Exxon™ butyl and halobutyl rubber

Model vulcanization systems

for butyl rubber and
halobutyl rubber manual

Country name(s)
2 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

Abstract
The vulcanization of isobutylene-co-isoprene rubber (IIR),
brominated isobutylene-co-isoprene rubber (BIIR), chlorinated
isobutylene-co-isoprene rubber (CIIR), and brominated
isobutylene-co-para-methylstyrene elastomer (BIMSM) differs
from that of general-purpose rubbers (GPR). Butyl rubber has
approximately 2% unsaturation in the backbone. Halobutyl
rubber (BIIR and CIIR) incorporates the butyl backbone with
either bromine or chlorine, which significantly increases the
chemical reactivity of the isoprenyl units located in the butyl
backbone. Similarly, in BIMSM the bromine atom is bonded to
the para-methylstyrene (PMS) group, thus affording the
completely saturated polymer backbone a site of chemical
reactivity. Utilization of the unique attributes of butyl rubber
and halobutyl rubbers with their minimal backbone
unsaturation and of BIMSM elastomers with no backbone
unsaturation is found in many areas of industry. These
properties are excellent vapor impermeation, resistance to
heat degradation, and improved chemical resistance as
compared to general-purpose rubbers. However, this low
amount of reactivity requires special consideration to vulcanize
these isobutylene-based polymers. The type of vulcanization
system selected is a function of the composite structure in
which it is used, and the cured product performance
requirements. Therefore, vulcanization systems vary and may
include an accelerator package along with resins, zinc oxide,
zinc oxide and sulfur, and quinoid systems. This review will
discuss the types and selection of appropriate vulcanization
systems for isobutylene-based elastomers.
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 3

1. Introduction......................................................................................................................................................................................................................................................... 4

2. Composition of isobutylene polymers.................................................................................................................................................................................. 5

3. General trends in vulcanization chemistry....................................................................................................................................................................... 7

4. Overview of the vulcanization of isobutylene-based elastomers.................................................................................................... 10

5. Vulcanization of butyl rubber...................................................................................................................................................................................................... 11

6. Halobutyl rubber........................................................................................................................................................................................................................................ 14

7. Vulcanization of brominated isobutylene-co-para-methylstyrene (BIMSM)...................................................................... 18

8. Model cure system formulary..................................................................................................................................................................................................... 20

9. Summary............................................................................................................................................................................................................................................................. 24

Appendix 1 ............................................................................................................................................................................................................................................................... 25

10. References......................................................................................................................................................................................................................................................... 26
4 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

1. Introduction
Isobutylene-based elastomers include butyl rubber,
halogenated butyl rubber, star-branched versions of these
polymers and brominated isobutylene-co-para-methylstyrene
(BIMSM). Due to their impermeability and resistance to heat
and oxidation, these polymers find application in tire
innerliners, innertubes, curing bladders and envelopes, and
other specialty applications where air retention and resistance
to heat and oxidation are desired. Butyl rubbers are produced
via a cationic polymerization in a methyl chloride diluent at
temperatures less than -90°C. These unique attributes and
difficult manufacturing requirements place butyl rubbers in the
special purpose elastomers category distinct from general-
purpose rubbers (GPR) such as polybutadiene rubber (BR),
natural rubber (NR), and styrene-butadiene rubbers (SBR) 1.
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 5

2. Composition of isobutylene polymers

Butyl rubber (IIR) is the copolymer of isobutylene and a small Copolymers of isobutylene and para-methylstyrene have a
amount of isoprene, typically in the order of 2%. Figure 1 is a random structure, again due to the monomer reactivity ratios
schematic of butyl rubber. being nearly equivalent. After polymerization and subsequent
bromination some of the para-methylstyrene
Figure 1 groups are converted to reactive bromomethylstyryl groups.
Structure of butyl rubber These saturated backbone polymers contain isobutylene, 1 to
5 mole-% of para-methylstyrene, and 0.5 to 1.3 mole-% of
  brominated para-methylstyrene (Figure 3)2. Their glass
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CH2 C CH2-­C=CH-­CH2-­
(0.8  -­  2.5    mole%)
with increasing para-methylstyrene content and is nominally
CH3
around -57oC. This compares to a nominal -59°C to -60°C for
Butyl  Rubber    (IIR)
halobutyl polymers.
Chlorobutyl (CIIR) and bromobutyl (BIIR) rubbers are
manufactured similarly to butyl rubber, but with an added Figure 3
subsequent halogenation step. Due to the nearly equivalent Structure of brominated isobutylene-co-para-methylstyrene,
reactivity ratios of the monomers and low concentration of BIMSM 2
isoprene, the isoprenyl units in these polymers are randomly Table I illustrates the commercial grades of isobutylene-based
distributed along the polymer chain.
  CH 3 CH 3
CH 2 C CH 2 CH CH 2 C CH 2 CH
Figure 2 illustrates the structures of the functional halogen CH 3 CH 3
containing groups found in bromobutyl rubber2,3. The majority
of the isoprenyl units are in the trans-configuration. Structure
II, the predominant structure in halobutyl rubber, represents CH 2 Br CH 3 currentpoint 1928
50%-60%, followed by Structure I representing from 30%-
40%. Approximately 5%-15% is Structure III; Structure IV is elastomers and their typical compositions that are currently
typically only 1%-3%. available from ExxonMobil Chemical company.

Figure 2
Structure of isoprenyl units in bromobutyl rubber

  CH3 CH2
CH2 C CH CH2 CH2 C CH CH2
Br
Structure I
Structure II

CH2Br CH3
CH2 C CH CH2 CH C CH CH2
Br
Structure III Structure IV
6 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

Table I
Commercial grades of ExxonMobil isobutylene-based elastomers

Elastomer Grade Mooney Viscosity Isoprene para- Halogen Halogen Halogen Typical Applications
(ML1+8 at 125°C) (mol%) Methylstyrene (wt%) (mol%)1
(wt%)
Butyl 065 32 1.05 Tubes, Baldders
(low viscosity) 165 32 1.50 Tubes, Baldders
365 33 2.30 Tubes, Baldders
Butyl 068 51 1.15 Tubes, Baldders
(medium viscosity) 268 51 1.70 Tubes, Baldders
Butyl
269 57 1.70 Tubes, Baldders
(high viscosity)
Chorobutyl 1066 38 1.95 CI 1.26 Tire Innerliners
White Sidewalls
Bromobutyl 2222 32 1.70 Br 2.00 Automobile Tires
2235 39 1.70 Br 2.00 Automobile Tires
2255 46 1.70 Br 2.00 Truck Tire Innerliners
2211 32 1.70 Br 2.10 Fast Cure Applications
2244 46 1.70 Br 2.10 Fast Cure Applications
Exxpro 3035 45 5.00 Br 0.47 Curing Bladders
3433 35 5.00 Br 0.75 Pharmaceuticals
3745 45 7.50 Br 1.20 Tires, Engineerd Products

Note: 1. Benzylic bromine content

2. Butyl, chlorobutyl rubber, bromobutyl rubber, and Exxpro polymers are used in pharmaceutical applications

This paper is an overview of the vulcanization of this group of

special purpose elastomers and identifies opportunities for
further improvement in final compound mechanical properties
and final product performance.
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 7

3. General trends in vulcanization chemistry

Five factors influence the development of vulcanization system Table II
technology: Nitrosamine limits in pharmaceutical, food utensils4

• Elimination of accelerators that may generate nitrosamines Location Nitrosamine Nitrosables

• Accelerators for improved scorch resistance and improved ppb maximum ppb maximum
ease of compound processing during final product Australia 20 400
assembly, e.g. a tire Denmark 5 100
• Vulcanization systems suitable for high-temperature curing
Netherlands 1 100
with associated benefits in productivity
Canada 60 N/A
• Improved reversion resistance
Switzerland 10 200
• Improvement in cured compound attributes such as
mechanical or dynamic properties Germany 10 200
UK 30 100
Nitrosamines USA 60 N/A
Nitrosamines are nitrogen-based compounds with attached
carbon-containing groups. Using ammonia as a reference, European Union directive 93/11/EEC concerns extractable
replacing one of the hydrogen atoms produces a primary N-nitrosamines for certain food applications. Accelerators that
amine. Substitution of two or three hydrogen atoms produces are considered to give rise to N-nitrosamines are listed below
secondary or tertiary amines, respectively. As shown in (see Appendix 1 for explanation of abbreviations):
equation 1, secondary amines found in accelerators such as
thiurams, dithiocarbamates, and some sulfenamides can react TMTD, TMTM, TETD, TBTD, DPTT, DTDM,
with nitrogen oxides in the air to produce a nitrosamine. ZDMC, ZDEC, ZDBC

  R NOx R Tetrabenzylthiuramdisulfide (TBzTD) and zinc

NH N N O
R Nitrogen
Oxides R
Secondary Amine
Nitrosamine
(1)
During the vulcanization process accelerators such as
tetramethylthiuram disulfide (TMTD) are partly decomposed to
their parent secondary amines. Reaction with atmospheric
nitrogen oxide can lead to N-nitrosamine generation. In
Germany, N-nitrosamine levels in the work place atmosphere
are controlled under factory regulation TRGS 552. This
directive permits a maximum atmospheric concentration of
only 1µg/m3 of regulated N-nitrosamines. The cabin space of
automotive vehicles now falls under the regulations that have
implications for rubber parts in this area, which includes the
door and window seals. Automotive vehicle manufactures
have also placed increasing emphasis on the removal of
N-nitrosamines from all parts of their vehicles including rubber
components such as gaskets, engine mounts, and hoses4.
Maximum nitrosamine levels are listed in Table II.
dibenzyldithiocarbamate (ZBEC) accelerators, though in some
instances might give rise to N-nitrosamines, are considered to
be outside the scope of regulatory attention5. The effect of
steric factors on thiuram and dithiocarbamate nitrosamine
formation has also been studied. Thiurams and
dithiocarbamates made from sterically bulky amines such as
diisobutylamine produce orders of magnitude lower levels of
nitrosamine than does tetramethylthiuram disulfide (TMTD). At
the same time, when used as a secondary accelerator for
cyclobenzothiazole sulfenamides, tetraisobutylthiuram
disulfide has better scorch safety, but vulcanizes at the same
rate as TMTD. Uniquely, tetraisobutylthiuram monosulfide
could act as a retarder as well as a secondary accelerator6.
Accelerators that cannot produce N-nitrosamines since they
are based on primary amines or do not contain nitrogen
include:
CBS, TBBS, DOTG, DPG, MBT, MBTS, ZMBT, Xanthates
8 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

Accelerators for isobutylene-based elastomers High temperature curing and reversion resistance
A broad range of accelerators can be found in formulas for As cure temperature increases, care must be taken to avoid
isobutylene-based elastomers. Some of the accelerators found reversion while achieving the desired mechanical properties of
are illustrated in Figure 47. These include the product. This infers no marching modulus and the
cyclohexylbenzothiazole sulfenamide (CBS), preservation of a stable crosslink network. Cure systems with
mercaptobenzothiazole sulfide (MBTS), tetramethylthiuram primary accelerators such as MBTS, or sulfenamides such as
disulfide (TMTD), diphenyl guanidine (DPG), and zinc TBBS, tend to meet such requirements. Depending on the cure
dimethyldithiocarbamate (ZDMC). system thiurams, dithiocarbamates, and xanthates tend to
have poorer reversion resistance.
Figure 4
Structure of selected accelerators7 Two reversion resistors have been of particular note. These are
bis(citraconimido-methyl) benzene (BCI-MX) and sodium
  N N N
C S NH C S S C hexamethylene-1,6-bisthiosulfide dehydrate. Both function
C S S exclusively as reversion resistors. BCI-MX (Figure 6) is
Cyclohexyl benzothiazole sulfenamide Mercaptobenzothiazole disulfide
understood to react with the polymer chain to form stable
CH3 S S CH3
flexible carbon-carbon crosslinks which substitutes for and
N C S S C N replaces sulfur crosslinks that disappear during reversion8.
CH3 CH3 NH
Tetramethylthiuram disulfide C NH Diphenyl guanidine
NH Figure 6
S S
Structure of 1,3-bis(citraconimidomethyl)benzene (BCI-MX)
CH3 CH3
N C S Zn S C N
CH3 CH3
Zinc dimethyldithiocarbamate C4H9 O O C4H9
S P S Zn S P S
S S C4H9 O O C4H9
C4H9 O C S S C O C4H9
Zinc Dibutylphosphorodithiate
Dibutyl xanthogen disulphide

Improved scorch resistance is currently achieved by addition of Alternatively, for resistance to high-temperature reversion,
magnesium oxide (MgO). In some instances, with a sodium hexamethylene-1,6-bisthiosulfide dihydrate (Figure 7)
sulfenamide-based cure system, N-(cyclohexylthio) may be evaluated since it breaks down and inserts a
phthalimide (PVI), whose structure can be found in Figure 5, is hexamethylene-1,6-dithiyl group within a disulfide or
used. MBTS can also serve as a pre-vulcanization inhibitor. polysulfide crosslink providing a hybrid crosslink. During
Calcuim oxide and magnesium oxide can be used in zinc extended vulcanization periods or accumulated heat history
oxide-cured halobutyl rubber. However, they will serve as an due to product service, polysulfidic-hexamethylene crosslinks
activator in amine accelerated systems. Calcium stearate and rearrange to produce thermally stable elastic monosulfidic
zinc stearate can act as retarders in chlorobutyl rubber crosslinks. At levels up to 2.0 phr, there is little effect on
compounds. Unlike their use in general-purpose elastomers, compound induction, scorch times, or other compound
benzoic acid and salicylic acid are not effective as scorch mechanical properties.
retarders.
Figure 7
Figure 5
Structure of PVI  
Na SO3 S CH2 S SO3 Na 2 H2O
6
  O   Hexamethylene-1,6-bis(thiosulfate)
C   disodium salt, dihydrate
N   S  
C  
The bifunctional silane-coupling agent, bis-(3-triethoxysilylpropyl)
O  
tetrasulfane has dual functions as both a sulfur donor and a
N  (  c  y  cl     o  h  e  x  y  l  t  h  i  o  )      p  h  t  h  a  l  i  mi     d  e  
reversion resistor9. This ability to maintain the polysulfidic or
other stable network throughout the curing process and
subsequent product service life while offering reversion
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 9

resistance can be beneficial (Figure 8)9. Natural rubber

compounds containing such systems are believed to display
improved abrasion resistance and wear properties.

Figure 8
EC cure system rheometer profile9
10 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

4. Overview of the vulcanization of isobutylene-based elastomers

In butyl rubber, the hydrogen atoms positioned alpha (a) to the Table III
carbon-carbon double bond of the isoprenyl unit permits Carbon-halogen bond energies and bond lengths10
vulcanization into a crosslinked network with sulfur and
organic accelerators. The low degree of unsaturation has Bond Energy Length
traditionally required the use of ultra-fast accelerators, such as J/mol nm
thiurams or thiocarbamates in order to cure under acceptable -C — C- 346 0.154
conditions of time and temperature. Phenolic resins, -C — H 413 0.109
bisazidoformates, and quinone derivatives can also be
-C — F 452 0.138
employed. Vulcanization introduces a chemical crosslink
-C — CI 327 0.177
approximately every 250 carbon atoms along the polymer
-C — Br 209 0.194
chain producing a covalently bonded molecular network.
Polysulfidic crosslinks have limited stability at elevated
The bromine-carbon bond in bromobutyl rubber has a lower
temperature and in many instances can rearrange to form
disassociation energy than does the chlorine-carbon bond in
monosulfidic and disulfidic crosslinks This rearrangement
chlorobutyl rubber (Table III). Epoxidized soybean oil (ESBO)
results in permanent set of vulcanizates exposed to high
can be added to suppress isomerization reactions and HBr
temperatures for long periods of time. Resin cure systems such
formation. Butylated hydroxytoluene (BHT) can be used to
as alkyl phenol-formaldehyde derivatives can provide carbon-
stabilize the polymer by serving as an antioxidant. Calcium
carbon crosslinks resulting in heat-stable vulcanizates1,2.
stearate is added to CIIR, BIIR, and BIMSM as an acid trap to
diminish dehydrohalogenation catalyzed by HCl or HBr.
Halobutyl rubber can be crosslinked by some of the same
Calcium stearate can also act as a cure retarder.
curatives used for butyl rubber such as zinc oxide, bismaleimides
and dithiols. Halogens are good leaving groups in nucleophilic
Brominated isobutylene-co-para-methylstyrene (BIMSM)
substitution reactions due to the low carbon-halogen bond
crosslinking involves the formation of carbon-carbon bonds,
energy (Table III). When zinc oxide is used to crosslink halobutyl
generally through Friedel-Crafts alkylation chemistry.
rubber, carbon-carbon bonds are formed through
Diamines, phenolic resins and thiosulfates can also be used to
dehydrohalogenation which results in a compound with a very
crosslink BIMSM elastomers. The stability of these carbon-
stable crosslink system affording a compound having good
carbon bonds combined with the chemically saturated
retention of aged properties and low compression set.
backbone of BIMSM yields excellent resistance to heat and
oxidative aging, and to ozone attack.
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 11

5. Vulcanization of butyl rubber

The major applications utilizing butyl rubber are tire phenol formaldehyde resin. Curing resins such as a heat
innertubes, curing bladders, pharmaceutical closures, and a reactive octylphenol formaldehyde resin, which contains
variety of engineered products such as mounts, sheeting, methylol groups, can be used3. Table IV contains a model
automotive flaps, and damping pads. These applications formula illustrating the resin cure system. For a faster cure,
require good compound aging resistance, oxidative resistance addition of a halogen donor such as polychloroprene or
and heat stability. Depending on the application of the final stannous chloride is required13. In this instance,
product, one of the following three cure systems have been polychloroprene has not been considered as part of the total
used11, 12. compound polymer content.

• Quinone dioxime Table IV

• Resin cure Model curing bladder formulation13
• Thiuram (i.e. TMTD) accelerated
Material phr
Quinone cure systems Butyl 268 100.0
The crosslinking of butyl rubber with para-quinone dioxime
Polychloroprene 5.0
(QDO) or para-quinone dioxime dibenzoate (DBQDO) proceeds
Carbon black N330 50.0
through an oxidation step that forms the active crosslinking
agent para-dinitrosobenzene. The use of metal oxides (such as Castor oil 5.0
PbO2, Pb3O4, MnO2) or MBTS as an oxidizing agent, increases Zinc oxide 5.0
the vulcanization rate allowing use in room temperature cures Octylphenol formaldehyde resin 10.0
such as in cements3. Figure 9 is a schematic illustrating the
reaction of a dioxime in the vulcanization of butyl rubber. The A more reactive resin cure system not requiring an activator is
dioxime vulcanization system can be used for dry rubber obtained when a portion of the methylol groups are replaced
applications. One example is electrical insulation systems, which by bromine. An example of this resin is brominated octylphenol
contain butyl rubber for improved ozone resistance. formaldehyde resin3.

Figure 9
Figure 10 is a schematic illustrating the reaction of a curing
Dioxime cure of butyl rubber3
resin (heat reactive octylphenol formaldehyde) in the
  N   O  H   N   O  
N vulcanization of butyl rubber. Following the elimination of
P  bO
   2   water in the reaction sequence, the exomethylene group and
O   carbonyl oxygen react with an isoprenyl unit in butyl rubber to
P  b3   O
   44   form a chroman ring. Chromonone ring structures are very
N   O  H   N   O   stable and are frequently found in natural product biosynthesis.
CC  H
H  3  
C  H  3  
C
C  H
C H  2   CC   C C  H
H   C
C  H
H  2  
C  H
H  2   C
C   C
C  H
H   C
C  H
H   Figure 10
N  OH
 H  
Resin curing of butyl rubber13

  OH OH OH O

HO CH2 R' CH2 OH HO CH2 R' CH2

heat
N  O  H  
- H2O
D  io    x  i  m  i  ne      cu    r  e    of      b  ut  y    l  r    ub    be   r    
C  H
H  2   C
C   C C  H
H   C
C  H
H   R R R R

C  H
C H  33  
CH2 CH3
Formation of a CH C
Chroman ring H CH

Resin cure systems OH O

Phenol formaldehyde curing resins are classified as resols, i.e. CH2 CH3 HO CH2 R' CH2
C
three-dimensional resin systems forming crosslink networks OH O CH
CH2 R R
which can serve as reinforcing resins versus novolac resins HOCH2 R'

which are linear. Resin curing of butyl rubber is a function of CH2 CH3 CH2 CH3
R R C C
the reactivity of the phenolmethylol groups in the reactive CH O O CH
CH2
CH3
R'
CH2 C CH CH2

Crosslinked Butyl Network Evolution

R R
12 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

Thiuram accelerated vulcanization Figure 12

Although thiuram and dithiocarbamate accelerators form Thiurams as sulfur donors14
nitrosamines, a number of published formulas use these S S
CH3 S S CH3 CH3 CH3
components as vulcanization agents. For completeness, we Zn+2...O-2 N C S S C N Zn+2 O- C N + -
S S C N
CH3 CH3
include the mechanism by which this class of materials is CH3 CH3

thought to function14; however, again we recommend the use

of alternative non-nitrosamine-generating accelerators.
Thiuram accelerated systems participate in the vulcanization CH3 S S CH3 CH3 S S CH3 S CH3
N C S S C N N C SSS C N S C N
process through formation of a zinc complex as shown in CH3 CH3 CH3 CH3 CH3

figure 11. The sulfur rich complexes are formed by insertion of -

S CH3
S S C N
the sulfur into the zinc dimethyldithiocarbamate molecule, CH3

which in turn is an active sulfurating complex. Rubber bounded

CH3 S S CH3 CH3 S S CH3
intermediates are subsequently produced followed by N C SSS C N N C S Sx S C N etc.
CH3
crosslinking to form polysulfidic crosslinks. These polysulfidic CH3 CH3 CH3
Sulfurating Compex
crosslinks evolve into monosulfide and disulfidic crosslinks.  

Peroxides and butyl rubber

Figure 11
Polyisobutylene and butyl rubber undergo degradation rather
Possible mechanism of thiuram accelerated vulcanization14
than crosslinking when treated with peroxides. It is believed
 CH3 S S CH3 S S
that scission occurs via a radical substitution mechanism
CH3 CH3
N C Zn C N
S S N C Sx Zn S C N (Figure 13).
CH3 CH3
CH3 CH3
S S
Figure 13
S6 CH3
Peroxide degradation of polyisobutylene14
S Zn S Sy C N
CH3
S S Polyisobutylene based polymer CH3 CH3
CH3 Zn S CH3
N C S Sy C N CH3 CH3 CH3 CH3 C CH2 C CH2
CH3 CH3 CH2 C CH2 C CH2 C CH2 C CH2
R H CH3 CH3
CH3 CH3 CH3 CH3

O
Polymer Chain CH3 CH3
S Sx S CH3 C CH3
Zn S CH3 CH2 C CH2 O C
S Sy C N CH3 CH3
CH3 New Terminal Chain End
R H
Dicumyl peroxide
 
In the absence of sulfur, TMTD can function as a sulfur donor
Other vulcanization systems for butyl rubber
(Figure 12). Increasing the rate of cure without a significant loss
Due to the inherent low reactivity of the nearly saturated butyl
of other properties can be obtained with the addition of thiurams
backbone, there are instances when a secondary accelerator is
or thioureas and zinc oxide at around 5 phr. Substitution of
required in the vulcanization system. Table V16 contains
nitrosamine generating thiurams such as TMTD with MBTS or
examples of an amylphenol disulfide polymer secondary
higher molecular weight thiurams such as TBzTD or
accelerator (Vultac series) that can be used.
dithiocarbamates such as ZBEC can be explored to eliminate the
future use of these accelerators. TBzTD is a high molecular
weight accelerator and functions as a sulfur donor. Due to its
molecular weight and stearic hindrance these accelerators can
have improved scorch resistance hence improving compound
processing. When used in combination with sulfenamides such
as TBBS, the nitrosamine concentration becomes negligible15.
The high molecular weight of the secondary amine,
dibenzylamine (DBA), produced by TBzTD is not as volatile as
those generated from lower molecular weight thiurams such as
TMTD, TMTM, or TBTD. DBA has a boiling point of 300°C and in
the presence of oxygen may decompose below this temperature.
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 13

Table V16
Vultac series of accelerators

Commercial Chemical Name & Function Formula Sulfur Softening

Name Wt% Point (°C)

Vultac 2 Amylphenol disulfide polymer Sulfur donor. Phenol, 4(1,1-dimethyl (C11H16O.Cl2S2)x 23 55

propyl)-polymer with sulfur chloride

Vultac 3 Amylphenol disulfide polymer Sulfur donor. Phenol, 4(1,1-dimethyl (C11H16O.Cl2S2)x 28 85

propyl)-polymer with sulfur chloride

Vultac 5 Amylphenol disulfide polymer Sulfur donor. (C11H16O.Cl2S2)x 18 85

Vultac 7 Amylphenol disulfide polymer Sulfur donor. Phenol, 4(1,1-dimethyl (C11H16O.Cl2S2)x 30 120
propyl)-polymer with sulfur chloride

Vultac 710 Amylphenol disulfide polymer Sulfur donor. Phenol, 4(1,1-dimethyl (C11H16O.Cl2S2)x 27 85
propyl)-polymer with sulfur chloride plus 10% stearic acid

The general structure and crosslink formed by polymeric

amylphenol disulfide accelerators is believed to be illustrated in
Figure 14. Though these accelerators contain sulfur, the
disulfidic group may not be readily assessable due to steric
hindrance of the phenol groups. The sulfur linkage is
predominantly a disulfide, but trisulfide and tetrasulfide
crosslinks have also been reported.

Figure 1416,17,18

  C H3
C H2 CH CH C
OH OH
S
S S S
C H3
C H3 C H2 C OH
C H3
C H3 C C H3 C H3 C C H3
S
C H2 C H2
C H2 CH CH C
C H3 C H3
n C H3
Amyl  Disulfide  Polymer Schematic   of   Phenol   S ulfide   C rosslink

Table VI shows that even though the apparent activation Table VI

energies of the amylphenol disulfide polymer accelerators can Vulcanization Systems Containing Vultac Accelerators
be higher than that of TMTD, the rheometer delta torque, DT,
MDR Rheometer Apparent
or state of cure which relates to tensile strength, elongation, Accelerator ΔT (dNm) at Activation Energy, Form
and modulus is higher particularly for Vultac 3. Note that these 160°C Ea (KJ/mol)
accelerators improve interfacial bonding in some cure system TMTD 4.64 81.77 -
blends19. For example, use of amylphenol disulfide polymers in
a NR/NBR blend has been investigated. It is suggested that to Vultac 2 4.79 79.52 Glass

have good activity the system may require use of up to 4.5 phr Vultac 3 7.23 99.96 Glass
of Vultac 320. Although the mechanism of amylphenol disulfide Vultac 5 6.66 100.97 Powder
polymer activity in vulcanization remains uncertain, it has been
Vultac 7 7.23 92.84 Pellets
shown that there was a lower degree of preferential
vulcanization in polymer blends when amylphenol disulfide Vultac 710 7.22 96.41 Pellets
polymer replaced free sulfur. It has been concluded that the
amylphenol disulfide polymer moiety played a role in increasing
the solubility of the vulcanization intermediates in natural
rubber and that a monosulfidic crosslink is created resulting in
better reversion resistance.
14 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

6. Halobutyl rubber
Commercially, chlorobutyl rubber (CIIR) and bromobutyl Amines
rubber (BIIR) are the most important derivatives of butyl • Zinc free compounds may be required in, for example,
rubber. Their predominant application is in tire innerliners with pharmaceutical applications. Curing of bromobutyl rubber
the performance of the modern radial tire being impacted by with diamines such as hexamethylene diamine carbamate
the amount of halobutyl rubber used in the innerliner may be one solution.
compound. Typical performance requirements of the tire Peroxide cure systems
innerliner are: • Halobutyl rubber can be crosslinked with peroxide cure
systems. A dicumyl peroxide with a coagent, such as
• Air retention bismaleimide, yields a low compression set, high heat
• Adhesion to tire carcass compound resistant vulcanizate3. Butyl rubber, however, will
• Resistance to fatigue and cracking depolymerize in the presence of peroxide.
• Heat resistance
• High tensile and tear strength Metal oxide curing
Metal oxides such as zinc oxide will react with the halogen in
Chlorobutyl rubber has an added application in white sidewall chlorobutyl and bromobutyl polymers. The most active
compounds. When blended with NR, SBR or BR, halobutyl halogen is in the allylic position. Zinc stearate or zinc octoate is
rubber may be used in tread compounds. The addition of required as a solubilizing agent and the mechanism is believed
isobutylene-based polymers increases the dynamic loss to be a nucleophilic substitution. Structure II (Figure 2) is the
modulus leading to improvements in wet and dry traction kinetically favored bromination product in bromobutyl rubber.
performance, braking performance, and vehicle stopping However, at curing temperatures, rearrangement leads to an
distance. increase in the amount of Structure III. Structure III then
dominates the equilibrium state that is achieved21. Figure 15
Vulcanization of halobutyl rubber presents a possible scheme for the role of zinc oxide in
The primary difference between chlorobutyl rubber and crosslinking. In the presence of magnesium oxide, the halogen
bromobutyl rubber is due to the higher reactivity of the on the polymer can react with ZnBr2 and reform ZnO and
carbon-bromine bond compared to that of carbon-chlorine MgBr2 as seen in the vulcanization of polychloroprene.
bond. The carbon-bromine bond has the lowest energy and
the longest length (Table III). Bromobutyl rubber has faster Figure 15
cure rates and a shorter scorch or cure induction period (with Zinc oxide in the vulcanization of bromobutyl rubber 21,22,23
productivity benefits), requires lower levels of curatives, and
enables one to use a wider range of accelerators than could be C H3 C H2Br C H3 C H3 C H2ZnOBr C H3
C H2 C C H2 C C H C H2 C C H2 C C H2 C C H C H2 C
possible for chlorobutyl rubber. A number of cure systems are
C H3 C H3 C H3 C H3
suitable for halobutyl rubber and halobutyl rubber/general-
purpose rubber (GPR) blends. Cure system selection will be a C H3 C H3
C H3 C H3
function of service conditions and the end use of the rubber C H2 C C H2 C C H C H2 C
C H3 C H2ZnOBr C H3 C H2 C C H2 C C H C H2 C
product. Typical cure systems for halobutyl rubbers include: C H3 C H2 C H3
C H3 C H2Br C H3 C H3 C H2 C H3
Metal oxides C H2 C C H2 C C H C H2 C C H2 C C H2 C C H C H2 C
C H3 C H3
• Zinc oxide will react with the halogen in polymers such as C H3 C H3
+
       Z nBr2
halobutyl rubber and polychloroprene. Magnesium oxide is  
effective as a retarder.
Sulfur cure systems This scheme was initially proposed based on model compound
• Sulfur cure systems can be used in tire innerliners where a studies such as 2,2,4,8,8-pentamethyl-4-nonene. The final
high state of cure, fatigue resistance, high tensile and tear crosslink structure is thought to be as illustrated in Figure 16.
strength, and adhesion to GPR in components adjacent to There would be less steric hindrance around the methylene
the innerliner is important. A typical tire innerliner sulfur group than at the -carbon rendering this interpretation more
cure system may include sulfur (0.5-1.0 phr), zinc oxide likely. Lowering sulfur or thiuram levels can control the greater
(1.0-3.0 phr), and MBTS (1.0-1.5 phr). reactivity of bromobutyl rubber. Mooney scorch and induction
periods can also be extended by:
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 15

• Increasing the MBTS level (since MBTS can also serve as a Table VII
retarder) Vulcanization retardation with magnesium oxide (MgO) 3, 6
• Replacing phenolic resins such as octylphenol tackifying 1 2 3 4
Compound
resins with hydrocarbon resins (phr) (phr) (phr) (phr)
• Lowering the stearic acid level or carboxylic acid content
TMTD 1.00 1.00 1.00 1.00
• Avoiding amine type antioxidants
• Adding magnesium oxide (retarder in bromobutyl rubber) MgO 0.00 0.25 0.50 0.00

• Adding polyethylene glycol since the ether functionality can Mooney Scorch at 126.5°C
serve as an efficient retarder for bromobutyl rubber.
t-5 5.0 15.0 30.0 8.0

Figure 16 Cured at 153.0°C, 45 minutes

Possible mechanism for crosslinking of halobutyl rubber24
Tensile Strenght (MPa) 17.9 18.8 16.6 17.8
X
ZnX3
Elongation (%) 315 335 380 320

+ 300% Modulus (MPa) 17.2 16.4 12.8 16.3

Formulation (phr): chlorobutyl 100, antioxidant 2246 1.0, HAF 50, stearic
acid 1.0, ZnO 5.0, cure system as above.

MBTS accelerated curing

Accelerators tend to be based on one of five structures shown
in Figure 1714, a thiazole, thiocarbamyl, alkoxythio carbonyl,
dialkylthio phosphoryl, or a diamino-2,4,6-triazinyl.

Figure 17
X
Fundamental structures of organic accelerators14
Magnesium oxide dual effects on halobutyl rubber systems
S S S
Table VII illustrates the effect of magnesium oxide (MgO) on N R2N N NR2
C RR' N C RO C (RO)2 P
cure rate for a TMTD/zinc oxide cure system6. Addition of 0.25 S thiocarbamyl alkoxythio dialkylthio N N
carbonyl phosphoryl
phr of MgO increases the Mooney scorch time by ten minutes Thiazole
diamino-2,4,6- triazinyl
without significantly effecting chlorobutyl rubber compound
properties such as tensile strength. If the level of magnesium As a thiazole, MBTS has a dual function in the vulcanization
oxide is increased to 0.5 phr, there will be a detrimental effect reaction. First is as a retarder and then as an accelerator in
on cure rate, with magnesium oxide acting as a retarder. As a sulfur crosslink formation where MBTS will react with ZnO to
retarder, magnesium oxide is effective with all vulcanization form a sulfurating agent. This intermediate can then react with
systems except amine-based cures. In that case magnesium the polymer to form crosslinks (Figure 18)14.
oxide will react with chlorine formed during crosslinking
preventing the appropriate vulcanization reaction with the Figure 18
curing agent. Illustration of sulfurating agent and crosslink formation14

  R
R R
N
NR3

N N N N
C S Zn S C C S S   Zn S C
8
S S S S

NR3
S S N
R R
R
S6

N Zn S N BtS Sx Sy Bt + Zn S
+
C S + Sy C R H
RSxSBt                   B tSSx  Z n  S ySBt   RSx  ZnSx   S Bt             +         B tSSy  S Bt
S S
R H
Polymer   C hain

Zn S N
S Sy C RSSxR        +         Z nS          +           HSxBt
S
R H
16 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

Although the final state of cure or crosslink density may be Figure 20

low, in the absence of zinc oxide MBTS may vulcanize rubber MBTS (phr) and MDR rheometer at 180°C, 0.5° arc
as shown in Figure 1914. Depletion of MBTS due to the initial
reaction with bromine could account for the delayed response 8
observed. Again, at higher levels MBTS can serve as a retarder. 7
6
5
Figure 19 4
3
MBTS accelerated crosslinking14 2
1
N N S8 N N 0 Delta Torque (dNm)
C S S C C S S Sx C tc90 (minutes)
1
S S S S 2 tc10 (minutes)
3
4
5
CH3 H

C H2 C C C H2
1 2 3 4 5
H C H3
C H2 tc10 (minutes) 0.68 1.04 0.99 0.96 0.95
1 2

C C 3   4

H C H C H2 1 CH
tc90 (minutes) 3.02 7.38 4.33 3.31 3.05
N N
2
C C H3 N
S
C S Sx C 3   C H Sx S C Delta Torque (dNm) 4.04 4.78 4.58 4.16 3.92
S S 4
C H2 S

C H2 C H3 The proposed retarding mechanism of MBTS is illustrated in

C C CH
C
H
C H
Figure 21. Depletion of MBTS due to an initial reaction with
Sx S +    M BT
CH Sx S N bromine would account for the delayed response observed.
S C
C H2
S

  Figure 21
Retarding action of MBTS
Table VIII illustrates the effect of MBTS concentration on
rheometer induction time, cure state, and rate of vulcanization. N N N
C S S C C S H
S S S
Table VIII 2

Retarding effect of MBTS

1 2 3 4 5
Compound C H3 C H2 C H3 C H3 C H2 C H3
(phr) (phr) (phr) (phr) (phr) C H2 C C H2 C C H C H2 C
C H2 C C H2 C C H C H2 C
C H3 C H3
Zinc oxide 2.0 2.0 2.0 2.0 2.0 C H3 Br C H3 S

C
Sulfur 0.5 0.5 0.50 0.50 0.50 N N S + HBr
C S H
MBTS 0.0 0.5 1.0 1.2 2.0 S

Rheometer (MDR), 180°C, 0.5° arc  

Mh - Ml (dNm) 4.04 4.78 4.58 4.16 3.92 Other halobutyl rubber cure systems
tc10 (minutes) 0.68 1.04 0.99 0.96 0.95
• Alternatives to TMTD accelerated curing in halobutyl
rubber: Nitrosamines result when curing with TMTD and its
tc90 (minutes) 3.02 7.38 4.33 3.31 3.05
use is not recommended. However, tetrabenzylthiuram
Rate (dNm/min) 1.83 2.34 2.38 2.62 2.84 disulfide (TBzTD) or its zinc derivative, zinc
dibenzyldithiocarbamate (ZBEC) with a sulfenamide
Figure 20 shows that the use of 0.5 phr of MBTS increases the accelerator such as CBS can readily match the compound
rheometer induction time (tc10 at 180°C) from 0.68 minutes properties of TMTD. Magnesium oxide may be added to
to about one minute. The rheometer tc90 cure times increased assist in controlling scorch and cure rate.
to 7.3 minutes then fell to 3.1 minutes as MBTS increased from • Vultac, amylphenol disulfide accelerators: the Vultac group
0.5 phr to 2.0 phr. This further illustrates the dual role for MBTS of sulfur donors can be used in chlorobutyl rubber-based
as a retarder and as primary accelerator in the halobutyl rubber tire compounds where good adhesion to natural rubber or
vulcanization process. NR/SBR blends is required. These compounds tend to
show high cure states, which can be controlled with MBTS
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 17

and MgO. However, magnesium oxide use can also increase

tack to calender rolls and increase mold fouling. With
bromobutyl rubber, the use of amylphenol disulfide polymer
results in reduction in scorch times thereby limiting their
application.
• Diamines and thioureas: diamines and thioureas are very
effective accelerators in curing of halobutyl rubbers.
• Peroxides: bromobutyl rubber may be crosslinked with
peroxides. For optimal cure, a co-agent is required such as
phenyl bismaleimide (HVA-2). Typically, 1.0 to 2.0 phr of
dicumyl peroxide and 0.5 to 1.5 phr of HVA-2 will provide
an adequate state of cure for both carbon black and clay
filled bromobutyl rubber compounds.
18 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

7. Vulcanization of brominated isobutylene-co-para-methylstyrene (BIMSM)

BIMSM elastomers display many properties superior to those ZnO + Stearic Acid > Zn(stearate)2 + Zn(stearate)(OH) + H2O (2)
found in general-purpose rubbers or other isobutylene-based
polymers. For example, BIMSM shows reduced impermeability, Generation of a Lewis acid results and is believed to be the
increased heat stability, increased ozone resistance, increased step controlling the induction period or compound scorch
oxidative stability and potentially higher tack levels when time. There is also an increase in the concentrations of Zn(OH)
compared to halobutyl rubber25. Figure 22 shows a typical Br, Zn(Br)(St), and ZnBr2 (equation 3).
schematic of a BIMSM crosslink.
Zn(St)2

Zn(OH)(St)
Figure 22 + ZnBr2          +       ZnBrSt        +          Z nBr(OH)
St  =  S tearic  A cid
Schematic of BIMSM crosslink
C H2Br C H2St
 
(3)
C H3
C H3
C H2 C C H2 CH
C H2 C C H2 CH A third step involves formation of crosslink networks through
C H3 ZnO C H3
alkylation between benzyl bromide groups and formation of
Stearic   acid
hydrogen bromide. Hydrogen bromide continues to react with
R
zinc oxide to form additional amounts of Lewis acids (equation
C H2
C H2Br
4)26.
R  =    -­‐‑  C H 2Br C H3
               -­‐‑  C H3
C H C H2 C C H2
C H3
 
Unlike bromobutyl rubber, BIMSM will display poor cure rates
and lower cure states with use of only ZnO. However, in many
instances, the use of 1.0 phr of ZnO and 2.0 phr of stearic acid This is manifested as an increase in cure state or increase in
in a carbon black filled BIMSM compound is sufficient to obtain rheometer torque. The concluding or forth stage in the curing
a reasonable cure state. Zinc stearate will also cure BIMSM and process is the maturation or plateau phase of the cure profile.
reversion may be minimized by addition of around 1.0 phr of Table IX illustrates the effect of zinc oxide concentration on
ZnO. Therefore, BIMSM cure systems that will produce a rheometer induction time, rate of vulcanization, and rheometer
vulcanizate with adequate scorch and reversion resistance and maximum torque, as a measure of cure state. Some general
good mechanical properties will contain a thiazole such as inferences are:
MBTS, sulfur, ZnO and stearic acid. Cure systems where zinc is
absent and peroxide systems will not be effective for BIMSM. • Reducing the ZnO concentration to a level below 1.0 phr
would result in an excess of benzylic bromide
Due to the absence of carbon-carbon double bonds in the • High benzylic bromide has a detrimental effect on aging
BIMSM backbone and the presence of the reactive benzylic • Excess stearic acid level results in increases in permeability
bromide, the vulcanization chemistry differs from that of other • A molar ratio of ZnO to bromine of 0.9 is preferred
isobutylene-based elastomers. Crosslinking of BIMSM involves
formation of carbon-carbon bonds via a Friedel-Crafts
alkylation reaction catalyzed by zinc bromide. Stearic acid
functions as an accelerator of BIMSM vulcanization2,25. Zinc
stearate formed as a product of the reaction between zinc
oxide and stearic acid, can react with BIMSM and displace
benzylic bromine. In the absence of stearic acid cure rates are
low.

Several distinct steps in the vulcanization of BIMSM have been

identified with zinc oxide26. In a classical curing process, the
initial step is formation of zinc salts of stearic acid (equation 2).
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 19

Table IX
Effect of zinc oxide level on vulcanization of BIMSM 26
Compound 1 2 3 4 5 6
ZnO 0.25 0.50 1.00 2.00 3.00 4.00

Stearic Acid 2.00 2.00 2.00 2.00 2.00 2.00

Induction Time (ODR Rheometer at 160°C)

t2 (minutes) 13.97 11.30 9.77 8.22 6.15 5.85

Cure Rate
3.09 5.85 9.83 11.18 11.26 9.12
(dNm/min)

Mh (dNm) 27.70 43.25 48.22 49.85 49.75 49.80

Table X shows that stearic acid has a significant effect on

induction times and cure rates. Although zinc stearate can
vulcanize BIMSM, such compounds tend to display short
scorch times. In the absence of zinc oxide, hydrogen bromide,
which is a strong acid and is formed in the alkylation reaction,
can react with zinc stearate to form the more stable ZnBr2.

Table X
Effect of stearic acid on curing of BIMSM 26
Compound 1 2 3 4 5 6
Stearic Acid 0.5 1.0 2.0 3.0 4.0 5.0

ZnO 1.0 1.0 1.0 1.0 1.0 1.0

Induction Time (ODR Rheometer at 160°C)

t2 (minutes) 60.9 31.7 9.5 7.1 6.2 5.2

Cure Rate
1.6 3.4 9.8 9.5 7.3 4.4
(dNm/min)

Mh (dNm) 52.2 54.2 49.2 47.2 52.5 29.1

Stearic acid is then reformed as shown in equation 5. (5)

  Z  nB
   r  2  
Z  nB
   r  S  t   +                      H  B  r  
R  
Z  n(    O  H  )  B  r   R      =        St,  OH,  Br,  Ph  -­‐-­‐    
C  H  2  
C  H  2B
   r  

An increase in stearic acid levels can cause lubricating effects

with a drop in apparent viscosity and compound stiffness as
measured using an oscillating disc rheometer. However,
reversion may also occur due to the increase in bromine
released via a free radical cleavage from the polymer chain.
This may be adjusted by increasing the zinc oxide level in the
compound.
20 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

8. Model cure system formulary

Isobutylene-based polymers will employ a variety of cure
systems depending on the requirements of the final cured
product. For example, tire innerliners require good resistance
to fatigue, tear strength, and adhesion to adjacent
components in the tire. Therefore, sulfur-based systems with
their co-curing ability, adequate fatigue and flex life are
preferred for liner compounds. Curing bladders, which
operate in high temperature environments and undergo many
cycles, must have stable crosslinks and not be susceptible to
reversion or other oxidative processes. In such instances, resin
based cure systems are preferred.
Halobutyl rubber
Table XII displays a set of model cure systems for halobutyl
elastomers. These include a resin, sulfur-accelerator based
system for a bromobutyl rubber radial tire innerliner, and a low
temperature cure system possibly suitable for pipe seals in
inaccessible locations. Again, these cure systems may provide
a starting point for further development.

Butyl rubber
Table XI illustrates quinone, resin, and sulfur-accelerator based
model cure systems for butyl rubber. These cure systems may
provide a starting point for further development.

Table XI
Model cure systems for butyl rubber 1,2
Sulfur
Cure System Quinone Resin Resin
Accelerator

Units phr phr phr phr

Electrical
Curing Curing
Application Cable Tube
Bladder Bladder
Cover
ZnO 5.0 5.0 5.0 5.0

MgO 2.0 - - -

Stearic Acid - - 1.0 2.0

Sulfur - - - 2.0

MBTS - - - 0.5

TMTD - - - 1.0

Polychloroprene - 5.0 - -

Resin (a) - 10.0 - -

Resin (b) - - 12.0 -

Benzoquinone
2.0 - - -
Dioxime

Total phr 9.0 20.0 18.0 10.5

Note: Resin (a) is a heat reactive octylphenol-formaldehyde resin

Resin (b) is a brominated octylphenol-formaldehyde heat reactive resin
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 21

Table XII
Model cure systems for halobutyl rubber 2,3
Sulfur Sulfur Zinc Oxide & Room
Cure System Peroxide3
Accelerator2 Sulfenamide2 Resin3 Temperature Cure3

Units phr phr phr phr

Application Innerliner Polymer Blends Pharmaceutical Sheeting Steam Hose

ZnO 3.0 2.0 3.0 5.0 -

ZnCl2 - - - 2.0 -

Stearic Acid 1.0 1.0 1.0 - -

Sulfur 0.5 1.0 - - -

MBTS 1.5 - - - -

TBBS - 1.5 - - -

Resin (a) - - 2.0 - -

Stannous Chloride (SnCl2) - - - 2.0 -

Dicumyl peroxide (DiCup) - - - - 2.0

HVA-2 - - - - 1.0

Total phr 6.0 5.5 6.0 9.0 3.0

Note: Resin (a) is a heat reactive octylphenol-formaldehyde resin

BIMSM elastomers
Table XIII presents a set of five cure systems for BIMSM.

Table XIII
Model cure systems for BIMSM elastomer2
Ultra Fast
Sulfur
Cure System Metal Oxide Accelerator Resin Amine
Accelerator
System

Units phr phr phr phr

Application Damping Device Innerliner Engineerd Products Curing Bladder Engineerd Products

ZnO 2.0 1.0 1.0 1.0 1.0

Zinc Stearate 3.0 - - - -

Stearic Acid - 2.0 2.0 2.0 2.0

Sulfur - 1.0 - 1.5 -

MBTS - 2.0 - 1.5 -

ZDEDC - - 1.0 - -

Triethylene Glycol - - 2.0 1.0 -

Resin (a) - - - 5.0 -

DPPD - - - - 0.5

Total phr 5.0 6.0 6.0 12.0 3.5

Note: Resin (a) is a heat reactive octylphenol-formaldehyde resin

22 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

Table XIV illustrates a selection of five model compound formulas one each for butyl rubber, chlorobutyl rubber, bromobutyl
rubber, and two for BIMSM elastomers. These model compound formulas illustrate typical properties obtained by utilizing
experimental sulfur-accelerator vulcanization systems.

Table XIV
Effect of cure system type on fundamental properties of isobutylene based elastomers
1 2 3 4 5
Model BIMSM with Model Butyl Model Chlorobutyl Model Bromobutyl
BIMSM Compound Zinc Stearate Compound Compound compound

Master Batch (phr) (phr) (phr) (phr) (phr)

BIMSM 100.0 100.0 - - -

Butyl 268 - - 100.0 - -

CIIR 1066 - - - 100.0 -

BIIR 2222 - - - - 100.0

Carbon Black N660 60.0 60.0 70.0 60.0 60.0

Naphthenic Oil 8.0 8.0 - 8.0 8.0

Paraffinic Oil - - 25. - -

Aromatic & Aliphatic

7.0 7.0 - 7.0 7.0
Hydrocarbon Resin Blend

Phenolic Tackifiying Resin 4.0 4.0 - 4.0 4.0

Hydrocarbon Resin - - 3.0 - -

Stearic Acid 1.0 1.0 1.0 1.0 1.0

MgO - - - 0.2 0.2

Final Batch (phr) (phr) (phr) (phr) (phr)

Sulfur 0.5 0.5 2.0 0.5 0.5

MBTS 1.5 1.5 2.0 1.5 1.2

Zinc Oxide 1.0 - 5.0 1.0 1.0

Zinc Stearate - 2.0 - - -

Zinc dibutylphosphorofi-
- - 2.0 - -
thiate (ZBPD)

Total (phr) 183.0 184.0 210.0 183.2 182.9

Typical Results (phr) (phr) (phr) (phr) (phr)

Mooney viscosity (ML1+4
69.0 65.0 45.0 55.0 56.0
at 100°C)

Rheometer (MDR) at 160°C, 0.5° arc

Delta torque (dNm) 7.3 2.3 7.3 3.1 3.5

tc10 minutes 2.5 4.4 - 0.9 2.2

tc90 minutes 6.1 4.4 25.0 3.3 12.8

Cure Rate Index 27.8 33.3 4.0 41.7 9.4

Tensile Strenght (MPa) 10.6 9.1 11.1 9.2 9.6

Elongation (%) 565 817 665 868 837

 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 23

300% Modulus (MPa) 10.6 9.1 11.1 9.2 9.6

Hardness (Shore A) 61 58 49 51 47

Tear Strenght (KN/m) 58.0 60.0 39.0 56.0 54.0

ExxonMovil Chemical Company Data

Isobutylene-based elastomers are highly saturated and

therefore have traditionally required ultra-fast accelerators
such as thiurams (TMTD) and dithiocarbamates (ZDMC) for
effective cure. Though a variety of replacements for
accelerators such as TMTD and ZDMC used in general-
purpose rubbers have been evaluated, no direct replacement
candidates have emerged.
Regardless of the cure system being used in a composite such
as a tire, vulcanization rates between adjacent components at
the cure temperature of the tire must be similar. Figure 23
illustrates two incompatible cure rates and while the individual
components have good mechanical properties, the composite
could separate since good interfacial adhesion is not created
during cure.

Figure 23
Cure rate compatibility 27

Interface
Creation
Compound B t90
(time to 90% cure)

Compound A t90
(time to 90% cure)
Rheometer Torque

Compound B t10
(time to 10% cure)

Compound A t10
(time to 10% cure)

Induction Time Time (minutes)

In conclusion, a new cure system must display the following

requirements:

• Adequate induction times

• High temperature reversion resistance (i.e., temperatures
above 160°C)
• Allow adequate adhesion between adjacent components in
a composite product

The model cure systems, which provide starting points in new

development programs, when used in experimental
compounds should be evaluated against the mission profile for
which the end-product is intended.
24 - Model vulcanization systems for butyl rubber and halobutyl rubber manual

9. Summary
The cure chemistry of isobutylene-based elastomers appears
more complex than that for general-purpose rubbers. The
backbone of isobutylene-based elastomers are highly
saturated, thus ultra-fast accelerators are required for efficient
vulcanization. Many of those accelerators are nitrosamine
generators, and therefore their use is not recommended. Cure
systems typically used for isobutylene-based elastomers tend
to be based on

• Resins cures
• Sulfur based accelerated curing
• Use of metal oxides such as zinc oxide
• Dioxime based systems

The selection of a specific system is a function of the polymer

type and the specific in-service requirements of the final cured
product.
 Model vulcanization systems for butyl rubber and halobutyl rubber manual - 25

APPENDIX 1
Recognized industry abbreviations for accelerators
Abbreviations or
commercial Chemical Name Function
Descriptions

CBS N-Cyclohexyl-2-benzothiazolesulfenamide Accelerator

BCI-MX 1,3-Bis (citraconimidomethyl) benzene Rversion Resistance

CTP, PVI N-(Cyclohexylthio) phthalmide Retarder

DBQDO Dibenzyl-p-quinone dioxime Quinone Cure

DCBS Dicyclohexylbenzothiazole sulfenamide Accelerator

DETU Diethylthiourea Accelerator

DBTU Dibutylthiourea Accelerator

DOTG Di-o-tolylguandine Accelerator

DPG Diphenyl guanidine Accelerator

DPPD N,N’-Diphenyl-p-phenylenediamine Anti-Oxidant

DPTU N,N’-Diphenylthiourea Accelerator

DTDM 4,4-Dithiodimorpholine Vulcanizing Agent

ETU Ethylenethiourea Accelerator

HTS Hexamethylene-1,6-bis (thiosulfate) Disodium Salt, Dihydrate Reversion Resistance

MBS 2-(4-Morpholinothio- benzothiazole Accelerator

MBT Mercaptobenzothiazole Accelerator

MBTS Mercaptobenzothiazole sulfenamide Accelerator

QDO p-Quinone dioxime Quinone Cure

TBBS tert-Butyl-2-benzothiazole sulfenamide Accelerator

TBSI N-t-Butyl-2-benzothiazole sulfenamide Accelerator

TBzTD Tetrabenzylthiuram disulfide Accelerator

TMTD Tetramethylthiuram disulfide Accelerator

TMTM Tetramethylthiuram monosulfide Accelerator

Vultac 2 Amylphenol disulfide polymer (23% Sulfur) Sulfur Donor

Vultac 3 Amylphenol disulfide polymer (28% Sulfur) Sulfur Donor

Vultac 5 Amylphenol disulfide polymer (18% Sulfur) Sulfur Donor

Vultac 7 Amylphenol disulfide polymer (30% Sulfur) Sulfur Donor

Vultac 710 Amylphenol disulfide polymer (27% Sulfur, 10% HSt) Sulfur Donor

ZDMC Zinc dimethyldithiocarbamate Accelerator

ZDEC Zinc diethyldithiocarbamate Accelerator

ZBDC Zinc dibutyldithiocarbamate Accelerator

ZBEC Zinc dibenzyldithiocarbamate Accelerator

ZIX Zinc isopropyl xanthate Accelerator (low temp.)

ZBPD Zinc dibutylphosphorodithioate Accelerator

ExxonMobil Chemical Company Data

26 - Model vulcanization systems for butyl rubber and halobutyl rubber manual
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Model vulcanization systems for butyl rubber and halobutyl rubber manual - 27
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