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CURRENT STATUS OF SULPHUR

VULCANIZATION AND DEVULCANIZATION
CHEMISTRY: PROCESS OF VULCANIZATION

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Rubber Science, 28(1): 82-121, 2015
82 REVIEW ARTICLE

CURRENT STATUS OF SULPHUR VULCANIZATION

AND DEVULCANIZATION CHEMISTRY:
PROCESS OF VULCANIZATION

Anu Mary Joseph, Benny George, K. N. Madhusoodanan and Rosamma Alex

Rubber Research Institute of India, Kottayam-686 009, Kerala, India
Received: 19 August 2014 Accepted: 21 January 2015

Joseph, A.M., George, B., Madhusoodanan, K. N. and Alex, R. (2015). Current status of sulphur vulcanization
and devulcanization chemistry: Process of vulcanization. Rubber Science, 28(1): 82-121.

The article presents the first part of the review on the current status of sulphur vulcanization and
devulcanization chemistry. The purpose of presenting a review of the chemistry of sulphur vulcanization
and devulcanization was to develop a devulcanization process and also to address the issue of very low
scorch during revulcanization.

Accelerated sulphur vulcanization is a very complex chemical process. Although consensus on various
reaction mechanisms are yet to reach, there is widespread agreement about three basic steps involved.
These are: (i) accelerator chemistry in which the reactions of accelerator, activator and sulphur leading to
the formation of an active sulphurating agent (ii) crosslinking chemistry which involves the reactions of the
active sulphurating agent leading to the formation of crosslink precursors and subsequent reactions of
these precursors to form polysulphidic crosslinks and (iii) postcrosslinking chemistry leading to chain
shortening and degradation of the polysulphidic crosslinks and other main chain modifications. The current
understanding of the chemical reactions and the underlying mechanism involved in these basic steps, both
in accelerator, activator and sulphur as well as accelerator- cum- sulphur donor and activator cure systems
are reviewed. Reaction mechanisms leading to scorch delay inherent to sulphenamide accelerators and
those involved by the addition of prevulcanization inhibitors are also presented.

Keywords: Accelerator chemistry, Crosslinking chemistry, Postcrosslinking chemistry, Sulphur

vulcanization

INTRODUCTION West Indies. The next landmark was the

The life history of natural rubber Spanish discovery of the use of latex for the
(Heideman, 2004; www.britannica.com.; water proofing of leather and fabrics in 1615.
Aprem, et al., 2005) can be dated back to 11 The rubber industry in Europe really started
June 1496, the day on which Christopher with Charles Macintosh in 1818, when he
Columbus returned from his second voyage, started exploiting the naphtha-based rubber
bringing back the first rubber balls from the solution as a water proofing layer between

Correspondence: Benny George (Email: georgebenni@hotmail.com)

CHEMISTRY OF VULCANIZATION 83

two fabrics. Two years later, in 1820, Thomas antioxidants, antiozonants, fillers and
Hancock discovered mastication. The reinforcing agents such as carbon black.
contributions of Sir Henry Wickham and Major effects of vulcanization (Bateman
Henry Ridley in rubber plantation also et al.,1963; Coran,1978; 2003) on use related
added on to the vast development and fast properties include increased tear strength,
growth of rubber industry. The final tensile strength, elastic recovery, fatigue life,
landmark in the early history of rubber was toughness, low hysteresis and compression
the discovery of vulcanization by Charles set, etc. The timeline of various
Goodyear in 1839 which revolutionized the developmental stages in the history of
use and applications of rubber, and changed sulphur vulcanization is given in Figure 1.
the face of the industrial world. Although the primary structural
Understanding the chemistry of requirement for vulcanization is covalent
vulcanization is important to develop a crosslinking of the rubber chains, other
devulcanization process and further modifications can occur at sites distant from
vulcanization of devulcanized rubber. This the crosslinks. In addition, there is generally
review primarily focuses on the chemical present extra network material such as ZnO,
aspects of vulcanization and the various uncombined sulphur present in the original
devulcanization methods. The review also mix, zinc soaps, zinc sulphide, zinc salts of
presents a picture of different stages of
vulcanization, revulcanization of
devulcanized rubber and a general outlook
on the recycling and reclaiming methods.
Thus, this review remains relevant as it
handles both the vulcanization and
devulcanization processes together.

VULCANIZATION
Vulcanization, named after Vulcan -
Roman god of fire- is the chemical process
of interlinking of rubber molecules to
change the predominantly plastic/viscous
properties to elastic properties. The
vulcanization system is mainly a collection Fig. 1. Timeline of various developmental stages in
of additives required to transform the the history of vulcanization of rubber
essentially linear polymer molecules into a
three dimensional network by the insertion
accelerators resulting from the vulcanization
of crosslinks (Rodger, 1979). Sulphur
reaction etc. Structural modifications of the
vulcanization is usually carried out
main chain which can occur during
industrially by heating the mechanically
plasticized rubber with sulphur and vulcanization process are (Bateman et al.,
auxiliary vulcanizing agents such as organic 1963).
accelerators, ZnO, long chain fatty acids or (i) Formation of pendent cyclic sulphides
the zinc soaps of these acids (activators). based on thiacyclopentane or
Additional ingredients may include thiacyclohexane rings
84 JOSEPH et al.

(ii) Changes in the olefinic pattern of the been chosen to designate the time required
original rubber after vulcanization has started until a
(iii) Scission of main chains satisfactory technical cure is reached. After
attaining the maximum torque, it may
Accelerators increase further (marching), or decrease
(reversion), or levels off. Stable cures are
Accelerator, in the rubber industry, is characterized by flat cure curves in which
added with a curing agent or sulphur to physical properties tend to reach a plateau
increase the rate of vulcanization. The as vulcanization progresses (Gehman, 1981).
8-membered ring and shorter chain
structure of sulphur molecule is important The expected qualities of a good
accelerator can be listed as
in vulcanization process. The process of
activation of sulphur occurs at high z It should give flat cure
temperatures and can be speeded up by z Should provide scorch safety
accelerators (Kerbs, 1957). z Should give good storage properties for
The most important characteristics of the uncured compound
accelerators are scorch time, cure time and z Should give good physical properties
vulcanization time (Garvey et al., 1953) are to the vulcanizates
being illustrated in Figure 2. The scorch time
Accelerators (Dinsmore and Vogt, 1928)
is the time available at a given temperature
generally contain sulphur and nitrogen like
before the stock begins to vulcanize where derivatives of benzothiazole and
much of the accelerator chemistry is thiocarbanilides such as sulfenamides
involved (Hoover, 1999). Cure time is the (Craine and Raban, 1989; Fukuda and
time a stock must be heated in a press at a Tsurugi, 1962; Scheele and Kerrutt, 1962),
given temperature until it reaches a thiazoles (Lorenz and Echte, 1957; Naunton
technically correct cure (optimum cure et al., 1934), thiuram sulfides (Bandyopadhyay
time). Vulcanization time is the term that has and Banerjee, 1979; Campbell, 1971; Guiliani

Fig. 2. A Typical rheograph showing different stages of cure

SULPHUR VULCANIZATION CHEMISTRY 85

and McGill, 1995; Langenbeck and Rhlem, by sulfenamides and thiazole derivatives.
1935), dithocarbamates (Cummings and Secondary accelerators are used as small
Simmons, 1928) etc. Later various other addition to primary accelerators to boost the
(Dogadkin et al., 1958) secondary speed and state of cure during vulcanization.
accelerators and specific accelerators like Of the secondary or ultra accelerators the
guanidines, xanthates (Palaty and Joseph, main categories are the thiurams and
2000; 2004; 2011; Waddel, 2007) and the dithiocarbamates. Thiurams are very fast
morpholines also emerged. accelerators suitable also for vulcanization
According to vulcanization rate, there of low unsaturated rubbers and are used
are two major classes of vulcanization also as sulphur donors. Dithiocarbamates
accelerators viz. primary accelerators or fast are ultra fast accelerators giving very fast
accelerators (semi-ultra) and secondary vulcanization practically without induction
accelerators or ultra accelerators. Primary period. In addition to these, guanidines form
accelerators are characterized by very good a class of slow (medium) accelerators with
scorch time and fast curing in the main short induction period and broad
vulcanization phase. Of the primary vulcanization plateau (en.wikipedia.org;
accelerators the major group is formed https://www.tut.fi/.htm). Classification of

Table 1. Classification and properties of accelerators

86 JOSEPH et al.
SULPHUR VULCANIZATION CHEMISTRY 87

accelerators based on structure and their molecular rubber chains (Amstrong et al.,
important features are given in Table. 1. 1944; Coran, 1964; 2003; Dogadkin and
Beniska, 1958; Heideman et al., 2004) and can
Activators there by change physical properties such as
The ability of metal oxides in improving hysteresis, abrasion resistance, etc. and
the efficiency of sulphur based cure systems dynamic properties. Zinc oxide is claimed to
has been discovered early in the history of benefit aged properties in certain
vulcanization, and the most useful metal formulations by acting as an acid scavenger
oxide applied in the “activating” role is zinc (Henning, 2007; Stiehler and Wakelin, 1948).
oxide. Zinc stearate, the most popular Zinc complexes such as zinc dimethyldithio
activator used today is necessarily formed carbamate (ZDMC) appeared to be
in-situ for optimum effect. The fundamental homogeneous catalysts (Nieuwenhuizen
role of vulcanization activators does not lie et al., 1998) for the processes of crosslink
in their influence on the kinetics of the formation (Geyser and McGill, 1996; Layer,
addition of sulphur to rubber, but rather in 1992), crosslink shortening (Bateman et al.,
their influence on the nature of 1963; Layer, 1992; Milligan, 1966) and
vulcanization structures formed and on crosslink breaking (Mc Sweeney and
changes in them in the course of Morrison, 1983; Morrison and Porter, 1984).
vulcanization (Henning, 2008; Kruger and The role of metal oxides in the process of
McGill, 1991; Morrison, 1984; Morrison and rubber vulcanization by thiuram disulphide
Porter, 1984). Vulcanization systems that lies mainly in the binding of dithiocarbamic
contain zinc oxide (ZnO) lead to very high acid (DMDCA) (Craig, 1956) whose
crosslink densities as ZnO assist the removal decomposition products accelerate oxidative
of pendent groups during cross-linking degradation of the vulcanizate network.
(Gradwell and McGill, 1996) thereby Fatty acids or zinc salts of fatty acids
increasing the fraction of the sulphur used are generally regarded as indispensible
for crosslink formation in the vulcanizate activators in conjunction with ZnO to
(Chapman and Porter, 1988) influencing the solubilize the ZnO and the accelerator to
heat stability and reversion effects of the form the actual catalyst (Dogadkin and
vulcanizates. Beniska, 1958; Feldstein et al., 1958). The role
ZnO has a significant effect on the of activators also depends on the type of
number and nature of crosslinks between the rubber, vulcanization accelerator and active
88 JOSEPH et al.

filler used (Feldstein et al., 1958). ZnO has Despite the beneficial role of zinc in the
the greater influence on the degree, while chemistry of sulphur vulcanization, there
stearic acid has the greater influence on the are questions regarding the impact of heavy
rate of the crosslinking reaction (Dogadkin metals on human health and ecological
and Beniska, 1958). systems when they are released into the
environment. Technologies considered for
As shown in Figure 3, radical mechanism
reducing zinc levels include zinc oxide
controls the formation of crosslinks from
loading rationalization by the use of
precursors in the absence of ZnO where as
alternative zinc complexes, activators based
the presence of ZnO stabilizes sulphur on other metal centers, application of
bonds through zinc chelation thereby multifunctional additives, etc. (Heideman
changing the most likely breakable bond et al., 2004; 2005; 2006; Henning, 2007;
(Ghosh et al., 2003). Such bond scission leads Versloot et al., 1994). The practical
to crosslink byproducts (accelerator applications of these innovations are yet to
polysulphides) that can further crosslink hit the scene in full swing as these strategies
and thus enhance the rate and efficiency of have not proven their merits beyond doubts.
vulcanization. On the other hand in the
absence of zinc species the bond cleavage ACCELERATED SULPHUR
during the conversion of a crosslink VULCANIZATION
precursor to a crosslink may result in
accelerator monosulphides which cannot Outline of basic steps
contribute to further crosslinking. The effect Accelerated sulphur vulcanization is a
of zinc ions on the efficiency of crosslink multidisciplinary field involving the aspects
formation is being depicted in Figure 3. of radical, ionic and organosulphur

Fig. 3. Effect of zinc ions in sulphur vulcanization

SULPHUR VULCANIZATION CHEMISTRY 89

Table 2. Apparent polar or free radical character of the vulcanization reaction as observed in SBR
Mechanism Curing method
Polar Unaccelerated sulphur, guanidine accelerated sulphur
Predominantly polar Thiuram disulphide accelerated-sulphur, dithiocarbamate accelerated-
sulphur, thiazole accelerated-sulphur,
Mixed polar and radical Thiazole- disulphide accelerated-sulphur, sulphenamide accelerated-sulphur
Inconclusive Thiuram disulphide cure
Free radical Peroxide cure, radiation cure

chemistry, reactions in heterogeneous phase,

homogeneous catalysis as well as co-
ordination chemistry (Nieuwenhuizen et al.,
1998). There has been considerable debate
concerning the mechanism of accelerated
sulphur vulcanization for quite a long time. Fig. 4. The reactive allylic carbon atoms (C and C )
Many researchers (Bevilacqua, 1959; Coran, in NR
4 5

1964; 2003; Scheele et al., 1956; Dogadkin and

Shershnev, 1960) advanced free radical
mechanisms for the accelerated sulphur sulphur as a crosslinking agent by
vulcanization of unsaturated elastomers. minimizing wastefully combined
However, Bateman et al., 1963 and Porter, sulphur by decreasing length of sulphur
1967 suggested a polar mechanism for chains in crosslinks, cyclic monosulphide
accelerated sulphur vulcanization. It is very formation and vicinal crosslinks.
difficult to generalize the discussion on The reactive sites—“cure sites”—during
accelerated sulphur vulcanization as there the process of vulcanization are allylic
are many unanswered questions and many hydrogen atoms lying adjacent to carbon-
reasons to believe that both free radical and carbon double bonds. In natural rubber
ionic reactions take place at different stages of (NR), the hydrogen atoms at positions 4 and
the overall vulcanization reaction depending 5 are most preferred and are being shown
on the vulcanizing system (Wolfe,1968, in Figure 4.
Shelton and McDonel, 1960). The conclusions During sulphur vulcanization, some of
obtained by the investigations to establish the these C-H bonds are replaced by chains of
free radical or polar nature of curing reactions sulphur atoms (one to eight) that link with
in styrene butadiene rubber (SBR) rubber is a cure site of another polymer chain. The
given in Table 2. sulphuration of NR by accelerated sulphur
In addition to the decisive role it plays systems or by sulphur donors normally
in the nature of crosslinking reactions the occurs exclusively by α-methylenic or
two major chemical functions of organic α-methylic substitution to give the crosslinked
accelerators when used in conjunction with structures represented in Figure 5.
ZnO and fatty acids are (Bateman et al., 1963) The initially formed crosslinks may
i) to increase the rate of sulphur undergo an allylic shift from the initial 4 and
combination with rubber and 5 positions and other configurations appear
ii) to increase the efficiency of utilization of in the crosslinked network during
90 JOSEPH et al.

Fig. 5. Major Types of crosslinks formed at allylic sites of NR

Fig. 6. New structures formed in the crosslinked network by shift of allylic crosslinks

vulcanization and post vulcanization time which involves rearrangement of the

(Porter, 1967) which is being outlined in polysulphidic crosslinks to the more stable
Figure 6. mono and di-sulphidic crosslinks, and
Disappearance of the crosslinks of the crosslink decomposition/degradation where,
disulphides and polysulphide type may polysulphidic crosslinks degrades to
elastically ineffective cyclic sulphides,
occur with the formation of conjugated
inactive pendant groups or other main-chain
trienes (Blow, 1982) simultaneously as seen
modifications. Thus, the main structures
in Figure 7.
formed in sulphur vulcanized natural rubber
The crosslinks that are formed initially are monosulphidic, disulphidic,
are usually polysulphides with high sulfur polysulphidic and vicinal crosslinks, pendent
rank, which subsequently can undergo two side groups, cyclic sulphides, conjugated
competing reactions crosslink desulphuration, unsaturations, etc. (Porter, 1967).

Fig. 7. Formation of conjugated structures by crosslink rearrangements

SULPHUR VULCANIZATION CHEMISTRY 91

Despite the uncertainities regarding Let us see in detail, the various steps
many processes taking place during the given in the generally accepted outline of
sulphur vulcanization, the widely accepted accelerated sulphur vulcanization of natural
basic steps during the vulcanization rubber as given in Figure 8.
reactions as outlined in Figure 8 can be
divided into (i) accelerator chemistry which Accelerator chemistry
includes the formation of activator-
Active accelerator complex
accelerator complex and the active
sulphurating agent, (ii) crosslinking chemistry The generally accepted scheme for
including the formation of crosslink accelerated sulphur vulcanization (Fig. 8)
precursors and reactions leading to the suggests the formation of an active
formation of crosslinks and (iii) post accelerator complex via a reaction between
crosslinking chemistry dealing with the the activator and the accelerator as the first
network maturing reactions such as crosslink step in the vulcanization process
degradation and crosslink desulphuration. (Heideman, 2004). But the sulphur

Fig. 8. Outline diagram showing different stages of vulcanization

92 JOSEPH et al.

Fig. 9. Formation of active accelerator

vulcanization literatures start with the Gradwell et al., 1999; Kapur et al., 1974).
formation of a range of active sulphurating When activators are present, the mercapto
agents which are being claimed to be benzothiazole (MBT) part of the accelerator
produced from the active accelerator resulting from the thermal decomposition
complex on reaction with molecular can form an intermediate with zinc to form
sulphur. Probably, the formation of active the active accelerator complex (Hoover,
form of accelerator under the influence of 1999; Hoover et al., 1999). The reaction steps
the vulcanization temperature through ionic involved in the formation of active
and radical path ways (Gradwell and accelerator are given in Figure 9.
McGill, 1994; Son et al., 1972) might be The reactions described in Figure 9
regarded as the activation process as shows a possibility even for the formation
observed in benzothiazole-sulphenamide of accelerator polysulphides (sulphurating
accelerated sulphur vulcanization. A variety agents) through repeated exchange and
of exchange and recombination reactions recombination reactions. Although such
were also supposed to follow the activation reactions have been described, it might be
process to form radicals of higher sulphur regarded just as a possible reaction
rank (Coleman et al., 1973; Ghosh et al., 2003; mechanism rather than a highly feasible
SULPHUR VULCANIZATION CHEMISTRY 93

reaction taking place during vulcanization, pathway. When ZnO is present as an

as in the vulcanization system in the activator in the vulcanization system, it
presence of sulphur there are better ways of catalyses the formation of complexes,
formation of sulphurating agents rather than resulting in structures XS-Sx-Zn-SX (Ghosh
this pathway. et al., 2003).
Even in the presence of ZnO, MBT
Active sulphurating agent
formed initially will quickly get converted
Active sulphurating agents are to 2, 2’-thiobisbenzothiazole (MBTS) the
accelerator polysulphides formed at the active accelerator, forming only small
beginning stages of vulcanization process amounts of zinc accelerator complex at that
(Kruger and McGill, 1991) through sulphur stage. Additional zinc accelerator complex
intake of the active accelerator (Bateman is formed from MBT during crosslink
et al., 1963; Krebs, 1957) by various formation. In short, XS-Sx-SX is the active
mechanisms as shown in Figure 10. These sulphurating agent in the absence of ZnO
are better sulphurating species than while both XS-Sx-SX and XS-Zn-Sx-SX may
molecular sulphur. In the absence of an be the active sulphurating agents in the
activator such as ZnO these polysulphides presence of ZnO. Sulphur insertion follows
of the type XS-Sx-SX (X is a group derived radical mechanism by sequential ring
from accelerator) are formed by a radical activation in the absence of activators where

Fig. 10. Formation of active sulphurating agent

94 JOSEPH et al.

as it may follow an ionic pathway also in precursors can be formed from both XS-Sx-
the presence of ZnO through sulphur ring SX and XS-Zn-Sx-SX species (Shelton and
incorporation (Bateman et al., 1963; Ghosh McDonel, 1960). Out of the radical (Coleman
et al., 2003; Krebs, 1957). et al., 1973) and concerted mechanisms
If the zinc coordinates with an amine (Coran, 1978; 2003) outlined in Figure 12 for
that is released from a sulphenamide or with the formation of crosslink precursors in the

Fig. 11. Structures of sulphurating agents stabilized with ligands

carboxylate ligands which are present with absence of ZnO, the latter seems more
stearic acid, the structure of the sulphurating acceptable.
agent can be represented as in Figure 11 The concerted mechanism involves the
(Ghosh et al., 2003; Hoover et al., 1999). This formation of an eight membered transition
chelation is supposed to give better stability state between the active sulphurating agent
to the accelerator complex. and rubber molecule before it gets separated
into the real crosslink precursor along with
Crosslinking chemistry
MBT as a byproduct (Campbell and Wise,
The crosslink precursor 1964).
Once the sulphurating agents are being In the presence of ZnO, the formation
formed, they react directly with the rubber of crosslink precursors through Bateman’s
molecule to give a rubber bound pendent polar mechanism involving nucleophilic
group (Parks et al., 1970) of structure R-Sx- hydride displacement (Bateman et al., 1963)
SX (R denotes the rubber chain) which act is widely accepted even though carbanionic
as precursors to crosslink formation and stepwise mechanism (Hoover et al., 1999;
hence the name. Desulphuration and Shelton and McDonel, 1960) and a
decomposition can also be the fate of these mechanism involving a radical intermediate
precursors in addition to crosslink formation (Hoover et al., 1999) were also proposed as
(Morrison, 1984). The existence of such given in Figure 13.
species which was first proposed by Scheele Bateman’s mechanism is based on the
and Franck (1959) were confirmed later by nucleophilic character imparted to the
many scientists (Campbell and Wise, 1964; sulphurating agent by the presence of zinc
Moore and Watson, 1964). The crosslink species. The increased nucleophilic
SULPHUR VULCANIZATION CHEMISTRY 95

Fig. 12. Formation of crosslink precursors in the absence of activators

Fig. 13. Formation of crosslink precursors in the presence of activators

96 JOSEPH et al.

character of the sulphur atom adjacent to the precursor, sulphurating agent and rubber
zinc ion drives it to attack the allylic site of molecule (Bateman et al., 1963) and through
the rubber hydrocarbon causing a hydride direct reaction of the crosslink precursor
ion elimination which will in turn with rubber molecule (Bateman et al., 1963;
specifically attack the sulphur atom upon Coran, 1965; 2003) were proposed. Free
which electro positivity is being created by radical mechanism advocated for activator
the presence of zinc ion. These reactions will free systems is given in Figure 14, whereas
lead to the formation of a crosslink precursor polar mechanisms which are supposed to
along with a possible sulphurating agent give rise to crosslinks in presence of
and zinc sulphide as byproduct. activators like ZnO is being given in
Figure 15.
Crosslink formation
Although both the mechanisms of
Formation of crosslinks is an inevitable crosslink formation in the presence of zinc
and immediate consequence of crosslink species are catalysed by zinc accelerator
precursor formation. Various mechanisms complexes the disproportionation reaction
have been proposed for the conversion of pathway seems to be more unlikely to
the crosslink precursors into crosslinks. happen because it needs two precursor
Crosslink formation via precursor- molecules to diffuse next to each other
precursor interaction (Dogadkin and which cause steric hinderances. Also the
Beniska, 1958), interaction involving formation of monosulphidic crosslinks has

Fig. 14. Formation of crosslinks in the absence of activators

SULPHUR VULCANIZATION CHEMISTRY 97

Fig. 15. Formation of crosslinks in the presence of activators

to be considered entirely as the result of mechanism also follows the same steps as
desulphuration process in the post that in the case with ionic mechanism. The
crosslinking period, if disproportionation is reaction involving persulphenyl radical and
the mechanism of crosslink formation. These another crosslink precursor and that with
objections indicates that the crosslink two persulphenyl radicals (Ghosh et al.,
formation through the exchange of groups 2003) are similar to that of the already
between precursor and rubber might be the discussed disproportionation reaction
prominent pathway (Ghosh et al., 2003). observed in the case of ZnO activated system
The radical mechanism of crosslink and hence this is probably not the primary
formation involves the splitting of the mechanism of crosslink formation. The
crosslink precursor into two active radicals crosslink formation involving the reaction
(Coran, 1964; 1965) which can undergo a of a persulphenyl radical with a
variety of reactions such as radical neighbouring rubber chain (Coran, 1964;
recombination (Gradewell et al., 1995; 1999; 1965) might be the major reaction pathway
Kapur et al., 1974), sulphur activation, contributing to crosslink formation
addition to another rubber molecule to form
another crosslink precursor etc. in addition Scorch delay reactions
to the crosslink formation (Ghosh et al., 2003). In order to explain the rather long delay
Crosslink formation by radical periods frequently encountered in
98 JOSEPH et al.

accelerated sulfur vulcanization, especially (MOR or MBS), or 2-(N,N-diisopropyl)

wherein thiazole, sulphenamides or other benzothiazolesulfenamide (DPBS) and the
scorch delay accelerators are used, a model differences noted between the rates were
scheme has been proposed by Coran (1964). concluded to be attributed to differences in
According to the model scheme given steric hindrance and stability (Kapur et al.,
in Figure 16, crosslink formation will be 1974). The mode of action of the above
minimum if the reaction k4 is much faster
proposed scheme and various other factors
than k3, until A is essentially depleted. Both
the reaction through k3 and that through k4 that can affect the scorch properties are
are assumed to be much faster than the listed below.
reaction through k2 and hence, after the
delay required for the depletion of A, Effect of zinc-accelerator complex
crosslink formation will proceed in a first- In MBS system, crosslinking reactions
order fashion. Thus the formation of can start only with the formation of the
crosslinks is indeed inhibited by the polysulphidic sulphurating species, from

Fig. 16. Coran’s model scheme for scorch delay

starting materials and/or their initial MBTS. If the release of MBT from MBS is
reaction products. This treatment of scorch delayed, MBTS cannot be formed thus
delay has been applied to sulphur delaying the crosslinking reaction as shown
vulcanization of natural rubber accelerated in Figure 17. The Delay observed in the onset
by 2,2’ -thiobisbenzothiazole (MBTS), 2- of crosslinking in presence of ZnO can also
(N-cyclohexyl) benzothizaolesulfenamide be attributed to the inactivity of zinc salt of
(CBS), 2-(N-morpholinothio) benzothiazole MBT (Zn(mbt)2), which must break down to

Fig. 17. Effect of zinc- accelerator complex in scorch delay

SULPHUR VULCANIZATION CHEMISTRY 99

MBT before participating in the Formation of amine-terminated precursors

vulcanization process (Gradwell and McGill,
Another reason for the scorch delay
1995; 1996; Heideman et al., 2004). Anyway,
observed with sulphenamide accelerators
this might not be the major contributing
during sulphur vulcanization is attributed
factor as a good cure rate follows the scorch
to exchange reactions (Ghosh et al., 2003;
period immediately even in the presence of
Gradwell and McGill, 1996; Gradwell and
molar excess of ZnO. van der Merwe, 1999) between the
Exchange reactions accelerator and crosslink precursors to form
amine-terminated precursors with lower
The delay observed in sulphenamide reactivity than benzothiazole terminated
accelerators may be due to exchange precursors. These amine terminated
reactions between various accelerator- precursors cannot form crosslinks unless
derived intermediates as depicted in Figure and until they are exchanged with MBT or
18. The crosslink precursors are being benzothiazole terminated precursor to

Fig. 18. Scorch delay due to exchange reactions

quenched by accelerator polysulphides or produce perthiol and sulphenamide or

such accelerator derived species until most crosslink respectively as shown in Figure 19.
of the accelerator polysulphides are
consumed after which the precursor could Action of prevulcanization inhibitor (PVI)
form crosslinks (Coran, 1964; Gradwell and
van der Merwe, 1999). Campbell and Wise It is a well accepted fact that the delay
(1964) have experimentally proved that the period provided by the various accelerators
rate of reaction of the intermediates with the through aforementioned mechanisms is not
accelerator itself is greater than its reaction sufficient for the necessary pre-cure
with NR during the scorch delay period processing of rubber in many manufacturing
through absorption chromatographic processes. Introduction of a prevulcanization
studies supporting the argument of inhibitor (PVI) can effectively increase the
exchange reactions. induction time before actual curing
100 JOSEPH et al.

Fig. 19. Scorch delay by amine terminated precursor

commences, while retaining other aspects of 4. They should not affect the colour of the
cure such as rate of cure, time to maximum mixing nor impair the ageing properties
cure, maximum crosslink density, etc. of the rubber
(Hopper, 1974; Sullivan et al., 1983; Trivette 5. They should be practically free from
et al., 1977). A typical PVI has an R-S-N odour
group, with an R group with no proton
6. They should be so active that only very
accepter site and the net activity of the PVI
small amounts are required to give the
increase by the increase in the number of S-
desired scorch retarding effect.
N groups. The characteristic properties
expected from a PVI along with scorch safety 7. They should have no adverse effect on
are (Twiss and Jones, 1935; Sullivan et al., the physical properties of the
1983) vulcanized rubber.
1. PVI should react with the actual The most widely used PVI; N-
catalytic accelerator fragment (MBT) (cyclohexyl thio) phthalimide (CTP) was
much faster than the primary commercially introduced by Monsanto in
accelerator. 1970 (Morita, 1980) in sulfenamide
accelerated sulphur vulcanization. The
2. The resulting asymmetric disulphide mechanism of action of PVI is based on the
must not take a primary role in fact that MBTS formation is the key step
crosslinking process, yet it must slowly towards crosslinking and hence if its
release the accelerator fragment as formation can be arrested, the whole
crosslinking proceeds. crosslinking mechanism can be checked.
3. The inhibitor must survive mixing and MBTS formation is being blocked by CTP
prevulcanization conditions with by consuming MBT thereby preventing any
minimum loss to unproductive side chance of MBT further reacting with
reactions. sulfenamides to form MBTS. Kinetic factors
SULPHUR VULCANIZATION CHEMISTRY 101

also favour this reaction as MBT has greater begins. The mechanism of action of PVI is
affinity for CTP than to sulfenamides and given in Figure 20.
hence it will react with CTP alone until all
the CTP has been consumed (Gradwell and Accelerated sulphur vulcanization via
Stephenson, 2001; Leib et al., 1970; sulphur donors
Mukhopadhyay and De, 1979; Scheele and A number of accelerators
Helberg, 1965; Son et al., 1972; Son, 1973). (tetramethylthiuram disulphide (TMTD),

Fig. 20. Mechanism of action of CTP in sulphenamide accelerated sulphur vulcanization

The by-product of CTP action is tetraethylthiuram disulphide (TETD),

2-cyclohexyldithiobenzothiazole (CDB) dipentamethylenethiuram tetrasulphide
has been proved to be a lesser scorchy (DPTT), etc.) can function both as
vulcanization accelerator than N- accelerators and sulphur donors. Generally,
oxydiethylene -2 benzothiazolesulphenamide sulphur donors are used where free sulphur
(OBTS or MBS or MOR), but with slower level is to be reduced with the objective of
cure rate (Son, 1973) will accelerate the improving thermal and oxidative ageing
vulcanization process when actual curing resistance, to eliminate bloom or to modify
102 JOSEPH et al.

processing and curing characteristics formation of a true alkenyl intermediate

(Rodger, 1979). Among the various organic seems to be more acceptable as C-C cross-
sulphur containing compounds, such as links are negligible in the NR-TMTD-ZnO
alkyl and cycloalkylene thiuramdisulphides system (Dogadkin and Shershnev, 1960;
and dithio and perthio- bis amines that can Moore, 1958; Savillle and Watson, 1967).
vulcanize unsaturated rubbers in the True alkenyl intermediate free radicals need
absence of elemental sulphur, TMTD has true carbon free radical from the rubber
been the most studied. Vulcanizates hydrocarbon for crosslinks. If that is the case
obtained using these compounds in the so formed carbon free radicals can also
combination with ZnO are characterized by react among themselves to form C-C
superior thermal and oxidative stability and crosslinks which is not observed with TMTD
negligible modulus reversion (Kruger and vulcanization of NR.
McGill, 1992) due to the special network
structure of the vulcanizate and the Radical mechanism
formation of a potent antioxidant, zinc According to radical mechanism given
dialkyldithiocarbamate (ZDMC) during
in Figure 21, the first step in TMTD-NR
vulcanization. The network formed in the
vulcanization should be the symmetrical
initial stages of vulcanization will be
and unsymmetrical decomposition of
structurally complex, but will become
TMTD into free radicals (Dogadkin and
structurally simpler as crosslinking
proceeds to the maximum crosslink density Shershnev, 1960; Kruger and McGill, 1992;
with little cis-trans isomerization of the Rooyen, 2007) at vulcanization temperatures
double bonds, scission of the main chain whose interactive recombination will lead
during cure, conjugated species and cyclic to the formation of accelerator
monosulphides (Bateman et al., 1963; Moore polysulphides (TMTPs) (Coleman et al.,
and Trego, 1964). 1973; Geyser and McGill, 1996; Kruger and
Although extensive research have been McGill, 1991; 1992). These sulphurating
undertaken, it is not able to conclude agents will form crosslink precursors on
(Shelton and McDonel, 1960) whether the reaction with rubber. Crosslink precursors
reaction follows a radical (Craig, 1956; can form crosslinks either interacting with
Dogadkin and Shershnev, 1960; Geyser and a precursor molecule or with a rubber
McGill, 1996; Wolfe, 1968) or polar or a molecule just as in the previous cases.
combination pathway of both (Coleman
Polar mechanism
et al., 1973; Shelton and McDonel, 1960;
Wolfe, 1968). Moore and Watson (1964), In the presence of zinc oxide, TMTD
Scheele et al. (1956), Coleman et al. (1973), vulcanization of NR may follow a polar
Bateman et al. (1963), Dogadkin and route also, as shown in Figure 22, in which
Shershnev, (1960), Versloot et al. (1994) and the active sulphurating agents are both zinc
Kruger and McGill, (1992) also put forth perthiomercaptides (ZDMC) (Duchacek,
their experimental observations for thiuram 1974; 1978; 1979) and thiuram polysulphides
accelerated vulcanization of isoprene (TMTPs) (Geyser and McGill, 1995; 1996;
rubber. Among the various mechanisms the Kruger and McGill, 1991). The findings of
combination of thiuram persulfenyl and Duchacek (1978; 1979) and kinetic
polyisoprenyl radicals through an investigations by Scheele and Franck (1959)
irreversible concerted reaction without the proved that the formation of zinc
SULPHUR VULCANIZATION CHEMISTRY 103

Fig. 21. Vulcanization by TMTD – radical pathway

perthiomercaptides (sulphurating agent) is reaction between the sulphurating agent and

followed by the formation of network bound the rubber chain in which the S-S bonds are
accelerator residues (pendent groups/ broken and new C-S bonds are formed
crosslink precursors) on reaction with through a concerted reaction without the
rubber hydrocarbon, which will form formation of true intermediates.
crosslinks (Geyser and McGill,1996) via Formation of mono or disulphidic
nucleophilic reactions just as in the case of crosslinks (efficient vulcanization) resulting
other vulcanization systems (Bevilacqua, in a reversion resistant vulcanizate network
1959; Bateman et al., 1963; Kruger and is being manifested as the highlight of using
McGill, 1992). The precursor may react with sulphur donating accelerators such as
a thiuram persulphenyl anion derived from TMTD as already mentioned. A progressive
ZDMC to form a rubber polysulphidic anion shortening of initially formed polysulphidic
or with ZDMC itself to form a zinc crosslinks is supposed to take place by the
containing precursor. These two species on extrusion of sulphur from the polysulphidic
reaction with another precursor or isoprene crosslinks by TMTM which would
chain respectively will give rise to crosslinks. eventually lead to a heat resistant network
As per the mechanism, the formation of with monosulphidic crosslinks (Kruger and
pendent groups proceeds via a concerted McGill, 1992 a, b). But when TMTD is used
104 JOSEPH et al.

Fig. 22. Vulcanization by TMTD – polar pathway

as an accelerator in the presence of sulphur, Shershnev, 1960; Kruger and McGill, 1992)
the degree of crosslinking is proportional to will decompose into dimethylamine
sulphur concentration and at higher sulphur (Me2NH) and carbon disulphide (CS2) which
concentration the vulcanizate tend to revert will further trigger various crosslink
(Scheele and Franck, 1959) as more number deteriorating reactions. Me2NH would be
of polysulphidic crosslinks are being very reactive towards dithiocarbamate
produced shifting the cure system to an species and enhance side reactions (Geyser
inefficient one. and McGill, 1996; Kruger and McGill, 1992)
The role of ZnO in TMTD vulcanization consuming various intermediate species
is more prominent than in other cases of required for vulcanization, resulting in
sulphur vulcanization, as in the absence of degradation of the vulcanizate network.
ZnO, dimethyl dithiocarbamic acid Various reactions that can occur in the
(DMDCA) formed as a by-product of absence of ZnO and the mechanism through
pendent group formation and crosslinking which they are being arrested in the
(Coleman et al., 1973; Dogadkin and presence of ZnO are given in Figure 23.
SULPHUR VULCANIZATION CHEMISTRY 105

Fig. 23. Role of zinc oxide in TMTD vulcanization

Postcrosslinking chemistry bonds and there will be relatively few

modifications of the cyclic sulphides or
As we have already mentioned,
conjugated triene type (efficiently
crosslink desulphuration and crosslink
crosslinked) (Conover, 1941; Morrel, 1982)
decomposition reactions dominate the post
or else there will be opportunities for
crosslinking chemistry (Morrison and thermal decompositions leading to
Porter, 1984). After the free sulphur is reversion or loss of crosslinks and to
consumed during vulcanization, the network modifications (inefficiently
accelerator complex continues to react with crosslinked) (Conover, 1941).
polysulphidic crosslinks as though it were
elemental sulphur. The reactions include Crosslink desulphuration reactions
extracting sulphur from the crosslinks Desulphuration reactions (Minoura,
(desulphuration), cleaving crosslinks 1950; Mori and Koenig, 1995;
(decomposition), formation of conjugated Nieuwenhuizen et al., 1999 a, b) involve the
unsaturation in the main chain etc. (Hoover, extraction of sulphur atoms from higher
1999). If the desulphuration proceeds ranked sulphur bonds, followed by insertion
rapidly the final network will be highly of the extracted sulphur atoms into the lower
crosslinked with mainly monosulphidic ranked sulphur crosslinks. Desulphuration
106 JOSEPH et al.

Fig. 24. Mechanism of zinc mediated desulphuration

of rubber bound intermediates would in is often accompanied by changes in position

effect, compete with crosslinking, as it will of crosslinks such that the initial allylic
eventually result in monosulphidic pendent crosslinks may get transformed to isoallylic
groups which are relatively unreactive and structures.
are not precursors to crosslinks. As the Bateman et al. (1963) proposed a
temperature of the vulcanizing system is mechanism for zinc mediated de-
increased, more accelerators are removed as sulphuration, involving an intermediate
unreactive monosulphidic pendent groups adduct formation between di- or
which appears to be a major contributor to polysulphidic crosslink and the zinc
the reduction in crosslinking efficiency in EV complex, followed by SNi or SNi’ attack
and semi EV systems with rise in temperature along with double bond rearrangement as
(Bateman et al., 1963; Nieuwenhuizen and shown in Figure 24. The reaction assumes
Reedjik, 1997). The shortening of crosslinks the involvement of trithio-zinc, implying
SULPHUR VULCANIZATION CHEMISTRY 107

Fig. 25. Scheme a: ZDMC mediated desulphuration reaction; Scheme b: the possible sigmatropic
rearrangements of trisulphidic crosslinks favouring the reaction

that desulphuration is a step wise reaction 1996) processes are either radical or polar
continuing till there is only monosulphidic in character, generally operate at high
crosslinks left. temperatures will lead to a net loss in
Figure 25 is an alternative mechanism crosslink density and hence impart reversion.
(Nieuwenhuizen et al., 1999) for desulphuration Poly sulphidic crosslinks can degrade to
of di and polysulphides involving dead ends and main chain modifications.
sigmatropic shift and isomerization of double Radical decomposition of polysulphidic
bond (Nieuwenhuizen et al., 1998). crosslinks is governed by bond dissociation
energies of the bond that is broken. Hence
Crosslink decomposition reactions
polysulphides of higher lengths are easily
Crosslink decomposition (Schotman et al., dissociated due to their lower bond
108 JOSEPH et al.

Fig. 26. Radical degradation of cross-links

dissociation energies (approx.150kJ mol-1). reversion reaction for monosulphides

Dissociation of di and tri sulphidic (McSwkeeney and Morrison, 1983; Morrison
crosslinks is more difficult due to their and Portor, 1984), that can produce trienes
higher bond dissociation energies (289 and as the final product. 1, 5 hydrogen shifts
193kJ/mol respectively). Similar degradation (Bateman et al., 1963; McSwkeeney and
of monosulphidic crosslinks (Morrison and Morrison, 1983; Nieuwenhuizen and
Porter, 1984) may lead to the formation of Reedjik, 1997) is the predominant degradation
C-C crosslinks where as such a possibility mechanism in other cases, if steric and
is rare in the case of polysulphidic crosslinks kinetic factors are favourable. Other possible
as S-S bond is more easily cleaved than C-S reactions (Nieuwenhuizen et al., 1999) for
bond. Also the rate of degradation of degradation of crosslinks, such as concerted
monosulphidic crosslinks will be far less than decomposition of monosulphides to yield
that of polysulphidic crosslinks considering α−β unsaturated thio aldehydes and polar
the bond dissociation energies of both decomposition of disulphides via zinc
systems. The radical degradation pathways diethyldithiocarbamate (ZDEC or ZDC)
of crosslinks are given in Figure 26. catalyzed 1,4-hydride shift yielding cyclic
But, some alternatives for the disulphides were also being investigated
degradation of monosulphidic crosslinks using reaction stage modeling (RSM)
other than the radical mechanism are also studies. The concerted mechanism is
found in literature. 1, 2-dehydrosulphuration assumed to operate even at vulcanization
has been established to be an important temperatures with the only pre-requisite
SULPHUR VULCANIZATION CHEMISTRY 109

Fig. 27. Degradation of monosulphidic crosslinks by polar pathways

that alpha carbon of the crosslinked sulphur 1996). This phenomenon leads to a reduction
should not be tertiary. Polar degradation in crosslink density and consequently loss
possibilities of monosulphidic crosslinks are of mechanical properties.
given in Figure 27. The best established compounding
method to reduce or minimize reversion is
Tackling reversion
the use of so called efficient cure system
As we have already seen, reversion thereby diminishing the number of
occurs in sulphur cured NR and synthetic polysulphidic crosslinks and generating
isoprene rubber (IR) when polysulphidic reversion resistant mono and disulphidic
crosslinks are exposed to temperature – time crosslinks. This approach is successful, if
treatment which causes decomposition of lowering of sulphur does not negatively
polysulphidic crosslinks (Schotman et al., affect other desired properties of the
110 JOSEPH et al.

vulcanizate. But lower sulphur levels will conjugated diene formed during reversion as
result in lower rubber to metal/fabric in Figure 27 with dienophile. The concerted
adhesion limiting the application of this (4+2) cycloaddition is shown in Figure 28.
approach to some extent (Schotman et al., Among the various retarders employed,
1996). BCI-MX is most commercialized due to its
The other two major approaches to higher efficiency in battling reversion. This
battle crosslink breaking involves may be attributed to the specialty of its

Fig. 28. Scavenging of conjugated dienes and trienes by dienophiles

deactivating the detrimental catalytic structure which can replace the short
activity of zinc dithiocarbamates and conjugated dimers with long BCI-MX
countering the effect of reversion by bridged dimers, whose lengths are
substituting a broken crosslink by an comparable to crosslinks consisting of seven
alternative one using anti-reversion coagents sulphur atoms. Also BCI-MX produces C-C
(Datta et al., 1997; Kok, 1987; Schotman et al.,
crosslinks which are thermally more stable
1996). Anti-reversion coagents are usually
allowing the rubber to operate at more severe
dienophiles like N-benzyl citraconamide,
1, 3- (bis-citraconimidomethyl) benzene service conditions (Schotman et al., 1996). The
(BCI-MX), tetracyanoethene, maleic structure of the adduct formed by BCI-MX
anhydride, etc. which can scavenge the dienes and a diene is shown in Figure 29.
and trienes to form Diels-Alder adducts Zinc dithiocarbamates may be
through a concerted (4+2) cyclo addition of a deactivated by adding complexing agents
SULPHUR VULCANIZATION CHEMISTRY 111

Fig. 29. Comparison of length of Diels Alder adduct formed by BCI-MX with polysulphidic crosslinks

like nitrogen containing ligands such as of sulphur and a high level of accelerator
1, 10– phenantroline and N-methylimidazole. along with a sulphur donor, where as
But these experiments are not yet successful conventional or inefficient system uses
(Nieuwenhuizen et al., 1999). higher amount of sulphur compared with
accelerator loading.
Accelerated sulphur vulcanization of other In NR, efficient vulcanization (EV) result
polydiene elastomers in higher proportion of monosulphidic and
Although we have discussed the disulphidic crosslinks along with minimum
chemistry of sulphur vulcanization taking main chain modifications giving rise to
the case of natural rubber (NR), accelerated higher thermal and oxidative ageing
sulphur vulcanization is also suitable for resistance. Conventional vulcanized NR has
other general purpose rubbers such as higher proportion of main chain
synthetic isoprene (IR), polybutadiene
modifications causing poor resistance to
rubber (BR), styrene butadiene rubber (SBR)
thermal and oxidative ageing. The term EV
and specialty elastomers such as nitrile
rubber (NBR), butyl rubber (IIR), is similarly applicable to other sulphur
chlorobutyl rubber (CIIR), bromobutyl vulcanizable polymers also. But for SBR,
rubber (BIIR) and ethylene propylene diene even conventional vulcanization gives a high
rubber (EPDM). Even though natural rubber proportion of monosulphidic crosslinks.
can be regarded as a general representative Table 3 gives the crosslink distribution
of the group, there are some areas upon pattern for NR and SBR for conventional and
which the behavior of sulphur vulcanization efficient vulcanization systems.
of natural and synthetic rubbers differs. Let
us have a brief discussion over some of such
aspects. Table 3. Crosslink distribution for NR and SBR
Vulcanization Crosslink type (%)
The terms efficient and inefficient have system NR SBR
already been outlined in terms of usage of S1 S2 + Sx S1 S2 + Sx
sulphur in the vulcanized network. These
Conventional 0 100 38 62
terms represent two extremes viz. efficient
vulcanization uses zero or a very low level EV 46 54 86 16
 112

Fig. 30. Summary of steps and processes involved in accelerated sulphur vulcanization
JOSEPH et al.
SULPHUR VULCANIZATION CHEMISTRY 113

A further difference between NR and SUMMARY

other synthetic rubbers is in the mechanism
of ageing and lack of reversion. In SBR, A detailed survey on the sulphur
oxidative ageing causes minimum main vulcanization of elastomers has been made
chain breaking and a higher degree of in this review giving special attention to
additional crosslinking resulting in accelerated sulphur vulcanization of natural
increased hardness and modulus and rubber. The process of vulcanization has
reduced elongation at break. Substantial been discussed under three different
improvements in oxidative ageing can be sections viz. accelerator chemistry,
obtained in synthetic polymers by EV crosslinking chemistry and post crosslinking
system. Also the fatigue life of EV cured chemistry. A general outlook of the
synthetic polymers is not reduced even with vulcanization process, vulcanization
substantial decrease in amount of sulphur. accelerators and the role of activators are
also discussed. The mechanism of various
In the case of EPDM rubber, as a result
reactions involved and the schemes of
of the small amount of unsaturation, the
various reactions are included along with
vulcanization rate is rather low in
descriptions of the prominent reaction in a
comparison with other polydiene
elastomers and a relatively large amount of group of possible reactions.
accelerators is needed. Due to the large The accelerator chemistry deals with the
difference in polarity between polar formation of the activator - accelerator
accelerators and non polar EPDM elastomer, complex which can effectively sulphurate
the solubility of the accelerators is limited the rubber chains giving rise to crosslink
and usually a mixture of upto five precursors. Crosslinking chemistry deals
accelerators is applied (Duin, 2002). with the formation of crosslink precursor

Fig. 31. Scorch delay reactions in a glance.

114 JOSEPH et al.

Table 4. Comparison of crosslink desulphuration and crosslink decomposition reactions

Effects Favouring Temperature Tackling
factors dependence methods
Results in stable Zinc – accelerator
monosulphidic complexes and extra
Crosslink crosslinks and ligands Occur even Deactivating
desulphuration recycling of extruded at room zinc –
sulphur High accelerator temperature accelerator
sulphur ratio along complexes
with zinc salt sufficient
enough to solubulize it
Causes modulus Conventional Efficient
reversion, low vulcanization forming Considerable vulcanization.
o
Crosslink crosslink efficiency polysulphidic at 140 C but Using
o
decomposition and main chain crosslinks less at 100 C anti-reversion
modifications Increase in temperature co-agents

and the reactions of this precursor leading vulcanizate depends on the balance between
to crosslinks and the various scorch delay the three competing reactions viz. the
mechanisms. Accelerated sulphur formation of crosslinks, the desulphuration
vulcanization via sulphur donors is used to of polysulphidic pendent groups and
minimize the sulphur loading and thereby crosslinks eventually into corresponding
obtain a reversion free curing due to the monosulphides and thermal decomposition
higher percentage of mono and disulphidic of crosslinks resulting in the formation of
crosslinks. The various processes involved
dead ends, conjugated structures etc. The
in the accelerated sulphur vulcanization are
use of anti-reversion coagents and
summarized (Fig. 30).
introduction of EV cure system has been
Scorch or premature vulcanization is a successfully employed to tackle the
technical problem often faced by rubber
detrimental effects of reversion. A
compounders. Although scorch delay to
summarized idea about the crosslink
some extend can be achieved through
delayed action accelerators, there are many desulphuration and crosslink decomposition
cases were accelerators alone cannot offer processes is given in Table 4.
the desired scorch time which is being
addressed by the use of prevulcanization
ACKNOWLEWDGEMENT
inhibitors (Fig. 31). The authors gratefully acknowledge the
The postcrosslinking chemistry deals financial support provided by Council of
with the decomposition and desulphuration Scientific and Industrial Research (CSIR),
of crosslinks. All the properties of the New Delhi to Ms. Anu Mary Joseph.

REFERENCES
Amstrong, R. T., Little, J. R. and Doak, K. W. (1944). Recent developments in crosslinking of
Chemistry of sulphur olefin reactions. elastomers. Rubber Chemistry and Technology,
Application to vulcanization. Rubber Chemistry 78: 458-488.
and Technology, 17: 788-801.
Bandyopadhyay, P. K. and Banerjee, S. (1979).
Aprem, A. S., Joseph, K., and Thomas, S. (2005). Sulfur vulcanization of natural rubber
SULPHUR VULCANIZATION CHEMISTRY 115

accelerated with 2-mercaptobenzothiazole Coran, A. Y. (2003). Chemistry of the vulcanization

plus tetramethylthiuram disulfide. Journal of and protection of elastomers: A review of the
Applied Polymer Science, 23: 185-200. achievements. Journal of Applied Polymer Science,
87: 24-30.
Bateman, L., Moore, C. G., Portor, M. and Saville, B.
(1963). In: The Chemistry and Physics of Rubber Craig, D. (1956). Mechanism of formation of
like Substances (Ed. L. Bateman). John Wiley and ZnDMDC in TMTD vulcanization. Rubber
Sons Inc., NewYork, pp. 449- 561. Chemistry and Technology, 29: 944-945.
Bevilacqua, E. M. (1959). Vulcanization with TMTD. Craine, L. and Raban, M. (1989). The chemistry of
Rubber Chemistry and Technology, 32: 721-738. sulfenamides. Chemical Reviews, 8: 689-712.
Campbell, D. S. (1971). Structural characterization Cummings, A. D. and Simmons, H. E. (1928). Some
of vulcanizates. XII. Efficient vulcanization using observations with ultra-accelerators. Industrial
a sulfenamide–thiuram disulfide accelerator and Engineering Chemistry, 20: 1173.
system. Journal of Applied Polymer Science, 15:
2661–2666. Datta, R. N., Schotman, A. H. M., Weber, A. J. M.,
Vanwijk, F. G. H., VanHarn, P. J. C., Hofstraat, J.
Campbell, R. H. and Wise, R. W. (1964). W., Talma, A. G. and Bovenkamp-Bouwman, A.
Vulcanization part II. Fate of curing system
G. V. D. (1997). Bis-citraconimides as anti-
during sulphur curing of NR accelarated by MBT
reversion agents for diene rubbers:
derivatives and activated by zinc stearate. Rubber
Chemistry and Technology, 37: 649-667. Spectroscopic studies on citraconimide-squalene
adducts. Rubber Chemistry and Technology, 70:
Campbell, R. H. and Wise, R. W. (1964). 129-130.
Vulcanization part I. Fate of curing system
during the sulphur vulcanization of natural Dinsmore, R. P. and Vogt, W. W. (1928). A scheme
rubber accelerated benzothiazole derivatives. for accelerator classification. The Rubber Age,
Rubber Chemistry and Technology, 37: 635-649. 23: 554-557.

Chapman, A. V. and Portor, M. (1988). Sulphur Dogadkin, B. A. and Shershnev. V. A. (1960). The
vulcanization chemistry. In: Natural Rubber interaction of TMTD with rubber and
Science and Technology. (Ed. A. D. Roberts). compounds containing a labile hydrogen atom.
Oxford Science Publications, London, 511p. Rubber Chemistry and Technology, 33: 401-411.
Coleman, M. M., Shelton, J. R. and Koenig, J. L. Dogadkin, B. A., Feldstein, M. S., Eitington, I. I. and
(1973). Raman and ESR spectroscopic studies of Pevzner, D. M. (1958). The action of some
accelerator systems II. Thermal degradation of heterocyclic disulphides as agents and
vulcanization systems and its significance to accelerators of vulcanization. Kauchuki Rezina,
vulcanization mechanisms. Rubber Chemistry and 17: 7-12.
Technology, 46: 957-980.
Dogadkin, B. and Beniska, I. (1958). The action of
Conover, F. S. (1941). Effect of various sulphur – vulcanization activators. Rubber Chemistry and
accelerator ratios in vulcanized rubber. Rubber Technology, 31: 329-342.
Chemistry and Technology, 14: 356-371.
Duchacek, V. (1974). Kinetics of thiuram accelerated
Coran, A. Y. (1964). Vulcanization part V. The sulphur vulcanization. Journal of Applied Polymer
formation of crosslinks in the system: NR-S- Science, 18: 125-132.
MBT-Zinc ion. Rubber Chemistry and Technology,
37: 679-688. Duchacek, V. (1978). Effect of thiourea on thiuram
accalarated sulphur vulcanization and its
Coran, A. Y. (1964). Vulcanization. Part VI. A model significance on vulcanization mechanism.
and treatment for scorch delay kinetics. Rubber Journal of Applied Polymer Science, 22: 227-237.
Chemistry and Technology, 37: 689-697.
Duchacek, V. (1979). Complexes of TMTD with zinc
Coran, A. Y. (1965). Vulcanization. Part VII. Kinetics dialkyldithiocarbamates and their role in the
of sulphur vulcanization of NR in presence of sulphur vulcanization of NR. Journal of Applied
delayed action accelerators. Rubber Chemistry and Polymer Science, 23: 2065-2071.
Technology, 38: 1-13.
Duin, M. V. (2002). Chemistry of EPDM crosslinking.
Coran, A. Y. (1978). Vulcanization. In: Science and
Kautschuk Gummi Kunststoffe, 55: 150-156.
Technology of Rubber (Ed. F. R Erich). Academic
Press, NewYork, pp. 321-366. en.wikipaedia.org/wiki/Natural_rubber
116 JOSEPH et al.

en.wikipedia.org/wiki/Accelerant Gradwell, M. H. S and McGill, W. J. (1995). Sulphur

vulcanization of polyisoprene accelerated by
Fledstein, M., Orlovsky, P. and Dogadkin, B. (1958). benzothiazole derivatives. II. Reaction of
The role of metal oxides as activators of 2-mercaptobenzothiazole and its zinc salt with
vulcanization, Rubber Chemistry and Technology, sulphur and ZnO in polyisoprene. Journal of
31: 526-538. Applied Polymer Science, 58: 2193-2200.
Fukuda, H. and Tsurugi, J. (1962). The chemistry of Gradwell, M. H. S and McGill, W. J. (1996). Sulphur
vulcanization. X. Accelerating mechanism of vulcanization of polyisoprene accelerated by
sulfenamide type accelerators. Rubber Chemistry benzothiazole derivatives. III. The reaction of
and Technology, 35: 491-497. 2-bisbenzothiazole -2, 2’-disulphide with
Garve, Jr. B. S., Youchum, D. W. and Morschauser, sulphur and ZnO in polyisoprene. Journal of
C. A. (1953). Accelerator compounding - heat Applied Polymer Science, 61: 1131-1136.
history and compounding. Rubber Chemistry and
Gradwell, M. H. S, and Stephenson, N. R. (2001).
Technology, 26: 919-934.
The action of n-(cyclohexylthio) phthalimide as
Gehman, S.D. (1981). Rubber structure and a prevulcanization inhibitor of 2-bis-
properties. In: Mechanics of pneumatic tyres benzothiazole-2, 2’-disulfide accelerated sulfur
(Ed. S. K. Clark). US department of vulcanization. Rubber Chemistry and Technology,
Transportation, National Highway Traffic safety 74: 44-56.
Administration. Washington, pp. 1-36.
Gradwell, M. H. S. and McGill, W. J. (1996). Sulphur
Gesyr, M. and McGill, W. J. (1996). Thiuram vulcanization of poly isoprene accelerated by
accelerated sulphur vulcanization. IV. Zinc benzothiazole derivatives. IV. The reaction of
dimethyldithiocarbamate accelerated sulphur polyisoprene with n-cyclohexyl benzothiazole
vulcanization. Journal of Applied Polymer Science, sulphenamide, Sulphur and ZnO. Journal of
60: 449- 454. Applied Polymer Science, 61: 1515-1523.
Gesyr, M. and McGill, W. J. (1996). Thiuram Gradwell, M. H. S. and McGill. W. J. (1994). The
accelerated sulphur vulcanization. III. The interaction of sulfenamide accelerators with
formation of crosslinks. Journal of Applied Polymer sulphur, ZnO and stearic acid in the absence of
Science, 60: 439-447. rubber. Journal of Applied Polymer Science, 51:
177-185.
Geyser, M. and McGill, W. J. (1995). A study of rate
of formation of polysulphides of TMTD. Journal Gradwell, M. H. S. and van der Merwe, M. J. (1999).
of Applied Polymer Science, 55: 215-224. 2-t-Butylbenzothiazole sulfonamide accelerated
sulphur vulcanization of polyisoprene. Rubber
Geyser, M. and McGill, W. J. (1996). Thiuram
Chemistry and Technology, 72: 65-73
accelerated sulphur vulcanization II. The
formation of crosslink precursor. Journal of Gradwell, M. H. S., Hendrikse, K. G. and McGill, W.
Applied Polymer Science, 60: 431-437. J. (1999). The reactions of 2-(4-morpholinothio)
and 2-(4-morpholinodithio) benzothiazole in the
Geyser, M. and McGill, W. J. (1996). Thiuram
absence of polyisoprene. Journal of Applied
accelerated sulphur vulcanization. I. The
Polymer Science, 72: 1235-1240.
formation of active sulfurating agent. Journal of
Applied Polymer Science, 60: 425-430. Gradwell, M. H. S., Morgan, B. and McGill, W. J.
(1995). Rate of formation of polysulphides of
Ghosh, P., Katare, S., Patkar, P., Caruthers, J. M. and 2-bisbenzothiazole - 2, 2’-disulphide in the
Venkatesubramanian, V. (2003). Sulphur presence of sulphur and 2-mercapto-
vulcanization of NR for benzothiazole benzothiazole. Journal of Applied Polymer Science,
accelerated formulations: From reaction 56: 1581-1588.
mechanism to rational kinetic model. Rubber
Chemistry and Technology, 76:592-693. Heideman, G. (2004). Reduced zinc oxide levels in
sulphur vulcanization of rubber compounds. Ph.D
Giuliani, B. V. M. K. and McGill, W. J. (1995). Thesis. University of Twente, chapter 2.
Tetramethylthiuram disulfide and 2- mercapto-
benzothiazole as binary accelerators in sulfur Heideman, G., Datta, R. N., Noordermeer, J. W. M.
vulcanization. II. Exchange reactions between and VanBaarle, B. (2006). Multifunctional
the accelerators and their zinc salts in the absence additives as zinc free curatives for sulphur
of rubber. Journal of Applied Polymer Science, vulcanization. Rubber Chemistry and Technology,
58: 1053–1061. 79: 561-588.
SULPHUR VULCANIZATION CHEMISTRY 117

Heideman, G., Datta, R. N., Noordermeer, J. W. M. Kruger, F. W. and McGill, W. J. (1992). Study of
and VanBaarle, B. (2005). Effect of zinc curative interactions in cis – 1, 4-polyisoprene.
complexes as activator for sulphur vulcanization VII. The IR-TMTD-ZnO system. Journal of
in various rubbers. Rubber Chemistry and Applied Polymer Science, 45: 563-571.
Technology, 78: 245-257. Kruger, F. W. H. and McGill, W. J. (1992). Study of
Heideman, G., Datta, R. N., Noordermeer, J. W. M. curative interactions in cis – 1, 4-polyisoprene.
and VanBaarle, B. (2004). Zinc loaded clay as VIII. Network maturing reactions in the cis-1,4-
activator in sulphur vulcanization. A new route polyisoprene- tetramethylthiuram disulphide-
for ZnO reduction in rubber compounds. Rubber ZnO system. Journal of Applied Polymer Science,
Chemistry and Technology, 77: 336-355. 45: 573-578.

Heideman, G., Datta, R.N., Noordermeer, J. W. M. Kruger, F. W. H. and McGill, W.J. (1992). Study of
curative interactions in cis – 1, 4-polyisoprene.
and VanBaarle, B. (2004). Activators in
VI. Interaction of some combinations of sulphur,
accelerated sulphur vulcanization. Rubber
TMTD and ZnO. Journal of Applied Polymer
Chemistry and Technology, 77: 512-541. Science, 44: 587-592.
Henning, S. K. (2007). Reduced zinc loading: using Kruger, W. H. and McGill, W. J. (1991). A DSC study
zinc monomethacrylate to activate accelerated of curative interactions. IV. The interaction of
sulphur
nd
vulcanization. Paper presented at the fall tetramethyl thiuramdisulphide with ZnO,
172 Technical meeting of the Rubber Division, sulphur and stearic acid. Journal of Applied
American chemical Society, Cleveland. Polymer Science, 42: 2669-2680.
Henning, S. K. (2008). Reduced zinc loading: Using Kruger, W. H. and McGill, W. J. (1991). A DSC study
ZMMA to activate accelerated sulphur of curative interactions. I. The interaction of ZnO
vulcanization. Rubber World, 238: 35-42. and stearic acid. Journal of Applied Polymer
Science, 42: 2643-2649.
Hoover, F. I. (1999). Review of vulcanization
chemistry. Rubber World, 220: 24-30, 101-102. Kruger, W. H. and McGill, W. J. (1991). A DSC study
of curative interactions. III. The interaction of
Hoover, F. I., Katritzky, A. R., Lobanov, V. S. and TMTM with ZnO, sulphur and stearic acid.
Karelson, M. (1999). Insights into sulphur Journal of Applied Polymer Science, 42: 2661-2667.
vulcanization from QSPR studies. Rubber
Chemistry and Technology, 72: 318- 333. Langenbeck, W. and Rhlem, H. G. (1935). The mode
of action of disulfide accelerators of
Hopper, R. J. (1974). New types of premature vulcanization. Kautschuk Gummi Kunststoffe, 12:
vulcanization inhibitors. Rubber Chemistry and 156-159.
Technology, 47: 79-87.
Layer, R. W. (1992). Recuring of vulcanizates. I. A
https://www.tut.fi/ms/muo/vert/5_rubber_ novel way to study the mechanism of
chemistry/2_accelerators_types.htm vulcanization. Rubber Chemistry and Technology,
65: 211-222.
Kapur, R. S., Koeing, C. J. and Shelton, J. R. (1974).
Raman spectral studies of 2-mercapto- Leib, R. I., Sullivan, A. B. and Trivette, C. D. (1970).
benzothiazole accelerator systems. Rubber Prevulcanization inhibitor chemistry of scorch
Chemistry and Technology, 47: 911. delay. Rubber Chemistry and Technology, 43:
1188-1193.
Kok, C. M. (1987). The effects of compounding
variables on the reversion process in the sulphur Lorenz, O. and Echte, E. (1957). The vulcanization
vulcanization of natural rubber, European of elastomers. 13. The vulcanization of natural
Polymer Journal, 23: 611-615. rubber with sulphur in the presence of mercapto
benzothiazole. II. Kautschuk Gummi Kunststoffe,
Krebs, H. (1957). The mechanism of accelerator 10: 81-88.
action. Rubber Chemistry and Technology, 30:
962-971. McSwkeeney, G. P. and Morrison, N. J. (1983). The
thermal stability of monosulphidic crosslinks in
Kruger, F. W. and McGill, W. J. (1992). A study of NR. Rubber Chemistry and Technology, 56:
curative interactions in cis-1,4-polyisoprene. IX. 337-343.
The role of ZnO in thiuram based vulcanization
systems. Journal of Applied Polymer Science, 45: Milligan, B. (1966). Vulcanization accelerator and
749-753. activator complexes. II. Chemistry of amine and
118 JOSEPH et al.

zinc carboxylate complexes of zinc and Naunton, W. J. S., Baird, W. and Bunbury, H. M.
cadmium benzothiazolyl mercaptides. Rubber (1934). Delayed action accelerators. Journal of
Chemistry and Technology, 39: 1115-1125. the Society of Chemical Industry, 53: 127-131.
Minoura, Y. (1950). Organic sulphides and poly Neiuwenhuizen, P. J. and Reedijk, J. (1997). Thiuram
sulphides. I. Desulfuration reactions. Journal of and dithiocarbamate accelerated sulphur
the Society of the Rubber Industry of Japan, 23: vulcanization from chemists’ perspective:
212-215. Methods, materials and mechanisms reviewed.
Moore, C. G. (1958). The nature of the crosslinks in Rubber Chemistry and Technology, 70: 368-429.
tetramethyl thiuram disulphide-zinc oxide- Neiuwenhuizen, P. J., Timal, S., Van Veen, J. M.,
natural rubber vulcanizates. Journal of Polymer Hansoot, J, G. and Reedijk, J. (1998).
Science, 32: 503-506. Homogeneous zinc complexes during
Moore, C. G. and Trego, B. R. (1964). Structural accelerated vulcanization. Kautschuk Gummi
characterization of vulcanizates. Part IV. Use of Kunststoffe, 51: 336-341.
triphenyl phosphine and sodium-n-butyl Neiuwenhuizen, P. J., VanVeen, J. M., Hansoot, J. G.
phosphite to determine the structures of sulphur and Reedijk, J. (1999). Homogeneous zinc (II)
linkages in natural rubber, cis – 1,4-polyisoprene catalysis in accelerated vulcanization. IV. The
and ethylene-propylene rubber vulcanizate mechanism of crosslink desulfuration. Rubber
networks. Journal of Applied Polymer Science, 8: Chemistry and Technology, 72: 43-54.
1957- 1983.
Nieuwenhuizen, P. J., Haasnoot, J. G. and Reedijk,
Moore, C. G. and Watson. A. A. (1964). Structural J. (1999). Homogeneous zinc (II) catalysis in
characterization of vulcanizates. Part III. The cis accelerated vulcanization. II. (Poly) olefin
– 1, 4-polyisoprene-tetramethyl thiuram oxidation, dehydration and reaction with anti-
disulphide- ZnO system. Journal of Applied
reversion coagents. Rubber Chemistry and
Polymer Science, 8: 581-602.
Technology, 72: 15-72.
13
Mori, M. and Koenig, J. L. (1995). Solid-state C
Nieuwenhuizen, P. J., Van veen, J. M., Haasnoot, J.
NMR studies of vulcanized elastomers. XIII.
G. and Reedijk, J. (1999). Homogeneous zinc (II)
TBBS accelerated sulphur vulcanization of
catalysis in accelerated vulcanization. III.
carbon-black filled NR. Rubber Chemistry and
Degradation modes of mono- and disulfidic
Technology, 68: 551-562.
crosslinks. Rubber Chemistry and Technology, 72:
Morita, E. (1980). S-N compounds as delayed action 27-42.
chemicals in vulcanization. Rubber Chemistry and
Palaty, S. and Joseph, R. (2000). Xanthate accelerators
Technology, 53: 393-435.
for low temperature curing of natural rubber.
Morrel, S. H. (1982).The chemistry and technology Journal of Applied Polymer Science, 78: 1769-1775.
of vulcanization. In: Rubber Technology and
Palaty, S. and Joseph, R. (2004). Synergism of
Manufacture, second edition (Ed. C. M. Blow).
Buttenvorths, London, p172. xanthate/dithiocarbamate accelerator in carbon
black filled NR compounds. Iranian Polymer
Morrison, N. J. (1984). The formation of crosslink Journal, 13: 85-91.
precursors in the sulphur vulcanization of NR.
Rubber Chemistry and Technology, 57: 97-103. Palaty, S., Devi, P. V. and Joseph, R. (2011). Use of
sodium and potassium butyl xanthate as
Morrison, N. J. (1984). Reactions of crosslink accelerators for room temperature
precursors. Rubber Chemistry and Technology, 57: prevulcanization of natural rubber latex. Journal
86-96. of Applied Polymer Science, 122: 1325-1332.
Morrison, N. J. and Portor, M. (1984). Temperature Parks, C. R., Parker, D. K., Chapman, D. A. and Cox,
effects on the stability of intermediates and W. L. (1970). Pendent accelerator groups in
crosslinks in sulphur vulcanization. Rubber rubber vulcanizates. Rubber Chemistry and
Chemistry and Technology, 57: 63-85. Technology, 43: 572-587
Mukhopadhyay, R. and De, S. K. (1979). Effect of Porter, M. (1967). Sulphur vulcanization of natural
curing systems and temperatures on the activity rubber. In: The Chemistry of Sulfides, (Ed. A. V.
of retarder in natural rubber mixes. Polymer, 20: Tobolsky), Interscience Publishers, New York,
1527-1530. pp. 165-184.
 SULPHUR VULCANIZATION CHEMISTRY 119

Rodger, E. R. (1979). Vulcanization systems. In: Kinetics and mechanism of the reaction
Developments in Rubber Technology (Eds. I. A. of 2-mercapto benzothiazole with
Whelaw and S. K. Lee). Applied Science N- (cyclohexylthio) phthalimide and related
Publishers Ltd. London, pp.105-150. compounds. Rubber Chemistry and Technology, 42:
1513-1531.
Rooyen, J. V. (2007). A comparison of the vulcanization
of polyisoprene by a range of thiuram disulphides. Stiehler, R. D. and Wakelin, J. H. (1948). Mechanism
Ph. D Thesis, University of Port Elizabeth, S.A. and theory of vulcanization. Rubber Chemistry
and Technology, 21: 325-343.
Saville, B. and Watson, A. A. (1967). Structural
characterization of sulphur vulcanized rubber Sullivan, A. B., Davis, L. H. and Maender, O. W.
networks. Rubber Chemistry and Technology, 40: (1983). Reactivity optimization of
100-149. prevulcanization inhibitors. Rubber Chemistry
and Technology, 56: 1061-1079.
Scheele, W. (1956). Vulcanization with thiuram
disulphides. III. Vulcanization of natural rubber Tambe, T., Solis, S., Brendan. R., Sharma, B. B. and
with thiuram disulphides. Part III. The energy Waddell, W. H. (2007). Xanthate accelerators in
relationships in thiuram vulcanization. Rubber vulcanizing isobutylene-based elastomers.
Chemistry and Technology, 29: 29-36. Rubber World, 235: 40-58.
Scheele, W. and Kerrutt, G. (1965). Vulcanization Trivette, C. D. Jr., Morita, E. and Maender, O. W.
of elastomers. 39. Vulcanization of natural and (1977). Prevulcanization inhibitors. Rubber
synthetic rubbers by sulphur and sulfenamides. Chemistry and Technology, 50: 570-598.
II. Rubber Chemistry and Technology, 38: 176-188.
Twiss, D. F. and Jones, F. A. (1935). The restraining
Scheele, W. and Franck, A. (1959). The vulcanization of vulcanization in rubber manufacture. Rubber
of elastomers. 20. Sulphur vulcanization Chemistry and Technology, 8: 230-238.
accelerated with thiuram compounds. I. Rubber
Chemistry and Technology, 32: 139-149. Versloot, P., Haasnoot, J. G., Nieuwenhuizen, P. J.,
Reedjik, J., van Duin, M. and Put, J. (1997). Sulfur
Scheele, W. and Helberg, J. (1965). Vulcanization of vulcanization of simple model olefins, part V:
elastomers. 40. Vulcanization of natural rubber Double bond isomerization during accelerated
and synthetic rubber with sulphur in presence sulfur vulcanization as studied by model olefin.
of sulfenamides. III. Rubber Chemistry and Rubber Chemistry and Technology, 70:106-119.
Technology, 38: 189-203.
Versloot, P., Haansoot, J. G., Reedjik, J., Van Duin,
Scheele, W., Lorentz, O. and Drummer, W. (1956). M., Dyunstec, E. F. J., and Put, J. (1994). Sulphur
Studies of the vulcanization of high elastic vulcanization of simple model olefins. Part II.
polymers.III. Vulcanization of natural rubber Charecterization and reactivity of intermediate
with thiuram disulphides. Rubber Chemistry and vulcanization products of 2, 3 - dimethyl- 2- butane.
Technology, 29: 29-36. Rubber Chemistry and Technology, 67: 252-262.
Schotman, A. H. M., VanHaern, P. J. C., Weber, A. J. Versloot, P., Hansoot, J. G., Reedjik, J.,van Duin, M.
M., VanWijk, F. G. H., Hofstraat, J. W., Talma, A. and Put, J. (1994). Sulphur vulcanization of
G., Steenbergen, A. and Datta, R. N. (1996). simple model olefins. Part III. Vulcanization of
Studies on a new anti-reversion agent for 2,3-dimethyl-2-butene in the presence of
sulphur vulcanization of diene rubbers. Rubber different metal complexes. Rubber Chemistry and
Chemistry and Technology, 69: 727-741. Technology, 67: 263-279.
Shelton, J. R. and McDonel. E. T. (1960) Investigations Wolfe, J. R. (1968). The chemistry of sulphur curing.
of radical and polar mechanisms in IV. Effects of organic accelerators on the reaction
vulcanization reactions. Rubber Chemistry and of cyclohexene with sulphur. Rubber Chemistry
Technology, 33: 342-356. and Technology, 41: 1339-1347.
Son, P. N. (1973). Some observations on the www.britannica.com/EBchecked/topic/511800/
mechanism of cure retardation. Rubber Chemistry rubber/289653/Development-of-the-natural-
and Technology, 46: 999-1006. rubber-industry.
Son, P. N., Andrews, K. E. and Schooley, A. T. (1972). www.iisrp.com/Web Polymers/00 Rubber_intro.pdf

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