Anin aATLAL CROIP

NOCIL LIMITED

Vulcanization & Accelerators

Vulcanization is a cross linking process in which individual molecules of rubber (polymer) are converted intoa
three dimensional network of interconnected (polymer) chains through chemical cross links(of sulfur).

Sulfur
Heat

Raw Rubber Vulcanized (Crosslinked) Rubber

Sulfur
Heat Sx

The vulcanization process was discovered in 1839 and the individuals responsible for this discovery were
Charles Goodyear in USA and Thomas Hancock in England. Both discovered the use of Sulfur and White
Lead as a vulcanization system for Natural Rubber. This discovery was a major technological breakthrough for
the advancement of the world economy.

Vulcanization of rubbers by sulfur alone is an extremely slow and inefficient process. The chemical reaction
between sulfur and the Rubber Hydrocarbon occurs mainly at the C = C (double bonds) and each crosslink
requires 40 to 55 sulphur atoms (in the absence of accelerator). The process takes around 6
for completion, which is uneconomical by any production standards. The vulcanizates thushours at 140°C
produced are
extremely prone to oxidative degradation and do not possess adequate mechanical properties for practical
rubber applications. These limitations were overcome through inventions of accelerators which
became a part of rubber compounding fomulations as well as subjects of further R&D. subsequently
Following is the summary of events which led to the progress of 'Accelerated Sulfur Vulcanization'.

Event Year Progress

|- Discovery of Sulfur Vulcanization: Charles Goodyear.
1839 Vulcanizing Agent
- Use of ammonia &aliphatic ammonium derivatives: Rowley. 1881 Acceleration need
- Use of aniline as accelerator in USA &Germany: Oenslager.
1906 Accelerated Cure
-Use of Piperidine accelerator- Germany. 1911 New Molecules
-Use of aldehyde-amine &HMT as accelerators in USA &UK
1914-15 Amine Accelerators
-Use of Zn-Alkyl Xanthates accelerators in Russia. 1919-20 New Molecules
-Use of Thiurams&Dithiocarbamates-Germany. Speed Control
-Effect of ZnO on cure rate, discovery of DPG, MBT, MBTS
1919-22 Delayed Action
-R &D efforts for more effective delayed action accelerators.
1930 Delayed Action
-Sulfenamide accelerator developed- USA. 1937 Delayed Action
-Several other Sulfenamide accelerators developed
1945 Delayed Action
-Pre Vulcanization Inhibitor CTP- USA 1970 PVI
-Post Vulcanization Stabilizers 1990s. PVS
 OCIL
ARVIND MsIATLAL CROUF
NOCIL LIMITED

Sulfur remains the most successful and economnical cross

linking agent even today!
Sulfur as vulcanizing agent has a limitation that, the elastomers must contain chemical unsaturation (C=C
double bonds) for sulfur cross
linking. The structure of speciality elastomers EPDM and Butyl had to be
chemically modified to make sulfur vulcanization possible for their commercial Success.
Other chemicals used for cross linking of
polymers are Sulfur Monochloride, Tellurium, Selenium, Thiuramm
accelerators, Polysulphide polymers, p-Quinonedioximes, Metallic Oxides, Organic Peroxides,
etc. (mostly for specialized applications). Di-isocyanates,

In the case of fully saturated

elastomers organic peroxides are often used for cross linking.
Accelerators:
An accelerator is defined as the chemical added into a rubber compound, to increase the
vulcanization and to permit vulcanization to proceed at lower temperature and with greater efficiency. speed of
Accelerator also Decreases the Quantity of Sulphur necessary for vulcanization and thus
properties of the rubber vulcanizates. improving 'aged

Classification of Accelerators:

Accelerators Chemical Group Vulcanization Speed

BA, HMT Aldehyde Amine Slow
DPG, DOTG Guanidine Slow
MBT, MBTS, ZMBT Thiazole Semi Ultra fast
ZBDP
Thiophosphate Ultra fast
CBS, TBBS, MBS, DCBS Sulfenamides Fast-Delayed action
ETU, DPTU, DBTU Thiourea Ultra fast
TMTM, TMTD, DPT, TBZTD Thiuram Ultra fast
ZDMC, ZDEC, ZDBC, ZBEC Dithiocarbamate Ultra fast
ZIX Xanthates |Ultra fast

Accelerators are also classified as Primary and / or Secondary accelerators based on the role they play in a
given compound.
Generally, Thiazoles and Sulfenamide accelerators play a role of being Primary Accelerators due to their
characteristics such as good processing safety, a broad vulcanization plateau and optimum cross link
as well as desired reversion delay that they offer. The Primary Accelerators are used at 0.5 to 1.5 density
in most rubber
phr dosages
compounds.
The basic accelerators such as Guanidines, Thiurams, and Dithiocarbamates etc are used as
accelerators to activate the primary accelerators. The use of secondary accelerators increases theSecondary
vulcanization substantially but at the expense of scorch safety. The dosages of the speed of
secondary accelerators are
generally between 10-40% of the primary accelerator.
 102 Chapter 8
temperatures involved. Such a product was introduced by Monsanto as San-
tocure, the brand name for N-cyclohexyl-2-benzothiazolesulfenamide.
Competi-
tors entered the large market that developed, and accelerators of these types were
labeled delayed action accelerator because of their safc processing quality.
Since the time of Oenslager, acc elerator development has concentrated on
nitrogen- and sulfur-containing organic compounds. Besides accelerating the
cure, these materials impart better aging to the compound. It was also found that
accelerators functioned best when accompanied by metallic oxides such as lead,
zinc, or magnesium oxides along with a fatty acid. Stearic acid is the one usually
used, but oleic and others have been employed. Together the oxides and fatty
acids are called activators and are discussed in Chapter 9.
There is a wide variety of accelerators available to the compounder. Including
single compounds and blends they would easily number over 100. For ease i
understanding, it is useful to classify accelerators by chemical structure. One
such classification. made by the ASTM 13], is as follows:
Class I. Sulfenamides
Class 2. Thiazoles
Class 3. Guanidines
Class 4. Dithiocarbamates
Class 5. Thiuram disulfides
Class 6. Thiurams other than tisulfides
Possibly because of lower usage n concerns about toxicity, two classes are
omitted from this list, namely alde hyde amimes and thioureas. Because of the
cumbersome length of the full chemical names, acronyms are commonly used for
accelerators and antioxidant (see I si ing in Appendix Il).
Three general precautions in tte use of accelerators might be noted here.
Along with age resisters. they usuz lly are the smallest in weight and volume of
all the ingredients of a batch. To avcid dusting loss in mixing, the
compounder
can use accelerators in various fonns (e.g., pellets), in elastomeric master
batches, or attached to carrier mate rials. To avoid precure, accelerators usually
are added at the end of the mixing cycle. This measure can also minimize loss of
accelerator by volatilization. Accelerators can cause unsightly bloom on rubber
vulcanizates, so their use in amounts greater than their solubility in rubber should
be avoided.
Although many accelerators are: sing)le organic chemical compounds, density
ranges are often quoted by suppliers. Frequently these limits are 0.03; for
example, density of N-cyclohexyl-2-benzothiazolesulfenamide is given as 1.28
0.03. This tolerance allows for the inclusion of various inert materials used to
increase handling ease of the proc uzt. Crystal-packing density may also play
a part. In compounding, the accelerator used in greatest amount is called the
primary accelerator; those in smaller amounts are the secondary accelerators or
kickers.
 Accelerators 103

Because accelcrators are so important to vulcanizate results, when a butch

cures unsafisfactorily, one of the first matters checked should be whether these
additives have been omitted from the balch. If a simple addition of accelerator to
a small portion of stock in the correct ratio gives normal results on vulcanization,
the batch usually can be saved. The stock is simply remixed with the addition of
the accelerator. If abnormal results still occur when a small portion of the stock is
tested, the accelerator used with that lot might be tested. perhaps simply by
testing its melting point with a good reference sample. Rubber compounds can be
compared on the basis of standard refcrence sampies of certain common acceler
ators, obtainable from the U.S. National Institute of Standards and Technology
The ideal accelerator (not yet developed) would be inexpensive and nontoxic,
and wouldn't stain, discolor, or bloom. It would be widely compatible with other
accelerators. The accelerator would be stable during all processing operations up
to and including flow into a mold, but would have a fast rate of cure at i normal
vulcanizing temperatures to give short, economical vulcanization times.

II. THEORY OF USE

It is remarkable that for 150 years sulfur has remained the most popular
over
vulcanizing agent for natural rubber and general-purpose synthetics. Ther
tions are complex: we are dealing with elastomers having various amounts of
unsaturation, as well as the action and interaction cffects of (usually) metallic
Oxides, fatty acids, accelerators, and sulfur. Although natural rubber has a fixed
amount of unsaturation, different lots can show different rates of cure
dependent
on the amount and kind of nitrogenous material present. Probably the most basic
and far-reaching studies in the field were made by the scientists associated with
the laboratornies of the Malaysian Rubber Producers Research Association in
England. Many of their findings were published in Natural Rubber Science and
Technology in 1988, edited by A. D. Roberts, available from The Oxford
University Press. Another comprehensive volume dealing with this field, Vulca-
nizing of Elastomers, cdited by G. Aliger and1. J. Sjothun (Reinhold Publishing
Corp., 1964), is a compilation of lectures on this subject at the University of
Akron under the sponsorship of the Akron Rubber Group.
As a starting point, the system natural rubber and sulfur might be considered
If such a mixture is heated, probably a free radical process is involved in which
the eight-atom sulfur rings break down into free radicals:

S S
These free radicals unite with olefins like natural rubber

S +2R-R-S R
When sufficient polysulfidic materials are present, they serve as polysulfenyl
 Accelerators 107

other properties might be included such as viscosity and boiling point of liquid
accelerators. 2-Benzothiazolesulfenamides are the most generally used accelera-
tors today. They are subject to degradation during long storage, however, and in
that condition their performance characteristics are impaired. A melting point
detemination may indicate deterioration, especially if a heating loss test is run as
well. A heating loss test essentially measures moisture, and degradation of this
accelerator may be caused by hydrolysis. Some accelerators have higher melting
points than usually occur in mixing. To achieve even dispersion, the powder
form should be used. Some evidence of dispersability is obtained by wet sieving
the accelerator-obviously if this is difficult, dispersibility is questionable.

A. Sulfenamides
The latest significant development in accelerators occuTed in the 1930s when
Zaucker and Bogemann discovered that sulfenamides were delayed-action accel-
erators of vulcanization [4]. Then in 1937 Harman discovered
N-cyclohexylben-
zothiazole-2-sulfenamide [5]. The delayed action this type of accelerator pos-
sessed became particularly in demand with the introduction of scorchy oil
furnace blacks in the 1940s. Since then developments have been directed to
developing still greater delayed action.
Sulfenamides are made in two ways: by the reaction of 2-mercaptobenzo
thiazole with an N-chloramine and by oxidation of the appropriate amine salt of
2-mercaptobenzothiazole. Most suppliers promote one or more sulfenamide-type
accelerators. The original N-cyclohexylbenzothiazole-2-sulfenamide, marketed
by Monsanto as Santocure, is sold as Vulkacit DZ by Bayer, as Vulcafor HBS by
Imperial Chemical Industries, and as Durax by Vanderbilt.
The various sulfenamides retlect in their scorch times and cure rates
differ
ences in the amines used in their manufacture. If the amine is
highly basic, the
scorch time is lower, the cure rate faster. In terms of
processing safety, N,N-
diisopropyl-2-benzothiazolesulfenamide (e.g., American Cyanamid's DIBS) is
probably the highest, with N-cyclohexylbenzothiazole-2-sulfenamide the lowest.
The trend is to use the modifications of the
original sulfenamide accelerators that
give greater processing safety. A popular accelerator is now N-tert-butyl-2-
benzothiazolesulfenamide (TBBS). Besides giving a longer scorch delay timec,
this product gives higher modulus than CBS, so
dosage can be reduced 10%.
In a 50-part HAF black natural rubber stock, 0.5 part of TBBS with 2.5
parts
sulfur gives a Mooney scorch time of
approximately 13 min. This resuit is the
time required for a 10-point rise in the
Mooney viscosity at 275°F. In an
equivalent SBR stock with a curative system of1.75 parts sulfur and 1.25
parts
TBBS, 1he scorch time under the same conditions is about 25 min.
frequently the sulfenamides are used with secondary accelerators like [Link]
Starting curing formulations in an NR stock might be 0.70 part sulfenamide,
 108 Chapter 8

0.10 TMTD, and 2.25 sulfur. In an SBR stock the proportions would be 0.90
sulfenamide, 0. 10 TMTD, and 1.90 sulfur.

B. Thiazoles
By far the most popular [Link] are the thiazoles and derivatives of the
thiazoles, the sulfenamides. Probalbly over 70% of the accelerators used are ot
these types. Their good qualities are the effective acceleration they provide at
medium and high temperatures and their wide range of curing rates and
scorchin8
characteristics. Quite frequently they are paired with a secondary accelerator to
derive maximum levels of process irg safety and vulcanization rate.
Raw materials for this class of accelerator are aniline, carbon disulfide, and
sulfur. The chief thiazole accelerators are 2-mercaptobenzothiazole, mercap-
tobenzolhiazole disulfide, and the zinc salt of 2-mercaptobenzothiazole. Two of
the oldest names in accclerators, going back to the 1930s, are Captax and Altax,
Vanderbilt's brand names for 2-mercaptobenzothiazole (MBT) and mercap-
tobenzolhiazole disulfide (MBTS). 1he zinc salt is supplied by several manufac-
turers, including Monsanto, which nakes Bantex. The zinc salt is rarely used in
dry compounding but is used more in latex foams and dipped goods. Both MBT
and MBTS can easily cause scor:t ing problems when used alone in furnace
black natural rubber stocks. MBTS is somewhat safer to process than MBT. It is
common practice to use a kicker with MBTS and MBT. MBTS is often used with
DPGto give a safe, fiexible system1 in many mechanical goods stocks. A starting
curative system for an SBR stock might be 1.5 MBTS, 0. 15 TMTD, and 2.80
sulfur.

C. Guanidines
The two main guanidine acceleraiors are diphenylguanidine (DPG) and di-o
tolylguanidine (DOTG). The guan dines are now rarely used as primary accelera-
tors because of their slow curing. They can be used as primary accelerators in
natural rubber roll-covering stocks, where long cure times are used at compara-
tively low temperatures to assure the most unifom state of cure throughout the
thick covering. Their main use s as a secondary accelerator in thiazole- or
sulfenamide-accelerated natural rubber or SBR stocks. A common ratio is 0.25
part DPG to I part of thiazole or sulfenamide accelerator. Although both
white powders, guanidines can stain to some extent so they are not used in the
best white or light-colored stocks

D. Dithiocarbamates
Dithiocarbamates, the metal salts and amine salts of dithiocarbamic acids, are
called ultra-accelerators because of their quick cuning characteristics. Popular
members of this class are the zirc methyl and cthyl dithiocarbamates. Salts of
 Accelerators 109

bismuth, cadium, copper, lead. selenium, and tellurium also are used. An
accelerator like selenium dimethyldithiocarbamate is useful in low sulfur or
sulfurless cures (discussed later).
Dithiocarbamates are so powerful that they are rarely used alone cxcept in
such specialties as spread goods (fabric covered with a rubber coating: c.g
hospital sheeting) cured in air at or slightly above room temperature. Usually
they are paired with thiazole or sulfenamide accelerators to adjust the cure rate of
a stock. A typical curing system with natural rubber might be 0.5 part of zinc
dimethyldithiocarbamate (ZMDC), 0.75 part of a thiazole accelerator, and 2.0
parts of sulfur. With SBR stocks the system might be 0.6 ZMDC, 0.75 thiazole,
and 1.8 sulfur. Usually nonstaining, the thiocarbamates are versatile accelcrators
and are used in lIR and EPDM as well as NR and SBR. Typical commercial
brands are Vanderbilt's Ethyl Tellurac (tellurium diethyl dithiocarbamate
TDEDC), Bayer's Vulkacit [Link] (zinc-N-dibutyldithiocarbamate, ZBDC), and
Monsanto's Methasan (ZMDC).

E. Thiuram Mono- and Disulfides

Like the thiocarbamates, thiuramsuifides are ultra-accelerators. They are made
from secondary amines and carbon disulfide. The most commonly used members
of this class are probably tctramethylthiuramdisulfidc (TMTD), tctracthy!thiur-
amdisulfide (TETD), and tetramethylthiurammonosulfide (TMTM). The stron-
gest of these three is the tetramethyldisulfide, followed by the tetraethyl and then
the monosulfide. TMTD is too scorchy to be used alone with natural rubber.
TETD is about the same, but the monosulfide can be used with care. If TETD is
substituted for TMTD, about 10% more accelerator should be used. Like the
dithiocarbamates, the thiuramsulfides can be used in light-colored stocks without
staining.
The thiuramsulfides are especially useful in curing systems containing low or
no elemental sulfur, but the monosulfide is not strong enough to cure satisfac-
torily without added sulfur. The most common use of the thiuramsulfides is as
a secondary accelerators to thiazole- or sulfenamide-accelerated compounds of
NR, SBR, IIR, and EPDM. For example, an EPDM stock might have a cure
system of 1.5 parts sulfur, 1.25 parts thiazole, and 1.5 parts TMTD. Typical
commercial accelerators of this class are Monsanto's Monothiurad (TMTM),
Imperial Chemical Industries Vulcafor TMTD (TMTD), and Vanderbilt's Ethyl
Tuads (TETD).

F. Thioureas
The thiourea accelerators are almost exclusively used as organic accelerators
in neoprene stocks. Among producers of these accelerators are DuPont with
NA 22F (ethylene thiourca, ETU) and Vanderbilt with Thiate H (NN-
 110
Chapter8
diethylthiourea).
These accclerators are
particularly useful in injection-molded
stocks, molded sponge, and liquid curing medium
(LCM) extrusion stocks.
Customary dosage is 0.5-0.75 on he rubber, usually neoprene W.
G. Aldehyde Amines
Aldehyde amines are reaction products of various aldehydes and
They vary from brown resins to amler liquids and are so primary amines.
formulas would have little meaning. A common complex that structural
combination of starting mate
rials isbutyraldehyde and anilin:, which gives such commercial products as
DuPont' Accelerator 808 and
Imperial Chemical Industries's Vulcafor BA.
Another accelerator in this class is Heptene Base, made
from heptaldehyde and aniline. by Naugatuck Chemical
Aldehyde amine accelerators now have limited use. The curing rate they
impart depends on the choice anc tatio of aldehyde and amine. These
tors can be used to give hard, accelera
nonb itle stocks like ebonite. For a natural rubber
ebonite, perhaps 2.5 parts of this accelerator might be used with 30-50
sulfur. A more common use is as a parts of
secondary accelerator at 0.20-0.30 part with
thiazole or sulfenamide accelerai ors.

IV. SPECIAL APPLICATIONS

Over the years three special types of organic accelerator cure system have been
developed, primarily for natural nibber but of value in SBR as well. They are
efficient cure systems, semiefficicnt cure systems, and soluble cure
systems.
Much earlier, when very little was known about vulcanizate structures, the first
was called sulfurlcss
curing, the se cond low sulfur curing. Solublc cure systems
are a relatively recent developr e t. In general, efficient cure systems use no
elemental sulfur, the sulfur for vulcanizing comes from sulfur donors such as
thiuramdisulfide accelerators. Vanderbilt's Sulfads, essentially dipentamethyl-
enethiuramhexasulfide, has 35% available sulfur, the more common TMTD
accelerator about 13.3%. In semie ficient cure systems the amount of sulfur used
is generally less than 1 part.
The advantage of efficient and semiefficient vulcanization systems in both NR
and SBR compounding is the inc rerased resistance to aging and reversion (deteri
oration caused by overcuring). Soluble curing systems, a variant of efficient
vulcanization systems, are designed to ensure high reproducibility from mix to
relaxation. The perfomance of a
mix and to improve resistance to creep or stress
sulfur vulcanizate is the result not only of the system used but also the solubility
stock and the solubilities of the reaction
of the components in the unvulcaized
or fatty acids used are above their
residues. If the amounts of sulfur, accelerators,
rnaterials can crystallize out within the nubber.
solubility limits in rubber, these
Excessive crystallization can result in
inhomogeneity in crosslinking and varia