Butyl Rubber (IIR)

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Chemical Structure
of IIR

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Permeability of Difference Rubbers to Air

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 Butyl Rubber
(IIR)
‡ Butyl rubber, also known as Isobutylene-isoprene (IIR) was introduced in 1942.

‡ Halogenated IIR was introduced in 1960’s.

‡ IIR is produced by low temperature cationic copolymerization of 1,1-dimethylethylene

(isobutylene) with about 1 to 3 % of isoprene using Lewis catalysts (AlCl3/CH3Cl)in
organic solvents.

‡ The isoprene provides the necessary unsaturation sites for crosslinking.

‡ Butyl is polymerized at a temperature of -100 °C, it is either dried and baled or

dissolved in an organic solvent and modified to produce halogenated butyl rubber.

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 Halogenated Butyl
Rubber (IIR)
Halobutyl-Rubber (HIIR), such as Bromobutyl (BIIR) or Chlorobutyl (CIIR) rubbers, is obtained through the
halogenation of the isoprene groups of the IIR, producing a rubber with improved properties and
characteristics. HIIR presents higher curing rates and can easily co-vulcanize in elastomer blends with other
rubbers, such as NR (Natural Rubber), BR (Butadiene Rubber) and SBR (Styrene-Butadiene Rubber).

The IIR and HIIR rubbers, thanks to their high gas and liquids impermeability, excellent mechanical
properties preserved in a wide range of temperature, good resistance to fatigue, and an elevated resilience to
most chemicals, find a large spectrum of applications. The major use is in the tyre industry (tyre curing
bladders, inner liners, tubeless tyres), and other applications include: adhesives, protective clothing, sealants,
pharmaceutical stoppers, fuel additives, vibration damping devices.

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 Production of Halogenated Butyl Rubber (IIR)
‡ The synthesis of halogenated-butyls involves reaction of a solution of butyl in hexane
with elemental halogens.

‡ Usual temperature 40-60 ˚C.

‡ The target is to produce a product in which no more than 1 halogen atom is introduced
into the polymer per unsaturated site initially present.

‡ The reaction with chlorine is very fast.

‡ The bromine reaction is considerable more slower than chlorine reaction.

‡ HCl produced by the reaction must be neutralized using aqueous NaOH solution.

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Structure II, the predominant structure in
halobutyl rubber, represents 50%-60%, followed
by Structure I representing from 30%-40%.
Approximately 5%-15% is Structure III;
structure IV is typically only 1%-3%.
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In summary:
· high impermeability to gases
· improved weather and ozone resistance
· improved chemical resistance
· good cure versatility
· faster cure rate with lower amount of curatives
· good cure compatibility with unsaturated rubber types
· high heat resistance

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 Compounding and Processing of Butyl Rubber

‡ Like other rubbers, for most applications, butyl rubber must be compounded and cured 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.

‡ 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.

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 Butyl Rubber Curing

‡ Three basic methods for curing.

‡ 1) Sulfur curing
‡ 2) Crosslinking with dioxime and related dinitroso compounds
‡ 3) Resin curing
‡ 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.

‡ CIIR and BIIR have more reactive points in the cross-linking if a curing agent (sulfur or
metal oxides) has been used in curing.

‡ Peroxides cannot be used, because they may break down the elastomer chains.

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Sulfur curing

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Dioxime cure of butyl rubber.

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Quinoid Curing of Butyl and Natural Rubbers

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Resin curing of butyl rubber

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 Halo Butyl Rubber
Curing

‡ In halobutyl, the allylic halogen allows easier cross-linking than does allylic
hydrogen alone, because halogen is a better leaving group in nucleophilic
substitution reactions.

‡ Zinc oxide is commonly used to cross-link halobutyl rubber, forming very stable
carbon-carbon bonds by alkylation through dehydrohalogenation, with zinc
chloride byproduct.

‡ Bromobutyl is faster curing than chlorobutyl and has better adhesion to high
unsaturation rubbers.

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Zinc oxide in the vulcanization of bromobutyl rubber

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Issue With Peroxide Curing of Butyl Rubber

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 Butyl for Tires
Tire Inner Liners
‡ Using halobutyl rubber within the tire inner liner helps the tire to maintain proper
inflation pressure.

‡ It is well known within the tire industry that a tire retaining proper inflation pressure
has improved rolling resistance and fuel economy compared to conditions where it is
under inflated.

‡ Halobutyl inner liners also protect vulnerable tire components from oxygen attack by
reducing intercarcass pressure.

‡ Bromobutyl and chlorobutyl are well-suited for the production of white sidewall and
non-staining black sidewall because of their resistance to weathering, adhesion,
bend and flex characteristics.
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 Properties of Butyl Rubber

‡ The properties of butyl rubbers depend on the length of the molecule chains and the
saturation degree. When the amount of double bonds is low, rubber has good oxygen
and ozone resistance. A greater amount of double bonds accelerates the curing process
and increases the amount of cross-links.
- Low gas permeability
- Resistance to oxygen, ozone and heat
- UV resistance
- Good resistance to chemicals
- Low elasticity and resilience
- Stable in long-term-use and at high temperatures
- Good weather resistance
- Low water absorption
_ Resistant to oxidizing agents, vegetable and animal fats and polar solvents

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Applications of IIR

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 Let’s Compare BR, SBR, and NR
with IIR
• Abrasion resistance,
• Low-temperature behavior (Tg)
• Elasticity
• Heat resistance
• Ozone resistance
• Uv resistance
• Chemical Resistance
• Electrical insulation
• Flame resistance
• Polarity

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 Bominated isobutylene-co-para-methylstyrene elastomer
(BIMSM)
Isobutylene paramethyl-styrene terpolymers (BIMSM) are specialty elastomers.

Halobutyl rubber specialty elastomers help the healthcare industry to meet ever-changing requirements related
to cleanliness, drug compatibility, low extractables and leachables.

Ideal for sensitive drugs and other demanding applications,

In the tire industry, BIMSM is used for high-performance bladders and envelopes

Benefits:
High temperature resistance
Greater heat stability compared to EPDM rubbers
Low permeability and high damping similar to butyl rubber
Wide latitude in cure and cocure with a variety of rubbers
Ozone/weathering resistance

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 Chemical Strucute of Bominated isobutylene-co-para-
methylstyrene elastomer
(BIMSM)

Structure of brominated isobutylene-co-para-methylstyrene, BIMSM

After polymerization and subsequent bromination some of the para-methylstyrene groups are converted to
reactive bromomethylstyryl groups.

These saturated backbone polymers contain isobutylene, 1 to 5 mole-% of para-methylstyrene, and 0.5 to 1.3
mole-% of brominated para-methylstyrene.

Their glass transition or second order transition temperature increases with increasing para-methylstyrene
content and is nominally around -57 °C. This compares to a nominal -59 °C to -60°C for halobutyl polymers.

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Bominated isobutylene-co-para-methylstyrene elastomer
(BIMSM) curing

BIMSM crosslink
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