Cure Reactivity - A Route To Improved Performance in Halobutyl Applications TI

Rubber Business Group
Technical
Information
Rubber
TITLE:
Cure Reactivity - a Route to Improved Performance in

Halobutyl Applications
TEXT:
Summary
The halogenation of butyl rubber with either
chlorine or bromine significantly increases
cure reactivity, provides compatibility with
unsaturated polymers, and enhances
adhesion as compared to regular butyl
rubber.
The differences in cure reactivity of
chlorinated and brominated butyl and their
versatility in responding to a wide range of
curing systems are illustrated. Significant
improvements in heat, ozone, flex fatigue
resistance and compression set can be
achieved
through
the
selection
of
appropriate curing systems.
The versatility and properties of halobutyl
rubber have led to significant growth in the
uses of butyl type polymers in a diverse
range of tire and non-tire applications which
are described in this Technical Information.
Introduction
The halogenation of polymers has been
studied extensively since Roxborough first
chlorinated natural rubber in 1801 (1). The
potential commercial utility of such a product
was not recognized until 1930 when small
quantities were produced for use in
protective coatings, inks, and adhesives.
Attempts were made to produce chlorinated
emulsion polyisoprene during World War II
and patents were issued to Bartovics (2) and
DIanni (3). The chemistry of the chlorination
of natural rubber was extensively studied by
Bloomfield (4).
Technical Information
KA-FK-0230e/02/05.01
Page 1 of 46
Extensive early references on the subject of

halogenation of isoprene polymers and other
rubbers were published by Davis and Blake
(5), and Whitby (6). Halogenation of butyl
rubbers was first studied by R.T. Morrissey
and co-workers at B.F. Goodrich Company
in the late 1940s (7). Their research led to
the commercialization of a brominated butyl

rubber, HYCAR 2202. The Goodrich work
was of great importance in demonstrating
the practical value of bromination; the ability
to form strong adhesive bonds between
butyl rubber and highly unsaturated rubber,
as well as the ability to obtain good
vulcanizate properties in blends, which was
unattainable prior to this work, had been
demonstrated for the first time.
The early types of brominated butyl rubber
were made by a batch process in which
regular butyl rubber was mixed in internal
mixers with a brominating agent and a
stabilizer. Despite its useful properties, the
polymer did not achieve widespread
industrial use and was subsequently
withdrawn from the market because of the
very high production costs and difficulties in
achieving consistency and stability.
The chlorination of butyl rubber was
emphasized by Exxon workers (8) in the
1950s and the first commercial product was
introduced in 1960. This was made in a
continuous process by reacting chlorine with
butyl rubber and was less costly to produce
than brominated butyl made by the early
batch process.
Despite its early limitations, brominated
rubber offered some potential advantages
over chlorinated butyl rubber in cure rate,
adhesion and vulcanizate aging. Hence, the
interest in brominating butyl persisted in the
rubber industry, particularly among tire
manufacturers
seeking
the
highest
performance standards in radial tire inner
liners. This interest led to the development
by Polysar Limited (now part of Bayer AG) of
a continuous solution process by which a
highly stable and uniform brominated butyl
rubber could be manufactured on a large
scale (9).

Technical
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Rubber
The development and commercialization of
brominated and chlorinated butyl rubber has
led to significant growth in the use of butyl
type polymers.
Fundamentals of Butyl and Halobutyl

Rubber
Butyl rubbers are copolymers of isobutylene
and isoprene, the isoprene being present at
levels between 0.5 - 2.5 mole % . They are
very impermeable to air, exhibit high
damping, and are reasonably flexible at low
temperatures, having a Tg of 72 C. This
combination of properties is unique. Other
polymers exhibiting low permeability and low
resilience, such as nitrile rubber, have
relatively high Tgs and exhibit poorer low
temperature flexibility, while polymers with
low Tgs, such as polybutadiene and
polyisoprene exhibit very high permeability
to air.
The impermeability of butyl rubber is largely
attributable to the isobutylene chains of
which it is primarily composed. Two methyl
side groups on every other carbon atom in
the backbone cause steric hindrance. The
chains, therefore, move relatively slowly so
that they block the passage of gas
molecules rather than moving aside and
letting them pass.
The bulky methyl groups also prevent the
chains taking up a regular configuration and
crystallizing, while at the same time they
have only small dipole movements which do
not give rise to strong interchain attractions.
Because of this structure, butyl rubbers have
good low temperature flexibility and high
damping characteristics.
The low level of isoprene units in butyl
rubber results in slower cure rates compared
to unsaturated polymers such as NR and
SBR, making it impractical to obtain good
vulcanizate properties in blends with these
and other highly unsaturated elastomers.
KA-FK-0230e/02/05.01
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Achievement of interfacial cured adhesion of

butyl to unsaturated rubber compounds is
also impossible. These covulcanization and
adhesion deficiencies of regular butyl

rubbers are overcome by halogenation. The
double bonds provided by the isoprene in
butyl rubber will react with the halogens,
bromine or chlorine, to give the bromobutyl
and chlorobutyl modifications of butyl rubber
which are much more reactive than the
parent polymer.
Halogenation of Butyl Rubber

As has been so often the case throughout
the history of the rubber industry, practical
developments in the applications for
halogenated butyl rubber have run ahead of
the fundamental knowledge of the chemistry.
In early patents, it was assumed that
bromination led predominantly to the
addition product, while it was understood at
a relatively early stage that substitution
products predominated in the chlorination
reaction, but methods for precise analysis
were not available until more recently. Work
by Poutsma (10) and others describe the
chlorination reactions of various types of
alkenes, and these reactions are now well
understood.
Using
model
compounds,
Vulkovs
investigation of the halogenation behavior of
butyl rubber brought about a better
understanding of these systems (11). Due to
steric hindrance imposed by the methyl
groups, the products of chlorination and
bromination differ from patterns typical of
other tri-substituted alkenes. In chlorobutyl
there are no observable addition products
across the double bonds, while in
bromobutyl, substitution products not
normally observed in reactions of other trisubstituted alkenes, are predominant.
In the bromination and chlorination
processes, the reaction is believed to
proceed by an ionic mechanism as shown in
Figure 1.

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Rubber
CH3 H
CH3
CH2
CH2
C CH2 + X2
CH2 H
CH2
C C
CH2
CH3 H
CH2
- H+
CH2
CH2
Fig. 1:
Halogenation
bromine / chlorine
with
molecular
A halogen ion is formed; a proton is

eliminated; and substitution takes place.
NMR (nuclear magnetic resonance) studies
indicate that up to 90 percent of the halogen
is allylic to the double bond. Most of the
unsaturation is retained although it is largely
isomerized
Curing Chemistry and Cure Systems

The introduction of bromine or chlorine into
the position allylic to the double bonds of the
isoprenic unit converts butyl rubber into a
more reactive, faster curing and more
versatile polymer. The CBr bond, being
weaker than the CCl bond, results in faster
cure rates and greater inherent reactivity for
bromobutyl compared to chlorobutyl. This
greater reactivity in bromobutyl leads to a
more versatile curing chemistry and
necessitates a higher level of stabilizer in the
raw polymer. Conversely, chlorobutyl,
having the lower reactivity, requires higher
levels of allylic halide for a satisfactory cure
rate and state of cure in commercial
polymers.
Fig. 2: Cure response
This unique sulfur cure of bromobutyl was

first described by Feniak et al (12) who
showed that either poly or disulfide
crosslinks are formed (Figure 3) and that
while the vulcanizates revert on heat aging,
the additional of any one of a number of
bases (e.g. ZnO) improved the aging
characteristics as well as increasing the
state of cure. Levels of sulfur as low as
0.5 phr will give a rapid and reasonable
degree of cure.
Br
~C
CH
~+
Sx
CH ~
~C
CH2
Sy
+ S 2 Br 2
CH2
~C
CH 2 Br
Br
~C
CH
CH
~+
SxBr 2
~C
~
Br
CH ~
S
S
Sulfur Cure
Figure 2 shows that both bromobutyl and
chlorobutyl will cure with zinc oxide, but only
bromobutyl will cure with sulfur alone, no
zinc oxide or accelerator being necessary.
KA-FK-0230e/02/05.01
Page 3 of 46
~C
CH2 Br
CH
~
Br
Fig. 3: Proposed mechanism for sulfur cure

of bromobutyl

Technical
Information
Rubber
In blends containing bromobutyl and natural
rubber with sulfur as the sole curative, the
natural rubber portion of the blend also
cures, which suggests that an intermediate,
such as sulfur bromide, is formed and
migrates from the bromobutyl into the
natural rubber phase causing rapid
crosslinking of the latter.
The difference in the cure response to sulfur
between bromobutyl and chlorobutyl is of
practical importance as well as theoretically
significant.
Zinc Oxide
Zinc oxide plays an important role in curing
halobutyl rubbers. Both polymers will cure in
the presence of zinc oxide alone, the higher
allylic halide content in chlorobutyl resulting
KA-FK-0230e/02/05.01
Page 4 of 46
in a higher state of cure than is achieved in

bromobutyl. The latter exhibits a better
balance of scorch and cure behavior.
Studies made of the mechanism of zinc
oxide curing of halobutyl using model
compounds (13) show two competing
processes occurring. The major one
generates a zinc halide which acts as a
catalyst for the crosslinking reaction.
Crosslinking proceeds in a manner
described by Baldwin (14) resulting in CC
bond formation. The elimination of hydrogen
halide causes the formation of conjugated
diene groups which do not participate in the
zinc oxide crosslinking reaction. The diene
groups form more readily in chlorobutyl than
in bromobutyl, resulting in a reduction in
crosslinking efficiency (based on original
halide content) (15). (Figure 4)

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Rubber
X
ZnO
Initiation
- Loss of HX
- Formation of ZnX3
+ ZnX2
Propagation
Catalysed with ZnX
2
zinc halide
+ ZnX3-
+
X
Termination
reaction
Continuation of crosslinking
Fig. 4: Mechanism of zinc oxide crosslinking
KA-FK-0230e/02/05.01
Page 5 of 46

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Rubber
Effect of Accelerators on ZnO/S Systems
25
Fig. 5: 100 % BB2030 / CB1240
Significantly higher levels of adhesion to

natural rubber and to itself are achieved with
bromobutyl, compared to chlorobutyl, in all
cure systems studied (Figure 6).
KA-FK-0230e/02/05.01
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While the ZnO/S/MBTS cure system had the

highest self-adhesion, zinc oxide, when
used as the sole curative, had the highest
adhesion to natural rubber. Sulfur alone
gave the lowest adhesion. Similar trends
were observed in chlorobutyl but all systems
resulted in significantly lower adhesion
relative to bromobutyl. Physical properties
for bromobutyl and chlorobutyl are similar,
the modulus of vulcanizates being
influenced by the cure systems.
BB 2030 / Self
BB 2030 / NR
CB 1240 / Self
CB 1240 / Natural
20
kNm at 100C
15
10
ZnO/S/MBTS
ZnO/S
ZnO
ZnO/S/MBTS
ZnO/S
0
ZnO
The effects of adding three different

accelerators MBTS, TMTD or alkyl phenol
disulfide (Vultac) to zinc oxide/sulfur cure
systems are shown in Figure 5. In
bromobutyl, TMTD and alkyl phenol disulfide
exhibit the fastest cure rate and highest
state of cure, whereas MBTS depresses the
cure rate and state of cure. MBTS is
extremely useful for adjusting scorch time so
as to increase scorch time and processing
safety, particularly if added early in the
mixing cycle. Similar effects are observed
when using chlorobutyl, but higher states of
cure are observed when using either TMTD
or alkyl phenol disulfide. MBTS is less
effective in increasing scorch time in
chlorobutyl than in bromobutyl.
Cure System
Fig. 6: Inner liner - hot adhesion
Other accelerators commonly used to modify

the zinc oxide/sulfur cure systems include
sulfenamides which, like MBTS, initially act
as retarders, but ultimately produce high
states of cure; thiuram sulfides, TMTD;
TMTM and DPTT in small amounts can be
used as secondary accelerators and are
used
extensively
for
faster
curing
compounds in industrial rubber products;
morpholine disulfides, dimorpholinyl disulfide
(Sulphasan
R)
and
4-morpholinyl-2benzothiazole disulfide (Morfax) provide
excellent scorch safety. These may be used
either as the sole source of sulfur in
conjunction with elemental sulfur, or with
secondary accelerators such as TMTD, or
guanidines. They also impart good aging,
adhesion and flex properties.
Dithiocarbamates, such as ZDC, can be
used in small quantities (0.25 to 0.75 phr) to
accelerate zinc oxide cures used in heat
resistant applications and to improve
compression set. They impart very fast cure
rates and can be useful in low-temperature
vulcanization processes but are not
recommended for open steam cures. Such
compounds are susceptible to scorch, hence
the accelerator level should be kept to a
minimum.
Because of the differences in cure reactivity,
lower levels and simpler cure systems are
effective in bromobutyl. The cure systems

Technical
Information
Rubber
70
BB 2030
50
40
30
20
HVA
HVA+DiCup
Curatives
SP 1045
DIAK
10
0
The cure reactivity of bromobutyl and

chlorobutyl in response to amines,
peroxides, dienophiles and phenolic resins
relative to the sulfur and zinc oxide cure
systems is illustrated in Figure 7.
CB 1240
60
ZnO
The introduction of bromine or chlorine into

the position allylic to the double bond
enables these polymers to be cured by a
very wide range of curatives, some of them
being unconventional. This versatility is an
advantage in that control over properties
such as heat resistance, compression set
and dynamic and static ozone resistance is
possible. As a result, a wide variety of
specific requirements can be met for high
performance applications.
These cure systems are not only of

theoretical interest from a mechanistic
viewpoint, but are of practical significance in
producing high performance vulcanizates
which exhibit excellent ozone resistance, low
compression set and exceptional stability
toward high temperature oxidation.
DiCup
Other Curatives
in all cures except for the sulfur cure

previously described. (Figure 8).
Torque increase (dN.m)
effective in chlorobutyl tend to reduce scorch

safety in bromobutyl. Therefore, when
substituting one halobutyl for another, an
adjustment to the cure systems used is
generally required.
Fig. 8: Effect of curatives on torque increase

with zinc oxide
70
BB 2030
CB 1240
Torque increase
60
50
40
30
20
Curatives
HVA
HVA+DiCup
ZnO
DiCup
DIAK
SP 1045
10
Fig. 7: Effect of curative on torque increase

without zinc oxide
As would be expected, bromobutyl exhibits

greater versatility and response to these
cure systems in the absence of zinc oxide.
Zinc oxide acts synergistically with all the
curatives in both polymers and enhances
the state of cure. The torque increase as
measured at 166 C is higher for chlorobutyl
KA-FK-0230e/02/05.01
Page 7 of 46
Peroxide Curing
While butyl rubbers based on copolymers of
isobutylene and isoprene degrade rapidly
when heated in the presence of organic
peroxides, (16) bromobutyl can be cured
with peroxides in conjunction with a coagent.
Vulcanizates with an unusually low
compression set, high heat resistance and
excellent ozone resistance are produced
(17).
The free-radical curing of bromobutyl is
probably initiated by homolytic scission of
the carbon bromine bond since the IR band
attributed to the exomethylene structure
disappears at about the same rate as cure
proceeds.
CH2
~C
CH ~
Br
At the same time a band appears which may

be due to

Technical
Information
Rubber
CH2
~C
CH ~
with no bromine allylic to the double bond.

This suggests that curing proceeds via
scission of the CBr bond but does not rule
out curing through the double bond as well.
The heat resistance and compression set of

vulcanizates
cured
with
peroxide,
peroxide + N, N m-phenylenedimaleimide
(HVA#2), and HVA#2 alone are compared to
the zinc oxide cured bromobutyl in Table I.
Table 1: Comparison of cure systems in black compounds

Test Recipe *
Bayer Bromobutyl X2
100.0
100.0
100.0
100.0
100.0
100.0 100.0
N774 black
50.0
50.0
50.0
50.0
50.0
50.0
50.0
Zinc oxide
5.0
--
--
--
--
--
--
Stearic acid
1.0
--
--
--
--
--
--
Dicup 40C
--
1.5
1.5
1.5
1.5
1.5
--
HVA#2
--
--
0.25
0.5
1.0
1.5
1.5
Viscosity ML 1+4 (100 C)
83
88
88
88
87
87
89
Scorch time at 135 C(min)
16
12
12
14
17
19
16
Cure time at 180 C (min)
15
20
Hardness, Shore A
48
40
51
54
54
56
58
Modulus at 100 % elongation (MPa)
0.9
0.5
0.9
0.12
0.12
0.15
0.19
5.2
1.8
6.8
9.5
10.0
10.2
Tensile strength (MPa)
12.4
8.9
9.9
10.5
10.0
10.0
13.6
Ultimate elongation(%)
580
680
420
325
300
265
360
Compression set,
70 h at 150 C (%)
58
53
40
28
20
17
13
Hardness (points)
+3
+3
-2
+4
+1
+1
-1
Modulus at 100 % elongation (%)
+10
-5
-15
-10
-2
-5
-12
Tensile strength(%)
-40
-60
-35
-25
-10
-30
-45
Ultimate elongation(%)
-35
+20
+20
+7
-10
-10
-8
Compound properties
Physical properties
Aged in air, 168 h at 150 C (change)
For details of Test Methods throughout the text see Appendix I Test Procedures
KA-FK-0230e/02/05.01
Page 8 of 46

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Information
Rubber
Continuous and intermittent stress relaxation
measurements
on
the
vulcanizates
(Figures 9 and 10) indicate the superior
thermo-oxidative and network stability of
peroxide + HVA#2 and of HVA#2 used alone
compared to the zinc oxide cure system, the
former being more stable in the long term.
Fig. 10: Intermittent stress relaxation
Bromobutyl compounds cured with peroxide

and HVA#2 alone and in combination,
produce vulcanizates with extraordinary
ozone resistance much better than
obtained with most other cure systems.
(Table 2)
Fig. 9: Continuous stress relaxation
Table 2: Ozone resistance

Test Recipe*
Bayer Bromobutyl X2
100.0
100.0
100.0
100.0
100.0
100.0
N774 black
50.0
50.0
50.0
50.0
50.0
50.0
Zinc oxide
5.0
Sulfur
1.5
Calcium hydroxide
3.0
Dicup 40C
1.5
1.5
1.5
HVA#2
1.0
SP-1055 resin
1.75
Ozone resistance rating
slight
cracking
slight
cracking
Appearance
KA-FK-0230e/02/05.01
Page 9 of 46
very slight no cracks no cracks

cracking
specimen
broke

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Information
Rubber
Dienophile Cure Systems
The mechanisms of crosslinking by
dimaleimides in the presence of peroxide
have been described by Kovacic and Hein
(18) and the uses of dimaleimides have
been described as curatives in various
elastomers.
While N, N m-phenylene-dimaleimide alone
will cure halobutyl rubbers to produce
vulcanizates having low compression set,
significantly higher states of cure can be
achieved when used in conjunction with zinc
oxide.
The unaged and aged properties of
halobutyl vulcanizates, containing mono and
bis dienophiles, are compared in Tables 3
KA-FK-0230e/02/05.01
Page 10 of 46
and 4. They exhibit very good heat and

ozone resistance combined with low
compression set.
Wilson and Vulkov proposed the respective
mechanisms for zinc oxide and mono and
bis maleimides (19). The formation of
conjugated diene groups which form on
heating with zinc oxide is followed by a
Diels-Alder type reaction. Using mphenylene bis maleimide (m-PBM), a
threefold increase in crosslink density is
achieved in the case of bromobutyl rubber,
and a five to sixfold increase in the case of
chlorobutyl rubber. By using a mixture of
mono and bis maleimide it is possible to
adjust
the
crosslink
density.
(See
Appendix III).

Technical
Information
Rubber
Table 3: Effect of dienophile cure systems
Test Recipe*
Bayer Chlorobutyl 1255
100.0
100.0
100.0
100.0
Stearic acid
1.0
1.0
1.0
1.0
N550 black
55.0
55.0
55.0
55.0
Paraffinic oil
10.0
10.0
10.0
10.0
Zinc oxide
5.0
5.0
5.0
5.0
N, phenyl maleimide
1.6
4.0
N,N'-phenylene bismaleimide
3.0
2.0
61
64
66
64
Mooney scorch time

(min at 125 C)
14
12
Monsanto rheometer at 166 C

(3 arc, 100 cpm, 0 preheat)
Tc 90 (min)
Hardness, Shore A
52
60
60
58
Modulus at 100 % elongation

(MPa)
1.4
2.8
2.4
1.4

(MPa)
6.5
8.5
8.3
4.7
11.8
10.6
11.9
10.8
Ultimate elongation (%)
510
390
480
730
70 h at 100 C
22
14
16
38
70 h at 150 C
57
18
31
51
Cure System
Compound properties
Physical properties
Compression set (%)
KA-FK-0230e/02/05.01
Page 11 of 46

Technical
Information
Rubber
Table 4: Effect of dienophile cure system on ozone resistance and heat aging
Cure System
NPM
1.6
4.0
NMPB
3.0
2.0
5.0
5.0
5.0
5.0
Zinc oxide
Static ozone resistance, 50 pphm, 40 C, 168 h

20 % strain (rating)
50 % strain (rating)
Hardness (points)
-4
-1
-4
-1
Modulus at 100 % elongation (%)
-30
-12
-30
-21
Tensile strength (%)
-86
-60
-86
-73
-22
-12
-22
-26
Dynamic ozone resistance, 50 pphm, 40 C, 168 h

0-25 % strain (rating)
Aged in air, 168 h at 150 C - change
Amine Cures
Substituted paraphenylene diamine antioxidants have been used to advantage to
improve the heat resistance of zinc oxide
cures in chlorobutyl and bromobutyl, (20)
and published work by Timar and Edwards
contain examples of this (21). The addition
of amine type antioxidants have also been
observed to increase cure rate, reduce
scorch time and induce poor shelf life in
uncured compounds, particularly in the case
of bromobutyl.
KA-FK-0230e/02/05.01
Page 12 of 46
Polyfunctional
amines,
such
as
hexamethylene diamine carbamate (Diak
No.1), have been used in sulfurless and zinc
oxide free bromobutyl compounds for
pharmaceutical stoppers required to pass
very stringent tests for chemical inertness
(reducing substances). These cure systems
are not effective in chlorobutyl. Studies by
Edwards (20) have shown that certain types
of aromatic amines interact synergistically
with zinc oxide in halobutyl elastomers to
provide a rapid and highly efficient type of
crosslinking system. The vulcanizates
exhibit good ozone resistance and are

exceptionally
stable
towards
high
temperature oxidation, combined with low
compression set.
The hypothesis underlying this work
proposed three principal curing mechanisms
for halobutyl compounds using zinc oxides
and difunctional amine antioxidants:
cationic cross linking due to zinc oxide as
proposed by Baldwin et al (9) and
supported by Vulkov (14) in more recent
studies using model compounds.
Hofmann type reactions in which only the
amine and the halide sites are involved
and,
a synergistic process whereby both zinc
oxide and amine antioxidant mechanism
proceeds by Friedel-Crafts alkylation of
the antioxidant molecules at more than
one site.
This third type of process is most rapid at
curing temperatures and capable of forming
thermally and oxidatively stable crosslinks.

Technical
Information
Rubber
The properties of compounds containing
ADPA 86 (reaction product of diphenylamine
and acetone - Aminox, supplied by Uniroyal
Incorporated) with, and without, zinc oxide,
and DNPD (di-beta-naphthyldiphenylamine Agerite White, supplied by R.T. Vanderbilt)

in conjunction with zinc oxide, are illustrated
in Table 5.
Table 5: Zinc oxide/amine cures in bromobutyl

Test Recipe*
Bayer Bromobutyl X2
100
100
100
100
N550 black
55
55
55
55
Paraffinic oil
10
10
10
10
Zinc oxide
5.0
5.0
5.0
ADPA 86
4.0
4.0
DNPD
3.0
Unaged
61
64
63
60
Aged 60 days at RT
62
75
97
68
30
14
12
11
9.3
9.4
10.8
12.1
1.4
1.6
3.8
3.8
6.3
5.9
10.2
9.4
455
600
340
370
Hardness, Shore A
47
50
58
59
Compression set, 70 h at 150 C (%)
77
100
47
28
0.7
0.7
3.7
2.4
0.7
0.6
3.2
2.0
100
20
120
160
Hardness, Shore A
48
61
63
62
Cure system
Compound properties
Mooney viscosity ML 1+4 (100 C)
Mooney scorch, t5 at 125 C (min)

Unaged properties
Aged properties, 7 days at 175 C
KA-FK-0230e/02/05.01
Page 13 of 46

Technical
Information
Rubber
The synergistic effect of the ZnO/amine
system results in very good heat resistance
after aging at 175 C and low compression
set observed after 70 hours at 150 C. The
cure rates shown in Figure 11 also illustrate
this synergistic effect. Of the systems
studied, DNPD plus zinc oxide in bromobutyl
compounds exhibited good scorch safety,
storage stability, and fast cure rate.
These systems are both economical and

effective in producing high performance
compounds
useful
for
demanding
applications involving high temperatures
combined ozone resistance, chemical
inertness, low permeability, and low
temperature flexibility.
Resin Cures
Resin curing of regular butyl provides
excellent heat resistance. In halobutyl, lower
levels of resin (2 3 phr) are effective, no
halide activation for the resin, as used in
curing butyl, being necessary.
Fig. 11: Monsanto Rheometer cure curves

166 C/1 arc
KA-FK-0230e/02/05.01
Page 14 of 46
Halobutyl can be used to activate resin

cures in regular butyl (Table 6). While the
dry heat resistance of resin cured halobutyl
is excellent, aging in high pressure steam is
not as good as that obtained when using
regular butyl cured with methylol resins.

Technical
Information
Rubber
Table 6: Resin cures *
Bayer Bromobutyl X2
100
--
10
Bayer Butyl 301
--
95
90
CR - Type W
--
--
Stearic acid
N339 black
50
50
50
Aromatic oil
Zinc oxide
1.75
Viscosity ML 1+4' (100 C)
67
70
70
Mooney scorch time t5 at 125 C (min)
16
30
30
Max. torque (N.m)
2.0
2.3
2.1
Optimum cure (min)
15
50
43
Hardness, Shore A
57
62
60
1.8
1.7
1.6
8.9
5.3
5.9
15.2
13.9
14.8
450
740
680
Tear resistance, Die C (kN/m)
30
48
39
43
65
56
31.3
2.6
1.6
8.3
7.0
5.8
14
14
230
490
550
Tear, Die C (kN/m)
25
41
40
Volume swell (%)
47
SP-1045 resin
Compound properties
Monsanto rheometer, 165 C, 1 arc, t90
Vulcanizate properties
Aged in steam, 72 h at 195 C

Hardness, Shore A
KA-FK-0230e/02/05.01
Page 15 of 46

Technical
Information
Rubber
Antioxidants
168h 150C
90
24h 175C
80
The relative heat resistance compared to

zinc oxide/TMTD and zinc oxide alone is
shown in Figures 12 and 13 and their effect
on compression set and ozone resistance,
relative to peroxide and dienophile cure
systems, is illustrated in Figures 14 and 15.
Retained (%)
24h 200C
60
50
40
30
20
10
0
CIIR
BIIR
--------- ZnO --------TMTD
Aminox + MBI
CIIR
BIIR
--------- ZnO --------TMTD
CIIR
BIIR
---------- ZnO ----------
Fig. 12 : Hot air aging - tensile effect of cure

system
168h 150C
24h 175C
80
72h 175C
Retained (%)
While this effect of amine antioxidants on

cure rate and cure state subsequently led to
the study of amines as curatives (20), the
use
of
ADPA 86
and
mercaptobenzimidazole (MBI) to improve heat
resistance in zinc oxide/TMTD cured
halobutyl compounds has proved to be of
practical benefit in a range of applications,
including retreading envelopes, hose and
gaskets which are exposed to high
temperatures.
72h 175C
70
24h 200C
60
40
20
0
CIIR
BIIR
CIIR
BIIR
--------- ZnO --------TMTD
--------- ZnO --------TMTD

Aminox + MBI
CIIR
BIIR
---------- ZnO ----------
Fig. 13: Hot air aging - elongation effect of

cure system
70
Brombutyl X2
60
50
Set (%)
The degradation of halobutyl vulcanizates

cured with zinc oxide and sulfur donor
accelerators
and
exposed
to
high
temperatures has been shown to be due
primarily to oxidation. Aging in nitrogen
shows that the networks formed by such
curatives are thermally stable. Evaluation of
antioxidants in such compounds has shown
that while many have little or no benefit in
improving resistance to high temperature hot
air aging, substituted para-phenylenediamine types, particularly when used in
conjunction with mercaptobenzimidazole,
are highly effective in improving heat
resistance in such compounds. Moreover,
they increase the state of cure and reduce
scorch times significantly, particularly when
used in compounds based on bromobutyl.
(21)
40
30
20
10
Fig. 14: Effect of cure system

compression set, 70 h at 150 C
KA-FK-0230e/02/05.01
Page 16 of 46
Hva #2
Peroxide/
HVA #2
Peroxide
ZnO/TMTD/
ADPA86/MBI
ZnO/ADPA86
ZnO/TMTD
ZnO
on

Technical
Information
Rubber
Fig. 15: Effect of cure system on ozone

resistance (50 pphm at 40 C)
Fig. 16: MH-ML data for HIIR/NR with TMTD

and MBTS
The compounds and their properties are

shown in Appendices III and IV.
This is related to the cure system being

optimized solely for 100 % halobutyl with the
NR providing more crosslinking sites. These
results suggest a greater degree of covulcanization for bromobutyl compared to
chlorobutyl. In both accelerator systems
100 % chlorobutyl has an equal or greater
degree of crosslinking as measured by delta
torque. As the XIIR content decreases in
both systems there is a crossover and at low
levels of XIIR the BIIR blends have higher
delta torque than CIIR blends. It appears
that in CIIR blends the curative package is
used predominantly by the NR while in BIIR
blends curing occurs more homogeneously
giving a greater degree of curing between
the two rubber phases present. A possible
explanation for this observation is the ability
of bromobutyl to cure with sulfur alone,
possibly via formation of S2Br2 (12) which
could diffuse between NR and BIIR
boundaries. This is also a possible
explanation for the higher adhesion of
bromobutyl compared to chlorobutyl,
especially to NR.
Blends Chemistry
Halobutyl rubber can be co-cured or covulcanized with a wide variety of saturated
and unsaturated polymers including natural
rubber, polybutadiene, SBR, NBR, EPR,
polychloroprene, and propylene oxide for a
wide range of tire and non-tire applications.
(22/23)
An important characteristic of elastomer
blends is the extend of interfacial bonding
achieved, particularly if the polymers have
different solubility parameters and different
reactivity. Zapp (24) has demonstrated the
influence of cure systems in chlorobutyl/BR
blends by using differential swelling
techniques with various solvents, while
Bauer et al (25) showed the influence on
dynamic behavior of such blends using
different cure systems to achieve interphase
crosslinking. These factors are important in
halobutyl blends both regarding adhesion to
other polymers and blends with more fully
unsaturated rubbers (e.g. natural rubber).
KA-FK-0230e/02/05.01
Page 17 of 46
Figure 16 shows the effect of adding NR to

the halobutyls in a S/ZnO/MBTS system. It
indicates that higher states of cure than
either of the individual components can be
achieved.
The ability of halobutyl rubbers to co-cure in

blends and adhere to unsaturated rubbers,
combined with their response to a wide
range of curatives, to produce vulcanizates
having the combined properties of heat
resistance, ozone and chemical resistance
and low compression set, with very low
permeability and high damping, makes them
extremely versatile polymers suitable for a
range of diverse applications.

Technical
Information
Rubber
Applications
The major uses for halobutyl have been
influenced by technological changes in tires,
particularly the widespread adoption of
tubeless and tubed-type steel radial ply
construction. (26) For such tires, halobutyl
inner liners, having low permeability to air
and moisture, combined with good heat
aging and flex fatigue resistance, contribute
to improved tire durability and integrity and
to the maintenance of low rolling resistance.
The service conditions for inner liners for

passenger and truck tires, described in
Table VII, require inner liner compounds to
have excellent resistance to heat (80 C to
100 C) and to flex cracking under air
pressures of 30 to 120 psi (210 kPa
840 kPa) and good adhesion to carcass
compounds. The service life can be as long
as eight years for passenger and five years
for radical truck tires.
Table 7: Service conditions tire inner liner

Severity
Medium to high
High to very high
Passenger
Truck
90,000
400,000
Typical service speed (km/h)
140 - 100
100 - 80
Average service time (riding)
> 1,000 h
> 4,000 h
Number of years of service

(riding - parking)
Up to 8
Up to 5
Tire temperature at service speed

(contained air, C)
80 - 90
90 - 100
> 40 Million
> 120 Million
19
2.0
8.0
Type of tires (radial)

Total tire life (km)
Incl. no. of retreads
Number of flexes when tire passes foot print

in total tire life
per second
Typical inflation pressure (bar)
KA-FK-0230e/02/05.01
Page 18 of 46
Inner liner compounds must also be highly

impermeable to air and water vapor to
prevent belt edge separation caused by
intra-carcass pressure build-up from air
migration into the carcass, or rusting of steel
cords due to moisture vapor transmission.
Low permeability of inner liners is also
essential to maintain the correct inflation
pressure in order to maximize tread
durability, and to ensure that low rolling
resistance and handling traction is
maintained. A drop in 4 psi (28 kPa) can
cause a ten percent rise in rolling resistance.
These market demands have brought

significant
changes
in
inner
liner
compositions (Table 8), away from blends of
halobutyl/natural rubber to the adoption of
low Mooney, easy processing bromobutyl
rubber (100 phr) in compounds having little
or no oil so as to ensure a minimum of both
air loss and moisture permeability. The
deleterious effects on permeability and
adhesion, when using blends of NR and
halobutyl compared to halobutyl alone, and
the superiority of bromobutyl compared to
chlorobutyl, were described by von Hellens
(27) and Walker (28).

Technical
Information
Rubber
Table 8
Technology
Push
Technological Change
Inner Liners
Bromobutyl (100 phr)
Market
Pull
Trend to tubeless radial
Easier processing
Minimum air loss
Lower Mooney
Higher pressure to
reduce rolling resistance
Low oil/No oil
Reduce corrosion
(steel belt)
Reduced permeability
Electron beam
Improve durability
Quality/Consistency
Quality
Processing efficiency
The results are illustrated in Figures 17 and

18. The benefits in reducing oil content in
bromobutyl compounds to further reduce
permeability are illustrated in Figure 19.
45
95C
65C
25C
40
35
Q x 10
30
25
20
15
10
BIIR:NR 0:100
BIIR:NR 20:80
BIIR:NR 40:60
BIIR:NR 60:40
BIIR:NR 80:20
BIIR:NR 100:0
Fig. 18: Cured adhesion to NR compounds

BIIR vs. CIIR in blends
Fig. 17: Bayer Bromobutyl 2030;

air permeability vs. test temperatures
KA-FK-0230e/02/05.01
Page 19 of 46
Fig. 19. Effect of oil content on inner liner

permeability

Technical
Information
Rubber
Sidewalls
Table 9: Tire white sidewall *
Another important application for halobutyl is

in the sidewalls of radial tires, where there is
a requirement for long life and outstanding
flex fatigue resistance.
Formulation (parts by weight
Chlorobutyl, in particular, is used in

compounds for white sidewall letters and
coverstrips used in radial ply passenger
tires.
EPDM rubber, used in blends with SBR, NR
or BR to improve ozone cracking and
weathering, lowers adhesion, and limits
mechanical properties. Adding chlorobutyl to
white
sidewall
compounds
provides
improved adhesion combined with improved
dynamic ozone and flex resistance, while
maintaining good mechanical properties.
The development of white sidewall and
coverstrip compounds and their properties
were described by Blackshaw (24) and
Herzlich (29). Examples of compounds and
their properties are illustrated in Tables 9
and 10.
60.0
Buna EP T 3950 *
7.5
NR (pale crepe)
32.5
Titanium dioxide
30.0
Nu-Cap 200 (aluminum silicate)
60.0
Stearic acid
1.0
Escorez 1102
3.0
Sunolite 240 wax
1.0
Ultramarine blue
0.2
Zinc oxide
5.0
Sulfur
0.5
Vultac 5
1.2
MBTS
0.7
Compound Properties
Mooney scorch time - large rotor
t5 at 125 C (min)
t5 at 138 C (min)
53
12.9
7.1
Mill shrinkage (%)
29
Tel-Tak (kPa)
to self
to stainless steel
true tack
310
76
234
Garvey Die extrusion

(# Royle, 120 C, 70 rpm)
Rate (cm/min)
Die Swell (%)
Appearance
89
109
A6
Monsanto rheometer, 165 C, 3 arc,

1.7 Hz (100 cpm)
MH (dN.m)
43.0
ML (dN.m)
11.0
MH-ML (dN.m)
32.0
t10 (min)
2.8
t50 (min)
5.9
t50-t10 (min)
3.1
KA-FK-0230e/02/05.01
Page 20 of 46

Technical
Information
Rubber
Table 10: Tire white sidewall
Cured 30 min at 166 C
Hardness, Shore A
49

(MPa)
1.7

(MPa)
6.1
10.8
510
Static peel adhesion

at 25 C (kN/m)
to 100 % NR carcass
5.8
Static ozone resistance,

50 pphm ozone,
25 % extension, 40 C
time to first cracks (h)
> 336
Dynamic ozone resistance,

50 pphm ozone,
0 to 25 % extension
37 cycles/min, 40 C
time to first cracks (h)
De Mattia flex
to 600 % cut growth (kc)
Fig. 20:
Parameters
performance
tread
> 336
> 250
Treads
Since the energy crisis of the early 1970s,
and as a consequence of the CAFE
Corporate Average Fuel Economy regulation
emphasis has been placed on reduced
rolling resistance of tires. Significant
improvements have been achieved through
tire design, new polymers and compounding.
These have been reviewed by Chang and
Shackleton (30) in their paper An Overview
of Rolling Resistance, and Schuring (31) in
his paper The Rolling Loss of Pneumatic
Tires. The factors influencing rolling
resistance, traction and wear are illustrated
in Figure 20.
KA-FK-0230e/02/05.01
Page 21 of 46
effecting
There is a body of option today that believes

that the emphasis is changing towards
improvements in traction and handling
without sacrifices in resistance or treadwear.
High performance tires with improved
handling and traction characteristics, as well
as good high speed performance and
durability, are the main focus. Halobutyl
rubbers have been used in blends with
general purpose rubber in tread compounds
to improve wet traction but their use has
been limited to specialty tires because of
their adverse effect on abrasion resistance
and rolling resistance.
There has been a renewal of research in
which the emphasis is to take advantage of
the good traction imparted by halobutyl
blends, and overcome the past deficiencies
of higher abrasion loss and rolling
resistance. Tyurina and Shuarts (32) noted
in their work using various ratios of
polybutadiene and chlorobutyl that the
coefficient of friction on wet concrete was
considerably higher than the additive values.

Technical
Information
Rubber
Hirakawa et al (33), in their patent, claimed
that reduced rolling resistance, improved
skid properties and acceptable wear
resistance were obtained using blends of
general purpose rubbers. In another patent,
Hirakawa (34) also demonstrated that a
reduction in rolling resistance without loss of
wet traction was possible when some of the
blend or all of the halobutyl was added late
in the mixing cycle. The effects of mixing on
the improvement in rolling resistance,
observed by Hirakawa, have also been
observed and reported by Briggs and Wei
(35), and by Hess (36). By preparing black
polymer masterbatches containing different
amounts of carbon black and then blending
in a second stage mixing process, they
demonstrated that rolling resistance was
reduced when compared to polymer blends
mixed with carbon black in a single-stage
process. This work suggests that, when
using halobutyl in tread compounds with
general purpose rubber, improvements in
rolling resistance without loss of traction can
be influenced by the mixing method, in
particular by preparing masterbatches
containing different levels of carbon black.
The effect of cure systems on the dynamic
properties of blends of halobutyl and
polybutadiene have been demonstrated by
Bauer (25) through interphase crosslinking
between the heterogeneous polymer
phases.
The dynamic behavior of such blends is

shown in Figure 21 and their abrasion
resistance in Table 11. The data suggest
that by increasing the level of high cis
polybutadiene in a blend of SBR/BR/BIIR,
abrasion resistance can be improved while
improving wet traction and rolling resistance.
25 SBR 65 BR 15 BIIR
50 SBR 35 BR 15 BIIR
65 SBR 35 BR
Fig. 21: Dynamic response SBR-BR-BIIR

ratios
The balance of traction rolling resistance
and tread wear for high performance radial
tires could be improved. This could be
achieved by compound research on the use
of halobutyl in treads, involving methods of
mixing to control the phase distribution of
carbon black in polymer blends, increasing
the polybutadiene content and identifying
cure systems to induce interphase
crosslinking.
Table 11: SBR/BR/BIIR, abrasion loss/tan delta

SBR
75
65
50
25
BR
25
35
35
60
BIIR
15
15
Akron 15
152
152
124
174
Akron 20
122
126
109
137
DIN (vol. loss)
114
98
118
84
-8 C to +8 C
0.329
0.294
0.371
0.310
+48 C to 64 C
0.185
0.184
0.186
0.165
Abrasion
Rheovibron tan ? (100 Hz)
KA-FK-0230e/02/05.01
Page 22 of 46

Technical
Information
Rubber
Inner Tubes
The general properties of bromobutyl and

chlorobutyl based compounds are shown in
Appendix V.
While regular butyl meets the needs for the

majority of inner tube applications, inner
tubes based on halobutyl provide the same
excellent air retention plus improved heat
resistance, splice durability and resistance to
growth and softening (Table 12). Inner tubes
based on halobutyl are a premium product
used under conditions of high severity when
good heat resistance is essential. Halobutyl
is also used where the incompatibility of
regular butyl with other rubbers cannot be
tolerated, or when a faster cure rate makes
a
major
contribution
to
increased
productivity.
The ability of halobutyl to co-cure with

natural rubber is used in special
circumstances to improve the air retention
and heat aging of natural rubber inner tubes.
This ability can also be utilized to assist in
the handling of heavy weight, uncured giantsize tubes where the green strength of
regular butyl may be inadequate. The
addition of natural rubber will improve the
uncured green strength.
Table 12: Tire inner tube heavy duty

Compound Properties
Bromobutyl X2
Chlorobutyl 1255
52
57
Mooney scorch t5 at 135 C (min)
Garvey die extrusion

#1 Royle, 104 C, 30 rpm
Rate (mm/min)
Die swell (%)
Appearance rating
1200
22
A9
1080
30
A9
Cure time at 166 C (min)
3.5
5.0
Physical Properties
Original
Aged
(10 days,
125 C)
Original
5.1
7.0
6.5
9.1
7.5
10.5
7.0
Ultimate elongation %
570
310
540
300
Hardness, Shore A
47
58
54
51
Unaged % of tensile
63
35
Aged (10 days, 100 C)
47
43
4,960
620
870
100
Splice Endurance
Cycles to Dynamic Failure

Unaged
Aged (10 days, 100 C)
KA-FK-0230e/02/05.01
Page 23 of 46
Aged
(10 days,
100 C)

Technical
Information
Rubber
Curing Envelopes
Compounds based on regular butyl having
low modulus and permanent set have been
used for many years for envelopes used in
curing precured treads for retreading tires.
The better heat resistance and lower set
characteristics imparted by halobutyl
increase the life of curing envelopes and
consequently improve the economics of the
process. (See Appendix II)
Non-Tire Applications
Halobutyl rubbers are used in numerous
applications, the principal ones being shown
in Table 13. These applications take
advantage of one or more of the desirable
characteristics, such as low permeability,
energy absorption, heat and chemical
resistance. They offer advantages in faster
cure rates, cure versatility and the ability to
vulcanize in blends with other rubbers.
Bromobutyl is used in preference to
chlorobutyl whenever faster curing and/or
higher adhesive strength can be used to
advantage.
KA-FK-0230e/02/05.01
Page 24 of 46
Table 13: Halobutyl non-tire applications

Sole
Elastomers
Blends
Ball bladders
Chemical plant
lining
Protective clothing
Gas masks
Pharmaceutical
closures
Mounts
Rollers
Hose
Conveyor belts
(heat resistant and
food)
Sealants
Extruded sponge
Gaskets (solid and

cork)

Technical
Information
Rubber
Blends
The rubbers that can be covulcanized with
halobutyl include NR, SBR, BR, C, NBR,
CSM, EPDM and CO (epichlorohydrin). The
following three practical examples illustrate
the value of blends:
Natural Rubber/BIIR for engine mounts.
NBR/BIIR for printing rolls.
EPDM/BIIR for CV extruded sponge.
Mounts
Natural rubber has been used successfully
for many years in automotive engine
mounts, suspension bushings, steering
couplings and a variety of other dynamic
applications, while butyl rubber has been
used in high damping applications such as
body mounts.
The
higher
operating
temperatures
prevailing in engine compartments of
passenger cars has introduced increased
demands for improved heat resistance for
mounts. Improvements in heat resistance,
flex cracking and permanent set can be
achieved in blends of halobutyl and natural
rubber.(37)
The addition of bromobutyl to natural rubber
compounds produces little effect on dynamic
values when measured at low frequencies
(3 5 Hz) but under high frequencies
(110 Hz) dynamic modulus increases with
the bromobutyl level (Figure 22). Resistance
to flex cracking, compression set, and heat
aging improve as the level of bromobutyl is
increased.
Depending upon the frequency response
required and the service temperatures
involved, such blends have been put to
practical use as described (38) in a number
of patents.
KA-FK-0230e/02/05.01
Page 25 of 46
Fig. 22: BIIR/NR blends - dynamic modulus

(Rheovibron Testing)
Solvent Resistant Rollers

Some printing rollers require resistance to
solvents containing ketones which is difficult
to achieve with polar rubbers such as nitrile
or polychloroprene.
Excellent resistance to solvents, such as
MEK, can be obtained by using blends of
NBR and bromobutyl. These blends also
exhibit improved resistance to ozone
cracking compared to nitrile rubber. (See
Table 14)
Other applications for which these blends
appear suited include milking inflations to
improve resistance to animal fats or ozone,
and molded goods for combined resistance
to chemicals and oils.
Table 14: Ozone and solvent resistance

of bromobutyl
Bayer Bromobutyl X2
Krynac 34.50
Ozone resistance
(h to cracking)
100
50
--
--
50
100
168 120
24
Volume swell in TCP (%)
17
54
Volume swell in MEK (%)
14
62
160
Volume swell in
ASTM Oil #3 (%)
180
46

Technical
Information
Rubber
Extruded EPDM
Pharmaceutical Closures
The usefulness of blends containing

halobutyl and EPDM in tires has been
described. The addition of bromobutyl to soft
cellular
extruded
EPDM
compounds
provides excellent skin formation, while in
solid EPDM extrusions the fast cure rate of
bromobutyl can be used to advantage for
jointing extruded profiles using shot molding
techniques. (See Appendix VI)
Halobutyl rubbers are widely used in

pharmaceutical rubber products, such as
closures, which play an important part in
packaging and medical administration
systems for pharmaceutical products. They
offer the manufacturer the possibility of
meeting the stringent requirements imposed
by this sophisticated sector of the rubber
industry.
Other applications for EPDM blends with

halobutyl include tank lining to improve
adhesion and any application where a
reduction in water vapor transmission is
desirable. For example, a 50/50 blend in
place of 100 % EPDM reduces the water
vapor transmission rate nearly threefold.
(Figure 23)
In many cases, pharmaceutical closures

come into direct contact with pharmaceutical
products, either dissolved or in other forms.
Therefore they must comply with existing
standards and regulations regarding the
contact of vulcanized rubbers with
pharmaceuticals.
The
most
common
pharmaceutical
applications are listed in Table 15. Halobutyl
rubbers are generally preferred because
they provide adequate protection of sterile
pharmaceutical products against external
contamination during storage and use.
However,
there
are
many
other
requirements which vulcanized rubber
closures must meet. (Table 16)
Water Vapour
- Transmission Rate -
g/m
0
100/0
75/25
50/50
25/75
0/100
Bromobutyl X2 / EPDM Ratio
Fig. 23:
blends
Bromobutyl
X2/Buna EP T 2460
Sole Elastomer Applications

The fast cure rates of halobutyl combined
with low permeability, and chemical
inertness have been used in a variety of
applications in compounds when they are
used as the sole elastomer. Three practical
examples are:
pharmaceutical closures
tank lining
sports ball bladders
KA-FK-0230e/02/05.01
Page 26 of 46
The diversity of requirements and stringent

specifications severely restrict the choice of
compounding ingredients. Taking these
restrictions into account Harmsworth and
Dolezal have described the effects of
compounding
ingredients,
including
accelerators, on the physio-chemical
properties of halobutyl rubbers for use in
these applications.
The choice of cure system depends upon
the type of halobutyl used. Factors which
must be avoided in curing systems for
pharmaceutical applications are:
Toxicity
Odor
Blooming
Reactivity with
preparation
Extrudability by
preparation
Too low cure rate
the
pharmaceutical
the
pharmaceutical

Technical
Information
Rubber
Table 15: Applications of Bayer halobutyl
rubbers in pharmaceutical products
Table 16: Performance requirements of

vulcanized rubbers in pharmaceutical
applications
Closures for infusion containers
Non toxicity
Closures for injectable vials
High resistance to - and compatibility

with - pharmaceutical products
Closures for freeze-dried products

Lyophilisation closures
Plungers for prefilled syringes
Plungers for empty, disposable syringes
Dropper bulbs
Pipette assemblies
Good physical properties

Excellent chemical properties
Low fragmentation/coring
Good sealing properties
Good resealing after puncturing
Baby teats
Sterilisability by standard (steam) as

well
as
non-standard
(radiation)
procedures
Sealing rings
Good color retention
Closures for insulin containers
Excellent resistance to aging, vapor,

and gas transmission, water and
vegetable oils
Curable by low extraction cure systems
Examples of typical halobutyl compounds,

and the effect of zinc oxide, resin and amine
cures, are illustrated in Table 17
KA-FK-0230e/02/05.01
Page 27 of 46

Technical
Information
Rubber
.
Table 17: Effect of cure systems in pharmaceutical compounds *
Curing systems
Bayer Bromobutyl 2030
ZnO/ZDMC
ZnO/Resin
DIAK No.1
100
--
--
100
--
--
100
--
Bayer Bromobutyl X2
--
100
--
--
100
--
--
100
--
--
100
--
--
100
--
--
100
100
--
100
100
--
100
100
Whitetex, No.2
--
--
100
--
--
100
--
--
Polyethylene AC-617
Paraffin wax
Zinc oxide
--
--
0.2
0.2
0.4
--
--
--
--
--
Schenectady 1045
--
--
--
2.5
2.5
--
--
--
Schenectady 1055
--
--
--
--
--
2.5
--
--
DIAK No.1
--
--
--
--
--
--
0.5
0.5
Mooney viscosity
ML 1+4 (100 C)
66
81
82
61
78
75
67.5
86
Mooney scorch,
t5 , 125 C (min)
13.9
11.2
25
25
8.0
7.6
Cure time at 170 C, min
12
10
10
20
Hardness, Shore A,
0 sec
3 sec
50
42
53
48
52
45
53
48
53
50
56
52
47
39
50
43
Modulus at 100 % elong (MPa)
0.8
1.1
1.1
1.0
1.5
1.2
0.7
1.0
Modulus at 300 % elong (MPa)
1.5
2.0
2.2
2.2
2.7
3.6
1.3
2.2
Tensile strength, (MPa)
5.6
6.2
6.0
5.9
7.8
6.5
4.5
5.3
Ultimate elongation, (%)
960
830
890
870
820
730
980
840
Tear strength, die C, (kn/m)
20
25
25
25
27
31
18.5
24.5
2.0
1.8
0.5
1.9
1.7
0.8
0.8
0.8
Calcined clay
ZDMC
Compound properties
Chemical properties
Japanese pharmacopoeia
Reducing substances,
ml 0.01 N Na2S2O3
U.V. light absorption at 410 nm 0.003 0.006 0.008 0.002 0.005 0.004 0.004 0.005
KA-FK-0230e/02/05.01
Page 28 of 46
pH change
0.1
0.3
0.5
+0.3
+0.3
+0.4
0.5
+0.1

Technical
Information
Rubber
Tank Lining
Excellent chemical resistance combined with
curing versatility have made halobutyl
rubbers, particularly bromobutyl rubber, the
preferred rubber for chemical resistant lining
applications. They offer superior cure rates
and ease of bonding compared with regular
butyl and EPDM rubbers.
A range of low temperature cure systems
suitable for on site or factory applications
has been developed for low temperature
curing in steam, water or hot air. The
replacement of zinc oxide, used in dispersed
form for health and safety reasons, will
reduce water swell (Figure 24).
Table 18: Cure systems for chemical

plant lining
BIIR
Cure System
CIIR
Zinc oxide
5.0
5.0
5.0
Sulfur
1.0
2.0
2.0
MBTS
1.0
--
1.0
--
--
0.5
2.0
--
--
Tetrone A
--
2.5
--
TMTD
--
1.0
--
DPG
HVA-2
Vulcanization time (90 % t90)

at 145 C (min)
30-40
15
40-45
at 100 C (h)
16-24
8-12
16-24
at 80 C (h)
30-48
20-24
48
Table 19: Chemical plant lining compound *
Fig. 24: Volume swell of bromobutyl lining

formulation in water at 100 C
Typical cure systems are shown in Table 18.

High loadings of carbon black and inert
fillers, such as barytes and talc, used in low
Mooney halobutyl polymers, impart ease of
calendering for a lining compound as
illustrated in Table 19.
100
N550 black
40
Barytes
75
Platy talc
50
Paraffinic oil
10
Petrolatum
Pb3O4 (50 % dispersion)
10
Vulkacit 576
ETU
2
297
Vulcanization time - 12 h in steam at 100 C
KA-FK-0230e/02/05.01
Page 29 of 46

Technical
Information
Rubber
Sports Ball Bladders
Regular butyl rubber has been the preferred
elastomer for sports ball bladders because
its low permeability maintains air pressure.
The faster cure rates of halobutyl and good
splicing characteristics, particularly of
bromobutyl, help significantly increase
productivity. This application (Table 20) now
represents a significant proportion of the
global non-tire usage of halobutyl. (39)
When higher green strength is required,
natural rubber (25 phr) is used in blends with
halobutyl. (See Appendix II)
These examples illustrate some of the
diverse range of non-tire applications for
halobutyl used alone or in blends with other
rubbers. Both types of halobutyl are used,
but bromobutyl is preferred whenever faster
curing is desirable, and/or its higher
adhesive strength is an advantage.
KA-FK-0230e/02/05.01
Page 30 of 46
Table 20: Sports ball bladder *

Formulation (parts by weight)
Bayer Bromobutyl X2
100
Stearic acid
N327 black
50
N990 black
20
Amberol ST 149
Silene D
10
Sunpar 115
10
Indopol H-100
10
Zinc oxide
Sulfur
0.5
MBTS
1.5
TMTD
0.5
Compound viscosity
ML 1+4(100 C)
59
Mooney scorch time

(min at 125 C)
14
Cured 10 min at 166 C

Hardness, Shore A
53
11.5
560

Technical
Information
Rubber
Conclusions
While both chlorobutyl and bromobutyl will
respond to a wide range of curatives and
cure systems, bromobutyl is more versatile
in its response. Bromobutyl can be cured
with sulfur alone or peroxides (i.e. without
zinc oxide or other accelerators present) and
exhibits greater curing efficiency when zinc
oxide is used as the sole curative.
Vulcanizates having excellent resistance to
heat, ozone and compression set can be
achieved when the zinc oxide cure is
modified by the addition of thiurams plus
paraphenylene diamines, and mercaptobenzimidazole; zinc oxide in combination
with other diphenylamines act synergistically
to yield fast curing and thermally stable
crosslinks, and the vulcanizates have good
ozone resistance and compression set.
Dienophiles can be used alone or in
conjunction with peroxides or zinc oxide to
produce vulcanizates having extreme
resistance to ozone, and very low
compression set at high temperatures.
Bromobutyl is significantly superior to
chlorobutyl as regards adhesion to natural
rubber and is faster curing in most
compounds. Both polymers will vulcanize in
blends with natural or other unsaturated
rubbers.
KA-FK-0230e/02/05.01
Page 31 of 46
The major uses for these polymers have

been identified, tire inner liners being the
largest. To obtain optimum tire performance,
air and moisture permeability through the
inner liner must be minimal. The most
practical and cost effective way to achieve
this is to use inner liner compounds based
on halobutyl alone. Advantages in adhesion
and the overall balance of properties favor
bromobutyl for high performance. The
unique balance of low temperature flexibility,
high damping characteristics and cure
versatility of halobutyl rubbers offers
potential for tread compounds in blends with
general purpose rubbers. Their weather
resistance, adhesive strength, and cure
compatibility with EPDM and NR, are used
to advantage in tire sidewalls and
coverstrips. A wide variety of non-tire
applications also take advantage of the
properties of chlorobutyl and bromobutyl.

Technical
Information
Rubber
Appendix I: Test procedures
Monsanto Rheometer
ASTM D 2084-81
Permeability to air
Bayer Test. Q = Volume of gas (cc at N.T.P.)

passing, per second, through a specimen of
1 cm2 area and 1 cm thickness when the
pressure difference across the specimen is
one atmosphere.
Static peel adhesion
Test specimen - 2 cm strips died from a

press-cured laminate cured to 100 % NR
carcass stock. Specimens lined top and
bottom with rubberized nylon fabric.
NR Carcass Formulation
SMR-5 CV
N550
Circosol 4240
Zinc oxide
Stearic acid
Santocure NS
Sulfur
KA-FK-0230e/02/05.01
Page 32 of 46
100.0
30.0
5.0
5.0
1.5
0.5
2.4
Monsanto fatigue to failure
Cam 24, not adjusted for set. Test results

reported as the geometric mean of 12
specimens.
Hardness
ASTM D 2240-85
Compression set
ASTM D 395-84
Stress strain
ASTM D 412-83
Mooney viscosity
ASTM D 1646
Abrasion resistance
Bayer Procedure 01.06.442.76

DIN 53 516 Jan. 77
Tel Tak
Mill shrinkage
ASTM D 1917-87
Garvey Die extrusion
ASTM D 2230-83
Ozone resistance (static)
ASTM D 1149
Ozone resistance (dynamic)

1.27 cm (0.5 in) wide specimens cut from test
sheets, lightly buffed and extended across
the grain. OREC Ozonator, 50 pphm O3 ,
60 C/140 F, 0-25 % extension, 32 cpm,
168 hours. Rating : 0 - zero cracks; 1 - visible
cracks under 10 X magnification; 2 - visible
cracks, naked eye; 3 - cracks easily visible;
4 - severe cracking, sample intact;
5 - separation.

Technical
Information
Rubber
Appendix I (Contd)
KA-FK-0230e/02/05.01
Page 33 of 46
Hot air aging
ASTM D 573-81.
Fluid aging
ASTM D 471-79.
Spice strength
(inner tubes)
Tensile strength measured across the splice

of an inner tube and calculated as a
percentage of the tensile strength of the inner
tube.
Dynamic splice fatigue

(inner tubes)
Determined as kc to failure using a standard

tensile dumbbell specimen taken across the
splice.
Tensile set
ASTM D 412-68

Technical
Information
Rubber
Appendix II: Formulations *
Solvent resistant rollers
Bayer Bromobutyl X2
Krynac 34.50
N550 black
N990 black
DOP
Paraplex G-62
Paraffin wax
Petrolatum
Zinc oxide
MC sulfur
DPTT
Vulkanox BKF
Curing Envelopes
100 50
--50 100
50
50
50
30
30
30
5
--5
5
5
2
2
2
1.5 1.5 1.5
5
5
5
1.25 1.25 1.25
1.0 1.0 1.0
1.0 1.0 1.0
Sports ball bladder

Bayer Bromobutyl X2
Natural rubber
MBTS
N660 black
Precipitated calcium carbonate
Paraffinic oil
Stearic acid
TMTD
Zinc oxide
Sulfur
75
25
0.5
50
30
10
1
1
3
0.3
Mounts
Natural rubber
Bayer Bromobutyl X2
Stearic acid
Zinc oxide
N330 black
Naphthenic oil
MC sulfur
TMTD
CBS
60.0
40.0
1.0
3.0
30.0
15.0
0.2
0.5
3.0
Inner Liner
Halobutyl
Natural rubber
N660 black
Paraffinic oil
Stearic acid
Zinc oxide
Sulfur
Accelerator
KA-FK-0230e/02/05.01
Page 34 of 46
100.0 to 40.0
40.0 to 60.0
60.0
7.0
1.0
3.0
0.5
Varied

Stearic acid
N660 black
ADPA 86
MBI
Maglite D (MgO)
Paraffinic oil
Zinc oxide
100.0
1.0
55.0
1.0
1.0
0.4
12.0
5.0
Test recipe for cure systems

Halobutyl
Stearic acid
N550 black
Naphthenic oil
Zinc oxide
Sulfur
Accelerators
100.0
1.0
55.0
10.0
0.0 to 5.0
0.0 to 0.5
Varied

Technical
Information
Rubber
Appendix III: Effect of cure systems in chlorobutyl on compression set, and heat and
ozone resistance
Test Recipe *(Appendix III)
100
Stearic acid
N550 black
55
Paraffinic oil
10
Zinc oxide
Compound Ref. 84-EV
20
21
22
23
Maglite D
Aminox
MBI
0.5
0.5
HVA #2
1.6
N-phenyl maleimide
2.0
Compound viscosity
ML 1+4 (100 C)
73
71
69
66
28.8
8.7
14
12.2
15
62.5
3.6
14.2
14.5
48
1.6
6.0
15
36
2.0
7.0
13.5
54
1.6
6.8
Cure, min at 166 C
14
Hardness, Shore A
63
54
52
60

(MPa)
3.3
1.8
1.4
2.4

(MPa)
10.0
7.9
6.5
8.3
12.0
13.1
11.8
11.9
Ultimate elongation
400
540
510
480
Compression set (%)

70 h at 100 C
70 h at 150 C
18
38
12
42
22
57
16
31
TMTD
Scorch time
(min at 125C)
Monsanto rheometer at
166 C (3 arc, 100 cpm,
0 preheat)
Min. torque
Max. torque
t2 (min)
tc 90 (min)
KA-FK-0230e/02/05.01
Page 35 of 46

Technical
Information
Rubber
Appendix III (Contd)

Ozone resistance 50 pphm at 40 C
Static, 168 h, 20 % strain
Dynamic, 168 h, 0-25 % strain
Hardness (pts)
+5
-5
-4
+1
+39
-46
-30
-4
-9
-88
-86
-53
-42
-26
-22
-46
TE (f)
0.52
0.09
0.11
0.25
Hardness (pts)
+2
-6
-7
+1
-3
-39
-44
-17
-26
-73
-77
-58
-35
-37
-37
-38
TE (f)
0.48
0.17
0.14
0.26
Hardness (pts)
-1
-9
-9
-27
-57
-57
-71
-52
-94
-95
-86
-42
-26
-20
-21
TE (f)
0.27
0.04
0.04
0.08
Hardness (pts)
-6
-16
-16
-8
-52
-72
-64
-54
-73
-86
-82
-73
-40
-11
+12
-23
TE (f)
0.15
0.12
0.19
0.21
Aged in air, 168 h/150 C - change
KA-FK-0230e/02/05.01
Page 36 of 46

Technical
Information
Rubber
Appendix IV: Effect of cure systems in bromobutyl on compression set, and heat and
ozone resistance
Test Recipe *(Appendix IV)
Bayer Bromobutyl X2
100
Stearic acid
N550 black
55
Paraffinic oil
10
Zinc oxide
Compound Ref. 84-EV
20
21
22
23
Maglite D
Aminox
MBI
0.3
0.3
HVA #2
1.6
N-phenyl maleimide
2.0
Compound viscosity
ML 1+4 (100 C)
74
70
72
66
Scorch time
(min at 125 C)
11.6
30
24.4
17
62.5
1.8
5.6
14
43
2.0
4.8
13
35.5
4.0
7.8
12.5
54
3.2
16
Cure, min at 166 C
16
Hardness, Shore A
63
54
53
65

(MPa)
3.0
1.7
1.3
2.3

(MPa)
8.3
7.9
7.2
8.4
10.4
12.5
11.0
11.4
440
500
440
480
Compression set (%)

70 h at 100 C
70 h at 150 C
19
45
44
68
15
34
TMTD
Monsanto rheometer at
166 C (3 arc, 100 cpm,
0 preheat)
Min. torque
Max. torque
t2 (min)
tc 90 (min)
KA-FK-0230e/02/05.01
Page 37 of 46

Technical
Information
Rubber
Appendix IV (Contd)
Ozone resistance - 50 pphm at 40 C
Dynamic, 168 h, 0-25 % strain
3/4
Hardness (pts)
+5
+5
+7
+2
+37
+29
+62
+52
-3
-59
-53
-12
-41
-40
-32
-37
TE (f)
0.57
0.24
0.32
0.55
Hardness (pts)
+1
+1
+2
+1
Modulus at 100% elongation
+13
-29
-15
+13
+12
-69
-69
-33
-39
-20
-9
-39
TE (f)
0.54
0.25
0.28
0.40
-2
-1
NIL
-3
+43
-51
-15
-17
-15
-92
-88
-75
-45
-34
-16
-39
TE (f)
0.46
0.05
0.1
0.15
Hardness (pts)
-5
-5
-5
-1
-30
-65
-55
-22
-53
-85
-89
-61
-32
+20
+36
-37
TE (f)
0.32
0.17
0.15
0.24

Hardness (pts)
KA-FK-0230e/02/05.01
Page 38 of 46

Technical
Information
Rubber
Appendix V: Inner tube compounds *
Comparison of bromobutyl with butyl and chlorobutyl
Butyl
Bromobutyl
Chlorobutyl
100.0
Bayer Bromobutyl X2
100.0
100.0
Stearic acid
1.0
1.0
1.0
N650 black
70.0
70.0
70.0
Circo light oil
25.0
25.0
25.0
Zinc oxide
5.0
3.0
5.0
MBT
0.5
MBTS
0.5
0.5
TMTD
1.0
ZMDC
0.1
0.7
Sulfur
1.5
0.5
0.5
Monsanto rheometer
Optimum cure time at 166 C
tc 90 (min)
Minimum cure time at 166 C
tc 65 (min)
16
7.75
5.5
Scorch time (min at 125 C)
20.5
15.5
Hardness, Shore A
50
43
46
1.2
1.0
1.1
5.5
6.0
7.3
9.2
10.6
9.7
560
520
400
Tensile set (%)
10
Hardness (pts)
+17
+20
+22
-56
-17
-34
-57
-45
Bayer Butyl 301
Cured Properties (Cured to tc 90)
Aged in air oven, 240 h at 125 C

Change in properties
KA-FK-0230e/02/05.01
Page 39 of 46

Technical
Information
Rubber
Appendix V (Contd)
Final property values

Hardness, Shore A
67
63
68
4.0
-17
370
225
220
Unaged
85
88
83
Aged - 48 h at 121 C
68
74
74
Unaged
10
59
42
Aged - 48 h at 121 C
27
16
Splice properties
Tensile (1 % of tube strength)
Dynamic fatigue
(kc to failure, 0-100 % extension)
KA-FK-0230e/02/05.01
Page 40 of 46

Technical
Information
Rubber
Appendix VI: Supersoft CV sponge weatherstrip * - salt bath process

Buna EP T 4969
160.0
20.0
N650 black
100.0
Whiting
70.0
Paraffinic oil
60.0
Zinc oxide
5.0
Stearic acid
1.0
Desical P
5.0
TE 80
2.0
Celogen AZ 130
5.0
Carboxwax 4000
1.0
TMTD
0.8
MBT
1.5
TEDC
0.8
DPTT
0.8
Sulfur
2.0
Total weight
434.9
Specific gravity (unexpanded)
1.207
Expanded density (g/cc)/ (lb/cu.ft)
KA-FK-0230e/02/05.01
Page 41 of 46
0.56/ 35.1
Water absorption, 70h at 20 C
1.7 %
Cure time at 205 C
3 min

Technical
Information
Rubber
ZnO
ZnO + TMTD
ZnO + TCBQ
ZnO + ZDC
ZnO + MBRS
ZnO + TMTD +
ADPA + MBI
Zn + ADPA
ZnO + MDB
Peroxide
Peroxide + HVA
KA-FK-0230e/02/05.01
Page 42 of 46
Miscellaneous
Low extractables
Also for blends
Also for blends
Blends with EPR & EDPM

Blends with NBR, EPR and
EPFM
HVA
ZnO + Phenolic
PbO + Phenolic
PbO + TCBQ
ZnO + DIAK
Excellent
Cure Rate
Scorch Safety
Water
Resistance
Adhesion
Flex
Resistance
Ozone
Resistance
Compression
Set
Cure Systems
Heat
Resistance
Appendix VII: Characteristics of cure systems in halobutyl
Fast cure - high modulus

Low water absorption
Water resistance
Pharmaceuticals
Very Good
Good
Good
Blank - Acceptable

Technical
Information
Rubber
Appendix VIII: Effect of blending halobutyl with natural rubber
Test Recipe *(Appendix VIII)
Halobutyl/NR
100.0
N660 black
60.0
Paraffinic oil
7.0
Pentalyn A
4.0
Stearic acid
1.0
Zinc oxide
3.0
MBTS
1.25
Sulfur
0.5
Halobutyl (phr)
100
80
60
40
BIIR
CIIR
BIIR
CIIR
BIIR
CIIR
BIIR
CIIR
Modulus at 300 % (MPa)
4.2
3.7
5.7
5.1
7.1
5.7
8.9
4.3
9.3
9.9
10.9
10.7
12.8
10.3
14.7
9.7
740
770
620
620
560
560
490
580
Modulus at 300 % (MPa)
6.8
5.5
7.6
7.9
8.4
7.7
6.7
3.6
10.0
10.9
9.8
11.0
9.3
9.2
8.8
5.8
550
640
420
465
320
365
370
475
Permeability to air, 50 psi at

65 C (Qx108)
2.9
2.9
5.4
5.7
9.2
7.5
13.8
13.2
to self (kNm)
16.8
4.4
14.7
4.7
15.2
9.1
15.4
5.2
to NR (kNm)
7.5
1.3
6.2
1.3
14.7
1.9
20.8
2.9
61.8
72.7
23.6
3.9
0.3
0.1
0.0
0.0
Unaged
Aged in air, 168 h at

100 C
Adhesion at 100 C
Flex fatigue, air aged

168 h at 120 C
Cam #24 (kcy)
KA-FK-0230e/02/05.01
Page 43 of 46

Technical
Information
Rubber
Appendix IX: Effect of cure systems on BIIR and CIIR
Test Recipe *(Appendix IX)
Halobutyl
100.0
N660 black
60.0
Paraffinic oil
7.0
Stearic acid
1.0
Resin (Pentalyn A)
4.0
Cure system
varied
ZnO
Sulfur
3.0 ZnO
0.5 Sulfur
1.25 Vultac
3.0 ZnO
0.5 Sulfur
1.0 TMTD
3.0
0.5
1.0
CIIR
BIIR
CIIR
BIIR
CIIR
BIIR
CIIR
BIIR
Mooney viscosity
ML 1+4 (100 C)
60
60
63
60
67
58
68
55
Mooney scorch
t5 at 125 C (min)
10
13.4
15.7
28
12.9
9.0
10.8
Monsanto rheometer
(3 arc, 166 C)
MH (dNm)
ML (dNm)
tc90 (min)
39.2
11.9
10.2
37.8
11.2
7.0
31.8
11.2
17.5
28.2
9.0
8.8
51.7
12.3
6.6
42.8
9.8
7.2
5.5
12.3
4.1
42.8
10.4
3.7
Cured at 166 C (min)
10
18
Modulus at 100 %
elongation (MPa)
1.2
1.6
1.0
1.3
1.7
1.9
1.7
1.3
Modulus at 300 %
elongation (MPa)
5.6
6.6
3.7
4.2
6.8
7.5
6.1
4.6
10.6
11.2
9.9
9.3
10.7
11.5
10.6
10.1
Ultimate elongation
(%)
560
550
770
740
550
560
620
700
Hardness, Shore A
51
60
52
62
56
60
57
53
Compound
Properties
KA-FK-0230e/02/05.01
Page 44 of 46
3.0 ZnO
0.5 Sulfur
MBTS

Technical
Information
Rubber
Appendix IX (Contd)
Aged 168 h at 100 C

Modulus at 100 %
elongation (MPa)
1.6
2.6
1.4
2.2
2.2
3.0
2.2
2.2
Modulus at 300 %
elongation (MPa)
6.6
8.6
5.5
6.8
8.2
9.2
7.5
6.6
11.5
10.7
10.9
10.0
11.3
11.0
10.5
9.5
Ultimate elongation
(%)
530
430
640
550
475
420
390
530
Hardness, Shore A
54
66
57
65
58
65
62
66
To self (kNm)
2.7
13.3
4.4
16.8
7.6
17.2
2.4
11.1
To NR (kNm)
1.2
14.8
1.3
10.3
2.0
6.2
1.0
9.8
26
16.2
72
61.8
12.3
13.5
19.9
12.8
Adhesion
Monsanto flex
Aged 168 h/102 C
Cam 24 (Kcy)
Registered Trademarks of Bayer AG:

Buna
Krynac
Vulkacit
Vulkanox
KA-FK-0230e/02/05.01
Page 45 of 46
Bibliography:
(1) Dawson, T.R., Shidrowitz, P., RAPRA
1937.
(2) Bartovics, A., (Firestone), U.S. Patent
2,537,641 (1951)
(3) DIanni et al, Ind. Eng. Chem. 38, 117181 (1946)
(4) Bloomfield, G.F.J., J. Chem. Soc.,
1943, 289-96.
(5) Davis & Blake, The Chemistry &
Technology of Rubber, Reinhold 1937.
(6) Whitby, Synthetic Rubber, John Wiley &
Sons, 1954.
(7) Morrissey, R.T., Ind. Chem., 47, 1582,
1955.
(8) Baldwin, F.P., Buckley, D.J., Kuntz, I.,

Robinson, S. B., Rubber & Plastics
Age, 500, 1961.
(9) Walker, J., Jones, R.H., Feniak, G.,
Revue General des Caoutchoucs et
Plastiques, 50, 565, 1973
(10) Poutsma, M.L., J. Am. Chem. Soc., 87,
2172 (1965)
(11) Vukov, R. Rubber Chem. and Tech.,
57, 275, 283, 1984.
(12) Feniak, G., Robinson, K.J., Walker, J.,
Int. Rubber Con., Prague, Czechoslovakia,
1973.

Technical
Information
Rubber
(13) Vukov, R., Zinc Oxide Crosslinking
Chemistry of Halobutyl - A Model
Compound Approach, ACS Rubber
Div., Denver, Colorado, Oct. 1984.
(14) Baldwin, F.P., et al, Rubber & Plastics
Age, 42, 500, 1961.
(15) Vukov, R., Wilson, G.J., Cross Linking
Efficiency of some Halobutyl Cross
Linking Reactions, ACS Rubber Div.,
Denver, Colorado, Oct. 1984.
(16) Loan, L.D., Journal of Polymer Science,
A22127, (1964).
(17) Walker, J., Dunn, J.R., Robinson, K.J.,
Int. Rubber Conf., Tokyo, Japan, 1979.
(18) Kovacic, P., Hein, R.W., Rubber Chem.
& Tech., Vol. 35, p.528, 62.
(19) Wilson, G.J., Vukov, R., ACS Rubber
Div., Denver, Oct. 1984.
(20) Edwards, D.C., ACS Rubber Div., New
York, April 1985.
(21) Timar, J., Edwards, W.S., ACS Rubber
Div., Boston, Oct. 1978.
(22) Kresge, E.N., Journal of Applied Sci.,
39, 37-57, 1984.
(23) Blackshaw, G.C., Kristensen, I., ACS
Rubber Div., May 1974.
(24) Zapp, R.L., Rubber Chem. & Tech., 46,
251, 1973.
(25) Bauer, R. F., Dudley, E. A., Rubber
Chem. & Tech., 50, 35, 1977.
(26) Walker, J., Horne, S.E., Int. Synthetic

Rubber Producers, San Francisco, May
1985.
(27) Von Hellens, C.W., ACS Rubber Div.,
Indianapolis, May 1984.
(28) Walker, J., Hopkins, W., Jones, R.H.,
IRC, Kyoto, Japan, 1985.
(29) Herzlich, H., et al, ACS Rubber Div.,
Miami Beach, April 1971.
(30) Chang, L.Y., Shackleton, J.S., ACS
Rubber Div., 1982.
(31) Schuring, D.J., Rubber Chem. & Tech.,
153, (3), 600, Aug. 1980.
(32) Tyurina, V.S., Shuarts, A.G., Int. Pol.
Science & Tech., 3, (1), K76/01/32,
1976.
(33) Pat., 4,323,485, Yokohama, April 1982.
(34) Pat., 4,321,168, March 1982.
(35) Briggs, G.J., Wei, J.K., Plastics &
Rubber Processing & Appl., 145-150,
1982.
(36) Hess, W.M., Chirico, V.E., Rubber
Chem. Tech., 501, 1977, 301.
(37) Ritchie, K., Weir, R.J., ACS Rubber
Div., New Orleans, Oct. 1975.
(38) Japanese Pat., Ishikawa, JP 31659,
1978, U.S. Pat., 4,177,337, 1979, U.S.
Pat. 4,146,689, 1979.
Kumbhani, K.J., Edwards, S., Polysar
Limited, Non-Tire Applications of
Bromobutyl.
Author(s):
Hopkins
Walker
Sumner (revised August 2000)
The above formulation is intended solely as a guide for our business partners and others interested in our products. As the conditions of use and
application of the suggested formulation are beyond our control, it is imperative that it be tested to determine, to your satisfaction, whether it is suitable for
your intended use(s) and application(s). This application-specific analysis at least must include testing to determine suitability from a technical, as well as
health, safety and environmental standpoints. Further, although the ingredients, quantities thereof and properties of compounds or finished goods
mentioned herein reflect our recommendation at the time of publication, this guide may not be subject to continuous review and/or updating, and you agree
that use is undertaken at your sole risk. All information is given without warranty or guarantee, and it is expressly understood and agreed that you assume,
and hereby expressly release us from, all liability, in tort, contract or otherwise, incurred in connection with the use of this guide.
This information and our technical advice - whether verbal, in writing or by way of trials - are given in good faith but without warranty, and this also applies
where proprietary rights of third parties are involved. Our advice does not release you from the obligation to check its validity and to test our products as to
their suitability for the intended processes and uses. The application, use and processing of our products and the products manufactured by you on the
basis of our technical advice are beyond our control and, therefore, entirely your own responsibility. Our products are sold in accordance with the current
version of our General Conditions of Sale and Delivery.
__________________________________________________________________________________________________________________________
KA-FK-0230e/02/05.01
Page 46 of 46
Bayer AG, D-51368 Leverkusen

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