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Butyl Rubber (IIR)
PROPERTIES AND APPLICATIONS
Butyl rubber (IIR) is the copolymer of isobutylene and a small amount of isoprene. First commercialized in 1943,
the primary attributes of butyl rubber are excellent impermeability/air retention and good flex properties, resulting
from low levels of unsaturation between long polyisobutylene segments. Tire innertubes were the first major use of
butyl rubber, and this continues to be a significant market today.
The development of halogenated butyl rubber (halobutyl) in the 1950’s and 1960’s greatly extended the usefulness
of butyl by providing much higher curing rates and enabling co-vulcanization with general purpose rubbers such as
natural rubber and styrene-butadiene rubber (SBR). These properties permitted development of more durable
tubeless tires with the air retaining innerliner chemically bonded to the body of the tire. Tire innerliners are by far
the largest application for halobutyl today. Both chlorinated chlorobutyl) and brominated (bromobutyl) versions of
halobutyl are commercially available. In addition to tire applications, butyl and halobutyl rubbers’ good
impermeability, weathering resistance, ozone resistance, vibration dampening, and stability make them good
materials for pharmaceutical stoppers, construction sealants, hoses, and mechanical goods.
CHEMISTRY AND MANUFACTURING PROCESS
Butyl Rubber typically contains about 98% polyisobutylene with 2% isoprene distributed randomly in the polymer
chain.
To achieve high molecular weight, the reaction must be controlled at low temperatures (-90 to -100 degC). The
reaction is highly exothermic. The most commonly used polymerization process uses methyl chloride as the reaction
diluents and boiling liquid ethylene to remove the heat of reaction and maintain the needed temperature. It is also
possible to polymerize butyl in alkane solutions and in bulk reaction. A variety of Lewis acids can be used to initiate
the polymerization. The molecular weight of butyl is set primarily by controlling the initiation and chain transfer
rates.
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In the most widely used manufacturing process (Figure 1), a slurry of fine particles of butyl rubber (dispersed in
methyl chloride) is formed in the reactor. The methyl chloride and unreacted monomers are flashed and stripped
overhead by addition of steam and hot water, and then they are dried and purified in preparation for recycle to the
reactor. Slurry aid (zinc or calcium stearate) and antioxidant are introduced to the hot water/polymer slurry to
stabilize the polymer and prevent agglomeration.
Then the polymer is screened from the hot water slurry and dried in a series of extrusion dewatering and drying
steps. Fluid bed conveyors and/or airvey systems are used to cool the product to acceptable packaging temperature.
The resultant dried product is in the form of small “crumbs”, which are subsequently weighed and compressed into
75 lb. bales for wrapping in PE film and packaging
etc...) and all unreacted monomer removed. Several different processes are currently used to prepare butyl solution
for halogenation.
Either reactor effluent polymer, in-process rubber crumb or butyl product bales may be dissolved in solvent in
preparation for halogenation.
Figure 1 Commercial Butyl Slurry Polymerization Process
Bromine liquid or chlorine vapor is added to the butyl solution in highly agitated reaction vessels. One mole of
hydrobromic or hydrochloric acid is released for every mole of halogen that reacts, therefore the reaction solution
must be neutralized with caustic (NaOH). The solvent is then flashed and stripped by steam/hot water, with calcium
stearate added to prevent polymer agglomeration. The resultant polymer/water slurry is screened, dried, cooled, and
packaged in a process similar to that of unhalogenated butyl.
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PROCESSING AND VULCANIZATION
Like other rubbers, for most applications, butyl rubber must be compounded and vulcanized (chemically cross-
linked) to yield useful, durable end use products. Grades of Butyl have been developed to meet specific processing
and property needs, and a range of molecular weights, unsaturation, and cure rates are commercially available. Both
the end use attributes and the processing equipment are important in determining the right grade of Butyl to use in a
specific application. The selection and ratios of the proper fillers, processing aids, stabilizers, and curatives also play
critical roles in both how the compound will process and how the end product will behave.
Care must be taken when processing Halobutyl that premature dehydrohalogenation does not occur due to high
temperature. Stabilizers (calcium stearate alone for chlorobutyl, supplemented with an epoxy compound such as
epoxidized soybean oil in the case of bromobutyl) are required to prevent dehydrohalogenation during processing.
Elemental sulfur and organic accelerators are widely used to cross-link butyl rubber for many applications. The low
level of unsaturation requires aggressive accelerators such as thiuram or thiocarbamates. The vulcanization proceeds
at the isoprene site with the polysulfidic cross links attached at the allylic positions, displacing the allylic hydrogen.
The number of sulfur atoms per cross-link is between one and four or more. Cure rate and cure state (modulus) both
increase if the diolefin content is increased (higher unsaturation). Sulfur cross-links have limited stability at
sustained high temperature.
Resin cure systems (commonly using alkyl phenol-formaldehyde derivatives) provide for carbon-carbon cross-links
and more stable compounds.
Butyl (and its primary derivative, halobutyl) is and will continue to be a high value polymer particularly well suited
for its primary application of air retention in tires. Its unique combination of properties (excellent impermeability,
good flex, good weatherability,
Co-vulcanization with high unsaturation rubbers, in the case of halobutyl) make it a preferred material for this
application. As miles driven, tire size, and market sensitivity to pressure retention are all increasing, the demand for
butyl rubber (specifically halobutyl) will continue to grow.
