07 - Chapter 1 PDF

Abstract
The
bportance
of
vulcanization
of
elastomers, major types, and mechanism of

action have been reviewed in
this inlmductoly
chapter, Attention har been made to
invgtigate accelerated aed nandvulumkfion Possible mechanistls by which

tbe~Ooistakiogpkceare~~
Chapter
role of accekators, activators, 4 &ilks&\s

been described. The different types of
cros~liinksand importance Of each type -oh
1
~nt;rodu&bn
the specific properties of th$ resulting

vulcanizates etc. are discussed. Various
aspects
of
compound
vulcanization
like
vulcanization,
model
nbsafnine
generation are discussed. The 3gum&

of
binary
accelerators
met- of *eir
md
action
,*&wssible
uw
mentioned The meihod of double

&malion,
which
&:
P.C
&,
is usefiil for the
impmvement in pqwties, is also
Tbe different methods for

n e h v h and different metbods for Cstimatiag
crosslink densities are well explained.
Part of this chapter has been submitted to "Progress in Polymer Science" for
publication
Prepared by BeeHive Digital Concepts Cochin for Mahatma Gandhi University Kottayam
N a t u r a l rubber is one of' the oldest and widely used polymers

known to man, which accounts for its use in a variety of applications.
Originally natural tubber was used in the uncured state, but there were
drawbacks like softening in warm weather and highly increased rigidity in
cold weather [I]. This led Charles GoodYear in United States and Thomas
Hancock in England to the discovery of the process of vulcanization in the
years 1839 and 1843 respectively. Hancock was the first to observe that
sulphur alone would vulcanize rubber, whereas GoodYear had actually
used the first inorganic accelerator, lead oxide.
Vulcanization is the key process in the technology of rubbers. It is
difficult to come up with an equally old industrial process where most of
the chemistry remains unclear. Thus, despite the fact that 160 years have
passed, since the discovery of vulcanization, the exact mechanism is still
far from completely understood.
The word 'vulcanization' has English roots and was derived from
the name of the Greek and Roman God 'Vulcanus'. Nieuwenhuizen wrote
in his review [ 2 ] , "Vulcanus' was the ugliest of all the Gods; this
symbolizes the fact that vulcanization is a bad-smelling process. Inspite of
the ugliness of Vulcamls, due to his talents and character he married
'Venus' the most beautiful of all. Indeed we find that vulcanized rubber is a
wonderful product. as rneasured by its versatility, usefulness and broad
application
--
----
Introduchon 3
The use of elastomers as a material for finished products dates back

to the 1830's. Vulcanizat~on is basically the process of introducing
crosslinks between hydrocarbon chains. According to the definition of
American Society for Testing and Materials (ASTM), 'Vulcanization is a
chemical process i:n which the long chains of the rubber molecules become
crosslinked by reactions w ~ t h the vulcanizing agent to form three
dimensional structure:'. This reaction transforms the soft, weak, plastic-like
material into a strong elastic product. The rubber loses its tackiness,
becoming insoluble in solvents and more resistant to deterioration,
normally caused by heat, light and ageing processes. (Scheme 1.l)
Sulphur alone was the vulcanizing agent up to the discovery of
organic acceleratol:~in the early part of 20" century. It was quickly realized
that the use of accelerators gave improved properties and significantly
reduced the required cure times. The first accelerators were arnine-based
compounds, with other classes of accelerators following quickly. Other
compounds used in vulcanization in addition to sulphur and accelerators
are zinc oxide and saturated fatty acids such as stearic acid. These materials
are termed as activators. Rubber formulations can also include fillers such
as silica and carbon black and compounds such as stabilizers and
antioxidants.
1.1.
Methods of Vulcanization
The formarion of network structure is one of the essential conditions
for generating the elastomeric properties. Sulphur vulcanization is the most

widely used curing technique for rubbers, preferably for unsaturated ones.
The other curing methods include peroxide, resin, moisture, urethane, metal
oxide and radiation crosslinking [3]
Uncrossli~lktdstate
Crosslinked state
Scheme 1.1 Elaritomer chains in the uncured and cured state
Since the 1963 Natural Rubber Producers Research Association

(NRPRA) overview on the fundamentals of vulcanization chemistry [4], it
has become more and more apparent that, for the purpose of understanding
vulcanization on a molec:ular level, the different vulcanization systems
should be treated sep:xately. Even though the different vulcanization
systems are broadly similar in reactivity, it can be easily understood that a
small change in the reactivity of one chemical may have an important
influence on a whole series of chemicals. Indeed during vulcanization
different reactions take place at the same time. Infact, rubber technology
makes ample use of the knowledge that the different vulcanization systems
result in rubber materials having different properties and specifications.
1.1.1. Peroxide Vulcanization
A w ~ d evariety of peroxides are used to crosslink most type of
elastomers. The crosslinks formed by peroxides are purely carbon-carbon

linkages. The importance of perox~desis their ability to crosslink saturated
elastomers such as low-density polyethylene, ethylene-propylene rubber

silicone rubber etc., which cannot be crosslinked with other types of
vulcanizing agt.nt:i. Thc advantages and disadvantages of peroxide
crosslinking are given in Table I . 1.
Table 1. I . Advantages and disadvantages of peroxide crosslinking [ 5 ]
-.-
p~~
--
p~
Advantages
Simple compounding
Disadvantages
Expensive crosslinking agent
Good heat ageing resistance
Low mechanical strength
Low tension set and strain
Higher curing time
No mould contamination
Difficult hot-a~rcure
"-
Transparent rubbe
In addition to the disadvantages described in Table 1.1, there are
several other important limitations for peroxide crosslinking of rubbers.
One of them is that antioxidants can react with peroxide generated radicals
and can result in reduced crosslinking eff~ciency[ 6 ] . Another potential
problem is that carbon-centered radicals can react with oxygen. This
reaction will produce hydroperoxides and can lead to tacky, unvulcanized
surfaces.
The mechar~islnfor peroxide crosslinking is shown in Scheme 1.2.
The crosslinking reaction involves the homolytic decomposition of the
peroxide to produce alkoxy radicals followed by hydrogen atom
abstraction. Studies with model compounds indicate that the hydrocarbon
radicals predominantly undergo coupling rather than disproportionation.
The coupling reaction forms crosslink between polymer chains. For
polydiene elastomers experimental evidence indicates that the primary
radical formed by pcroxide decomposition abstracts a hydrogen atom from

a carbon alpha to the tlouble bond. In the case of natural rubber the methyl
group is also reactlve towards hydrogen atom abstraction.
KOOR
KO
P-ll
2P
heat or hght
---.
-
__t
C roc41nk
2 RO.
ROH + P.
P-P
Scheme 1.2. Mechanism of peroxide crosslinking (P-H saturated or

unsaturated elastomer)
1.1.2. Resin Crosslinking
Resin crosslinkir~gwas discovered around 1940's. It has been used

for curing unsaturated rubbers. Resin curing systems are extensively used
with butyl rubber for high temperature applications. Resin cures are slower
than accelerated sulphur cures and high temperatures are required, and they
can be activated only hy zinc oxide and halogen atoms. The resin has got
adhering capacity. l o molecular weight resin molecules diffuse into
rubber and thereby stiflens the rubber. An example of recipe for butyl
rubbers is given In 7ahlc 1 .I. In this SP-1055 is the phenolic curative.
Table 1.2. Recipe for vulcan~zat~on

by reslns
-
- -
Ingredients
Amount (phr)
Butyl rubber
100
Stearic ac~d
I.:esin SP- 10.55
12
Typical vulcanization conditions

Ttmperaturc ("c)
T m e (mln)
The phenol-resin crosslinking of butyl rubber is accelerated by
adding benzocarbonium ions to the double bond, forming a cyclic coumarone
structure or a non-cyclic compound as illusbated in the Scheme 1.3.
Scl~erne1.3. Mechanism of resin crosslinking,
Crosslinking
IS
considered to proceed via a mechanism such that a
coumaronc ring is procluced by a L)iels-Alder (4+2)-cyclo-addition reaction

of quinomethine. Compared to butyl rubber the resin crosslinking rates of
EPDM and nitrile rubber are low. Volintu et al. [7] have reported the
crosslinking of nitrile rubber with p-octyl-phenol formaldehyde resin.
1.1.3. Silane Crosslinking
This type of crosslinkmg is also called moisture crosslinking.

Alkoxysilane compounds ;Ire used as crosslinking agents together with water.
The silanes carry timctional groups, which are likely to react with rubbers.
Scheme 1.4. Mechanism of silane crosslinking
Introduchon 9
--
The moisturc crosslinking of polyethylene using vinyl silane is shown in

Scheme 1.4. Thc c n ~ s s l i i n greaction includes two steps; (I) the reaction of a
silane compound with a polymer (grafting) and (2) the condensation of the
silanol groups productd by hydrolysis of the alkoxysilyl goups. This process
was used for EPR for 1hc cable ~ndushy[El. The major advantage of this type of
cure is the applicability at relatively low temperature.
1.1.4. Metal Oxide Crosslinking

Chloroprene rubbers are generally vulcanized by the action of metal
oxides [Y, 101. The primary crosslinking agent is zinc oxide, which is used
along with magnesium oxide. Lead oxides are sometime used when low
water absorption is required. The reaction is thought to involve the vinyl
group of the elastomer, which is the result of 1, 2 polymerisation. A typical
recipe for metal oxide crosslinking is given in Table 1.3.
Table 1.3. Metal oxide systems for chloroprene rubber
--
Ingredients
-
--
Amount (phr)
--
Chloroprene rubber
100
100
100
ZnO
MgO
Calcium sttarate
4
5.5
Stearic acid
TMTM
DOTG
ETU
0.5
0.5
Sulphur
-
- --
1
----
Vulcanization conditions
-
Temperature ('c)
153
153
153
Time ( m ~In
15
15
15
Two routes have been proposed for the curlng. One requires the
incorporation of zinc atoms into the crosslink [Scheme 1.51; the other leads
to ether crosslinks [Scheme 1.61.
ZCHZ = C:H
CI
+ ZnO + MgO
Scheme 1.5. Mechanism of crosslinking in 1,2-poly chloroprene involving

incorpor;%tionof Zn atom [9]
mz + h'go
- zm
+ h'gc12
Scheme 1.6. Mechanism showing crosslinking in 1,2-poly chloroprene

through the formation of ether crosslinks [lo]
1.1.5. Radiation Induced
The most rccent type of crosslinking is- the md&-induced

crosslinking. This includes electron beam crosslinking, photo-crosslinking,
microw;~ve cro.;slinliing, ultrasonic crosslinking etc. Radiation induced
crosslinklng
IS a
physically induced chemical reaction, which is easier and
preferable for continuous curing technologies, and thus it has some

potential for the future. The radiation dose required for rubber differs.
Radiation crosslinkinp: of different rubbers are reported. [ I 1-13]. Upon
irradiation free radicals are formed in rubber molecules. The free radicals
can combine to f o m ~crosslinks as in the case with peroxide crosslinking. In
radiation crosslinkir~gof rubbers, kneaded rubber is placed in an aluminium
die and is pressed at 100-200'~for 5-10 minutes. It is then allowed to cool
under pressure and then exposed to radiation. The radiation dose required
for proper crosslinking is 90 M rad for NR, 17 M rad for NBR, 40 M rad
for CR, 10 M rad for silicone rubber and 10 M rad for CFM. The
mechanism
IS
shown in Scheme 1.7. The use of sensitizers can reduce the
required dose and radiation m e . Halogen compounds, frou us oxide, sulphur

monochloridc, and bases l i e amine, ammonia etc are used as sensitizers [14].
Radiation vulcanization for NR latex, SBR and functional monomers have
been reported [ I S 1.
l<;rd~c~lysis
of N K
H.H
P + H
Kad#)lysisof water
(haft polymersabon
K.+
nM
C'han transfer
P. + RH
KP. RH
R" P
Vl. +RP
l ' mmtton
~
R* l i '
+
RP.4 R.
RP.
P + P
RP+ R'
RP.
RP
R-R
Scheme 1.I. Mechanism of radiation vulcanization using sensitizer
1.1.6. High Temperature Crosslinking

This type of crosslinking is also called high velocity crosslinking
and is canitul out uves a te:mperature range of 170-230'~. However it is often
associated ~ v ~ t lsevesslcNn.
i
Chen and coworkers [I61 have shown that the
phenomeno~iot seversloii seems to appear when two competing reactions occur
during vulcan~i*lt~on.
Thest: two reactions are crosslinking and desulphuration.
The process
15
;t\\oc~ated with the formation of a trans-methine structure
(Figure 1 . I ) hy the tlesulphuration reaction. Morrison and Porter [I71
confumed that the obseirved reduction in vulcanizate properties is caused by two

reactions proceeding in parallel, i.e. desulphuration and decomposition.
Loo [I81 h z demonstrated that as the cure temperature rises, the crosslink
density drops and the degree of reversion increases. A constant level of
crosslinking is observed beyond the optimum cure time at temperatures
above 160"~.Temperature is thus a major factor than the duration of
vulcani7ation in detm~iningthe degree of crosslinking. Loss of properties at
elevated temperaturts could be avoided by two ways (1) opthimtion of the
accelerator/sulphur ratio and (2) use of an accelerator, which is less sensitive to
increased temperatures.
Figure 1.1
Structure of trans-methine
1.1.7. Dynamic \7ulcanization

Dynamic bulcanization is the process of vulcanizing the elastomer
during the melt-mixing process, with a non-vulcanizable molten
thermoplastic. One of the most interesting applications of accelerated
sulphur vulcanization is in the preparation of thermoplastic elastomers by
dynamic vulcan~z;ltion.
In this process, small rubber droplets are vulcanized to give

vulcanized rubber partrcles with stable domain morphology which are then
dispersed in the molten thermoplastic polymer to allow the blend to be
fabricated into finished products in thermoplastic processing equipment.
The diameters of the t:lastomer particles are reported to be in the 1-2 pm
range. Various blends of EPDM with polypropylene were dynamically
vulcanized with accelerated vulcanizing systems consisting of sulphur, zinc
oxide, stearic acid, tetramethyl thiuram disulphide and benzothiazyl
disulphide [ 191. Perox~de:jare also used for dynamic vulcanization.
Recently, new vulcanizing agents were introduced for dynamic
crosslinking of elastomer blends 1201. They were found to be eff~cientin
crosslinking and impant good mechanical properties to the resulting
vulcanizates.
1.1.8. Sulphur Vulcanization

Rubber vulcani~ationby sulphur, without any accelerators takes several
hours and is no longer of commercial importance. With the use of accelerators,
optimum curing can now be achieved in periods as short as 2-5 min.
Accelerated sulphur vulcanization is suitable not only for natural rubber (NR)
and its synthetic counterpart isoprene rubber (IR) but also for other
synthetic 1-ubbers >uch as polybutadiene rubber (BR), styrene butadiene
rubber (SBR). r~~trile
rubber (NBR), butyl rubber (IIR), and ethylenepropylene-diene rubber (EPDM). Sulphur vulcanization can be divided into
two categories; unaccelerated and accelerated sulphur vulcanization.
IInaccelerated hr~nulationstypically consist of sulphur, zinc oxide and a
fatty acid while a.ccelerated fbrmulations include an accelerator in the

system. A sub category of accelerated sulphur vulcanization is sulphur free
systems, which are also referred to as sulphur donor systems. In these
systems the sulphur needed for network formation is supplied by the
accclcrator. wh~chfunctions both as an accelerator and sulphur donor. It
should be noted that while un-accelerated sulphur systems are no longer of
commercial signif~cance,they are of interest as a starting point to the
understanding of accelerated sulphur vulcanization systems.
1.2.
Unaccelerated Sulphur Vulcanization

Unaccelera1:ed sulphur vulcanization, which is also referred to, as
'sulphur only' vulcru~izationIS the oldest form of vulcanization practices.

Sulphur only vulcanization chemistry involves many reactions that either
do not occur or, to much lesser extent in accelerated systems. These
reactions range from double bond migration, isomerisation and saturation
to chain cleavage, cyclisation and formation of vicinal crosslinks [21, 221.
Information about sulphur only vulcanization has been derived from model
compound reactions and subsequent analysis of these materials. Shelton
and McDonnel [.23:/ used .radical scavengers to evaluate vulcanization
mechanisms. From their studies they concluded that unaccelerated sulphur
vulcanization is a polar process. Another approach, which was used by
Blokh [241 ~nvolvedelectron paramagnetic resonance studies. Based on the
absence of a radical signal in the EPR studies, Blokh also concluded that
unaccelerated sulphur vulcanization proceeds via polar mechanism.
A major cause of disagreement on the mechanism of unaccelerated
sulphur vulcan~zatior~arises from the possible reactions of elemental

sulphur. The S, ring is; capable of undergoing homolytic (radical) and
heterolytic (polar) ring opening reactions. The mechanism by which the
vulcanization occurs is still open for debate. The free radical sulphurization
tells the formation of sulphur radicals via homolytic scission of the octet
sulphur ring as shown in Scheme 1.8. The sulphur radical abstracts a proton
from the rubber to form a carbon radical on the elastomer. The elastomer
radical opens the Sx ring to form a rubber bound sulphur radical capable of
forming crosslink structures. The polar mechanism is given in Scheme 1.9.
The key step in the polar mechanism is the formation of the threemembered sulphur-carbon charged ring. A major source for the uncertainty
has arisen from the inbactable nature of the cured vulcanizate. Cured
elastomers are insoluble; this eliminates most analyhcal techniques for
examining polymeric structures. To avoid these problems several methods
have been used; including model compound work [25-271, electron spin
resonance (ESR) 1281, ctienlical probes [29, 301, radical scavengers [23], solid
state C- 13-NMR (31-36], and analysis of the extra net work materials 1371.
The chemical probe work has allowed characterization and
quantification of the number of mono, di and poly sulphidic crosslinks. The
model compound work has been useful in providing information for
mechanistic studies by allowing comparison of products predicted by a
mechanism to the products obtained from model compound work [38].
Scheme 1.8.
Proposed radical mechanism for unaccelerated sulphur

vulcanization [4]
Electron spin resonance and radical scavenger work have been used
to examine whether radical processes are active during vulcanization with
various formulations and elastomers. Solid-state NMR work has been used
to elucidate the produ'cts of vulcanization. Analysis of extra network
materials has provided. insights ~ n t o the nature of the vulcanization
chemistry by analysis of content of various intermediates as cure
progresses [39].
Scheme I .9
1.3.
Proposecl polar mechanism for unaccelerated sulphur

vulcan~~ation
[4]
Accelerators
The discovery of acceleration of vulcanization using organic
compounds in 1006 1401 is next in Importance to ihe discovery of
vulcanizat~on ~tseif.in the carly days, vulcanization took several hours to

get completed. Today it has been reduced to a few minutes. Accelerators
reduced the vulcanization time drastically. The temperature can be reduced
and
111 some
case5 vt~lcanlzahoncan be done at room temperature. Furthennore
the proport~onuf sulpliur is reduced from 8-10 parts to 1-3 parts. The proportion
of' accelerator
IS
u:jually 1 part. The lowering of sulphur gives much better
oxidation resistance and some accelerators are good antioxidants.

The first ac.celerators were inorganic compounds. Among the basic
salts and metals owides, which are or have been widely used as
accelerators, htharge, lime magnesium oxide and zinc oxide are the most
important ones. Organic vulcanization accelerators were first utilized in the
~
140-461. Oenslager [41]
rubber industry in the beginning of the 2 0 century
in 1906, introduced the organic bases aniline and thiocarbanilide as
accelerators in rubber compounds to improve the quality of low grade
rubber and to accelerate the rate of vulcanization. Thus organic bases were
the first vulcanizatior~accelerators of rubber [47-491. Other accelerators
such as diphenyl guanidine (DPG) diorthotolyl guanidine [50-511 (DOTG)
and hexamethylene t&amine (HEXA) came in to use around 1910 and
were a great relief fair the people in the rubber industry because of their
relative non-toxlc character compared to the former ones.
Dithiocarban~atesand xanthates were widely used as accelerators.
Because of then instability, fast reactivity and poor processing safety they
are generally used in low temperature processing and curing and in accelerator
combinations. In 1925 Sebrell et al. [52-541 and Bruni et al. [55] discovered
independently that 2.-mercapto benzothiazole, its homologues, its disulphides
[56, 571 and its metal salts are very effective accelerators, which yields
vulcanizates of improved physical properties. 2, 2' dihobenzothiazole (MBTS)

was developed to give greater scorch safety at the use of fme furnace blacks,
delayed action accelerators like sulphenamide type (eg. Benzothiazyl derivative
of sulphcnamide) were developed for long processing safety and
satisfactory cure rates. L~ttemptsto modify the extraordinary fast ammonium
dithiocarbamates resulted in the zinc dialkyl dithiocarbamates. Further efforts
to substitute the mercaptan sulphur in dithiocarbamate resulted in tetra alkyl

thiuram disulphldcs like iretra methyl thiuram disulphide (TMTD), tetra methyl
ttuuram mono sulphides (TMTM) and thiuram tetra disulphida [58-601. They
are used as ultra accelera1:ors and vulcanizing agent itself. All of these
products are currently used in a large scale as accelerators.
Thus the
discovery of various types of accelerators which differ in their effects on

the rate of scorching, ageing etc. of rubber compounds and on the structure
of the resultant vulcanlza1:es which determines the ultimate property have
revolutionized the rubbt:r industry.
Based on the nature of curing and chemical nature, accelerators are
classified into several groups. The generalized classification is shown in
Table 1.4.
Table1.4. Principal
classes o f accelerators
vulcan~sationo f elastomers
used
in the sulphur
Compound
Property
Structure
~~
2-mercaptoben~oth~d~ole Seml-ultra
accelerator.
(MBT)
scorchy
2-2' dithiobenzothiazole
(MBTS)
Delayed action
semi ultra
accelerator
Sulphenamides
N-cyclohexyl benzothiazole Semi ultra
accelerator,
2- sulphenamide (CBS)
delayed action
N-t-butyl benzothlazoie
2-sulphenamide (TBBS)
i' TH3
Delayed action
- N ~ - C H ~
AH3
2-morpholinoth~o
benzothiazole (MBS)
Delayed action
N-dicyclohexyl
benzothiazole 2sulphenamide (DCBS:I
Delayed action ,
Thiurams
fast accelerator
a
a:>-
--
Tetramethyl th~urarn
monosulphide
(TMTM)
Ultra accelerator
Tetramethyl thiuram
disulphide (TMTD)
Ultra accelerator,
vulcanizing agent.
CH3
--
~ithiocarbamates Zinc diethyl dithio

carbamate (ZDEC)
cH\
N--C-S
/
CH3
Ultra accelerator
N--C
-C-N
PH3
\cn3
-s-SA-N
fi
/CH3
\ C H ~
Ultra accelerator,
low temperature
curing
Zinc isopropyl xanthate

(ZIX)
--
--
.-
R-0--C-
I1
S -
Na
Diphenyl guanld~ne
Mehum accelerator
]usedalong w ~ t h
(otheraccelerators
Di-orthotoly l
guanidine
Medium
accelerator
1.4.
Zn
II
Water soluble ultra

Sodium isopropyl xanthate
accelerator for latex
(SIX)
work
Amines
2+
0-- C - S
R-
Accelerated Sulphur Vulcanization

Accelerated
sulphur
formulations
are
the
most
common
vulcanization systems u:jecl in commercial and industrial applications. Due

to this reason, a large amount of work is going on in the fundamental and
applied aspects of accelerated sulphur vulcanization. The study of
accelerated sulphur vulcanization suffers from the same problems as
unaccelerated sulphur vulcanization including the ability of sulphur to
undergo both radical ancl ionic react~onsand the intractable nature of cured
vulcanizatcs. The necessity of understanding how the accelerators and
act~vators Interact and how these interactions affect the vulcanization
mechanism complicates the situation further.
A major contrtbuting factor to the disagreement over mechanisms is
the poss~blereact~onsthat sulfur and accelerators undergo. Sulphur occurs
naturally as an eight membered ring. This ring is capable of both homolytic

cleavage to form radicals or heterolytic cleavage to form ions [61]. Also,
the pr-cclse interaction of the accelerator and sulphur in the vulcanization
process has not been clearly elucidated. It is known that accelerator
complexes are found, but the action of actual sulphurating species has not
been determined. This fact and the possible reactions of sulfur and
accelerators have made it impractical to eliminate the radical or polar
mechanism. Several 1,esearchers have concluded that both radical and polar
mechanisn~sare operative (62-681, and that the precise nature is dependent
on the formulation.
The scorch delay or induction period is where the majority of
accelerator chemistry occurs. It should be noted that the scorch delay
varies widely between accelerators. In thiuram accelerated systems there is
little induction time: whereas in MBT accelerated system there is a short
induction time. In sulphenamides there is a long scorch delay. During the
scorch delay various accelerator complexes are formed. Early workers
have proposed 1691 a variety of conclusions to the exact nature and role of
these complexes. T:ypical cure curves for samples cured with different
accelerator systems are given in Figure 1.2.
Time
Figure 1. 2
Typlcal cure curve with different accelerator systems

A-Dithiocarbamates, B-Thiurams, C-Thiazoles,
D-Sulphenamides
While it is clear that specific complexes do form, it is still open for

debate that whether these complexes are the active sulphurating species or
whether an activated intermediate is formed. Accelerated sulphur
vulcanization has been found to consume the accelerator in the system at a
rate far greater than the ate of crosslinking [70]. This has led to the proposal
that accelerated vulcar~ization proceeds through an intermediate [71].
Subsequent research has provided strong evidence for the existence of this
species 126, 28, 67, 721. Coran [72j in his work, isolated a compound and
identified it as a complex consisting of the zinc salt of the accelerator
stabilized by interaction with stearlc acid. He modelled the mechanistic
scheme
fbr
the
formation
of
this
complex
crosslink~ng/sulphurizationas:
and
subsequent
where .A
accelerator, B = intermediate, B*
active intermediate (sulphurating
agent) Vu ==crosslink and a, p =constants to adjust stoichiomehy.

Research by Baneiee and co-workers [67,69,73-741 led to the
wnclus~ons that both polar and radical mechanisms are operative during
vulcaniiation. Their work indicated that several wmmorl accelerators including
MBT and TMTD were capable of undergoing both polar and radical reactions.
The propose:d radical mechanism of accelerated sulfur vulcanization
is shown in Scheme 1.10. The intermediate cleaves to form persulfuryl
radicals, which then abstract protons. The rubber radical reacts with
another intermediate to form a rubber-bound intermediate. Two rubber
bound intermediates then form the actual cross-link. Maturity of the
network occurs through sulfur exchange reactions. Isomerization, which is
widely observed in vulcanization [75], occurs through alkyl radical.
XSSxZrlSxSX
XSSx.
+ RH
R- + X,SS,ZnSxSX
RSxX
ihy
XSSx. + XSxZn*
---+XSSxH
+R.
---+ RSyX + XSx-y

+
RSxR+ XSyX
Scheme 1.10. Radical Mechanism of accelerated sulphur vulcanization

The proposed polar mechanism is shown in Scheme 1.1 1. The key
step is a concerted reaction of a ring structure leading to the formation of
the rubber hound in~rennediate on the sulfur crosslink.
Isomeriiition
occurs by loss of the rubber bound intermediate as an ion.
Scheme 1.11. Proposed polar mechanism of accelerated sulphur vulcanization

There are varying opinions on the concentration of the rubber
bound intermediate at any given time in the reaction process. The exact
nature of accelerated j u l f ~ rvulcanization is still a topic of much debate.
Recent advances in instrumental techniques have been able to provide
more information about the resulting structures, but the actual chemistry
involved is still not sufficiently clear. It is probable that both free radical
and polar mechanism, are operative and that the exact nature of the
vulcanization process will vary between different curing systems [ 7 6 ] .
The chemical structure, molecular weight and conformation of the
elastomers affect the efficiency of sulphur vulcanization and the physical
properties [77]. The sulphur vulcanization with unsaturated rubbers occurs
through complicated radical mechanism in terms of mono, di or
polysulph~dic bridges artd sulphur containing intra-cyclisation with the
polymer tnolecules. The crosslink density and distribution affect the
physical properties and the stab~lity on ageing and ;are dependent on
accelerator type, ratio of accelerator to sulphur, reaction temperature and
time 1781.
p
-
lntroduchon 27
--
Various structures formed in sulphur vulcanized natural mbber is

shown in Sche~nc1.12.
OTHER MODIFICATIONS
-7P
R
PENDENT
SIDE GROUP
(R=accelerator residue)
CYCLIC SULFIDES
-C-C-cc-c-c-c-cCONJUGATED UNSATURATION
Scheme 1.12. Gencmlizd structures in sulphur v u l d nahual rubber [79]

As the rate of vulcanization is directly related to productivity, it is
desirable to increase the rate by raising temperature. However at higher

temperature the el'fectiveness of sulphur cross-links is lower with a
sacrifice of the physical properties caused by the dissociation of sulphur
bonds and mbber chains. Thus the reactivity was controlled by additional
amounts of sulphur and accelerator instead of raising temperature. The
increase of sulphur addition leads to increase in crosslink density and the
proportion of po1y:;ulphidic linkage, causing a decrease in the stability on
ageing. With the increase of accelerators the effectiveness of sulphur
vulcanization having mono and disulphidic linkages is improved to give
stability on ageing [80]. The sulphur level determines the overall extension
of sulphurization, while the accelerator concentration determines the

efficiency of the formulation [36)
Layer 181 j used the unique approach of 'vulcanizate recurring' to
probe the role of sul.phur and accelerators in the curing and reversion
process. He concluded that sulphur determines the overall amount of
reaction, but the accelerator determines the length of sulphur chains. He
proposed that the key step in the curing reaction was the sulphur exchange
reaction [81, 821.
Model compound vulcanization (MCV) is the vulcanization of a
low molecular weight model for the rubber polymer. It is a prime research
technique applied to gain information about the chemistry of vulcanization.
?be compound selec1:ed for MCV should contain atleast one allylic
hydrogen, since crosslink fonnation involves the substitution of allylic
hydrogen for a sulphur link [ 2 ] .
The objective of an MCV study is to obtain information regarding
the chemistry of the repeating rubber unit, to elucidate the structure of the
crosslinked products that are produced during vulcanization and to study
the reactions of curatives in a rubber like environment. Ultimately this
knowledge would fu~nish information about the mechanism of the
vulcanization reactions [3!),83-84).
A typical cure curve obta~ningfrom rheometer is shown in the
Figure 1.3. The init~alportion of the curve is called the induction or scorch
period where much of the accelerator chemistry involves. As time goes on
torque increases and a~lainsa rnaximum value. This point indicates the
maximum torque. The time required to attain 90% of the maximum torque
is teni~edas the opti:mum cure time (tYO)where as the time required to
attain 10% of the n~aximumtorque is termed as the scorch time (t,,). After
attaining a maximum torque the crosslinks formed will be shortened or
destroyed. 'l'liis behavior is different for different compounds and the type
of curing.
Time
Figure 1. 3. Typical rheograph showing different stages on curing
Depending on the acceleratorlsulphur ratio desulphuration or

decomposition may occur. An out line of the mechanism is shown in
Scheme 1.13. Depe:nding on the type and nature of vulcanization the cure
curves exhibit different nature. After attaining the maximum torque, it may
increase further (m;arching), or decrease (reversion). (Figure 1.4) or levels
off.
Tune
Figure 1.4. Rheograph showing different behavior in modulus development
The choice of the accelerator in the process of sulphur vulcanization

determines the kind of network structure and consequently, Leads to the
specific material properties [ 8 5 , 861. The chosen accelerator affects the
cure rate and scorch sa,fety, as well as the numerosity and the average
length of the formed crosslinks. Both the number and the length of the
crosslinks
have
an
influence on physical properties
of rubber.
Monosulphidic crosslinks are regarded as being unable to exchange,

rearrange or break to relieve mechanical stresses without cleaving main
chains. Polysulphidic crosslinks on the otherhand are able to rearrange
under stress, through breaking and reforming and this is partly associated
with high incchanical strength. Also, changes during service are
determined in consid~srable measure by the strength of the crosslinks.
Shorter mono and disulphide crosslinks contain thermally stronger C-S-C
and C-S-S-C: bonds. which are associated with superior thermal and
oxidative itah~litier;. Studies have
been
undertaken
on
network
character~zatlonof n,atural rubber vulcanizates [87].

Accelerator + Activators
Active accelerator complex
Active sulphurating agent
1"
Rubber bound intermediate (RSyX)
Initial Polysulphidic crosslinks (RSxR)
I
I
Crosslink shortening with additional

crosslinking
Crosslink destruction with main chain
modification
S-S bond interchange
Final Vulcanizate Network

R-rubber chain, H- allylic hydrogen and X- accelerator residue
Scheme 1.13. Generalized mechanism of Vulcanization 1171
Based on the amount of accelerator and sulphur present, the
vulcanization systems are classified in to conventional (CV), semi-efficient
(semi-EV) and efficient (EV). The amount of accelerator and sulphur
present in these systems are given in Table 1.5
Table 1.5. Compos~tionof conventional, semi EV and EV cure systems [88]

--
-- --
Type of system
Conventional
Solphur (phr)
Accelerator (phr)
AIS ratio
2.0-3.5
1.2--0.4
0.1-0.6
The properties of the resultant vulcanizates are given in Table 1.6.

As seen from the mechar~ismof vulcanization given by earlier researchers
[4, 891 the active sulphurating agent is the zinc perthio mercaptide
complex. The concentration of this complex determines the type of
crosslinks formed. As the CV system has got greater amount of sulphur
compared to the accel~eratorthe possibility of forming more polysulphidic
linkages is higher for CN system. As the concentration of accelerator increases
two reactions viz., desulphuration or decomposition may occur. Desulphuration
results in mono and dimlphidic linkages while decomposition leads to cyclic

sulphides, conjugated dimes, cyclic sulphides etc. When the temperature is
increased the polysulphidic lmkages break into mono and di sulphidic
linkages. This explains the reversion shown at higher temperatures. This
leads to low strength and modulus. Properties like compression set and
thermal stability are better for EV systems. This is primarily due to the
lower amount of polysulphidic linkage in the EV system.
T h e general nature and amount of crosslinks present in an efficient
vulcaniz~ngsystem anti c:onventional system is given in Figures 1.5 and 1.6

respechvely.
It 1s seen that the amount of monosulphidic linkages is a
maximum in the effi~zientsystem and it increases initially and decreases

with cure time. A t the same time amount of polysulphidic and disulphidic
linkages decrease5 with tlme. The final network formed after the
desulphuratlon and decomposition reactions will be highly crosslinked with
mainly monosulph~dicbonds and there will be relatively few modifications
of the cyclic rulphide or conlugated triene type [4]. Such a network is
tenned efficlcntiy crosslinked.
61
'a
.,f-..-
Total
/'Monosulphide
RSSl
0.4
6.0
CBS
I.
zno
~ o u r i c~ c i d
*'.\,
6.0]
1.O
Polysulphide
.db\,_Dlsulphide
-- xs
2
3
4
Cure time at 1 4 0 0 ~
(h)
Figure 1.5. Features of NR vulcanizate produced by an efficient c r o s s l h g

system PI1
On the other hand desulphuration process proceeds slowly as in the
case of the compound depicted in Figure 1.6. Here the amount of
polysulphidic linkages is higher. There will be opportunities for thermal
decomposition, leading to reversion or loss of crosslinks and to networks
containing modific;itions. Further the crosslinks, which do survive, will be
di or polysulphidic and hence will be liable to further decomposition. These
networks are s a ~ dto be inefficiently crosslinked.
RSSI
CBS
ZnO
5.0
Cure time at 1 4 0 (h)

~ ~
Figure 1.6.
Features of NR vulcanizate produced by a conventional

crosslin~ki~ng
system [4]
Table 1.6. Vulcaniz~tea structure & properties of the different sulphur

curing systems [88]
Properties
CV
SemiEV
EV
Poly and disulphidic crosslinks (%)
95
50
20
Monosulphidic crosslinks (%)
50
80
Cyclic sulphide comcentration
High
Medium
Low
Low lemperature crys,tallization

resistance
High
Medium
Low
Heat ageing resistance
Low
Medium
High
Reversion resistance
Low
Medium
High
30
20
10
Compression set 22 hours at 70 OC (%)
1.5.
Role of Activators
Fatty aclds are ;generally regarded as indispensable activators in
conjunction w ~ t hzinc oxide. The function of fatty acid activators such as

stearic a c ~ d is
, to solubil~izethe zinc oxide, a secondary effect is an increase
in the amount of zinc sulphide produced. The zinc salts of fatty acids,
which are a type of surfactant, also solubilize insoluble accelerators to
form the actual catalyst. A general scheme of accelerated sulphur

vulcanlzatlon that clemonstrates the role of zinc oxide, in conjunction with
fatty acids
IS
shown ]In Scheme 1.15. [89]. Duchacek [90] noted that the
increasing the zinc oxide concentration increased the rate of extent of
crossl~nklngup to a certain zinc oxide concentration; this concentration is

believed to he the minimum level of zinc oxide needed to completely
convert the accelerator to the zinc-accelerator-sulphur complex. He also
noted that the optimum zinc oxide content to minimize reversion was
slightly greater than this minimum. Corm [72] also noted that the
induction timc had a dependence on the zinc oxide concentration in excess of
that required for fonnation of the accelerator-zinc complex. This suggests that
zinc exerts an influence lbeyond inclusion in the accelerator complexes.
ZnO
R'COOH
L
SX
-zr
-SX
- I
I
- - I
Rubber
Znccomplex
-
sx
Bnc complex
S,
Crosslink precursor
Scheme 1.15.
Role of ZnO, fatty acid and activator in accelerated

sulphur vulcanization [88]
X= Accelerator resiclue L = Ligand (basic nitrogen or zinc carboxylate)
Physical properties of vulcanizates depend on the type of crosslink
and the extent to which they are formed. When some of the properties
depend fully on degree of crosslinking some depend partly on crosslinking.
A brief out line of properties and their dependence on the degree of
crosslinking is given in Table 1.7

Table 1.7. Intluence of degree of crosshkmg on Physical Properties [I71
Property
--
- ----
Change with increase in

degree of crosslinking
Propert~csdependent only on degree of crosslinktng
Stlffne5s
Increase
Hardness
I ~ncrease
Properties partly dependent on degree of Crosslinking
Breaking elongation
Res~l~ence
Increase
Heat build up
Decrease
Solvent swelling
Decrease
Creep, Stress relaxation
Decrease
Set
Decrease
Abrasion resistance
Increase
Fatigue cracking
lncrease
Low temperature crysta11'lzatlon
decrease m rate
Tens~lestrength1 tear strength
--
--
Recently research work on safe accelerators has gained a lot of interest

[Yl-931.
Some of the accelerators are reported to be unsafe due to the
formation of carcinogenic compounds such as nitrosamines. It is reported

that accelerators derivvd from secondary amines are usually evolving
nitrosamines [911 Avoida~nceof unfavorable conditions, elimination of
secondary amine containing accelerators and elimination of formed

nitrosamines are the various possibilities of reducing nitrosamine
formation (921. N~trosaminecan be generated during the processing stage
of rubber. The faster the amine is produced from cure or the earlier it is
produced in the process cycle. the greater the opportunity for nitrosamine
formation 1931. This makes the synthesis of safe accelerators a field of
great interest.
1.6.
Sulphur Dorior Systems

Apart from using free sulphur as a crosslinking agent other
materials which could donate sulphur to the system are used for curing.
Tetramethyl thiurarn disulphide is found to act as a crosslinking agent in
the absence of sulphur. It is not known whether the reaction involves the
intermediate formation of elemental sulphur or whether the disulphide
itself is the active agent. It appears that under cure conditions and in the
presence of zinc onide, two thirds of the thiuram disulphide invariably
appears eventually as the zincdithiocarbamate.
3 R2N.CS.S.S.C.S.NR2
:?R2N.CS.SZn.S.CS.NIt2
+ 7
Rubber
'The network structures of sulphurless systems are similar to those
obtained from accelerated sulphur systems discussed in the preceding

section. It has been suggested that thiuram disulphides function during cure
by decomposit~on to yield active sulphur and Z I X , which together
constitute an accelerated sulphur system. In the past the opinion has been
that TMTD vulcanizes via the intermediate formation of TMTM and active
sulphur 1941 and recently the reverse has been suggested [95] ie., TMTM
vulcanizes in the presence of sulphur via the intermediate formation of
TMTD.
Another approach! for sulphur donor vulcanization was the use of
model compounds. This study by Gregg and Lattimer [25] used the cyclic
tebamer shown in Figure 1.7 to model cis-polybutadiene. Their conclusions
were similar to previous findings and elaborate about an ionic mechanism
involved in the process.
Figure 1.7. ('ornplex formed in the presence of sulphur donors
Another techn~quetax analys~sof sulphurless wlcanization has been the

use of DSC coupled w ~ t h chemical probe/equilibrium swelling 1961. The
results of this work ~ndicatedthat zlnc oxide dramatically increases the
lntroductlon 39
efficiency of vulca:nization, but is not required for sulphurization. The

advantage of sulphurless cure using TMTD is that the vulcanizates have
low sulphur conter~t;and excellent ageing properties. Further more the
curing 1s more effic~enl;than the normal efficient vulcanization (EV).
1.7.
Influence of Fillers
Reinforcmg and non-reinforcing fillers are used in rubbers. Fillers
are known to influence crosslinking reaction during vulcanization. Channel

blacks retard cure wh.en compared to furnace blacks, some silicas when
compared to silicates and hard clay when compared to whiting. All these
behavior depends on particle size. In most cases the cause of this
retardation 1s due to the greater or lesser acidity of the filler which
influences the kineticis of the crosslinking reaction. Fillers contribute to
crosslink~ngby adsorption of the molecules on their surface and appear to
be capable of modifying the course and efficiency of vulcanization reactions
either directly or through adsorption of curatives. Studies by Kraus [97] have
shown that regardless of the nature of the apparent fdler contribution it is
desirable to have the 'filler effect included in the 'degree of cure'.
Carbon black contains not only carbon atoms but also a number of
other elements such as hydrogen, oxygen, nitrogen and sulphur [98]. These
heteroatoms belong to the carboxyl, lactones, phenols and quinones present
on the surface of the black [99]. The physical and chemical interactions
between the black and the other ingredients can influence the chemistry of
curing and remforcement due to the fillen. Porter reported [loo] that the
crosslink density of a black reinforced vulcanization system increased about
25% compared to the corresponding unfilled one. Carbon black also increases
the rate of vulcankation and improves the reversion resistance [loll. The
degree of improvemerit depends largely on the size of the carbon black
particles. Structurally the black filled vulcanizate is found to contain fewer
polysulphidic linkages than the corresponding unfilled vulcanizate [102].
However the stmctural changes appearing will be small when compared
with the large effects of The fillers on the physical-mechanical properties of
the vulcanizates. Black tilled vulcanizates have a faster rate of cure and
better reversion resistance [103]. This has been related to the formation of
trans-methine structure in the vulcanizates in the reversion process.
In the presence of carbon black trans-methiie content is decreased.
This may be attributed to two reasons. (1) polymer-filler interaction or (2)
the improved crosslinking efficiency. The trans-methine structure of the main
chain modification is ,formed from the thermal instability of the polysulphidic
linkages through a desull~hurationprocess [104]. The amount of trans-methine
formation is a function o'f the initial concentrations of polysulphidic crossluk.
If the polymer-tiller interaction exerts a binding effect on the double bond
migration, some polysulphidic linkages, which would otherwise break up
through desulphuration in the unfilled systems, may survive in the black
filled vulcanizates. Thus in the reversion stage, the filled sample, in general
would be expected to contain more polysulphidic linkages than the unfilled
one. As the polysulphidic linkages have greater thermal stability in the
black filled samplt:. the trans-methine formation is reduced and the
reversion
resistance
11simproved [ 1031.
Introduction 41
~~~
1.8.
~~
Binary Accelerator Systems

The use of binary accelerator system is an aspect of vulcanization
that has been generating increased interest in recent years. Due to the
increased conlplexity of these systems only recently have papers begun to
probe the intr~caciesof binary system.
A binary accelerator system refers to the use of two accelerators in
a given formulation. Several authors have studied the synergistic behavior

of these systems (105-1101. Technically the use of binary accelerators is
quite old. Many amines such as diphenyl guanidine (DPG) are used in
combination with other accelerators such as MBT or sulphenamides to activate
the vulcanization reachon. However present day binary accelerators usually
consist of benzothiazole and thiocarbamate derivatives. Additionally MBT
and sulphenamidei; are often added to thiuram systems to increase the
scorch delay of these systems. There have been several approaches
analyzing the vulcanization behavior of binary accelerators. It is believed
that the improved properties of binary systems resulted from the formation
of combination acc.elerator complexes.
One way to illustrate this effect is to measure mechanical or physical
the optimum property
properties as a function of accelerator ratio and co~~elate
with the complex fixmation as shown in Figure 1.8. [110]. The effect of binary
accelerator combin,ation in natural rubber and butyl rubber, on the modulus
is given in the F~.gure1.8. In both the rubbers synergism in modulus is
observed for the accelerator combinations. It is observed from the figure
that for the sa:me accelerators synergism is observed at different
Ir\]
compositions I t means that optirnum concentration (complex formation) 1s
attamed at different c<Jm~posltion

of accelerator for different rubbers
-J
Ci
OTOS
Figure 1.8.
Isoprene-Isobutylene rubber
OBTS
Effect of binary accelerators in mechanical properties of

vu1canizate:s [110]
OTOS- N-oxydieth~~lerzethiocarbarnyl-N'-og~diethylene
sulphenamide.
0 B I - S V-oxydiethylene-2-benzolhiazolesulphenamide.
Now-a-days binary accelerators are widely used in industry. They

are becoming rncreaslr~gl,ypopular due to the fact that such mixed systems
(1) permit vulcanization to be carried out at lower temperature in lesser time
(2) produce vulcanirate with superior physical and mechanical properties

compared to those of a ajtock cured with a single accelerator.
lntroduchon 43
--
Though a great deal of work has been done on elucidating the

mechanism of vulcanization by single accelerators, little attention has been
paid so far to the chemishy of vulcanization with binary accelerator systems.
Dogadkin and co-workers [l 111 and S h e r and Watson [112, 1131
investigated a number. of popular accelerator combinations and found
mutual activation with many of them.
Depending on the experimental results obtained in the vulcanization
with var~ouscombinations of most generally used accelerators, Dogadkin

and co-workers [I 141 classified the various binary accelerators into the
follow~ngthree different groups
( 1)
Systems with synergistically active accelerators
This group consists of disulphides or mercaptans with

nibogen containing organic bases and disulphides eg. MBTS
TMTDMBT with MBSICBS etc.

(2)
Systems in which the mutual activity of the pair does not

exceed the activity of the most active accelerator used and
This group consists of sulphenamides with nitrogen
containing organic bases
(3)
Systenls ,with an additive action of the accelerators.

They include sulphenamides in combination with
TMTDl and those containing combination of accelerators

belonging to the same class.
lntroductran 44
Based on these observations Dogadkin and coworkers [I141

suggested that in the initial stage of vulcanization, the accelerators interact
with one another to ]form an active complex, which then disintegrate with
the formation of active free radicals responsible for initiating the
interaction of rubber with sulphur. Though the above classification of
binary accelerator systems is very useful, the mechanism suggested cannot
explain all the facts exhibited by the mixed accelerator systems. The
schematic representation1 of the action of binary accelerator proposed by
Dogadkin is shown in Scheme 1.16. But it could not fully explain all the
observed properties shown by binary accelerator vulcanization. Studies are
going on in search of more details about the mechanism of acceleration
performed by binary systems.
RSSR
R'KNH
-4
(disulphide) (amines w
sulphenamides)
Scheme 1.16.
{ ];\;
RSH + RS + RUN
inismediate
comolexes
(free radicals)
Schematic representation of the action of binary acaclerators
The synergistic activity of two or more different accelerators arise

from the interaction of the accelerators to form new intermediate
compounds which again actively take part in the vulcanization reaction
leading to enhancement of crosslink density and the rate of vulcanization
reaction [ 1151. Further investigations [I 16-1251 with binary accelerator
systems have provided more valuable information regarding the
mechanism of their action.
Moore et al. [1;!6] made investigations on the TMTD-TU binary
accelerator system. A novel mechanism was suggested to explain the
synerglstlc acuvity. This theory recognizes the importance of the

polybulphid~cintenmediates ( A ) formed during the vulcanization process,
which suhscquently react with the rubber chain to yield further
intenncdiates IB). These intermediates finally react to yield sulphurated
crossl~~rhs
RI1
XS,X
RH
RS,-IX
za3
---+
----
ZnO
RS,, IX
RSm-? R+-
E x s ) ~Zn
~~a
'C
(XS)zZn+
Scheme 1.17. Mechanism of the action of T M T D T h i o a binary system [126]

In the above niechanlsm X represents (CH3) N-C
S) and RH is
the rubber hydrocarbon. The crosslinking reaction shown in Step 3 follows

from the products of !Step 2 which itself requires the thiwam polysulphides
(A) produced in reactlon Step I . Hence it follows that any acceleration of

the latter must also lead to a corresponding increase in the overall
vulcanization rate.
Thiourea and i~tsderivatives have been used as accelerators in dry
rubber and lattices. In the works of Mathew et al. [120-1241 the
accelerating activity of several thiourea derivatives were compared.
Dithiobiurets of vaq~ingnucleophilicity were synthesized and compared.
Mini et al. [I251 has used amidino thiourea as a binary accelerator. In these
studies attempts h;ave been made to optimize the amount of the new
accelerator based on .the physical properties of the resulting vulcanizates.
The nucleophilic r~ahlreof thiourea and its derivatives is suggested as
responsible li~r tile ~ . u r eactivating nature of those binary accelerators.

Binary accelerators are e.rpected to improve the cure rate by improving the
crosslinking
111
rubber. l'his could be responsible for the improvement in
mechanical properties.
1.9.
Concept of Double Networks

The niodulus and strength of materials with flexible chain polymers
can be increased by orienration and crystallization of polymer chains. In

plastics and fibers, molecular chain orientation is maintained after
proc:essing as the chains are frozen by glassy state or crystallization. On the
other hand, in rubbers, orientation produced during simple processing will
decay after proceshirig.
Double network rubber refers to an elastomer that has been
crosslinked tw~cc.the second time while in a deformed state. The
deformation employed 1s simple tension, resulting in a rubber whose final
length exceeds the length after the initial, isotropic crosslinking. The ratio
of these two lengths relimed to, as residual strain does not uniquely define
a double net\\ork elastomer. A gl\en residual strain can be achieved with
different c o ~ ~ i l ~ ~ ~of
i ustrain
t i ~ ~ and
r ~ s crosslinking apportionment; between
the two n u t \ \ i l r h \ j 1271.
I)o~~l)le
nct\\ork rubbers ul'lkr a route to obtain superior mechanical
propertic\.
III
r l ~ a tthey may allou circumvention of the usual compromise
betwecir \t~l'tnessand strength. Santangelo and Roland [I271 have shown

that
~ L I I I Iriaturi~lrubbe1
double i~etworkcrystallizes at lower strain and can
have cilha~ic~~tl
tcilslle strength and fatigue life compared to conventional
single nct\\orks IJrepari:ng double networks or composite networks could

produce r-uhbcr v~rlcanizatesw ~ t hpermanent chain orientation.
D o ~ ~ b lnetwol-ks
e
can be viewed, as interpenetrating networks in
L ~ ~ I C I I 1111.
\:II~C
chain segnlcrrts bclong to both networks and more
rmpor-tanfly thc ~wmponentn e t ~ o r k sare oriented. It is this orientation that

gives rlse to enhancement and anisotropy in properties [128-1301. The
expectatlun. borne out by experiment is that the n~odulusof a double
network rubber will differ from the modulus of the compounding isotropic
elastomer. A1 h~gherresidual strains, the equilibrium modulus is higher.
Mott and Roland [I301 have studied mechanical and optical behavior of
double networked rubbers.
The network f o ~ m e dwhen a rubber is crosslinked will have an
equilibrium set of chain configurations. These configurations are usually
associated with a macroscopic state of zero strain, since this corresponds to
a condition of zero st!res,s[ I 3 I].
When the rubber 1s cured away from elastic equilibrium,
configurations prevailing during crosslinking will shift the subsequent
equilibrium state away from zero strain [132, 13311. However when the
crosslinking reaction takes place in a deformed state, an anisotropic crosslink
network will be prod~lced[134].
I h e properties of elastomeric network depend not only on the
density ol'lunetions but also on the distribution and orientation of the chains
when the junctions are formed. Llouble networks can also arise spontaneously
,via chain sciss~on[I351 and vla strain-induced crystallization [I361 or in the
presence of reinti)rclng fillers (137, 1381. The strength of oriented

networks are fbund to depend on the extent of orientation and crosslinlung.
The strain-induced crystal1iz:ation of natural ~ b b e imparts
r
the superior strength
to it. This is accon~plishedby the crystallization induced due to orientation.
Studies have to be made In order to find if any effect of crosslinking would help
to irnprove the strenyh o:Fdouble networks.
1.10. Characterization of Networks

Network structure of ordinary rubber vulcanizates is too complex to
be eluc~dated.The network structure of a vulcanized rubber could not be
related directly to its macroscopic properties. Different methods are
available for characteriza1:ion of rubber networks. The important methods
are ( I ) swelling method (2) freezing point depression method (3) dynamic
mechanical analys~s(4) stress-straln method and (5) NbIR measurements.
Swelling of vulcanizates in solvents has been proved to be an
effective nicthod to dett:rnmine the chemical crosslink density. Flory-Rehner
theory 1139) is used for the determination of molecular weight between
crosslinks. Flury Kehncr equation can be applied to the results of swelling
of rubber i n .;ultablc solvents.
In( 1-1 I . V q 7
x V, L ]
I i
V ) I M . . .. . . .........
. .
....( 1.4)
where L, I S rile equilibrium volun~efraction of rubber in swollen gel, p the

denslty I
~rihher. an interact~on constant characteristic of rubber and
swcll~ngI I L ~ L I I ~ i l n d V , the molar \olurne of the swelling liquid [140].

lrea1n1c.111
o t thc ~ ~ ~ I c a n i z aw
t e~st hdifferent thiols [I411 cleaves the mono,
dl and polysulph~diccrosslinks preferentially. This helps to find the relative

proportlun of crosslir~ks. I t has long been known that an anomalous
frce~111g
polnt depression of the swelling solvent in swollen gels was
observcd and that the magnitude of the depression was closely related to
the degl-ec of crosslinking and or the structure of swollen gels [142]. The
:stress-strain behav~or of rubber like networks
are influenced by
contr~but~ons
ol constraints caused by the uncrossability of the network
chains. IJsing theoretical results based on the tube approach to polymer
melts and networks [143], a well-founded separation of crosslink and
constralnt contributions to the stress-strain behavior can be achieved and a
reliable neth hod for the evaluation of the network prameters can be
developed. The Mooney equation [I441 is used for calculating the crosslink
density from stress-strain data. It was then modified by Rivlin and
Saunders j 1451.
where 'o'1s the force to extend a sample of cross-sectional area 'A: to

extension ratio ' 2 ,'p' is the density, 'R' is the gas constant and 'T' is the
absolute temperature.
Dynam~c mechanical measurement
is used to estimate the
entanglement density of the rubber vulcanizates. 'The modulus of the

rubbery plateau region is a direct measure of the entanglement density.
According to thc statistical theory of rubber elasticity, the crosslink density
for a tetra funct~onalnetwork can be calculated according to the equation,
where E' is the storage modulus in the rubbery plateau region, 'd' is the
density of the vulcanizate, 'R'is the gas constant and 'T'is the absolute
temperature.
A recent promising approach to direct analysis of the crosslink
structure and distribution in sulphur vulcanizates was the application of

solid state C" NMR spec;troscopy [75,146,147]. In a work on unaccelrated
sulphur vulcanization, a number of signals were also assigned to
n~onosulphidic crossliilks on the basis of calculated chemical shifts of
proposed structures [1'38]1. Chemical shifts differences between disulphidic
and trisulphidic crosslinks are of the order of 0.1 ppm. Crosslinking results
in broadening of the peaks. Recent studies [149, 1501 have shown that C"
high-resolution solid state NMR spectroscopy is a valuable method to
analyze the formation of polysulphidic and monosulphidic crosslinks at
various sites on the monorner unit in NR.
1.11. Scope and Objectives of the Work

As delineated frcm the previous discussions, studies on vulcanization,
which leads to, the mechmism of the curing proms is a hot topic of elastomer
research. Despite the ongoing work, little effort is being made in order to
elucidate the mechanisnn of curing with accelerator combinations. Several
opinions do exlst regarding the pathways of the curing process. Model
compound vulcanization and structural analysis of the adducts formed by
the interaction of additives have helped to go further into the discrepancies
prevailing in the comple:~process going on in the vulcanization process.
Recently vulc:anization using thiourea derivatives have gained

interest in the fields o'f elastomer research. Studies have been reported [125,
15I ] regarding the nucleophilic activity of thiourea based compounds. They
have been tried as secondary accelerators in rubber vulcanization. Mathew et al.

[ 120-I241 compared the accelerating capability of various dithiobiurets in
elastornem. They used dithiobiurets as a secondary accelerator instead of tetra

methyl thiuram disulphide. However no systematic efforts have been done to
evaluate the acceleraing capacity of the 1-phenyl -2,4dithiobiuret
The work {embodied in this thesis focuses on the synthesis and
characterization of 1-phenyl-2, 4-dithiobiuret (DTB) and the use of it as a
binary accelerator with sulphenamides in the vulcanization of rubbers. The
investigation canied out on the effect of DTB as a binary accelerator in natural
rubber, styrene butadiene rubber and their blends are addressed to evaluate the
curing behavior, cure kinetics, mechanical properhes, net work chamderktics
and dynamic mechanical properhes. The important objectives of the thesis are
listed below.
1.ll.aInfluence of DI'B/DCBS as a binary accelerator system in NR
DTB was used as a secondary accelerator with dicyclohexyl
benzothiazole sulphmamide (DCBS) in natural rubber. The efficient and

conventional curing !systems were studied. The purpose of the study was to find
an optimum concentration for the new binary accelerator system. Studies have
been done on mechanical proper!ies, chemical chamterhtion, dynamic
mechanical behaviour etc.
1.ll.b. Influence of DTBlTBBS binary system in NR

The effect of DTB as a secondary accelerator with TBBS in NR is
carried out. Studies have been done on the cure characteristics, cure
kinetics, mechanical properties, dynamic mechanical properties and
network characterization of the vulcanizates.
1.ll.c. Effect of DTH/MBS system on NR

Processing characteristics, mechanical properties and network
characteristics of MB&I)TB cured NR vulcanizates were done in this
section. The effect of' fillers like carbon black and silica on the technical
properties of rubber vulcanizates was also investigated. Dynamic
mechanical analysis was performed to study the effect of DTB on
crosslinking and the damping behaviour. A systematic comparison is made on
the effect of DTB with DCBS, TBBS and MBS on the vulcanization of NR.
1.ll.d. DTB as a binary accelerator in SBR
Since SBR is also a general-purpose rubber, studies have been

extended to SBR vulcanization using DTB. Owing to its lower
unsaturation, greater amount of accelerator is expected to be required in
SBR vulcanization. DTB was added to SBR and the curing behaviour
along with the technical properties has been analysed.
Introduction 53
1.ll.e. Technical properties of NRJSBR blends cured with DTB
The Influence of DTB as a secondary accelerator in the curing

behavlour, mechanical properties, dynamic mechanical properties and
network character~stlcshas been studied In this section.
1.ll.f. Double network formation in Natural rubber
The introductioa of double networks was expected to impart better

mechanical properlies to elastomers. The influence of the binary
accelerator systems on the double network formation in NR was studied.
The influence of the extent of crosslinking and different residual extension
ratios were tried in order to get a clear idea of the factors influencing the
formation and stability.of these networks.
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Abstract

elastomers, major types, and mechanism of

chapter, Attention har been made to

invgtigate accelerated aed nandvulumkfion Possible mechanistls by which

role of accekators, activators, 4 &ilks&\s

the specific properties of th$ resulting

generation are discussed. The 3gum&

mentioned The meihod of double

is usefiil for the

impmvement in pqwties, is also

Tbe different methods for

N a t u r a l rubber is one of' the oldest and widely used polymers

The use of elastomers as a material for finished products dates back

for generating the elastomeric properties. Sulphur vulcanization is the most

Scheme 1.1 Elaritomer chains in the uncured and cured state

Since the 1963 Natural Rubber Producers Research Association

elastomers. The crosslinks formed by peroxides are purely carbon-carbon

elastomers such as low-density polyethylene, ethylene-propylene rubber

Good heat ageing resistance

Low mechanical strength

Low tension set and strain

Higher curing time

radical formed by pcroxide decomposition abstracts a hydrogen atom from

Scheme 1.2. Mechanism of peroxide crosslinking (P-H saturated or

Resin crosslinkir~gwas discovered around 1940's. It has been used

Table 1.2. Recipe for vulcan~zat~on

I.:esin SP- 10.55

Typical vulcanization conditions

Scl~erne1.3. Mechanism of resin crosslinking,

considered to proceed via a mechanism such that a

coumaronc ring is procluced by a L)iels-Alder (4+2)-cyclo-addition reaction

This type of crosslinkmg is also called moisture crosslinking.

Scheme 1.4. Mechanism of silane crosslinking

The moisturc crosslinking of polyethylene using vinyl silane is shown in

1.1.4. Metal Oxide Crosslinking

Table 1.3. Metal oxide systems for chloroprene rubber

Scheme 1.5. Mechanism of crosslinking in 1,2-poly chloroprene involving

Scheme 1.6. Mechanism showing crosslinking in 1,2-poly chloroprene

1.1.5. Radiation Induced

The most rccent type of crosslinking is- the md&-induced

physically induced chemical reaction, which is easier and

preferable for continuous curing technologies, and thus it has some

shown in Scheme 1.7. The use of sensitizers can reduce the

required dose and radiation m e . Halogen compounds, frou us oxide, sulphur

Scheme 1.I. Mechanism of radiation vulcanization using sensitizer

1.1.6. High Temperature Crosslinking

;t\\oc~ated with the formation of a trans-methine structure

(Figure 1 . I ) hy the tlesulphuration reaction. Morrison and Porter [I71

confumed that the obseirved reduction in vulcanizate properties is caused by two

1.1.7. Dynamic \7ulcanization

In this process, small rubber droplets are vulcanized to give

1.1.8. Sulphur Vulcanization

fatty acid while a.ccelerated fbrmulations include an accelerator in the

Unaccelerated Sulphur Vulcanization

'sulphur only' vulcru~izationIS the oldest form of vulcanization practices.

A major cause of disagreement on the mechanism of unaccelerated

sulphur vulcan~zatior~arises from the possible reactions of elemental

Proposed radical mechanism for unaccelerated sulphur

Proposecl polar mechanism for unaccelerated sulphur

compounds in 1006 1401 is next in Importance to ihe discovery of

vulcanizat~on ~tseif.in the carly days, vulcanization took several hours to

case5 vt~lcanlzahoncan be done at room temperature. Furthennore