8

Exxon™ butyl rubber compounding and applications
manual
Table of Contents
Introduction ................................................................................................................... 4
Butyl Rubber Development ......................................................................................... 4
Polymerization Chemistry of Butyl Rubber ................................................................. 4
Manufacturing of Butyl Rubber .................................................................................... 6
Chemistry And Characteristics of Butyl Rubber ........................................................ 9
Chemistry of Butyl Rubber ......................................................................................... 9
Molecular Structure of Butyl Polymers ..................................................................... 10
Exxon™ Butyl Grades .............................................................................................. 11
General Properties of Butyl Rubber .......................................................................... 11
Unsaturation Effect on Butyl Heat Resistance ................................................ 12
Unsaturation Effect on Butyl Curing & Cured Properties .......................................... 12
Effect of Molecular weight on Stress Strain Properties of Butyl Polymers ................ 14
Vulcanization of Butyl Rubber ................................................................................... 15
Sulfur Cures ............................................................................................................. 16
Thiuram accelerated Vulcanization .......................................................................... 17
Phenolic Resin Cures ............................................................................................... 21
Quinone Cure Systems ............................................................................................. 25
Butyl Rubber Compounding ...................................................................................... 26
Butyl: Polymer Blends .............................................................................................. 26
Butyl: Compounding with Carbon Black ................................................................... 30
Butyl: Compounding with Mineral Fillers .................................................................. 32
Butyl: Effect of Plasticizers ........................................................................................ 35
Butyl: Effect of Processing aids ................................................................................. 38
Optimizing Key Butyl Compound Properties ............................................................ 40
Butyl: Permeability ................................................................................................... 40
Butyl: Heat Resistance ............................................................................................. 41
Butyl: Dynamic Damping .......................................................................................... 42
Butyl Compound Processing ..................................................................................... 40
Butyl: Mixing ............................................................................................................. 45
Butyl: Extrusion ....................................................................................................... 47
Butyl: Calendering .................................................................................................... 48
Butyl Applications ....................................................................................................... 51
Butyl: Innertubes ...................................................................................................... 51
Butyl: Ball Bladders and Curing Bladders ................................................................ 53
Summary ...................................................................................................................... 57
References ................................................................................................................... 63
2
Abstract
Butyl rubber and other isobutylene polymers are widely used due to their low
impermeability. Polyisobutylene polymers have a highly saturated back bone. For
crosslinking isobutylene polymers, a small amount of isoprene is incorporated in to the
saturated backbone by co-polymerization. Isobutylene polymers are polymerized by a
cationic mechanism, using a Brønsted acid as an initiator and a Lewis acid as a co-
initiator, e.g., water and aluminum chloride.
The glass transition temperature (Tg) of polyisobutylene is about –60°C, and the
polymer is amorphous in the unstrained state. The polymers exhibit a broad damping
peak and a low plateau modulus. They display an exceptionally low permeability to
gases, and are widely used as air retention barriers in tires. Optimum physical
properties are obtained by compounding with carbon black and other fillers. Various
mechanisms are used to cross-link the compounds into elastomeric vulcanizates. Sulfur
is used to provide polysulfidic cross-links, while resin and zinc oxide cure systems give
carbon–carbon cross-links. Besides inner tubes and innerliners, butyl rubbers are used
in blends to improve cut-growth resistance and wet-skid resistance. Blends with
thermoplastic resins improve toughness. Polyisobutylenes enjoy extensive use as
adhesives and caulks, and are chemically modified for use in lubricants as dispersants.
3
Introduction
Butyl Rubber Development
The development of Butyl rubber can be traced back to the early 1870’s, when
Gorianov and Butlerov, and later Otto (1927), polymerized isobutylene at room
temperature in the presence of BF3 and sulfuric acid to yield low molecular weight, oily
polymers. In 1930, I.G. Farben workers succeeded in producing higher molecular
weight polymers by reacting a dilute hydrocarbon solution of isobutylene with BF3 at
very low temperatures.
In the 1930’s W.J. Sparks and R.M. Thomas of Standard Oil Company of New
Jersey invented the vulcanizable form of isobutylene rubber. They incorporated small
amounts of diolefin into the polymer molecule by copolymerizing isobutylene with low
levels of isoprene1. This required very low temperatures, pure monomers, Friedel-Crafts
type catalysts, and alkyl halide solvents. The Sparks and Thomas discovery introduced
the first concept of limited olefinic functionality for vulcanization in an otherwise
saturated copolymer1. Vulcanizates of the new copolymers (now known as butyl rubber)
were found to possess unique and desirable properties, e.g., low gas permeability, high
hysteresis and outstanding resistance to heat, ozone, chemical attack and tearing.
Subsequent development progressing to commercialization was spurred during the
early 1940’s by the U.S. Government as part of its rubber procurement program in
World War II. Standard Oil Company of New Jersey built and operated the first
commercial Butyl rubber facility in cooperation with the government, and in 1955
purchased the commercial plants in the U.S.A.
Polymerization Chemistry of Butyl Rubber.
Commercial butyl rubber grades are prepared by copolymerizing small amounts

of isoprene, 1 to 3% of the monomer feed, with isobutylene, catalyzed by AICI3
dissolved in methyl chloride. The reaction is extremely rapid, proceeding via cationic
polymerization at very low temperatures (approximately -95°C) to completion in less
than a second. Monomer purity is important to achieve the desired polymer molecular
weights. The methyl chloride diluent and monomer feed must be carefully dried to avoid
poisoning the reaction. The principal monomers used in the preparation of Butyl rubbers
are isobutylene (2-methylpropene) and isoprene (2-methyl- 1, 3-butadiene)1.
Commercial supplies of isobutylene are derived from thermal or catalytic cracking

of petroleum fractions. Until the late 1960’s, C4 streams were extracted with sulfuric
acid. Currently, high purity isobutylene is produced by dehydration of t-butyl alcohol or
decomposition of methyl t-butyl ether. A liquid C4 stream containing 15-45% isobutylene
is treated with 50-60 wt. % acid in multistage countercurrent devices. The isobutylene is
hydrated to t-butyl alcohol in an exothermic, proton- catalyzed reaction at 20-40°C. The
acid-extract phase is stripped to remove dissolved n-butenes and contacted with steam
in a regenerator tower to convert t-butyl alcohol back to isobutylene and water. The
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vapor from the regenerator is washed with water, compressed, and fractionated to
produce polymerization- grade isobutylene of greater than 99% purity.
Isoprene is the most readily available industrial byproduct of the thermal cracking
of naphtha or gas oil. It is extracted as a side product in the production of ethylene.
Acrylonitrile is a typical extractive - distillation solvent.
Production of the high molecular-weight, elastomeric grades of Butyl rubber

require isobutylene of greater than 99.5 wt. % purity. Isoprene of greater than 98 wt. %
purity is desired. Isoprene enters the polymer chain primarily by 1,4-addition in the
trans-configuration. Recent work indicates that approximately 94% of the isoprene is in
this form, the remainder is in a 1,2-addition form.
The mechanism of cationic isobutylene polymerization with Lewis acid is highly

complex. Friedel-Crafts type Lewis acids at low temperature give an extremely high
polymerization rate. In the first step, the initiation reaction as given in figure 1, a
carbenium ion-counteranion pair is formed between a Lewis acid coinitiator, initiator,
and the monomer. Typical Lewis acid co-initiators include AICI3, BF3, etc. whereas
initiators are Bronsted acids such as HCl, H2O etc.
Initiation
Figure 1
Proposed Polymerization Mechanism- Initiation 2
+ -
HA H A
+ -
HCl + AlCl3 H AlCl4
CH2
CH3
- -
+
H AlCl4 CH3 – C – CH3 - CH - C+
2 AlCl4
CH3
5
Propagation
Initiation is followed by propagation reactions where monomer units add to the

carbenium ion forming the chain as given figure 2. These reactions are fast and highly
exothermic.
Figure 2
Proposed Polymerization Mechanism- Propagation2
CH3 - CH3 CH3 CH3

kp -
CH2 C + AlCl4 + H2C C CH2 C CH2 C + AlCl4
CH3 CH3
CH3 CH3
The chemistry of the propagation is affected by the temperature, polarity of the solvent
and counter ions, the propagation proceeds until chain transfer or termination occurs.
In the chain-transfer step, the carbenium ion chain end reacts with isobutylene,
isoprene, or a species with an unshared electron pair, i.e., RX, solvents, counterion, and
olefins. Reaction with these species terminates the growth of this macromolecule and
permits the formation of a new chain. The activation energy of chain transfer is larger
than propagation, thus the molecular weight of the polymer is strongly influenced by the
polymerization temperature. Lower temperatures lead to higher molecular weight
polymer. As comonomers exhibit their own chain-transfer characteristics, the presence
of comonomer can also influence the final molecular weight of a copolymer. Termination
results from the irreversible destruction of the propagating carbenium ion and
discontinuance of the kinetic chain. Termination reactions include the collapse of the
carbenium ion–counterion pair, hydride abstraction from comonomer, formation of
dormant or stable allylic carbenium ions, or by reaction of the carbenium ion with
nucleophiles, e.g. alcohols or amines. Certain chemicals can act as quenching agents
terminating the reaction thereby controlling the molecular weight. The reaction rates are
strongly affected by the polymerization conditions.
Manufacturing of Butyl Rubber
A schematic diagram of a typical slurry-process Butyl plant is shown in figure 3.

The feed, a 25% solution of isobutylene (97-98%) and isoprene (2-3%) in methyl
chloride, is cooled to -100°C in a feed tank. The catalyst aluminum chloride is also
dissolved in methyl chloride. These streams are continuously injected into the reactor
where polymerization is almost instantaneous in an exothermic reaction. Cooling is very
important, and liquid ethylene is boiled continuously through cooling coils to keep the
reactor at about -95°C. On polymerization, a slurry of very small particles suspended in
methyl chloride is formed in the reactor.
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Figure 3
Block Diagram for the Synthesis of Butyl Polymers3
An alternative solution process uses a C5–C7 hydrocarbon as solvent and an

aluminum alkyl halide as the initiator3. The polymerization is conducted in scraped
surface reactors at −90 to −50æC. The solution process avoids the use of methyl chloride,
which is an advantage when butyl rubber is to be halogenated. However, the energy
costs are higher than for the slurry process because of the higher viscosity of the
polymer solution. Consequently, it is unlikely that the well-established slurry process will
be displaced.
Significant fouling occurs during polymerization. At high solids concentrations, a

Butyl film deposits on heat-transfer surfaces, blocks cooling tubes and impairs slurry
circulation. One of the common theories to explain fouling in a Butyl reactor is that
rubber particles in the reactor slurry are not completely glassy because of diluent and
the monomers in the surface layer. This causes them to be sticky as well as
agglomerating, and the particles will stick to the heat-transfer surfaces in the reactor.
This causes the heat-transfer resistance to increase and the slurry temperature to warm.
A cyclic operation is used in which some reactors operate while others are washed with
hot solvent to remove fouling. Typical runs last from 18 to 60 hours, depending on feed
purity, slurry solids concentration, and production rate. Recent patents have described
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the use of block-copolymer stabilizing agents to create steric (entropic) repulsion forces
between slurry particles to prevent or slow the fouling.
After the polymer particles are formed, the slurry overflows into a flash drum that
contains hot water. The mixture is vigorously agitated and the diluent and unreacted
hydrocarbons are evaporated and recovered. An antioxidant and zinc stearate is
introduced at this point. The antioxidant is added to prevent polymer breakdown in
subsequent high temperature finishing. Salts of fatty acids are added to prevent the
polymer particles from sticking together during the finishing operations.
The slurry is then vacuum-stripped of residual hydrocarbons. In the finishing

operation, the Butyl slurry is dewatered in a series of extruders to bring the water
content to 5-10% for final finishing. Drying is accomplished in a high pressure extruder
when the compressed polymer melt is forced through a die to form an exploded crumb
as the pressure is released. The crumb is air conveyed to an enclosed fluidized bed
conveyor, where water vapor is removed and the crumb is cooled prior to baling and
packing.
Commercial Status and Worldwide Capabilities
Butyl is produced by ExxonMobil Chemical at Kawasaki (Japan) and Notre Dame

de Gravenchon (France). Technical laboratories at Baytown, U.S.A., Machelen, Belgium
and Bangalore, India, carry out research and development, and support the
manufacturing and marketing activities. Worldwide offices for chemical products provide
trained personnel for sales and customer service activities.
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Chemistry and Characteristics of Butyl Rubber
Chemistry of Butyl Rubber
Butyl rubber is a copolymer of isobutylene and isoprene and is produced by

reacting isobutylene with a very small amount of isoprene. During the development of
Butyl, the concept of a highly- saturated polymer containing a limited level of chemically
reactive functionality was introduced. The level of functionality is sufficient to provide
cross-linked networks with high strength and elastic physical properties after
vulcanization. The Butyl rubber grades are distinguished by molecular weight (Mooney
viscosity) and mole percent (%) unsaturation. They have typical viscosity average
molecular weights of 350,000-450,000, and mole percent unsaturation levels (resulting
from the isoprene) of 0.5 to 3.0. The structure of isobutylene isoprene co-polymer is
given in figure 4.
The term “mole percent unsaturation” refers to the number of isoprene molecules
in 100 monomer molecules in the polymer. Thus, a one mole percent unsaturation Butyl
would contain one molecule of isoprene and 99 molecules of isobutylene. This is
illustrated in figure 4, in which ‘n’ represents the moles of isobutylene combined with ‘m’
moles of isoprene. In a typical case, ‘n’ would equal 98, and ‘m’ would equal 2. In
comparison, natural rubber would have ‘n’ equal to zero and ‘m’ equal to 100, since this
molecule is 100% polyisoprene. It could be called 100-mole-percent unsaturated.
Figure 4
Structure of Isobutylene Isoprene Co-polymer2
In a single Butyl macromolecule made up of thousands of monomer units, the

isoprene units are distributed at random. Such a macromolecule contains about 30
enchained isoprene units and 3,000 units derived from isobutylene.
Figure 5 compares the structure of Butyl rubber with Natural rubber (polyisoprene)
on a spatial basis. The figure indicates the average molecular weight between the
points of chemical unsaturation in the two elastomers; it clearly illustrates that Butyl is a
limited functionality elastomer. For example, Butyl rubber with one mole percent of
unsaturation would have a molecular weight between points of unsaturation of well over
5000. Natural rubber, on the other hand, has a molecular weight between points of
unsaturation of only 68, the molecular weight of an isoprene molecule.
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Figure 5
Structure of Butyl Rubber and Natural Rubber2
Polyisobutylene Polyisoprene
Molecular Structure of Butyl Polymers
The isoprene unit enters the butyl chain randomly and primarily in a trans-1,4
configuration (although approximately 6% of the isoprene enters in a 1,2 configuration).
These two forms of isomers of isoprene in the Butyl polymer chain are depicted below in
figure 6
Figure 6
Isoprene Configuration in Butyl Polymers2
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The butyl polymerization system, in the past, has been limited in molecular
topology (i.e., MWD and branching) latitude. The inert nature of the polymer and its
nervy consistency have made processing difficult compared to other general purpose
rubbers. Hence, Butyl polymers require special attention in processing for major
applications. Molecular weight variation has been the only commercially available
polymeric parameter influencing processing.
In butyl rubber, isoprene is enchained predominantly (90–95%) by 1,4-addition

and head-to-tail arrangement7,8,9,10. The remaining minor isoprene species may be
interpreted spectroscopically either as 1,2-enchained9,10 or as branched species from
1,4-addition11. Depending on the grade, the unsaturation in butyl rubber is between 0.5
and 3 mol %. The glass-transition temperature of butyl rubber is about −60æC12. With
the low content of isoprene and a near-unity reactivity ratio between isoprene and
isobutylene, a random distribution of enchained isoprene monomer in butyl rubber can
be achieved. The molecular weight distribution in butyl rubber is mostly with Mw/ Mn of
3- 5.
Grades of ExxonTM Butyl
Table I gives typical properties of several grades of Exxon Butyl rubber. The
grades differ in polymer viscosity, which is related to the molecular weight of polymer,
unsaturation, which determines the cure rate capability of the polymer, and branched
molecules, which governs the processability. Ash, water content and additive levels are
similar for all grades.
Table 1
Typical Properties of Butyl Polymers Marketed by ExxonMobil Chemical4
Exxon Butyl
Properties / Grades Butyl 065 Butyl 068 Butyl 268 Butyl 365
ML (1+8)@125°C 32 ± 3 51 ± 5 51 ± 5 33 ± 3
Antioxidants (wt %) 0.03 min 0.03 min 0.03 min 0.03 min
Volatiles (wt%) 0.3 0.3 0.3 max 0.3 max
Un-saturation (mol%) 1.05 ± 0.20 1.15 ± 0.20 1.7 ± 0.20 2.3 ± 0.30
General Properties of Butyl Rubber
The tight molecular packing of the polyisobutylene structure of the

macromolecule enables Butyl rubber to exhibit its low permeability to air, other gases
and water vapor. The low permeability is apparently due to a low diffusion constant
caused by low chain mobility and to low solubility of gases in the polymer. In the
vulcanized form, Butyl exhibits higher vibration damping than general purpose rubbers.
The polymer chain displays excellent thermal stability. With the selection of the proper
cure system such as the resin cure, Butyl polymers can yield vulcanizates with excellent
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heat resistance. Where faster cure is needed, sulfur-based cure systems can be used
that display good heat resistance at moderate temperature. The physical constants of
butyl rubber is given in table 2
Table 2
Physical Constants of Butyl polymer2
Physical Constants of Butyl Rubber and Isobutylene.

Expansion Coefficient
Linear Expansion 1.74 x 10-4 /°C Pure Gum
50 phr Black
Linear Expansion 1.17 x 10-4 /°C compound
Cubical Expansion 5.67 x 10-4 /°C Pure Gum
Thermal Conductivity @ 23°C
( 1.254 of S.G. ) 2.66 cal/hr (hr.cm.°C/cm) Butyl Sheet
Decomposing Temperature 327 °C Pure Gum
3
Density ( 26 to 27 °C) 0.91 g / cm Pure Gum
Thermal Diffusivity
60°C / 140°C 0.89 x 10 -3 / 0.51 x 10 -3 cm /s Pure Gum
60°C / 140°C 1.34 x 10 -3 / 0.65 x 10 -3 cm /s 50 Black / 20 oil
Heat of Reaction
Heat of Formation( 1 atm ,25°C) 21.25 kg - cal / mole PIB
Heat of Combustion( 1 atm ,25°C) 628.14 kg - cal / mole PIB
Heat of Polymerization ( In Hexane) 12.8 kg -cal / mole PIB
Refractive Index ND ( 27.1°C) 1.5045 PIB
Specific Heat ( 26 -27 °C) 0.464 cal /g . °C Pure Gum
Brittle Point (Tb, °C) -46 50 Black / 20 oil
Glass Transition Point ( Tg , °C) -65 50 Black / 20 oil
Solubility Parameter 7.8 50 Black / 20 oil
Gas Permeability ( air , 30°C )
ml (STP) mm/m2.760 mm Hg.hr 3.5 70 Black / 20 oil
Electrical Property
Dielectric Constant 3.4 100 Clay / 10 black
Power Factor ( %) 0.8
Volume Resistivity ( Ω- cm) 2 X10 15
Due to its highly saturated character, Butyl rubber also has excellent chemical
resistance. Oxidative degradation is slow and may be further reduced with antioxidants,
although they are not normally needed. Oxidative attack results in compound softening
due to loss of molecular weight through chain scission, rather than embrittlement.
Radiation also degrades Butyl through chain scission. Butyl rubber is readily soluble in
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nonpolar liquids. It dissolves easily in cyclohexane, less soluble in benzene, and is
insoluble in methyl ethyl ketone.
Toxicology of Butyl Rubber
Butyl polymers are safe to process, fabricate and use under normal conditions
where good industrial hygiene is practiced. Health aspects and handling of the Butyl
grades are covered in the Material Safety Data Sheets (MSDS) for the products. These
sheets may be obtained through local ExxonMobil Chemical Offices.
Unsaturation Effect on Heat Resistance
Heat resistance increases as unsaturation increases because reversion is

reduced as a result of the greater opportunity for reformation of broken cross-links.
Higher unsaturation also yields higher crosslink density. This is true for sulfur cures and
resin cures but not for quinoid cures where unsaturation is not significant.
Unsaturation Effects on Ozone Resistance
Ozone resistance varies greatly with unsaturation content. Ozone resistance

decreases with higher unsaturation. If the application requires maximum ozone
resistance, Exxon Butyl 065 should be used even though cure time is increased
Unsaturation Effects on Cure Characteristics and Cured Properties of Butyl Polymers
As shown in table 3, cure rate and aging properties of compounded Butyl rubber
stocks are directly affected by the mole per cent unsaturation (the number of isoprene
monomeric units per 100 monomer units) of the base polymer. The effects of
unsaturation on butyl cure properties are given in figure 7.
Table 3
Effect of Unsaturation on Butyl Compound Properties
Percentage ExxonMobil Cure Ozone Heat

Unsaturation (mol %) Grade Rate Resistance Resistance
065 Slow Excellent Good

0.8
068
1.5 268
2 365 Fast Good Excellent
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Figure 7
Effect of Unsaturation on Butyl Curing Characteristics at 160°C
Effect of Molecular weight on Stress Strain Properties of Butyl Polymers.

In Butyl rubber, with the same level of unsaturation, higher physical properties
are obtained with higher Mooney (high molecular weight) polymers as shown in figure 8
and table 4
Figure 8
Effect of Molecular Weight on Stress Strain Properties
As the molecular weight increases, the mechanical properties increase.
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Table 4
Effect of Molecular Weight on Properties of Butyl Compound
Material Units Butyl Butyl

268 High Mw
Butyl 268 PHR 100.0 --
Butyl (High Mw) 100.0
Chloroprene Rubber 5.0 5.0
N 330 50.0 50.0
Castor Oil 5.0 5.0
Stearic Acid 1.0 1.0
ZnO 5.0 5.0

Octylphenol Formaldehyde Resins 10.0 10.0
Typical Properties: Mooney Viscosity Test Method Units
Mooney Viscosity ML 1+4, @ 100 °C ASTM D 1646 MU 75 78
Rheometric Properties @ 190° C, 60 minutes, Arc ± 0.5°
Minimum Torque (ML) ASTM D 5289 dN.m 2.6 2.6
Maximum Torque (MH) ASTM D 5289 dN.m 12.4 12.1
Delta Torque (MH-ML) ASTM D 5289 dN.m 9.8 9.5
Time for two unit rise in torque.(ts2 ) ASTM D 5289 minutes 3.3 2.9
Time to 50% rise in torque. (tc50 ) ASTM D 5289 minutes 8.3 6.5
Stress Strain Properties, Samples cured @ 190°C tc90 + 2 minutes.
Hardness ASTM D 2240 Shore A 58.0 58.0
100 % Modulus ASTM D 412 MPa 1.4 1.6
Tensile Strength ASTM D 412 MPa 13.7 14.2
Elongation at break ASTM D 412 % 630 650
Tear Strength ( Die B ) ASTM D 624 kN/m 46.1 57.8
Tension Set ASTM D 412 % 29.0 24.0
Typical Stress Strain Properties- Air aged at 125°C ,168 hrs
Hardness ASTM D 2240 Shore A 85 84
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Vulcanization of Butyl Rubber
Butyl rubber can be vulcanized with a variety of cure systems which show good
levels of processing safety. Vulcanization or curing in isobutylene polymers introduces
chemical cross-links via reactions involving either allylic hydrogen or allylic halogen in
butyl. The cure systems are divided into the following five basic types;
1) Conventional Sulfur
2) Sulfur Donor
3) Low Sulfur-High Accelerator
4) Quinone
5) Resin
The above five cure systems in Butyl rubber can be divided into three general classes of
cross-links.
1) Disulfide / Polysulfidic —predominant cross-links from conventional sulfur -C-S-S-C.

2) Monosulfide-predominant cross-link from sulfur donor and low sulfur -C-S-C.
3) Nonsulfide - Quinone -C-N-C-.
Resin -C-C-C-.
Vulcanization introduces chemical cross-links along the polymer chains, binding

them together in a three dimensional network. The isoprene sites provide the necessary
reactivity in Butyl rubber. The normal range of temperatures for curing Butyl is 150-
180˚C; however, in some special cases where one cannot get enough heat e.g. site
vulcanization of Butyl tank lining; temperatures as low as l00˚C or lower with longer cure
time and faster curing system (Quinone cure) are used.
To cure thick items, high temperatures above 180°C with more heat stable cure
systems e.g. sulfur donor, Quinone and resin cures are suggested. The temperature
coefficient of vulcanization for carbon black-filled Butyl rubber compounds is about 1.8
per 10˚C. This means that the vulcanization time, to a given state of cure, should be
multiplied by 1.8 for every 10°C decrease in temperature, or divided by 1.8 for every
10°C increase in temperature. To activate the crosslinking of Butyl polymers, organic
accelerators are required. Zinc oxide is required in the sulfur cure system as an
activator along with stearic acid and is normally used at the 5 phr level. Good zinc oxide
dispersion is desirable to obtain the optimum butyl compound properties.
Sulfur Cures
The basic cross linking agent for Butyl rubber is elemental sulfur, as it is for other
elastomers containing active unsaturation sites. Ultra-accelerators are employed in
Butyl polymer crosslinking to achieve acceptable rates and states of cure, due to low
unsaturation in Butyl rubbers in comparison with general purpose rubbers. To activate
accelerators and to stabilize cross-links already formed, Butyl compounds require zinc
oxide. Sulfur cross-links rearrange at elevated temperatures as a result of their low
16
bonding energy that could lead to creep and permanent set in strained Butyl at high
temperatures. Secondary accelerators such as thiazoles or sulphenamides are added
as needed to modify properties and cure rate. Figure 9 gives the structure of different
accelerators that can be used for vulcanizing butyl polymers.
Figure 9
Structure of Selected Accelerators Used for the Vulcanization of Butyl Rubber
S
S
N
N
S Zn S
S S
S
N
N
Tetrabenzylthiuram disulfide (TBzTD) Zinc dibenzyldithiocarbmate (ZBEC)
N
S HN
S S
S S S
N
N
Cyclohexyl benzothiazole sulfonamide Benzothiazyl disulfide (MBTS)

(CBS)
S N
SH
N N
H H S
Dibutyl thiourea (DBTU) Mercaptobenzothiazole (MBT)
Thiuram Accelerated Vulcanization
Thiurams and dithiocarbamate accelerators form nitrosamines, and are not

currently recommended for the vulcanization of Butyl polymers. Thiurams and
dithiocarbamates with bulky ‘phenyl’ groups e.g. TBzTD and ZBEC are currently used
17
as ultra-fast accelerators for the vulcanization of butyl polymers. These accelerators
generate fewer amounts of carcinogenic nitrosamines and volatility of nitrosamines are
lower due to bulky phenyl groups. Thiuram accelerated systems participate in the
vulcanization process through formation of a zinc complex as shown in Figure 10. The
sulfur rich complexes are formed by insertion of the sulfur into the zinc dibenzyl
dithiocarbamate molecule, which in turn is an active sulfurating complex. Rubber
bounded intermediates are subsequently produced followed by crosslinking to form
polysulfidic crosslinks. These polysulfidic crosslinks evolve into monosulfide and
disulfidic crosslinks. It is generally accepted that vulcanization proceeds via hydrogen
abstraction from a methylene group alpha to a double bond in the polymer chain. This
results in the formation of a dialkenyl polysulfide cross-link, with the possibility of some
alkyl-alkenyl cross-links. It has been shown that the crosslink is C-Sx-C, where x is one
to four or more.
Figure 10
Possible Mechanism of Thiuram Accelerated Vulcanization14
The addition of thiazoles like MBTS and MBT improves the processing safety.
Table 5 and 6 gives data on crosslinking butyl polymers with ultra- accelerator systems.
18
Table 5
Crosslinking of Butyl Polymers with Ultra-Accelerator Systems
Unit
Ingredients Comp1 Comp 2
Butyl 268 PHR 100.0 100.0

N 660 PHR 70.0 70.0
Paraffinic Oil PHR 25.0 25.0

Escorez 1102 PHR 3.0 3.0
Zinc Oxide PHR 5.0 5.0
Stearic Acid PHR 1.0 1.0
Sulfur PHR 2.0 1.0
CBS PHR 1.5 --
ZBEC PHR 1.5 --
DBTU PHR -- 2.0
Typical Properties: Mooney Viscosity
ML 1+4,@ 100 °C MU ASTM D 1646 46 46

Mooney Scorch (t5) @ 125°C Minutes ASTM D 1646 22.5 13.0
Typical Properties: MDR Rheometer, 160°, 60 minutes, arc ±0.5°,
Minimum Torque (ML) dN.m ASTM D 5289 1.4 1.5

Maximum Torque (MH) dN.m ASTM D 5289 10.2 8.5
Delta Torque (MH-ML) dN.m ASTM D 5289 8.8 7.1
Time for two point
minutes ASTM D 5289 3.6 4.5
rise in torque. (ts2 )
Time to 50% rise in torque. (tc50 ) minutes ASTM D 5289 6.2 10.0
Time to 90% rise in torque. (tc90 ) minutes ASTM D 5289 21.7 33.0
Typical Stress Strain Properties- Unaged
Hardness Sh. A ASTM D 2240 51 44

100 % Modulus MPa ASTM D 412 1.6 1.2
300 % Modulus MPa ASTM D 412 4.3 3.5
Tensile Strength MPa ASTM D 412 11.5 12.0
Elongation at break % ASTM D 412 610 680
Tear Strength ( Die B ) N/mm ASTM D 412 62.9 74.1
DeMattia crack initiation at 200 kC mm ASTM D 460 >25 No cracks
Fatigue to failure kC ASTM D 4482 18.0 38.0
Oxygen Permeation rate @ 40°C, EM Method
282.0 320.0
Oxygen conc.:21% [ mm-cc/[m²-day]
Oxygen Permeability coefficient @ 40°C, EM Method
0.419 0.486
Oxygen conc.:21% [ mm-cc/[m²-day]*mmHg
19
Table 6
Crosslinking of Butyl Polymers with Ultra-Accelerator Systems
Ingredients Unit Comp 1 Comp 2 Comp 3 Comp 4

Butyl 268 PHR 100.0 100.0 100.0 100.0
N 660 PHR 70.0 70.0 70.0 70.0
Paraffinic Oil PHR 25.0 25.0 25.0 25.0
Escorez 1102 PHR 3.0 3.0 3.0 3.0
Zinc Oxide PHR 5.0 5.0 5.0 5.0
Stearic Acid PHR 1.0 1.0 1.0 1.0
Sulfur PHR 1.0 1.0 1.0 0.2
MBTS PHR 0.5 0.5 0.5 0.5
TMTD PHR 1.5 -- -- --
ZBEC PHR -- 1.5 -- 1.5
TBzTD PHR -- -- 1.5 --
Caprolactum disulfide PHR -- -- -- 2.0
ML (1+4)@ 100 °C MU 55 56 55 53
Mooney Scorch t5 @ 125°C minutes 16.1 11.2 20.2 29.0
Minimum Torque (ML) dN.m 1.3 1.3 1.3 1.3
Maximum Torque (MH) dN.m 10.2 7.3 7.7 7.0
Delta Torque (MH-ML) dN.m 8.9 6.0 6.4 6.7
Time for two point rise in torque(ts2 ) minutes 1.7 1.1 1.7 2.2
Time to 90% rise in torque. (tc90 ) minutes 4.0 4.9 5.2 3.8
Hardness Sh. A 54 48 49 46
100 % Modulus MPa 1.5 1.0 1.1 0.9
300 % Modulus MPa 4.7 3.3 3.4 2.8
Tensile Strength MPa 11.9 11.7 11.8 10.7
Elongation at break % 680 760 770 760
Tear Strength ( Die B ) N/mm 35.0 39.1 39.3 36.3
Typical Stress Strain Properties- Air Aged at 125°C 168hrs
100 % Modulus MPa 1.4 1.5 1.4 1.4
Tension Set @105°C, 50 % Strain,5hrs % 16.0 18.8 19.8 18.0
Oxygen Permeability coefficient @ 40°C,
0.361 0.398 0.372 0.381
Dynamic Mechanical Properties, Test temperature 100°C, 1 Hz , 10% strain
Complex Modulus MPa 8.7 6.5 6.6 5.6
Tan delta 0.14 0.17 0.16 0.17
20
The Monosulfide Cross-link.
High levels of dithiocarbamates and low levels of sulfur favor the formation of the
more stable monosulfide cross-links. The use of sulfur donors in place of elemental
sulfur also promotes monosulfide bonds. Caprolactam disulphide can be considered as
an effective sulfur donor for butyl rubber. Butyl compound properties with caprolactam
disulphide system show not only improved heat resistance but also outstanding flexing
properties and low compression set. The results are given in table 6.
Figure 11
Structure of Caprolactam Disulphide
N S
S N
Phenolic Resin Cures
The resin-cure cross-linking of Butyl rubber is based on the reactivity of the

phenol-formaldehyde resin methylol groups. The generic structure of para-tertiary
octylphenol curing resin is illustrated in figure 12. The resin cure in butyl rubber is based
on the reaction of the methylol groups in the phenol formaldehyde resin with allylic
hydrogen in butyl, usually with a Lewis acid catalyst, to yield carbon–carbon cross-links
that are thermally stable. Resin cure is preferred in butyl tire-curing bladders for their
required thermal fatigue stability. The proposed crosslinking mechanism of Butyl rubber
with octyl phenol formaldehyde resin is given in figure 13 and figure14.
Figure 12
Generic Structure of Octylphenol Formaldehyde Resin
OH OH OH
H2 COH CH 2 CH 2 CH2 OH
R R R
n
21
Curing resins are believed to function by forming cyclic ether via the reaction
between its phenolic groups (resin) and the isoprenyl unsaturation of the butyl rubber
backbone (Figure 5). The stable leaving group of the reaction (water) is made possible
due to the terminal methylol group of the curing resin. As mentioned above, such resin-
based cure systems typically require a halogen donor such as polychloroprene or
stannous chloride.
Figure 13
Reaction of a Curing Resin with Carbon – Carbon
Double Bonds on an Elastomer Backbone 16,17
R1
CH R1
CH CH
H
HO O C R2
R2
CH2
R CH2 OH R + H2O
Heat
tOctyl tOctyl
Brominated octylphenol formaldehyde resin has a similar structure to that in figure 12

but has bromine atom in place of the terminal hydroxyl group and where the bromine
content in the resin can be between 3.5 and 4.0 weight percent. The use of bromine can
result in a faster cure rate, still show adequate scorch resistance, and does not require
the addition of a halogen donor. The crosslink chemistry is assumed to be similar to that
reported for the non-halogenated resin (Figure 14).
Figure 14
Reactivity of Brominated Octylphenol Formaldehyde Resin 16,17
R1
CH
R1
O CH
CH
H
R2 O C R2
CH Br
CH2
R
Heat
tOctyl
tOctyl
22
Figure 15
Curing Curves of Butyl Rubber at 190°C with Octylphenol
Formaldehyde Resin and Brominated Octylphenol Formaldehyde Resins 14,16
14.0
12.0
10.0 Octylphenol formaldehyde resin

Torque (dN.m)
8.0
6.0
Brominated octylphenol formaldehyde resin
4.0
2.0
0.0
0.0 10.0 20.0 30.0 40.0 50.0 60.0
Time (mins)
The low levels of unsaturation in Butyl rubber require resin cure activation by
halogen-containing elastomers such as polychloroprene rubber. The curves in figure 15
illustrate the activating effect of octylphenol formaldehyde resin and brominated alkyl
phenol formaldehyde resin and the stability of the resultant crosslink to reversion upon
prolonged heating. The resin cure raises the limit of heat resistance of Butyl compounds
to over 200˚C. This excellent performance is utilized in tire curing bladders and related
applications.
A more reactive resin cure system requiring no external activator is obtained if

some of the methylol hydroxyl groups are replaced with bromine. As shown in figure 15
and table 7, it is apparent that the use of brominated octylphenol formaldehyde resin
resulted in a considerably faster curing compound. However, the brominated
octylphenol formaldehyde resin compound had a much shorter scorch time which may
present processing difficulties. Hot air aging is a more severe aging condition than hot
water although the temperature and time are the same. After hot air aging, the stock
containing the polychloroprene rubber exhibited higher modulus increase and shorter
elongation than the self-activating resin compound; however it showed better retention
of tensile strength. Generally the unmodified resin with Neoprene tends to yield a better
balance of heat resistance properties (in hot air and hot water) and is preferred for
curing bladder.
23
Table 7
Crosslinking of Butyl Polymers with Octylphenol Formaldehyde Resin Systems
Material Units I II
Butyl 268 PHR 100.0 100.0

Chloroprene Rubber 5.0
N 330 50.0 50.0
Castor Oil 5.0 5.0
ZnO 5.0 5.0
Octylphenol Formaldehyde Resins 10 --
Brominated Octylphenol formaldehyde Resin -- 10.0
Time for two point rise in torque. (ts2 ) ASTM D 5289 minutes 3.3 1.2
Hardness ASTM D 2240 Shore A 58.0 59.0
Typical Stress Strain Properties- Air Aged at 125°C ,168 hrs
Typical Stress Strain Properties- Steam Aged at 190°C. 96 hrs
24
Quinone Cure Systems
The crosslinking of Butyl rubber with para-quinone dioxime (QDO) or para-quinone

dioxime dibenzoate (DBQDO) proceeds through an oxidation step that forms the active
crosslinking agent para-dinitrosobenzene. The use of metal oxides (such as PbO2,
Pb3O4, MnO2) or MBTS as an oxidizing agent, increases the vulcanization rate allowing
use in room temperature cures such as in cements. Figure 16 is a schematic illustrating
the reaction of a dioxime in the vulcanization of butyl rubber. The dioxime vulcanization
system can be used for dry rubber applications. One example is electrical insulation
systems, which contain butyl rubber for improved ozone resistance.
Figure 16
Dioxime Cure of Butyl Rubber14
N OH N O
PbO2
O
Pb3O4
N OH N O
CH3
CH3
CH2 C CH CH2
CH2 C CH CH
NOH
NOH
CH2 C CH CH Dioximine cur e of buty l rubber
CH3
25
Butyl Rubber Compounding
As with almost all rubbers, the applications of isobutylene copolymers in rubber
goods require compounding and subsequent vulcanization, or cross-linking. During
compounding, various fillers, processing aids, plasticizers, tackifiers, curatives, and
antidegradants are added. Selection of the proper grade is the first consideration in
compounding with Butyl rubber since polymer choice directly influences the physical
properties, cure rate, and processing characteristics of Butyl rubber compounds. The
polymer grades with the highest mole percent unsaturation have the fastest cure rates
and a somewhat lower resistance to ozone and environmental attack than the more
saturated grades. In compounds with low filler and plasticizer loadings, Butyl polymers
with lower Mooney viscosities give smoother extrusions and calendered sheets. In
highly loaded and plasticized Butyl compounds such as innertube stocks, grades with
higher Mooney viscosities should be used to ensure adequate “green strength”.
The properties of a vulcanized Butyl compound depend on the nature and degree
of crosslinking as affected by the curatives, the type and concentration on the other
compounding ingredients, and the relative degree of dispersion of each of the
ingredients. The compounding ingredients used with Butyl include carbon black and
mineral fillers, plasticizers, processing aids, tackifiers, and occasionally antidegradant
agents. It is important to note that tensile strength of Butyl vulcanizates is highest in
“gum” stocks containing 5 phr or less filler, and almost invariably decreases with
increased additions of any filler. For better processing mineral fillers can be considered.
In extrusion applications, at least 30 volumes of carbon black or 40 volumes of mineral
fillers should be used. Beyond these levels, the choice of type and amount of fillers to
use depends on the processing and performance properties needed, as well as on the
economics of the application involved.
Polymer Blends
Butyl rubber is often blended with other elastomers to broaden the range of
vulcanization properties available to the compounder. Elastomeric behavior can be
tailored by proper blending of filled elastomers. Major reasons for the usage of blends
are to reduce compound cost, to improve processability, and to enhance final product
performance. But, in this case, selective filler partition may alter the blend morphology
and produce significant changes in blend properties. Elastic and fracture properties,
such as resilience, tear strength, and fatigue resistance, of rubber blends have been
found to depend strongly on filler phase distribution. Polymer blend compatibility is
governed by three parameters:
• Thermodynamics: Micro domain formation is achieved by surface energy reduction (i.e.

use of processing aids), and vulcanization.
• Viscosity: Oil/filler levels in dissimilar elastomers can be adjusted in mixing.
• Cure Rate: Where the respective polymers have significantly different cure rate
Solubility parameter can be used to predict miscibility of the blends. As an

empirical guide, the solubility parameter difference between two polymers must be less
26
than 1.0 to be compatible. Butyl rubber is completely compatible with the halobutyl
rubber and ethylene-propylene-diene rubbers. Butyl rubber cannot be blended with the
high unsaturation rubbers such as natural rubber and Styrene Butadiene rubber. Even
small amounts of highly unsaturated polymers can contaminate Butyl rubber (although
up to 5 phr of very well dispersed SBR and Neoprene are used in specific butyl stocks
for special properties). Contamination with high unsaturation rubbers generally results in
improper cure, reduction in ozone resistance, higher compression set and the loss of
other important properties.
Blend of Different Grades of Butyl Rubber
Different grades of butyl polymers can be blended to improve required properties like,
 Blend with low Mooney viscosity grades to improve processability, e.g. mixing,
flow within mold.
 Blend with high Mooney viscosity grades to improve compound properties
 Blend with low unsaturation grades improves ozone resistance
 Blend with low unsaturation grades to improve fatigue properties
 Blend with high unsaturation grade improves heat resistance and hardness.
Butyl-Halobutyl Blends.
Butyl-Halobutvl blends should be formulated with sulfur-accelerator or sulfur

donor accelerator cure systems having zinc oxide. The major properties of Butyl-
Chlorobutyl blends are shown in table 8. Increasing the halobutyl amount in a Butyl
compound, the modulus of blend compound is increased while the elongation is
reduced without hurting the tensile strength. The scorch properties of the Butyl are
retained until the halobutyl level in the blend is 20% of the total rubber hydrocarbon.
With halobutyl - butyl rubber blends, elastomer structures are essentially the same, but
the different reactive functionalities provide different vulcanization chemistry. Low level
blending of butyl rubber into halobutyl rubber increases the scorch time and improves
the processing safety of the compound. Blends with up to 20 phr of butyl rubber exhibit
halobutyl rubber-like adhesion. Since Butyl has the same permeability coefficient as
halobutyl rubber, blending it into a halobutyl rubber compound does not alter the
compound permeability.
Butyl-EPDM Blends
Ethylene propylene diene terpolymers (EPDM) can be used to improve the ozone
resistance of Butyl polymers. Butyl and most EPDM’s can be blended in all proportions
and co-vulcanized with sulfur-based cure systems. Typical applications are roofing
sheets and innertubes. The former have a wider blend ratio of EPDM such as 20-70%
of the total rubber hydrocarbon (EPDM blend ratio depends on the need for ozone
resistance/splice performance). The latter use a 10-30 phr blend and the major aim is
reducing the stickness of the tube to the tire especially for truck bias tires which gives
higher heat buildup.Typical physical properties of these applications are given in table 9.
27
Table 8
Typical Properties of Butyl – Halobutyl Blend Compounds
Material Units I II
Butyl 268 PHR 100.0 90.0
Chlorobutyl 1066 -- 10.0
Carbon black N 660 70.0 70.0
Paraffin oil 25.0 25.0
Escorez 1102 3.0 3.0
CBS 1.5 1.5
ZBEC 1.5 1.5
Sulfur 2.0 2.0
ZnO 5.0 5.0
Tear Strength ( Die B ) ASTM D 624 kN/m 30 32
Typical Stress Strain Properties- Air Aged at 125°C ,72 hrs.
Fatigue to failure ASTM D 4482 kC 38 51
0.76 0.75
28
Table 9
Properties of Butyl EPDM Blend Compounds
Material Units IIR 268 IIR +

compound EPDM
compound
ExxonTM Butyl 268 PHR 100 80
VistalonTM 2605 PHR 20
Carbon Black N 660 PHR 70 70
High Viscosity Paraffinic Oil PHR 25 25
PF Resin PHR 4.0 4.0
Sulphur PHR 2.0 2.0
CBS PHR 1.5 1.5
ZBEC-70 PHR 1.5 1.5
Stress Strain Properties, Samples cured @ 160°C, tc90 + 2 minutes.
Tear Strength ( Die C ) ASTM D 624 kN/m 33.9 32.5
Typical Stress Strain Properties- Air Aged at 125°C 72 hrs
Hours to
Static Ozone testing 40°C. 50pphm O3 EM Method 8.0 120.0
crack
De-Mattia Crack Initiation @ 200kC EM Method mm 0.0 25
Tension Set (Method B)105°C/ 5hrs / 50%
ASTM D 412 % 18.1 20.7
strain
EM Method 0.49 0.73
29
Carbon Black.
The primary purpose in compounding carbon black and butyl rubber is to create
bonds between the carbon black particles and the polymer molecules to strengthen, or
reinforce, the resultant vulcanizate. In addition to the reinforcement, fine and particulate
fillers, most notably carbon black, suppress elasticity of gum rubbers and render better
processability, such as less die swell, less shrinkage, less melt fracture, and less nerve
(or less elastic spring-back in uncured state). Physical interactions between carbon
blacks and rubber are strong but can yield upon stressing. Response of butyl rubber to
carbon blacks is generally similar to that of other synthetic elastomers, although butyl
has lower affinity for carbon black as compared to highly unsaturated rubber. Usually
three properties are considered in choosing a particular carbon black for a specific
application: particle size, structure, and surface activity. However the surface activity is
not a first priority to select the grades for a certain purpose since the furnace black is
dominant for rubber applications with fewer variations to select. Therefore, particle size
and structure are only discussed hereafter, but ultimate choice of a particular carbon
black is a compromise between processability, desired physical properties and cost.
The three principal processing techniques used in processing Butyl rubber are
Banbury and mill mixing, extruding, and calendering. Table 10 summarizes the effect of
carbon black properties on each process operation.
Table 10
Effect of Carbon Black Properties on Processing
Operation Particle Size Structure
Banbury, Mill Mixing Large High

Extruding Small/Intermediate High
Calendering Intermediate High
A good balance of compound mixing and processing, reinforcement and physical
properties is obtained with GPF (N660) carbon black at a 50-70 phr loading.
Approximately 8-25 phr process oil (generally aromatic oil is avoided) should be used to
plasticize the compound, depending on the viscosity of the polymer and the level of filler
used. For increased vulcanizate strength, hot elongation, hot tear strength, and
abrasion resistance, HAF (N330) carbon blacks can he used. However, they require
intensive mixing to ensure good dispersion. HAF carbon blacks tend to adversely affect
extrusion performance, and in many applications, HAF carbon black is used in blends
with FEF carbon black (N550) or GPF carbon black to enhance extrusion. High
structure ISAF carbon blacks can also be used to improve extrusion smoothness.
Where blends of HAF carbon black and other carbon blacks are used, the HAF carbon
black should predominate in order to achieve the desired improvement in physical
properties. Compounds containing FEF carbon black have the best balance of
properties for either final or mold- preparation extrusions. Thermal carbon blacks are
often blended into high tensile stocks containing furnace blacks to give resilience and
lower heat buildup. Table 11 summarizes the effect of different carbon blacks on Butyl
compounds.
30
Table 11
Effect of Carbon Black on Butyl Polymer Compounds
Ingredients Unit N 220 N 330 N 550 N 660 N 762

Butyl 268 PHR 100.0 100.0 100.0 100.0 100.0
N 220 PHR 70.0 --- --- --- ---
N 330 PHR --- 70.0 --- --- ---
N 550 PHR --- --- 70.0 --- ---
N 660 PHR --- --- --- 70.0 ---
N 762 PHR --- --- --- --- 70.0
Paraffinic Oil PHR 25.0 25.0 25.0 25.0 25.0
Escorez 1102 PHR 3.0 3.0 3.0 3.0 3.0
Zinc Oxide PHR 5.0 5.0 5.0 5.0 5.0
Stearic Acid PHR 1.0 1.0 1.0 1.0 1.0
Sulfur PHR 2.0 2.0 2.0 2.0 2.0
CBS PHR 1.5 1.5 1.5 1.5 1.5
ZBEC PHR 1.5 1.5 1.5 1.5 1.5
ML 1+4,@ 100 °C MU 57 48 45 41 33
Mooney Scorch t5 @ 125°C minutes 21.2 21.2 20.4 23.6 26.8
Minimum Torque (ML) dN.m 2.6 2.0 1.3 1.3 1.1
Maximum Torque (MH) dN.m 14.4 13.1 11.4 10.3 8.9
Delta Torque (MH-ML) dN.m 11.8 11.1 10.1 9.0 7.8
Time for two point rise in torque(ts2 ) minutes 3.2 3.3 3.4 3.8 4.3
Time to 90% rise in torque. (tc90 ) minutes 24.1 24.2 22.5 22.6 23.1
Hardness Sh. A 60 57 57 52 48
100 % Modulus MPa 1.4 1.3 1.5 1.3 1.1
300 % Modulus MPa 4.0 3.9 4.3 3.5 2.9
Tensile Strength MPa 13.7 12.9 10.0 10.7 10.5
Elongation at break % 710 710 650 670 700
Tear Strength ( Die B ) N/mm 36.2 35.6 31.1 29.0 25.6
Hardness Sh. A 63 59 55 47 45
100 % Modulus MPa 1.9 1.7 1.8 1.3 1.1
Tensile Strength MPa 9.9 9.8 7.6 7.7 6.8
Elongation at break % 480 530 480 550 600
Tension Set @105°C,50% strain,5hrs % 24.4 23.4 22.9 20.2 19.3
0.65 0.71 0.76 0.69 0.79
31
Vulcanizate Properties
For Best Performance

Property Particle Size Structure
Reinforcement Small High
High Modulus Small High
Abrasion Resistance Small High
Tear Strength Small High
Adhesion Large Low
In the general case, the following table can be used to determine which blacks are
suitable for a specific end-use.
End-use Application Carbon Black To Obtain

Innertube GPF, FEF, SRF Modulus Green Strength
Dynamic Mount HAF, MT, FT, SRF Damping, Fatigue Resistance,
Adhesion.
Industrial Goods
Sheeting HAF, SRF Reinforcement, Processability.
Hose FEF, SRF, HAF Processability, Reinforcement
Permanent Set.
Mineral Fillers
Compounders use mineral or non-carbon black fillers for a number of purposes,

most important of which are the improvement of physicals or processabilties and the
cost reduction of a rubber compound. These properties may be obtained by using
mineral filler(s) alone or in blends with carbon black. All of the common mineral fillers
can be used with Butyl rubber. Mineral fillers have a wide range of particle size.
Depending on type and particle size, they are used as semi-reinforcing or inert fillers.
The small particle sized fillers (reinforcing) result in higher tensile strength, modulus and
hardness. The large particle-sized mineral fillers (inert) exhibit little, if any, reinforcement
and in general have poor tear, flex and abrasion resistance.The type of filler and the
loading volume have definite effects upon the physical properties of the compound.
Except for the fine particle-sized hydrated silica, mineral fillers usually show much less
heat build-up during processing than the carbon blacks. They also tend to develop lower
modulus and poorer compression set. A brief description and general comments about
some of the more representative mineral fillers used in Butyl are listed below.
a. Calcium Carbonate.
It is one of the two most widely used non-carbon black fillers, the other one is
clay. The reason for its popularity is that very high loadings can be used to dilute rubber
with little loss of softness, elongation, or resilience. This results in cost reduction without
objectionable stiffening of the cured rubber products. Cured stocks loaded with calcium
carbonate are soft and have low modulus. Resistance to tear is only fair to poor and
32
abrasion is poor. No matter how calcium carbonate is made, it produces easily mixed
stocks that are soft in the uncured rubber state. Calcium carbonate has little covering
power and is of no value as a whitening agent in rubber. However, it is used sometimes
to the extent of 100-200 phr with other pigments in white stocks and for this reason
color is important. It is not absorptive and unlike clay, and has little effect on cure.
Calcium carbonate is widely used in sponge compounds because stocks loaded with it
are soft in the uncured state and blow well.
b. Clay
Clay is a low cost filler, but unlike calcium carbonate has an increasing effect on
modulus of compounds. It also imparts hardness and fair abrasion resistance. Rubber
clays consist principally of flat platelets which accounts for their effect on modulus and
hardness. The effect on modulus varies considerably with different clays, those causing
the most increased modulus being classed as hard clays and those causing less
increased modulus being called soft clays. Hard clay is a good material for use where
stiffness at low cost is desired either in cured or uncured stocks. Hard clay is useful in
extrusion compounds to prevent sagging or collapse during cure. The reinforcing value
and abrasion resistance of soft clay is less than that of hard clay and it is used where
less stiffening is needed. Both types are acid resistant and are often used to load tank
lining stocks. Clay loading in rubber compounds varies widely. Clays are not difficult to
mix into rubber and produce dry compounds. They tend to retard cure because they
absorb such accelerators as DPG and generally have an acid pH. This tendency can be
overcome by the use of small amounts of triethanolamine or diethylene glycol in the
compound.
A problem often encountered with the use of hard clay is the development of high
surface tack and mill sticking which results in rough extrusion and difficult handling. This
situation can be rectified by the partial or whole substitution of the clay with other
mineral fillers such as Mistron Vapor Talc, calcium carbonate, or hydrated silica. Where
hard clay is used, release aid should be added to help overcome any stickness. Silane-
treated clays improve physicals such as modulus, tensile strength and abrasion
resistance.
c. Hydrated Silica.
Hydrated silica is the best non-carbon black reinforcing pigment so far developed
and comes closest to carbon black properties as any available material. Present
reinforcing silicas already have a particle size as fine as that of carbon black and they
also have extremely active surfaces. Hydrated silica provides an answer to the problem
of producing high quality non-carbon black butyl rubber compound. The clays and
calcium carbonate do not give satisfactory tensile strength nor tear resistance. Calcium
silicate is too difficult to disperse in butyl. By the use of hydrated silica, easy
processable stocks can be made with excellent physical properties. It mixes easily into
butyl and disperses without difficulty if handled in the same manner as the finer carbon
blacks. Diethylene glycol will increase the cure rate of silica loaded stocks.
33
d. Talc
The term “talc” (magnesium silicate) is used as a general reference for

commercial filler representing either a single structural type, like platy talc or any
combination of the other three basic types, fibrous, acicular, and granular.
The latter have little, if any, reinforcing value in butyl rubber compounds, and are used
as inert fillers where large quantities can be used without increasing the hardness
excessively. However, platy talc (Mistron Vapor Talc) is moderately priced filler which
imparts high physical strength and good electrical properties with low moisture
absorption. Tensile and modulus properties of butyl vulcanizates containing platy talc
are markedly improved over butyl compounds containing calcined clay.
e. Hydrated Sodium Alumino Silicate
Zeolex is made from clay and is sometimes termed as regenerated clay, but it
should not be classified with clays because it is finer and has better reinforcing
properties. Zeolex imparts properties much the same as calcium silicate, but is
preferred over the latter because of ease of incorporation.
f .White Pigments and Colors.
The most widely used white pigment is titanium dioxide, which has the highest
refractive index of any white pigment and combines the properties of high tinting
strength, chemical inertness, and light fastness than any other white pigment developed
to date. Coloring pigments other than white used in rubber are of two types: the
inorganic mineral pigments, which are relatively cheap and generally give dull colors
and the organic colors, which are more expensive, but which are essential where bright
colors are needed.
Waxes
Paraffin wax is very effective in increasing extrusion speed and smoothness. Up

to 3.0 phr can be used in Butyl rubber stocks without objectionable bloom. At 1.0-2.5
phr, paraffin wax is an effective antiozonant. At higher doses, low temperature flexibility
and compression set are impaired. They are however, less effective in dynamic
conditions. High melting point microcrystalline waxes improve extrusions while
maintaining relatively hard, dry surfaces.
Antioxidants and Antiozonants
Butyl generally does not require the addition of antioxidants or antiozonants due
to its low unsaturation. Very small quantities of antioxidant are added during
manufacture. Where very high carbon black and oil levels are used, however, oxidation
and ozone resistance may not be sufficient to meet long term storage requirements
without enhancement. Commercial protectants such as the N,N’-dioctyl-p-
phenylenediamine antiozonant can be used where staining or discoloring is not a
34
concern, but should be combined with wax to facilitate migration to the surface of the
article.
Plasticizer
Petroleum-based oils are commonly used as plasticizers to lower compound

viscosity and to improve processability and low temperature properties but with an
increase in compound air permeability. Plasticizers are selected for their compatibility
with isobutylene polymers and for their low temperature properties. Butyl rubber has a
solubility parameter that is similar in value to that of polybutene, and paraffinic and
naphthenic oils for which they are preferred. Although not to be considered as solvating
agents, paraffin waxes and low molecular weight polyethylene are added for improved
processing. For an improvement in low temperature flexibility, ester-type plasticizers
such as adipates and sebacates, can be used.
Various types of plasticizers are used in Butyl rubber compounding and they are:
1) Hydrocarbon (petroleum based) oils.

2) Petrolactum.
3) Waxes.
4) Ester
Hydrocarbon oils
Paraffinic and naphthenic oils are mostly used in Butyl rubber because they
solvate Butyl polymers more efficiently than aromatic oils. Aromatic oils and highly
unsaturated plasticizers when added with Butyl rubber often retard vulcanization of the
compound. Aromatic oils also yield poor low temperature performance.
High quality paraffinic oils are preferred for the best low temperature
performance, outside the use of ester plasticizers. In the latter case, care must be taken
to select esters that will be nonfugitive during processing and heat aging. Typically, 8-25
phr of oil are used in carbon black filled compounds. The higher levels improve
compound plasticity and low temperature flexibility but impairs permeability and ozone
resistance. The level used is determined by the viscosity of the polymer, the level of
fillers (especially carbon black) used, and the processing and performance needs of the
application involved. When high amounts of oil are used, wax should he considered to
help protect the vulcanizate against ozone attack. Table 12 show the effect of different
process oils on Butyl rubber compounds. High viscosity process oils generally improve
the impermeability of Butyl stocks in comparison with their low viscosity counterparts.
35
Table 12
Effect of Processing Oil on Butyl Polymer Compound Properties
Ingredients Test Method Unit Comp1 Comp 2 Comp 3

Butyl 268 PHR 100.0 100.0 100.0
N 660 PHR 70.0 70.0 70.0
Paraffinic Oil, Low Viscosity PHR 25
Paraffinic Oil, High Viscosity PHR 25
Naphthenic Oil PHR 25
Zinc Oxide PHR 5.0 5.0 5.0
Stearic Acid PHR 1.0 1.0 1.0
Sulfur PHR 2.0 2.0 2.0
CBS PHR 1.5 1.5 1.5
ZBEC PHR 1.5 1.5 1.5
Mooney Viscosity
ML 1+4,@ 100 °C ASTM D1646 MU 41 42 38
Mooney Scorch t5 125°C ASTM D1646 Minutes 23.6 25.8 23.6
Minimum Torque (ML) ASTM D 5289 dN.m 1.3 1.3 1.2
Maximum Torque (MH) ASTM D 5289 dN.m 10.3 9.6 9.8
Delta Torque (MH-ML) ASTM D 5289 dN.m 9.0 8.3 8.6
ts2 ASTM D 5289 minutes 3.8 4.0 3.8
tc50 ASTM D 5289 minutes 6.3 6.5 6.2
tc90 ASTM D 5289 minutes 22.6 22.5 22.5
Hardness ASTM D 2240 Sh. A 52 50 50
100 % Modulus ASTM D 412 MPa 1.3 1.1 1.2
Tensile Strength ASTM D 412 MPa 10.7 11.0 11.0
Elongation at break ASTM D 412 % 670 730 700
Tear Strength ( Die B ) ASTM D 624 N/mm 26.2 32.9 28.6
Typical Stress Strain Properties- Aged at 125°C 72 hrs
Hardness ASTM D 2240 Sh. A 47 48 48
Tensile Strength ASTM D 412 MPa 7.7 7.6 7.2
Elongation at break ASTM D 412 % 500 600 550
Tension Set @105°C, 5hrs EM Method % 20 22 20
0.694 0.515 0.772
36
Zinc Oxide
In Butyl, the zinc oxide functions as a cure activator and table 13 shows the
effect of zinc oxide loading varied from 1 to 10 phr.
Table 13
Effect of Zinc Oxide Doses on Butyl Polymer Compounds
Ingredients Unit Z1 Z2 Z3 Z4 Z5 Z 10
Butyl 268 PHR 100.0 100.0 100.0 100.0 100.0 100.0

N 660 PHR 70.0 70.0 70.0 70.0 70.0 70.0
Paraffinic Oil PHR 25.0 25.0 25.0 25.0 25.0 25.0
Escorez 1102 PHR 3.0 3.0 3.0 3.0 3.0 3.0
Zinc Oxide PHR 1.0 2.0 3.0 4.0 5.0 10.0
Stearic Acid PHR 1.0 1.0 1.0 1.0 1.0 1.0
Sulfur PHR 2.0 2.0 2.0 2.0 2.0 2.0

CBS PHR 1.5 1.5 1.5 1.5 1.5 1.5
ZBEC PHR 1.5 1.5 1.5 1.5 1.5 1.5
ML 1+4,@ 100 °C MU 40.7 40.1 39.9 40.8 40.3 40.9
Mooney Scorch (t5) @125°C mins 23.9 23.8 24.2 23.8 28.8 23.5
Typical Properties: MDR Rheometer, 160°, 60 minutes, arc ± 0.5°,
Minimum Torque (ML) dN.m 1.2 1.2 1.2 1.2 1.2 1.2
Maximum Torque (MH) dN.m 8.5 9.7 10.0 10.2 10.2 10.3
ts2 mins. 3.8 3.8 3.8 3.8 3.8 3.8
tc90 mins. 11.7 18.3 21.6 22.0 22.3 23
Hardness Sh. A 47 49 50 50 49 50
100 % Modulus MPa 1.1 1.3 1.5 1.4 1.5 1.4
300 % Modulus MPa 4.1 4.4 4.1 4.2 4.4 4.1
Tensile Strength MPa 11.5 10.9 10.6 10.5 10.9 10.1
Elongation at break % 750 690 640 660 670 660
37
Higher doses of zinc oxide don’t change the curing and mechanical properties of
Butyl compounds. 2 – 3 phr of zinc oxide gave optimum properties. 5 phr of zinc Oxide
is always recommended as the dispersion of zinc oxide is difficult.
Tackifiers
Tackifiers are sometimes used in Butyl stocks and cements to facilitate splicing
or assembly of two component structures. Typical examples are Butyl based caulking,
sealants and Butyl cements used on a pre-cured Butyl valve which must be adhered to
a Butyl innertube prior to vulcanization of the tube. Generally, self-tack of Butyl
compounds can be improved with 2-4phr of hydrocarbon resins such as Escorez 1102.
In the case of the cement stock used on the pre-cured Butyl valve, 10 phr of resin is
suggested and 20-30phr of Escorez 1102 is recommended for caulks and sealants.
Blowing agents
Although the applications are limited, Butyl rubber is used in sponge as the single
polymer (for carpet underlay, footwear) or in blend with EPDM to get low sponge density
for air conditioning pipe insulation. The most cost effective blowing agent is sodium
bicarbonate but its blowing efficiency is insufficient. On the other hand,
azodicarbonamide gives uniform microcells and has penetrated the market. Generally,
blowing agents have a relatively high decomposition temperature, and blowing
promoters are used to lower the decomposition temperature to meet the applied
vulcanizing temperature.
Processing aids
The key requirement for processing aids is to improve the processability with
minimum effect to the physical properties. There are many areas where processing aids
are needed. The following four areas are most common:
+ Dispersion /Homogenizing of ingredients or polymers.

+ Improving release properties.
+ Improving flow properties.
+ Tack adjustment.
a. Dispersion Homogenizing Aids.
One of the most important criteria in compound production is a satisfactory

dispersion of all ingredients in the rubber compound. It is known that certain fillers have
different affinity for different polymers which may lead to differences in concentration.
Addition of 2-10 phr of dispersion or homogenizing agents have performed quite well in
terms of dispersion improvement and some other side effects such as shorter mixing
cycle which can contribute to energy savings. Struktol 60 NS or Struktol 40MS are the
typical ingredients for this purpose and should be added in masterbatch mixing.
38
b. Release Agents.
Stearic acid is the most commonly used ingredient in rubber compounding and
processing aid acting as a release agent. Zinc stearate also works well. Butyl rubber is
more prone to stick to the mill, calender roll etc, during the processing of uncured
compounds. Release agents are also effective to get easier mold release after cure.
Low molecular weight polyethylene added at 3-5 phr for smooth extrusions reduces die
drag, and aids mold release of Butyl compounds. Low levels do not affect physical
properties appreciably. Mixing at least three minutes at a minimum temperature of
121˚C is recommended to ensure adequate dispersion.
c. Flow Improver
Flow improvers are effective to get better extrudability, better mold flow
properties in injection molding or in complicated mold configurations.
However, processing aids which are effective for releasing are also effective for
improving flow properties. Similar to release agents, they should be mixed in the final
stage together with the accelerators.
39
Optimizing Key Properties of Butyl Compounds
Application requirements dictate the development of formulations that will exhibit

the best balance of critical properties. The compounding design to meet specific
requirement needs filler and cure system modification. However, care must be taken to
get a good balance of quality and processing. Primary uses of polyisobutylene and
isobutylene copolymers of butyl, halobutyl, star branched butyl, and brominated
poly(isobutylene-co-p-methylstyrene) in elastomeric vulcanized compounds rely on their
properties of low air permeability and high damping.
Permeability
In comparison with many other common elastomers, polyisobutylene and its

copolymers are notable for their low permeability to small molecules (table 14). This is
due to their efficient intermolecular packing as evidenced by their relative high density
(density of 0.917 g/cm3). This efficient packing in isobutylene polymers leads to their low
fractional free volumes and low diffusion coefficients for penetrants. In combination with
the low solubilities of small-molecule diffusants in isobutylene polymers, low
permeability values for small molecules, such as He, H2, O2, N2, CO2, and others, are
observed in isobutylene polymers as compared with other elastomers. The permeability
of elastomeric films to the passage of gas is a function of the diffusion of gas molecules
through the membrane and the solubility of the gas in the elastomer.
Table 14
Permeability of Various Elastomers to Gases at 25ºC 22,23
(Relative to Natural Rubber Gum Vulcanizates = 100)
As shown in figure 17, diffusion coefficients of nitrogen in both various diene

rubbers and in butyl rubber increase with increasing differences between the
measurement temperature and the corresponding rubber’s glass-transition temperature.
However, although the rate of increase in diffusion coefficient with T−Tg is about the
40
same between diene rubbers and butyl rubber, the absolute values of diffusion
coefficient in butyl rubber are significantly less than that of diene rubbers. The
isobutylene backbone of butyl imparts low permeability to gases and moisture which is
unique among vulcanizable elastomers, leading to the preference for innertubes based
on butyl rubber. Gases such as helium, hydrogen, nitrogen, and carbon dioxide are well
retained by a Butyl membrane.
Figure 17
Diffusion of Nitrogen Through
Butyl Polymers in Comparison with Other Polymers24
The gas permeability of compounded stocks can be improved (decreased) by:

+ Increasing filler content.
+ Reducing oil level.
+ Using platy fillers such as Mica, Talc etc.
Heat Resistance
Sulfur vulcanizates of butyl rubber tend to soften during prolonged exposure to

elevated temperatures of around 150°C. This deficiency is largely the result of the
polysulfide crosslink, coupled with low polymeric unsaturation which allows no
compensating oxidative (crosslinking) hardening.
41
Among the butyl grades, Exxon butyl 268 and 365 are best for heat resistance.
As a general rule, antioxidants are not used to improve heat resistance of butyl rubber
stocks. Carbon blacks are preferred over mineral fillers for heat resistance. Furnace
blacks yield the best performance, with the more reinforcing types being best. Cure
system selection is very important in achieving vulcanizates having the ability to
withstand prolonged service at elevated temperatures. Heat stable monosulfide or,
preferably, carbon-carbon cross-links and the low functionality of the butyl polymer
combine to produce excellent heat resistance.
Monosulfide cross-links are obtained through the use of low levels of sulfur
donors with no elemental sulfur present. Carbon-carbon bonds are obtained through the
use of active curing resins, as discussed. Conventional sulfur cures are effective in heat
resistance up to about 120˚C. Low Sulfur and sulfur donor cures are good up to about
150˚C. Over 150°C, quinone or resin cures are preferred heat resistant systems for
Butyl compounds. Butyl stocks can be compounded for very high temperature (around
or a little over 200˚C), short term heat resistance. The resin cure of Butyl rubber can
provide this short term-heat aging resistance.
For best heat resistance, low amounts of process oil (up to about 5 phr) should
be used: petrolatum and wax can be used at somewhat higher levels.
Coumarone-indene resins at about 10 phr will improve heat resistance as well as
extrusion performance. They also increase Shore A hardness by about 10 points after
curing.
Dynamic Damping
Polyisobutylene and isobutylene copolymers are high damping at 25°C, with loss
tangents covering more than eight decades of frequencies even though their glass
transition temperature is less than −60°C. This broad dispersion in PIB’s dynamic
mechanical loss modulus is unique among flexible-chain polymers and is related to its
broad glass–rubber transition24. The narrowness of the glass–rubber transition, as
defined by the steepness index, for PIB is 0.65, which is much smaller than most
polymers. In addition, PIB has the most symmetric and compact monomer structure
among amorphous polymers, which minimizes the intermolecular interactions and
contributes to its unique viscoelastic properties PIB and its copolymers have high
entanglement molecular weights and corresponding low plateau moduli which, in turn,
contribute to their high tack or self-adhesion in the uncross-linked state. Entanglement
molecular weight of PIB is about 9000 as compared with 1300 for polyethylene, 1700 for
ethylene–propylene copolymer, 2000 for 1,4-polybutadiene, 3000 for styrene–butadiene
copolymer, and 6100 for hevea rubber.
Tear Strength
Filler loading, cure system and state of cure strongly influence the tear strength
of butyl rubber stocks, as does the polymer itself. As butyl polymer unsaturation
increases, tear resistance increases, reaches an optimum then decreases depending
42
on crosslink density. As polymer molecular weight increases, tear resistance increases.
Highest tear strength is obtained with fine particle furnace black and silica fillers.
High Tensile Strength
Higher reinforcing carbon blacks having smaller particle size give higher tensile
strength. As to mineral fillers, silica is more effective in increasing both tensile and tear
strength. Carbon blacks such as SAF or ISAF are the highest reinforcing carbon blacks,
but such very small particle sized fillers are generally hard to disperse well. Most
applications of Butyl rubber do not require very high levels of tensile strength. To obtain
the desired performance, the important factor is the quality of mixing.
Green Strength
It has long been recognized that understanding the behavior of unvulcanized

compounds is very important as the compounds are subjected to large deformation
during processing. Such large deformations can be of concern. For example, in the
manufacture of innertubes, such large deformations increases the defect rate. The
preforming operation of the innertubes requires the uncured tube to be inflated on a
forming ring and held in this condition for several minutes before being inserted into the
mold for curing. During this process, the crown of the tube is stretched up to 100% or
more and thin or bruised areas on the tube are highly susceptible to flow. This usually
results in increased rejects due to thinning or fold breakdown of the tubes before or after
curing. The “Green Strength” of the compound is often a very convenient parameter to
assess the processability of the compound. Stress decay time and stress relaxation
speed of butyl compounds depends on three general factors
• Compounding variables
• Environmental temperature
• Speed at which the green compounds are extended.
Heat treatment with poly p-dinitrosobenzene is the most effective way to improve the
green strength. Lowering the carbon black loading is also helpful. An SRF/FEF carbon
black combination is shown to be best, in terms of stress decay time and stress
relaxation speed, among the non-heat treated compounds. The dual carbon black
system is advantageous for increasing the stress decay time and reducing the stress
relaxation rate, especially at low extension speeds. High extension speed reduces the
stress decay time, but increases green strength. High extension speed gives
undesirable faster stress relaxation rate. Environmental temperature has a large effect
on stress decay time and green strength (higher temperature reduces both properties),
while it has no effect on stress relaxation rate.
Ozone Resistance
Butyl polymers inherently resistant to ozone compared to polydiene rubbers

because of its saturated backbone. Among the butyl grades, the lower unsaturation
43
polymers such as Exxon Butyl 065 provide better ozone resistance. Ozone resistance is
influenced by all the ingredients in the compound, and not just by the polymer. Higher
filler loading reduces ozone resistance. This is true for both carbon black and mineral
fillers, but is particularly true for reinforcing carbon blacks. Wax may be used for
improving the ozone resistance of the highly loaded stock. The presence of butyl
reclaim reduces ozone resistance. This is related to the effect of the reclaiming process,
the oil used, and the risk of contamination by high unsaturation rubber. In general, low
modulus compounds have better ozone resistance as long as they are well cured.
Ozone resistance declines gradually as the butyl rubber compound becomes overcured.
Steam / Water Resistance
Good resistance to dry steam is readily achieved with Butyl compounds, but hot
water and wet steam exposure require special care. Maximum resistance to hot water
and wet steam is attained using the resin cure and fillers having low level of water
soluble ash. Among the mineral fillers, silica is preferred because of the polymer filler
interaction that can be achieved during mixing.
Weather Resistance
Carbon black filled butyl compounds have good resistance to weathering. Light
coloured butyl compounds must be compounded to minimize degradation induced by
ultra violet rays. Ultraviolet degradation of butyl stocks usually shows up as surface tack
or softness, often combined with dirt retention. The following compounding techniques
are suggested for maximum weather resistance in mineral filled compounds.
• Obtain a high state of cure

• Use a low content of high quality paraffinic oil
• Include ultraviolet absorbers such as Titanium dioxide
• Depending on application, use 10 phr of paraffinic wax
• To the extent possible, avoid clays especially hard clays. Calcium carbonates
talc and silicas generally perform better.
• Incorporate a small amount of EPDM.
Low Temperature Flexibility
Butyl rubber has generally good low temperature flexibility and does not
crystallize or become brittle at temperatures down to about -60°C. However,
compounded stocks do stiffen or increase in modulus as temperature decreases.
Proper selection of plasticizers can help minimize this behavior. Low temperature
stiffening of butyl rubber can be minimized by using low viscosity paraffinic mineral oils.
Esters are more effective in preventing low temperature stiffening. Dioctyl sebacate and
Diisooctyl sebacate are suggested. Large particle size carbon blacks help to maintain
low temperature flexibility.
44
Butyl Compound Processing
Generally, the rubber compounds go through several steps e.g., mixing, first
stage forming/assembling, second stage forming/assembling and vulcanization to the
final products. The key point is to produce the designed quality with minimum
processing cost. Defect rate directly affects final production cost. However, if the actions
taken to reduce the defect rate push up the production cost significantly, they would be
of no value. Therefore, the balance of production cost and rejection cost is important.
Generally, if the result of one step is poor, it is difficult to correct it in the next processing
steps. Hence, it is important to establish the best processing standard for each process.
Special attention should be paid to the impermeability of Butyl rubber which is a desired
property in the final product, but which can act as a negative factor during processing,
because once air is entrapped it is difficult to remove.
Unlike natural rubber, Butyl rubber does not require premastication. However,
premastication of 30-45 seconds in a Banbury to a temperature of 80-90˚C provide both
polymer breakdown and a reduction in polymer Mooney viscosity, thus giving better
homogeneity of polymer/filler and other ingredients. Recently more emphasis is being
placed on production efficiency with mix cycles getting shorter, not allowing the use of
premastication. In this case, heating the polymer in a hot room (40-60˚C) is
recommended. This is especially important in winter to prevent having undispersed
polymer in the mixed compounds.
Mill mixing
Mill mixing for master batch is only done if no Banbury mixer is available. However,
it is still common for finalization. Mill mixing is best accomplished with mill friction ratio
of 1.15-1.25:1, and roll temperatures of 40˚C on the slow and 55˚C on the fast roll.
Gum Butyl rubber is difficult to band on a mill, but improves after about 10 phr of filler
have been incorporated.
A suggested mill mix procedure is as follows.
+ Band part of the Butyl rubber in a continuous band with a small rolling bank.
Preferably, leave a small amount of the previous Butyl batch on the mill to facilitate
adding the fresh polymer. If a seed band cannot be used, begin adding fillers as
soon as possible to the polymer on a tightly set mill.
+ Add stearic acid, protective chemicals (if used) and ¼ of the fillers in small
increments
+ Add remaining Butyl polymer, opening the mill as necessary to maintain a small
rolling bank.
+ Add fillers in small increments, opening the mill to maintain a small bank as batch
weight increases. Add small particle, reinforcing fillers first without plasticizers.
Plasticizers can be added incrementally with non-reinforcing fillers.
+ The addition of release agents may be desirable to eliminate mill sticking of highly
loaded mineral –filled stocks.
45
+ Curatives are added as the last step of the mixing cycle, provided that the batch
temperature is below approximately 105˚C.
Mixing
The following mixing recommendations apply to Butyl compounding in general and Butyl
innertube compounding in particular.
General Guidelines.
+ Mixing is usually done in two stages. The first stage contains all the ingredients
except the curatives.
+ The batch weight generally should be 10-20% higher than that used for a
comparable compound containing general purpose rubbers.
+ Preferably, the polymer should be premasticated in the banbury for 30-45
seconds prior to adding the fillers
+ For improved dispersion, Zinc oxide should be added early in the mixing of Butyl
rubber stocks.
+ Reinforcing fillers should be added early in the mix cycle before plasticizers are
added. Plasticizers, particularly process oils, minimize the shear rate which may
prevent agglomerate breakdown and dispersion.
+ For optimum physical properties, stocks should be mixed to a high temperature
in the first stage.
+ Tackifying resins, waxes, oils and plasticizers can be added incrementally with
non-reinforcing fillers to facilitate their incorporation.
+ A typical mix cycle can be as follows,
Banbury Mixing Cycles (40 rpm)
First Stage Cycle
Time Operation
0 min. Load Butyl Polymer
0.5 min. Add 2/3 carbon black, zinc oxide
2.0 min. Add 1/3 carbon black, stearic acid, oil
160˚C Dump.
+ For enhanced polymer and /or carbon black dispersion (of particular importance
to innertubes where small particle carbon blacks are used), prewarm the polymer
alone in the mixer for up to 0.5-1 minute (depending on rotor speed) before
adding any black. This improves the rate of incorporation of the carbon black
into the polymer and can result in shorter overall mixing time.
+ Plasticizer and process aids are held back to allow maximum shear development
early in the cycle. This is especially important when small particle fillers such as
HAF carbon black are used
46
+ Dump temperatures above 150˚C are suggested (as long as curatives are not
present) to aid in removing volatile materials that may cause porosity in
subsequent processing.
+ Where chemical agents are used to enhance the interaction between Butyl and
carbon black, the temperature should reach at least 160˚C to ensure the
chemical is completely reacted. Some materials may require even higher dump
temperature, and the supplier’s recommendations should be followed. Unless
adversely affected by another material, the Butyl polymer tolerates this high
dump temperature very well.
Second Stage Cycle
Time Operation
0.0 min. Load first stage mix plus curatives
2.0 min Dump at 100-105°
Cool immediately
Use 100% load at 20 rpm or 80% load at 40 rpm.

+ Care should be taken not to trap anti-tack material or water in the folds of the
stock when stacking, as this can be a source of blisters during subsequent
processing operations such as extrusion.
+ Curatives can also be added to Butyl compounds on a mill. If added just prior to
extrusion, a second feed mill is desirable to ensure complete and uniform
dispersion of the curatives. Use of curative pre-dispersions can avoid this
requirement.
Solubility parameter, difference of Mooney viscosity and compatibility of

polymers with ingredients are the factors which affect the quality of the mixes. Co-
vulcanization between rubbers also affects blending, hence, selection of cure systems
suitable for each polymer is important. Differences in Mooney viscosity, incompatibility
of polymers and carbon black are corrected with modified mixing methods e.g. pre-
mastication of polymer pairs, preparing master batch first with each polymer then blend
together etc.
Extrusion
Compounding for Extrusion
Extrudability is largely affected by the plasticity of rubber compounds. The

plasticity has a close relation with the loading volume of fillers and plasticizers, and
generally higher loading gives better extrudability. As a brief guideline, the minimum
filler loading level for extrudability is 25 phr for carbon black and 30 phr for mineral fillers.
Feeding to the Extruder
47
A two-mill operation (warm-up mill followed by a feed mill) is preferred to ensure
constant quality and temperature of the feed. Preferred feed strip temperature is 80°-
90°C and the rolling bank on the feed mill should be kept as small as possible to
minimize air entrapment. The feeding volume of the compound should be adjusted as
slightly larger than extruding volume. If both volumes are the similar, small variation in
take-off conveyor speed will cause porosity/blisters or irregular dimension of the
extrudates. Desirable conditions for feeding are
• Constant and forced feeding with conveyor/feed roller
• Thin feed stocks since thick stocks from the feeding mill tend to contain more
porosity and blisters.
So, if feed volume is changed for different sizes, the best practice is to change the cut
width while keeping the roll clearance constant.
Extrusion of Innertubes
Extrusion of Butyl rubber is best illustrated in its most important application,

namely innertubes. The extruder die should be pre-warmed to approximately 110˚C.
After extrusion is started, the external heat is generally removed to prevent excessive
stock temperature that may limit reworking the stock. Frictional heat generated by the
stock itself will usually maintain the temperature necessary for good extrusion. The
barrel of the extruder is generally cooled to about 90°C and the screw is cooled
continuously in order to prevent excessive stock temperature and to maintain good
stock flow through the extruder. The extruded stock temperature should be 100-110°C
for good surface texture. The extrudate should be cooled as quickly as possible for
minimal heat history. Extruder, take-off belt and wind-up speeds should be
synchronized to prevent stretching more than about 2%. Excessive stretching causes
variable shrinkage, which in turn causes difficulties with final dimensions.
When rework is used care must be taken to dry it and maintain a constant feed (10-20%
ratio to the fresh stock).
Calendering
Feeding to the Calender
The following three methods are common practice in the industry.
1. Feed strip from the open mill is continuously fed to the calender roll through the
swing arm to supply the stock evenly on the roll length.
2. Three or four feed strips from the open mill are continuously fed vertically to the
calender roll axis. Feeding is done through an extruder. This method can minimize
air entrapment.
3. The rolled up sheet on the open mill is fed to the calender manually. This practice is
done only in small factories and will likely cause blisters.
48
Calendering /Sheeting
Butyl stocks intended for calendering require at least 20 volumes of filler for
satisfactory performance. At least one part stearic acid should be used for good roll
release. Mineral-filled stocks, usually more tender and tacky when hot, may require two
or more parts of stearic acid for satisfactory release. Small, active rolling banks of
stocks should be maintained on both the mills and the calender to facilitate release of
any trapped air. Butyl compounds follow the cooler roll. A temperature difference of at
least 15˚C between the two calender rolls is recommended. Initial calender roll
temperature should be
1 2
First Roll 80-90 (˚C) 100-110 (˚C)
Second Roll 70-80 (˚C) 85-95 (˚C)
If calendered sheets are plied up, they should be brought together at an angle
sufficient to keep them from contact until a point of positive consolidation pressure is
reached. This is important to minimizing trapped air blisters. Uniform consolidation
pressure is also important to minimize trapped air. The speeds of the calender rolls,
cooling drums and wind-up mechanism should be synchronized to prevent more than
1.5-2.0% total stretch. Excessive stretch leads to excessive shrinkage and possible
difficulties in subsequent fabrication operations. Cotton, polypropylene, or embossed
polyethylene film can be used to store the calendered stock. The calendered stock
should age overnight to ensure complete cooling and allow stress relaxation to take
place.
Butyl compounds can be formulated to have fast cure rate, good hot tear strength,
and good mold release and flow characteristics, and can be molded into highly intricate
designs. Compounding for proper cure rate and scorch safety is essential for adequate
mold flow and knitting. For intricate moldings, internal mold-release agents are preferred
over lubricants and sprays applied to the mold, as the latter tend to interfere with good
knitting. Satisfactory internal release agents include stearic acid, methyl hydroxy
stearate, paraffin wax, and phosphate ester plasticizers. Proprietary agents such as
Struktol WB212 may also be useful. Mold design and proper placement of stock in the
mold are very important when molding intricate Butyl parts because of the polymer’s low
permeability. Stock preforms should be free of trapped air. Molds should have carefully
placed vents so that air is not trapped in blind spots, and should be designed to prevent
entrapment of air by flowing stock.
49
Figure 18
Calender Configurations
50
Butyl Applications
The major application for Exxon Butyl is in innertubes for tires ranging in size
from small bicycles to large commercial trucks and tractors. Low permeability, good
heat and flex resistance, and ease of processing make Exxon Butyl particularly suited
for innertubes. The higher molecular weight/medium unsaturation polymers Exxon Butyl
268 serve best for this application. Tire curing members are another very important
application for Exxon Butyl. With the use of resin cure, Butyl compounds yield a
combination of properties including excellent heat resistance that cannot be duplicated
by other polymers. The high molecular weight/medium unsaturation polymer Exxon
Butyl 268 is primarily used, although in many cases it is blended with the lower
molecular weight/ lower unsaturation Butyl Exxon Butyl 065 in order to achieve better
stock flow while minimizing the use of plasticizers. Also, the lower average unsaturation
obtainable through the use of polymer blends is sometimes of interest to avoid the
possibility of overcure with subsequent loss of hot elongation and tear strength.
Automotive and stationary dynamic parts benefit from Butyl’s unique internal
structure which permits it to absorb large deforming forces, releasing the energy in the
form of the heat. Preferred Butyl polymers include the high molecular weight, medium
unsaturation Exxon Butyl 268 as well as the medium molecular weight, high
unsaturation Exxon Butyl 365. The latter offers fast cure rate with very good heat
resistance.Butyl compounds offer excellent resistance to attack by many chemicals and
natural fats. These properties lead to the use of Butyl in applications ranging from
potable water systems to chemical tank lining. The chemical structure of Butyl provides
the basis for excellent blends with polyolefin thermoplastics where it is used to provide
additional stress cracking resistance and improved impact strength. Butyl rubber is
accepted worldwide as a food packaging material without restriction as to food type. It
can be found on the positive lists for food contact ingredients in all countries where such
lists exist.
Innertubes
A large proportion of the world’s tube type tires, from bicycle through truck and
earthmover sizes rely on innertubes to retain their pressure. Correct inflation pressure
retention is now more than ever recognized as a key factor in maintaining operation
safety, low rolling resistance for minimum fuel or energy consumption and long life for
all classes of tires. The innertube of a pneumatic tire assembly has a number of
performance requirements which includes,
1. Retention of air pressure during the tire and innertube service life (low permeability).
2. Durability (oxidation, ozonolysis, heat, and aging resistance).
3. Tear resistance.
4. Low growth (low tension set) during service.
5. Non-stickiness of the innertube to the tire casing during service (heat resistance &
retention of physical properties).
51
Table 15
Butyl Based Tire Innertube Formulations
Material Units Comp. 1 Comp. 2

ExxonTM Butyl 268 PHR 100 100
Carbon Black N 330 PHR 50
Carbon Black N 660 PHR 70 --
High Viscosity Paraffinic Oil PHR 25 20
PF Resin PHR 4.0
Escorex 1102 3.0
Sulphur PHR 2.0 1.0
CBS PHR 1.5
MBTS 1.0
ZBEC-70 PHR 1.5 2.86
Stress Strain Properties, Samples cured @ 160°C, tc90 + 2 minutes.
Tear Strength ( Die C ) ASTM D 624 kN/m 33.9 40
ExxonMobil
Tension Set (Method B)105°C/ 5hrs/ 50% % 18.1 21.4
Method
ExxonMobil Method 0.49 0.18
52
Butyl rubber innertubes can meet all of these performance criteria much better
than innertubes made from general purpose rubbers. Butyl rubber has good heat,
oxygen and ozone resistance as well as good dynamic properties which enhance the
long-term durability of innertubes. This is important given common stringent operating
conditions such as long distance travel at higher operating speeds, and heavier
payloads under difficult weather and temperature conditions. The growth of the radial
tire market brought with it additional performance demands for Butyl innertubes in terms
of compound and splice durability which must withstand the higher degree of flexing of
the radial tire sidewall and the innerliner splice must continue to do so throughout the
much longer life of a radial tire. Typical innertube formulations suitable for bias ply and
heavy duty tubes are given in table 15. These formulations provide a good balance of
processing and physical properties.
Bicycle innertubes cover a range of small section innertubes used on bicycles,

motorized bicycles (mopeds) and small motorcycles. These innertubes are
characterized by high inflation pressure, thin walls and high surface area to volume ratio.
This can lead to rapid air loss when the innertubes are made of natural rubber and SBR
rubber. Thus, the superior air retention properties of butyl rubber offer particular
advantages for bicycle innertubes A detailed description of Butyl Innertube
manufacturing is provided in the Exxon™ Butyl Rubber Innertube Technology Manual
(visit www.butylrubber.com).
Ball Bladders
Ball Bladders are another major application of butyl rubber. Table 16 shows the
standard Butyl recipe for ball bladders. When manufacturing innertubes for soccer balls,
basketballs, volleyballs and footballs, four pieces of calendered sheets are spliced to
form a spherical shape. Good spliceability of the four seaming lines is the key
requirement. The thickness of the calendered sheet for volleyball bladders is about 0.7
mm, so a reasonable level of green strength is needed to prevent excess thinning
during the processing. Different polymer compositions are required for different ball
constructions.
Curing Bladder
Curing bladder is one of the most severe applications in terms of heat and flexing
resistance. The use of resin cured Butyl is the best technology to meet these
requirements. To achieve optimum performance of the Butyl bladder compound,
dispersion of the ingredients, especially polychloroprene, carbon black, zinc oxide and
curing resin is essential. There is a trend toward injection molding of bladders to
improve production efficiency and uniformity of the tires. Better flow properties are
therefore required. Table 17 gives typical formulations for tire curing bladders.
53
Table 16
Butyl Based Tire Ball Bladder Formulations
Material Units I II
Butyl 268 PHR 100.0 100.0

N 550 70.0 --
N 330 -- 50.0
Paraffinic Oil 22.0 20.0
Escorez 1102 3.0 3.0
ZnO 5.0 5.0
MBTS 0.5 1.0

Sulfur 1.5 1.0
ZBEC 2.0 5.0
TBzTD 0.0 2.0
Mooney Viscosity ML 1+4,@ 100 °C ASTM D 1646 MU 47 50
Time for two point rise in torque.(ts2 ) ASTM D 5289 minutes 2.9 6.7
Tear Strength ( Die B ) ASTM D 624 kN/m
Tension Set @105°C / 5hrs / 50 % Strai EM Method % 17.5 21.1
Oxygen Permeability coefficient @ ExxonMobil Method 0.46
0.46
40°C,Oxygen conc.:21% [ mm-cc/[m²-day]*mmHg
54
Table 17
Butyl Based Tire Curing Bladder Formulations
Material Units I II
Butyl 268 PHR 100.0 --
Butyl 065 -- 100.0
Chloroprene Rubber 5.0 5.0
N 330 50.0 50.0
Castor Oil 5.0 5.0
ZnO 5.0 5.0
Octylphenol Formaldehyde Resin 10 10
Test Method Units
ML 1+4,@ 100 °C ASTM D1646 MU 75 59.8
Minimum Torque (ML) ASTM D5289 dN.m 2.6 2.3
Maximum Torque (MH) ASTM D5289 dN.m 12.4 6.9
Delta Torque (MH-ML) ASTM D5289 dN.m 9.8 4.6
Time for two point rise in
ASTM D5289 mins 3.3 20.9
torque.(ts2 )
Time to 50% rise in torque. (tc50 ) ASTM D5289 mins 8.3 25.4
Time to 90% rise in torque. (tc90 ) ASTM D5289 mins 23.5 52.2
Hardness ASTM D2240 Shore A 58.0 60
Hardness ASTM D2240 Shore A 85 81
Typical Stress Strain Properties- Steam Aged at 180°C. 96 hrs
Hardness ASTM D2240 Shore A 85 86
55
Butyl Dynamic Parts
Butyl finds acceptance in vibration control applications due to its high damping,
reversion resistance cures and good aging properties. Table 18 gives typical formulation
for butyl based compounds for dynamic applications.
Table 18
Butyl Based Compounds for Dynamic Application
Shore Shore Shore Shore

Ingredients Unit
A 35 A 45 A 55 A 60
Butyl 268 PHR 100.0 100.0 100.0 100.0
N 330 PHR 30.0 50.0 50.0 30.0
N 660 PHR -- -- -- 55
Paraffinic Oil PHR 20.0 25.0 10.0 5.0
Zinc Oxide PHR 5.0 5.0 5.0 5.0
Stearic Acid PHR 1.0 1.0 1.0 1.0
Sulfur PHR 1.0 1.0 1.0 1.0
MBTS PHR 1.0 1.0 1.0 1.0
ZBEC PHR 2.0 2.0 1.5 2.0
ML 1+4,@ 100 °C MU 46 44 69 75
Minimum Torque (ML) dN.m 1.2 1.5 2.5 2.3
Maximum Torque (MH) dN.m 6.3 7.8 11.3 11.6
Delta Torque (MH-ML) dN.m 5.1 6.3 8.8 9.2
Time for two point rise intorque,ts2 minutes 4.7 4.1 4.0 3.7
Time to 90% rise in torque. (tc90 ) minutes 20.4 19.9 25.3 23.3
100 % Modulus MPa 0.8 1.0 1.4 1.7
300 % Modulus MPa 2.1 2.6 4.0 5.2
Elongation at break % 875.0 773.0 743.0 598.0
Tear Strength ( Die B ) N/mm 38.9 47.8 59.7 43.8
100 % Modulus MPa 1.1 1.9 2.0 2.3
Tension Set @105°C % 16.6 22.0 19.1 18.9
56
Recommended Formulations
ExxonMobil Chemical model starting point formulations for a variety of

applications including innertubes, tire curing bladders and ball bladders can be found at
www.butylrubber.com. These model starting point formulations can be an excellent way
to help initial development studies.
Global Supply and Support
ExxonMobil Chemical produces Butyl polymers at France. Over the years,

ExxonMobil Chemical has made significant improvements in product quality through a
wide variety of raw material and process control programs.
Research and development laboratories in Baytown, Texas, Clinton, New Jersey

(USA), Machelen, Belgium (near Brussels), and Bangalore, India provide technical
support for manufacturing and marketing operations. Worldwide offices for chemical
products provide trained personnel for sales and customer service activities. Please
visit “www.butylrubber.com” for information on grades, datasheets, MSDS, applications,
formulary, and other news items and useful links.
Summary
Butyl rubber, based on isobutylene and isoprene, is an important synthetic

elastomer. It is widely used in tires and pharmaceutical applications, due to its high
impermeability. Butyl rubber is also preferred elastomer for tire curing bladders and tire
innertubes. This review presents some basic information on different grades of butyl
rubbers that are manufactured by ExxonMobil Chemical and available commercially.
This review also gives some insight on how butyl rubbers are manufactured.
Compounding guidelines of butyl rubber along with processing of the final rubber
formulations through a production facility are discussed in this review. Precautions such
as maximum compound mixing non-productive drop temperatures, productive stage
drop temperatures, and optimized calendering conditions are outlined. The review also
discusses the impact of different compounding ingredients on important compound
properties like impermeability, heat resistance, adhesion, compound viscosity, green
strength, and shrinkage resistance. The review also gives an overview of the butyl
applications with special reference to tire innertubes and tire curing bladders.
This review focuses on grades, manufacturing, processing and applications of

different grades of butyl polymer.
57
APPENDIX 1
Recognized Industry Abbreviations for Polymers
AU Polyester urethane
BR Polybutadiene
BIIR Brominated isobutylene-isoprene rubber (Bromobutyl rubber)
BIMS Brominated Isobutylene-co-para-methylstyrene rubber
BHT Antioxidant. Protects against degradation.
CIIR Chlorinated isobutylene-isoprene rubber (Chlorobutyl rubber)
CR Chloroprene rubber
CSM Chlorosulfonyl polyethylene
EAM Ethylene-vinyl acetate copolymer
EPDM Terpolymer of ethylene, propylene and a diene with a residual unsaturated
portion in the chain
EPM Ethylene propylene copolymer
ESBO Epoxidized soybean oil. Epoxy groups capture any acids, including excess
stearic acid. Level is approx 1.3%
GPR General Purpose Rubber
IIR Isobutylene isoprene rubber
IR Synthetic polyisoprene
NBR Acrylonitrile butadiene rubber
PIB Poly Isobutylene
SBR Styrene butadiene rubber
E-SBR Emulsion styrene butadiene rubber
S-SBR Solution styrene butadiene rubber
X-NBR Carboxylated acrylonitrile butadiene rubber
X-SBR Carboxylated styrene butadiene rubber
Y-SBR Block copolymer of styrene and butadiene
58
APPENDIX 2
Recognized Industry Abbreviations for Accelerators
Abbreviation &
Commercial
Descriptions Chemical Name Function
CBS N-cyclohexyl-2-benzothiazolesulfenamide Primary Acc.

BCI-MX 1,3-bis(citraconimidomethyl) benzene Reversion Res.
CTP N-(cyclohexylthio) phthalimide Retarder
DBQDO p-quinone dioxime dibenzoate Quinone Cure
DCBS Dicyclohexylbenzothiazole sulfenamide Primary Acc.
DETU Diethylthiourea
DBTU Dibutylthiourea
DOTG Di-o-tolylguanidine Secondary Acc.
DPG Diphenyl guanidine Secondary Acc.
DPPD Diphenyl-p-phenylenediamine Accelerator
DPTU N,N’-diphenylthiourea
DTDM 4,4-Dithiodimorpholine Vulcanizing Agent
ETU Ethylthiourea Accelerator
HTS Hexamethylene-1,6-bis(thiosulfate) Reversion Res.
Disodium salt, dihydrate
MBS Oxydiethylene benzothiazole-2 Primary Acc.
-sulfenamide Primary Acc.
MBT Mercaptobenzothiazole Accelerator
MBTS Mercaptobenzothiazole disulfide Primary Acc.
QDO p-quinone dioxime Quinone Cure
TBBS tert-Butyl-2-benzothiazole sulfenamide Primary Acc.
TBSI N-t-butyl-2-benzothiazole sulfenimide Primary Acc.
TBzTD Tetrabenzylthiuram disulfide Secondary Acc.
TMTD Tetramethylthiuram disulfide Secondary Acc.
TMTM Tetramethylthiuram monosulfide Secondary Acc.
Vultac ® TB 710 Alkylphenol disulfide polymer Accelerator
ZDEC Zinc diethyldithiocarbamate Secondary Acc.
ZDBC Zinc dibutyldithiocarbamate Secondary Acc.
ZBEC Zinc dibenzyldithiocarbamate Secondary Acc.
ZIX Zinc isopropyl xanthate Low temp. Acc.
ZBPD Zinc dibutylphosphorodithiate Accelerator
MBMTBP 2,2'-Methylene-bis Antioxodant
(4-methyl-6-tert-butylphenol
6 PPD N-(1,3-Dimethylbutyl)- Antiozonant
N'-Phenyl-p-Phenylenediamine
TMQ Polymerised 1.2 dihydro-2, 4 Antioxodant
trimethyl quinoline
59
Appendix 3
List of Common Terms for Miscellaneous Compounding Ingredients
Altax Benzothiazyldisulfide
Barytes Barium sulfate
BHT Antioxidant Butylated hydroxytoluene
DEG Diethyleneglycol
Escorez TM 1102 Petroleum based resin
Flexon 876 Paraffinic mineral oil
Flexon 641 Naphthenic mineral oil
Flexon 580 Naphthenic mineral oil
Flexon 391 Aromatic mineral oil
MBI Mercaptobenzimidazole
MBT Mercaptobenzothiazole
MBTS Benzothiazyl disulfide
Mineral Rubber Blends of maltenes, asphaltenes
Morfax 4 – morpholinyl – 2 benzothiazole disulfide
Parapol 2225 Low molecular weight isobutylene–butane copolymer
Retarder W Salicylic acid
Ultramarine blue Blue pigment
Wood Rosin Derivatives of abietic acid
MP Resin Octylphenol formaldehyde resins
60
List of Tables
Table 1: Specification of Butyl Polymers marketed by ExxonMobil Chemical4 ............. 11

Table 2: Physical Constants of Butyl polymer2 ............................................................. 12
Table 3: Effect of unsaturation on Butyl cured properties ............................................. 13
Table 4 : Effect of Molecular weight on properties of Butyl polymers ........................... 15
Table 5: Crosslinking of Butyl polymers with ultra-accelerator systems ....................... 19
Table 6: Crosslinking of Butyl polymers with ultra-accelerator systems ....................... 20
Table 7: Crosslinking of Butyl polymers; Octylphenol formaldehyde resin systems ..... 24
Table 8: Typical properties of Butyl – Halobutyl blend compounds .............................. 28
Table 9: Properties of Butyl EPDM blends ................................................................... 29
Table 10: Effect of Carbon black properties on processing .......................................... 30
Table 11: Effect of Carbon black on Butyl polymer compounds ................................... 31
Table 12: Effect of processing oil on Butyl polymer compounds .................................. 36
Table 13: Effect of Zinc Oxide doses on Butyl polymer compounds ............................ 37
Table 14: Permeability of Various Elastomers to Gases at 25ºC 22,23........................... 40
Table 15: Butyl based tire innertube formulations ........................................................ 52
Table 16: Butyl based tire ball bladder formulations ..................................................... 54
Table 17: Butyl based tire curing bladder formulations................................................. 55
Table 18: Butyl based compounds for dynamic application.......................................... 56
61
List of Figures
Figure 1: Proposed Polymerization Mechanism- Initiation............................................. 5

Figure 2: Proposed Polymerization Mechanism- Propagation ....................................... 6
Figure 3: Block diagram for the synthesis of Butyl polymers ......................................... 7
Figure 4: Structure of Isobutylene Isoprene co-polymer ................................................ 9
Figure 5: Structure of Butyl rubber and Natural rubber................................................ 10
Figure 6: Isoprene configuration in Butyl polymers ..................................................... 10
Figure 7: Effect of unsaturation on Butyl curing characteristics at 160°C .................... 14
Figure 8: Effect of Molecular weight on Stress Strain properties ................................. 14
Figure 9: Structure of accelerators used for the vulcanization of butyl rubber ............ 17
Figure 10:Possible Mechanism of Thiuram Accelerated Vulcanization ........................ 18
Figure 11:Structure of Caprolactum disulphide ............................................................ 21
Figure 12:Generic Structure of Octylphenol formaldehyde Resin ................................ 21
Figure 13:Reaction of a Curing Resin with C=C Bonds on an Elastomer Backbone .... 22
Figure 14:Reactivity of Brominated Octylphenol Formaldehyde Resin ........................ 22
Figure 15:Curing curves of butyl rubber at 190°C with octylphenol formaldehyde resin
and brominated octylphenol formaldehyde resins ....................................... 23
Figure 16:Dioxime Cure of Butyl Rubber ...................................................................... 25
Figure 17:Diffusion of Nitrogen through Butyl Polymers in comparison with other
polymers .................................................................................................... 41
62
References
1. R. M. Thomas and W.J. Sparks, U.S. Patent 2,356,127, 1937

2. H Nagano; Exxon Butyl Rubber Compounding and Applications
3. Robert N Webb, Thimothy D Shaffer & Andy Tsou: Vol 4 ,433 Kirk-Othmer
Encyclopedia of Chemical Technology
4. www.butylrubber.com
5. R. T. Morrissey, Rubber World 138, 725 (1955).
6. F. P. Baldwin, Rubber Chem. Technol. 52, 677 (1979).
7. D. Coddington, Rubber Chem. Technol. 59, 905 (1979 )
8. C. Y. Chu and R. Vukov, Macromolecules 18, 1423 (1985).
9. I. Kuntz and K. D. Rose, J. Polym. Sci., Part A: Polym. Chem. 27, 107 (1989).
10. D. M. Cheng, I. J. Gardener, H.-C. Wang, C. B. Frederick, and A. H. Dekmezian,
Rubber Chem. Technol. 63, 265 (1990).
11. J. E. Puskas and C. Wilds, Rubber Chem. Technol. 67, 329 (1994).
12. J. L. White, T. D. Shaffer, C. J. Ruff, and J. P. Cross, Macromolecules 28, 3290
(1995).
13. GW Burrowes, B Rodgers. Compound Development and Applications. In ‘Rubber
Compounding, Chemistry and Applications’. Ed B Rodgers. Marcel Dekker, Inc.
New York. 2004.
14. Model Vulcanization Systems for Butyl Rubber, Halobutyl Rubber, and BIMSM
Elastomer ,https://www.exxonmobilchemical.com/Chem-
English/productsservices/butyl-rubber-manuals.aspx
15. S Solis, MB Rodgers, N Tambe, BB Sharma, WH Waddell. A Review of the
Vulcanization of Isobutylene-Based Elastomers. Presented at a meeting of the
American Chemical Society Rubber Division, San Antonio TX. 2005
16. ExxonTM butyl rubber curing bladder resin vulcanization systems;
www.butylrubber.com.
17. ExxonTM butyl rubber curing bladder technology manual; www.butylrubber.com
18. R.A. Crawford and R.T. Morrissey. U.S. Patents: 2,681,899, June, 1959;
2,698,041, Dec. 1954; 2,720,479, Oct. 1955.
19. F.P. Baldwin, R.M. Thomas, US Patent. 2,944,578, July, 1960.
20. F. P. Baldwin, D.J. Buckley, I. Kuntz, S.B. Robinson, Rubber and Plastic Age,
London, Vol 42, Page 500. 1961
21. F. P. Baldwin, I. Kuntz, Encyclopedia of Chemical Technology, 2nd Suppl.
Interscience, 1960.
22. GJ van Amerongen. Diffusion in Elastomers. Rubber Chemistry & Technology.
Vol 37. P1065-1151. 1964.
23. ExxonTM Innertube technology manual
https://www.exxonmobilchemical.com/Chem-English/productsservices/butyl-
rubber-manuals.aspx
24. WH Waddell, AH Tsou. Butyl Rubber. In ‘Rubber Compounding, Chemistry and
Applications’. Ed B Rodgers. Marcel Dekker, Inc. New York. 2004
63
25. JV Fusco, P Hous. Butyl and Halobutyl Rubbers. In Rubber Technology, 3rd
Edition. Editor M Morton. Van Nostrand Reinhold. 1987.
26. DM Cheng, IJ Gardner, HC Wang, CB Frederick, AH Dekmezian. Spectroscopic
Studies of the Structure of Butyl and Chlorobutyl Rubbers. Rubber Chemistry and
Technology. Vol 63 (2). P265 – 275. 1990.
27. JL White, TD Shaffer, CJ Ruff, JP Cross. Incorporation of Isoprene in Isobutylene
/ Isoprene Copolymers: NMR Identification of Branching in Butyl Rubber.
Macromolecules. Vol 28. P 3290-3300. 1995
28. S Solis, MB Rodgers, N Tambe, BB Sharma, Alkylphenol Disulfide Polymer
Accelerators and the Vulcanization of Isobutylene Based Elastomers. Presented
at a meeting of the American Chemical Society Rubber Division, Cleveland, 2007
29. HG Moneypenny, KH Menting, FM Gregg. General Compounding. In ‘Rubber
New York. 2004
30. Sung W Hong, Antioxidants and other protectant system. In ‘Rubber
New York. 2004
31. WA Wampler, TF Carlson, WR Jones. Carbon Black. In ‘Rubber Compounding,
Chemistry and Applications’. Ed B Rodgers. Marcel Dekker, Inc. New York. 2004
32. DC Young, Application of fatigue Methods Based on Fracture Mechanics for Tire
Compound Development. Rubber Chem. Tech., Vol. 63,1990, p.567-581.
©2014 Exxon Mobil Corporation. While the information is accurate to the best of our knowledge and
belief as of the date compiled, it is limited to the information as specified. No representation or
warranty, expressed or implied, is made regarding the information, or its completeness,
merchantability, or fitness for a particular use. The user is solely responsible for all determinations
regarding use and we disclaim liability for any loss or damage that may occur from the use of this
information To the extent the user is entitled to disclose and distribute this document, the user may
forward, distribute, and/or photocopy this copyrighted document only if unaltered and complete,
including all of its headers, footers, disclaimers, and other information. You may not copy this
document to a Web site. ExxonMobil does not guarantee the typical (or other) values. Analysis may
be performed on representative samples and not the actual product shipped. The information in this
document relates only to the named products or materials when not in combination with any other
product or materials. We do not represent, warrant, or otherwise guarantee, expressly or impliedly,
the merchantability, fitness for a particular purpose, suitability, accuracy, reliability, or completeness
of this information or the products, materials, or processes described. The user is solely
responsible for all determinations regarding any use of material or product and any process in its
territories of interest. ExxonMobil makes no representations or warranties against patent
infringement or non-infringement of the intellectual property rights of any third party. Likewise
ExxonMobil does not grant any license, express or implied, under any patents or patent
applications owned by ExxonMobil to make, use, sell, offer for sale or import any product based
upon this formulation. We expressly disclaim liability for any loss, damage, or injury directly or
indirectly suffered or incurred as a result of or related to anyone using or relying on any of the
information in this document. There is no endorsement of any product or process, and we
expressly disclaim any contrary implication. The terms “we”, “our”, “ExxonMobil Chemical”, or
“ExxonMobil” are used for convenience, and may include any one or more of ExxonMobil Chemical
Company, Exxon Mobil Corporation, or any affiliates they directly or indirectly steward. ExxonMobil,
the ExxonMobil Logo, the “Interlocking X” Device and all other product names used herein are
trademarks of ExxonMobil unless indicated otherwise.
64
2006 Expansion of halobutyl capacity by 17,000 tons per year at
Kashima (Japan) plant
2008 Expansion of halobutyl capacity by 60 percent at Baytown (USA)

plant
First application of Exxcore™ DVA resin based tire innerliners,

setting the stage for lighter and more durable tires that hold air
longer and help reduce fuel consumption and CO2 emissions
Saudi Basic Industries Corporation (SABIC) and affiliates of

ExxonMobil Chemical sign a Heads of Agreement (HOA) to
progress detailed studies for a new elastomers project at their
petrochemical joint ventures at Kemya and Yanpet (Saudi Arabia).
The project would establish a domestic supply of over 400 KTA of
carbon black, rubber and thermoplastic specialty polymers
including butyl rubber, EPDM, TPO and SBR/PBR to supply local
and international markets.
2009 Successful pilot-plant demonstration of next generation of butyl

rubber, benefiting from nanocomposite technology, with the goal
of doubling the number of tire innerliner applications that can be
served from existing halobutyl capacity to meet growing demand.
At the forefront of technology 2010 Increase in butyl rubber production capacity by 18,000 tons
and innovation per year at the Japan Butyl Co. Ltd. (Kawasaki) Plant. This
expansion will increase plant capacity by 23% to 98,000 tons
ExxonMobil Chemical has been at the per year utilizing new ExxonMobil proprietary process technology.
forefront of technology and innovation in
the rubber industry since inventing and 2013 ExxonMobil Chemical will build facilities to manufacture premium
patenting butyl rubber in 1937. Today halobutyl rubber and Escorez™ hydrogenated hydrocarbon resin
we market high-quality synthetic rubber in Singapore, completion anticipated in 2017. This expansion
worldwide and are a global leader in project will add production capacity of halobutyl rubber to 140,000
butyl technology, services and products. tons per year and hydrogenated hydrocarbon resin production
capacity to 90,000 tons per year.
Let our technology-driven focus and
commitment to improve processes and
products help your business meet its
supply requirements and grow profitably.
Benefit from access to our global marketing
and product expertise, as well as our
state-of-the-art technology centers.
Learn more at:
butylrubber.com
B0813-896E50

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Exxon™ butyl rubber compounding and applications

Polymerization Chemistry of Butyl Rubber.

Commercial butyl rubber grades are prepared by copolymerizing small amounts

Commercial supplies of isobutylene are derived from thermal or catalytic cracking

Production of the high molecular-weight, elastomeric grades of Butyl rubber

The mechanism of cationic isobutylene polymerization with Lewis acid is highly

Initiation is followed by propagation reactions where monomer units add to the

CH3 - CH3 CH3 CH3

Manufacturing of Butyl Rubber

A schematic diagram of a typical slurry-process Butyl plant is shown in figure 3.

An alternative solution process uses a C5–C7 hydrocarbon as solvent and an

Significant fouling occurs during polymerization. At high solids concentrations, a

The slurry is then vacuum-stripped of residual hydrocarbons. In the finishing

Commercial Status and Worldwide Capabilities

Butyl is produced by ExxonMobil Chemical at Kawasaki (Japan) and Notre Dame

Chemistry of Butyl Rubber

Butyl rubber is a copolymer of isobutylene and isoprene and is produced by

In a single Butyl macromolecule made up of thousands of monomer units, the

Molecular Structure of Butyl Polymers

In butyl rubber, isoprene is enchained predominantly (90–95%) by 1,4-addition

Grades of ExxonTM Butyl

General Properties of Butyl Rubber

The tight molecular packing of the polyisobutylene structure of the

Physical Constants of Butyl Rubber and Isobutylene.

Toxicology of Butyl Rubber

Unsaturation Effect on Heat Resistance

Heat resistance increases as unsaturation increases because reversion is

Unsaturation Effects on Ozone Resistance

Ozone resistance varies greatly with unsaturation content. Ozone resistance

Unsaturation Effects on Cure Characteristics and Cured Properties of Butyl Polymers

Percentage ExxonMobil Cure Ozone Heat

065 Slow Excellent Good

2 365 Fast Good Excellent

Effect of Molecular weight on Stress Strain Properties of Butyl Polymers.

As the molecular weight increases, the mechanical properties increase.

Material Units Butyl Butyl

ZnO 5.0 5.0

1) Disulfide / Polysulfidic —predominant cross-links from conventional sulfur -C-S-S-C.

Vulcanization introduces chemical cross-links along the polymer chains, binding

Tetrabenzylthiuram disulfide (TBzTD) Zinc dibenzyldithiocarbmate (ZBEC)

Cyclohexyl benzothiazole sulfonamide Benzothiazyl disulfide (MBTS)

Dibutyl thiourea (DBTU) Mercaptobenzothiazole (MBT)

Thiuram Accelerated Vulcanization

Thiurams and dithiocarbamate accelerators form nitrosamines, and are not

Butyl 268 PHR 100.0 100.0

Paraffinic Oil PHR 25.0 25.0

ML 1+4,@ 100 °C MU ASTM D 1646 46 46

Minimum Torque (ML) dN.m ASTM D 5289 1.4 1.5

Hardness Sh. A ASTM D 2240 51 44

Ingredients Unit Comp 1 Comp 2 Comp 3 Comp 4

Phenolic Resin Cures

The resin-cure cross-linking of Butyl rubber is based on the reactivity of the

Brominated octylphenol formaldehyde resin has a similar structure to that in figure 12

10.0 Octylphenol formaldehyde resin

A more reactive resin cure system requiring no external activator is obtained if

Butyl 268 PHR 100.0 100.0

The crosslinking of Butyl rubber with para-quinone dioxime (QDO) or para-quinone

• Thermodynamics: Micro domain formation is achieved by surface energy reduction (i.e.

Solubility parameter can be used to predict miscibility of the blends. As an

Butyl-Halobutvl blends should be formulated with sulfur-accelerator or sulfur

Material Units IIR 268 IIR +

Banbury, Mill Mixing Large High

Ingredients Unit N 220 N 330 N 550 N 660 N 762