WITH MORE THAN 50% AND UP TO 90%

STYRENE CONTENT ARE KNOWN AS HIGH STYRENE
RESINS. THESE ARE IMPORTANT COMPOUNDING
INGREDIENTS TO IMPART INCREASED HARDNESS AND
STIFFNESS E.G., TO OBTAIN LEATHER LIKE
PROPERTIES IN SHOE SOLING.
 COMMERCIAL GRADES:
AS PER THE INTERNATIONAL INSTITUTE OF SYNTHETIC
RUBBER PRODUCERS INC., SBR IS NUMBERED AS
FOLLOWS:

1000 – HOT POLYMERS

1100 – HOT BLACK MASTERBATCH WITH 14 OR LESS
PARTS OF OIL PER HUNDRED PARTS OF SBR.
1500 – COLD POLYMERS
1600 – COLD BLACK MASTERBATCH WITH 14 OR LESS
PARTS OF OIL
1700 – COLD OIL MASTERBATCH
1800 – COLD OIL BLACK MASTERBATCH WITH MORE THAN
14 PARTS OF OIL
1900 – MISCELLANEOUS DRY POLYMER MASTERBATCHES
2000 – HOT LATICES
2100 – COLD LATICES
 SOLUTION SBR:

ATPRESENT, SUCCESSFUL SOLUTION COPOLYMERISATION

OF STYRENE AND BUTADIENE HAS BEEN CARRIED OUT
ONLY WITH LITHIUM AND ALKYL LITHIUM CATALYSTS. THE
CATALYST IS ADDED TO THOROUGHLY DRIED MIXTURE
OF MONOMERS AND HYDROCARBON SOLVENT. AS THE
POLYMERISED SOLUTION LEAVES THE LAST REACTOR,
STOPPER AND STABILISER ARE ADDED.

SEVERAL SOLUTION SBR ARE OFFERED COMMERCIALLY.

THE RANDOM CO-POLYMERS ARE RUBBERY AND LIKE
EMULSION SBR BUT WITH SEVERAL IMPROVED
PROPERTIES.

THE BLOCK POLYMERS TEND TO BE THERMOPLASTIC AND

ARE NOT RECOMMENDED FOR TYRE USE.
RANDOM SOLUTION SBR HAVE NARROWER MOLECULAR
WEIGHT DISTRIBUTION, LESS BRANCHING, HIGHER CIS-
CONTENT, LIGHTER COLOUR, AND LESS NON- RUBBER
CONSTITUENTS THAN THE EMULSION SBR. THEREFORE,
THEY ARE REPORTED TO HAVE BETTER ABRASION
RESISTANCE, BETTER FLEX, HIGHER RESILIENCE, AND
LOWER HEAT BUILD UP WHEREAS TENSILE, MODULUS ,
ELONGATION AND COST ARE COMPARABLE.
 PHYSICAL PROPERTIES:
THERE ARE HOST OF PHYSICAL PROPERTIES WHICH ARE OF
IMPORTANCE TO RUBBER TECHNOLOGISTS FOR DETERMINING
THE SUITABILITY OF A PARTICULAR RUBBER FOR A PARTICULAR
USE.

THE SINGLE MOST IMPORTANT PROPERTY FOR CLASSIFYING A

MATERIAL AS AN ELASTOMER IS THE GLASS TRANSITION
TEMPERATURE. THIS IS THE REGION WHERE A VISCOUS OR
FLEXIBLE MATERIAL ABOVE THE TRANSITION TEMP. CHANGES
TO A STIFF AND BRITTLE MATERIAL BELOW.
THE GLASS TRANSITION TEMPERATURE MAY BE READILY
MEASURED BY INSTRUMENTS DESIGNED FOR DIFFERENTIAL
THERMAL ANALYSIS OR DIFFERENTIAL THERMAL
CALORIMETRY.
Tg WILL BE HIGHER IF STYRENE CONTENT IS HIGHER. IN CASE
OF SOULUTION SBR, Tg WILL BE SLIGHTLY LOWER THAN
EMULSION SBR WITH THE SAME STYRENE LEVEL BECAUSE THE
BUTADIENE PORTIONS OF SOLUTION SBR ARE LOWER IN VINYL
STRUCTURE AND HIGHER IN CIS STRUCTURE.
MOLECULAR WEIGHT AND ITS DISTRIBUTION ARE ALSO
IMPORTANT IN DETERMINING POLYMER PROPERTIES.

ALTHOUGH, A HIGH MOLECULAR WEIGHT IS DESIRABLE

TO OBTAIN BETTER PHYSICAL PROPERTIES, A LOW MOL
WT. POLYMER PROCESSES MORE READILY.

FOR EMULSION SBR, THE DISTRIBUTION VARIES WITH

REACTION CONVERSION, TYPE OF MERCAPTAN MODIFIER
USED, REACTION TEMPERATURE AND THE COMMERCIAL
SOURCE.

SOLUTION SBR TEND TO HAVE VERY NARROW

MOLECULAR WEIGHT DISTRIBUTION. TO IMPROVE
PROCESSING, IT IS OFTEN DESIRABLE TO DELIBERATELY
BROADEN THE DISTRIBUTION BY ADDING SOME
BRANCHING REAGENT IMMEDIATELY AFTER
POLYMERISATION.
 COMPOUNDING AND PROCESSING:
MODERN SBR NO LONGER REQUIRES THE REPEATED MIXING CYCLES AS
THE EARLIER PRODUCTS. ITS EXTRUSION PROPERTIES ARE SUPERIOR TO
THOSE OF NATURAL RUBBER. ITS STOCKS HAVE LESS TENDENCY TO
SCORCH IN PROCESSING. ALTHOUGH COLD SBR IS PREFERABLE TO HOT
FOR OPTIMUM PHYSICAL PROPERTIES, USE OF HOT SBR CAN ALSO
CONTRIBUTE TO BOTH PROCESSING AND PRODUCT IMPROVEMENTS.

FOR MANY USES, BLEND OF SBR WITH NR AND PBR ARE MADE.
ALL TYPES OF SBR USE THE SAME BASIC COMPOUNDING RECIPES AS DO
OTHER UNSATURATED HYDROCARBON POLYMERS. THEY NEED
SULPHUR , ACCELERATORS, ANTIOXIDANTS, ACTIVATORS, FILLERS,
SOFTENERS AND EXTENDERS. SBR REQUIRES LESS S THAN NR FOR
CURING. THE USUAL RANGE IS 1.5-2.0 PHR . SBR DUE TO LESS
UNSATURATION THAN NR IS SLOWER CURING AND THEREFORE, REQUIRES
HIGHER ACCELERATION.

COMPOUNDING RECIPES CONTAINING LOW SULPHUR OR ORGANICALLY

BOUND S ( AS IN A THIOZOLE) IMPROVE AGING PROPERTIES BUT ARE
SLOWER CURING. ZINC OXIDE AND STEARIC ACID ARE THE MOST
COMMON ACTIVATOR FOR SBR. RECIPES ALSO CONTAIN TACKIFIERS,
SOFTENERS, WAXES, RECLAIM ETC. IT IS NOT UNUSUAL TO FIND A RECIPE
WITH 15 OR MORE INGREDIENTS.
A TYPICAL PASSENGER TYRE FORMULATION BASED ON
SBR AND PBR IS AS FOLLOWS:

SBR : 103.0 ( OIL EXTENDED RUBBER)

PBR : 25.0
STEARIC ACID : 2.0
ZINC OXIDE : 3.0
ANTIOXIDANT : 2.0 ( NAPTHYLAMINE TYPE)
ANTIOZONANT : 4.0 (DIAMINE TYPE)
PROCESSING AID : 5.0
MC – WAX : 1.0
PROCESS OIL : 7.0
ISAF C- BLACK : 65.0
ACCELERATOR : 1.5 (SULPHENAMIDE )
SULPHUR : 1.8
PROCESSING OF SBR COMPOUNDS IS SIMILAR TO THAT OF
NATURAL RUBBER. THE INGREDIENTS ARE MIXED IN INTERNAL
MIXER OR ON MILLS, AND MAY BE EXTRUDED, CALENDERED,
MOULDED AND CURED IN CONVENTIONAL EQUIPMENT. MIXING
PROCEDURES VARY WITH

THE COMPOUND. IN GENERAL, THE RUBBER, ZINC OXIDE,

STEARIC ACID , ANTIOXIDANT ARE MIXED, THEN THE CARBON
BLACK IS ADDED IN PORTIONS WITH THE SOFTENERS OR OILS.
AFTER THIS ACCELERATOR IS ADDED AND SULPHUR IS ADDED
LAST.

FOR MAXIMUM TENSILE PROPERTIES AND ABRASION

RESISTANCE, COLD SBR IS PREFERABLE TO HOT.

IN CASE OF NATURAL RUBBER, IT IS NECESSARY TO PLASTICIZE

THE RAW RUBBER MECHANICALLY AS A SEPARATE OPERATION
BEFORE MIXING WITH OTHER INGREDIENTS. HOWEVER, IN
CASE OF SBR SMALL PLASTICIZATION IS REQUIRED AND
EXCESSIVE MILLING LEADS TO GEL FORMATION AND POORER
EXTRUSION.
ONE OF THE MAJOR DRAWBACK WITH SBR STOCKS IS
THE LACK OF GREEN TACK. FOR THIS REASON, WE MUST
APPLY A LAYER OF NATURAL RUBBER CEMENT TO OBTAIN
ADHESION ON ALL SURFACES OF THE TREAD WHICH ARE
TO BE JOINED TO OTHER SURFACES WHEN THE TYRE IS
BUILT.

IF SBR STOCK IS USED FOR COATING OF FABRIC ON A

CALENDER, IT IS NECESSSARY TO USE SLIGHTLY MORE
CROWN ON THE CALENDER ROLL.
 USES:
WHILE PASSENGER TYRES AND TYRE PRODUCTS
ACCOUNT FOR THE MAJOR PORTION OF SBR
CONSUMPTION, OTHER BRANCHES OF THE RUBBER
INDUSTRY ALSO MAKE EXTENSIVE USE OF SBR IN
FABRICATION OF A WIDE VARIETY OF PRODUCTS AS
PER DETAILS GIVEN BELOW:

TYRES : 70%
WIRE AND CABLES : 2%
MECHANICAL GOODS : 4%
FOOTWEAR AND SHOE : 5%
BELTING / HOSES : 2%
MISC. SOLID RUBBER : 10%
LATEX USES : 5%
SPONGE & ADHESIVES : 2%