ACCELERATOR

When accelerator is added to the system

(NR/S/ZNO/fatty/acid) the rate of reaction is greatly
increased but the efficiency is unchanged. Addition of
accelerator increases both rate and efficiency. The effects of
accelerator are as under:-

1. Increase in rate of cure

2. Lower curing temperature are possible.

(lower the curing temperature better the vulcanisate)

3. Sulphur may be reduced.

( by adding higher accelerator the amount of sulphur
can be reduced.) Hence better ageing.
4. Smooth out curing curve.( plateau effect )

5. Increase range of vulcanisate properties.

6. Assist in smoothing out variabilities in raw rubber.

A. Slow Type

Aldehyde Amines

1. B.A. – Butyldehyde aniline primarily used in ebonite.

It is a liquid product and stains quite a lot.

2. EFA – Ethylchloride formaldehyde aniline – staining

type.

3. Substituted Thiourea and Guanidines.

It is a slow accelerator cause yellowing stain, poor ageing
characteristic. It is absorbed by channel blacks. It is boosting
Thiozoles ( MBT, MBTS) Sulphenamides ( CBS ).

Di – orthotolye guanidine

DOTG – It is derived from Aniline NH2 Which

Is a basic material.
It is little bit faster than DPG.

4 Ethylene thiourea – This is an accelerator of w type of

Polychloroprene which is a non – sulphur modified normally
0.3 – 1.0 Phr. Along with Zno-5, Mgo-4 is used
B MEDIUM FAST

Thiozoles

MBT is made by condensation under pressure and at

elevated temperature of aniline and carbon disulphide in
presence of sulphur. MBTS is made by the oxidation of
MBT and the sulphenamides by the reaction of a suitable
amine with MBT.
Mercapto benzothiazole
Creamy colour solid rather bitter taste. Non toxic accelerator
MBT is quite scorchy with HAF, ISAF & SAF.
It gives a good plateau effect, low modulus and high
abrasion resistance. Below 1500C. MBT is faster than
MBTS. MP approx 1770c. Soluble in acetone, ethyl acetate,
ethyl alcohol.

Dibenzothiazyl Disulphide
MP is approx. 1700C. Soluble in benzene, carbon
tetrachloride acetone etc. It activates basic accelerators and
when used small quantities as an additional accelerator
with thiurams and dithiocarbamates it delays the onset of
cure. It acts as retarder in PCP Compound.
ZINC MERKAPTO BENZOTHIAZOLE
ZMBT speed is same as MBT. Does not bloom on uncured
stock. Yellow powder. MP 3200c accompanied by
decomposition. Not easily soluble in ethyl alcohol, ethyl,
acetate, benzene. Used mainly in latex compounds.
Activates basic accelerators. The compression modulus of
the foam is improved by adding this accelerator.

SULPHENAMIDES

Sulphenamides obtained by the replacement of thiol H by

and amines.
CYCLOHEXYL BENZOTHIAZYL SULPHENAMIDE

MP 1000C. soluble in benzene, ethyl, acetate, acetone etc. It

is a delayed action accelerator gives high modulus, highest
state of cure than MBT. It is slower than MBT. Safe to use
with most of the furnace blacks. Combination with TMTD or
ZDC are very fast but safe. CBS is one of the best accelerator
for SBR rubber. Application in tyre (car) tread compound
The Sulphenamides with better scorch safety and delayed
action are available now a days.
1. Tert – Butyl sulphenamide (TBBS) MP 1060C NZ
2. Benzothiazyl Sulphene Morpholide (MBS) MP800C MOZ
3. Benzothiazyl Dicyclohexyl Sulphenamide (DCBS) MP
950C DZ

All the above accelerators have got better scorch safety than
CBS. They are primarily used in tyre compounds. DCBS is
safest in the lot and used in tread rubber, radial tyre
compounds. The storage of such accelerator is poor as such
one has to see that stock should not be kept for more than
½ months.
C. FAST / ULTRA

It is very fast, fairly non – staining and very wide curing

range 100 - 2000C. It is extremely useful as a booster of
MBT, MBTS, CBS. The mixture of ZDC and TMT are
valuable as fast curing accelerator for butyl rubber. This is
widely used in latex products specially foam rubber.
PIPRIDINE PENTAMETHYLENE DITHIOCARBAMATA ( PIP- PIP)

This is used as peptizing agent of g – type PCP.

THIAZOLE CLASS

The accelerator residue after vulcanization have good

antioxidant properties hence good ageing properties. These are
acidic accelerators. Thiazole accelerator can not be used for
products coming in contact with food because of bitter taste
they impart.

SULPHENAMIDE

With non acidic blacks the tyre tread compounds containing

thiazole accelerators became too scorchy, however, with
sulphenamide, compounds could be safely processed. An ideal
accelerator will give a very long induction time. Suitable for tyre
compound or where long scorch safety is required.
THIURAM CLASS

TMTD give off about 13% its weight and tetron a about 27 %
its weight of sulphur in atomic form which combines with
rubber to give monosulphidic stable x – links. Excellent heat
ageing properties at high temperature. 0.1-0.2 phr. Sulphur
addition helps to achieve tight cure and better compression
set.

DITHIOCARBAMATE (ZDC)

Used at lower temperature cure. For hot air cures it can be

used with MBT.
NORMAL SULPUR SYSTEM (SULPUR ABOVE 1.5 PHR)

ADVANTAGES IN NR DISADVANTAGES

1. BETTER WEAR AND TEAR PROPERTIES 1. REVERSION

2. BETTER FLEX FATIGUE RESISTANCE 2.POOR AGEING

CHARACTERISTICS AT
HIGH TEMPERATURE
AGEING.

3. POOR COMPRESSION
SET RESISTANCE AT HIGH
TEMPERATURES.
Reduction in sulphur levels with increase in accelerator
dosages to reduce the proportion of unstable polysulfidic
crosslinks and increase that of stable mono-and di – sulfidic
crosslinks.
Sulphur level – phr

Normal sulphur above 1.5

Semi ev 0.8 – 1.5
thiuram cure 0 – 0.3
Using 2 -2.5 phr

Cure time at 1600c

 TMTD

Sulphur donors

Chemicals which during cure release sulphur to give only

monosulfidic crosslinks.
 COMPOUND FOR FASTER RATE OF CURE

1. Change from thiazole to sulfenamide (MBT + amine during

vulcanisation)
2. Higher dosage of accelerator
3. Use of booster accelerators

A. Thiazole + basic accelerators

Accelerator ( guanidine or amine acc.)- Synnergism
Or
+Thiuram or dithiocarbamate accelerator

B. Sulfenamide + thiuram or dithiocarbamate

Accelerator accelerator
 NR BASED TYRE TREAD COMPOUND
ACCELERATOR PHR SCORCH TIME CURE TIME TENSILE 300%
MNTS AT 1000C MNTS AT 1400 C MODULUS
MPA

MBT 0.5 35 31 23 10.9

MBT 05 15 15 23 13
DPG 0.2

CBS 0.5 56 23 26 12.7

CBS 0.5
DPG 0.2 44 19 26.5 13.8

CBS 0.5
TMTD 0.1 46 10 26.5 14.7

CBS 0.5
ZDC 0.1 41 10 26.5 14.2
NATURAL RUBBER TYRE TREAD TYPE COMPOUND

ACCELERATOR DOSAGE 0.5 PHR, SULPUR 2.5 PHR

ACCELERATOR SC/T OPTC/T TS M300

THIAZOLE CLASS

(MBT) 35 32.5 23 10.9

(MBTS) 50.5 32.5 22 10.8

(ZMBT) 48 35.5 22 10

MIXTURE OF 38 24 24.5 11.6

MBTS +DPG+HEXA
 SULFENAMIDE CLASS
SC/T OPTC/T TS M300
(CBS) 56 21 26 12.7

(TBBS) 64 23 26 13.4

(MBS) 70 25 26 11.9

(DCBS) >120 36 24.5 11.4

SC/T: SCORCH TIME – MINUTES AT 1100C

OPT.C/T: OPTIMUM CURE TIME – MINUTES AT 1430C
TS: TENSILE STRENGTH – MPA
M300 : 300 % MODULUS – MPA

Thiazoles acidic accelerators

Basic materials like amines, basic accelerators act as
activators or boosters.

Basic fillers cause scorchiness. Acidic materials like acids,

silica fillers, act as retarders
Sulfenamide accelerators
Longer processing safety,
Faster cure rate,
Higher degree of crosslinkages.
Very well suited for tyre compounds.

Sulfenamide accelerators are chemical condensation products of mbt

and an amine.

Vulcanization reaction does not proceed till all the sulfenamide

accelerator quantity has been converted back into MBT + amine –
better processing safety with higher dosage.

Once decomposition is complete, the rate of cure is that of the

combination MBT + amine – fast rate of vulcanization.
A good curative system should give adequate scorch safety
fast rate of vulcanization, long plateau and a vulcanizate
With good physical properties and good ageing characteristics.

Curative system decided by the curing characteristics desired

in the manufacturing process and the functional requirements
of the vulcanizate.

Different curing characteristics desired in compounds

designed for

A) Hot air cure- Very fast onset of

vulcanization
fast rate of cure at lower
temperatures.

B) Open steam cure- Fast onset of vulcanization.

C) Compression moulding- Adequate mould flow time.

D) Injection moulding- Adequate mould flow time good
reversion resistance.

E) Vulcanization of Excellent reversion resistance.

thick articles

A wide range of accelerators is necessary to fulfill these

requirements and a wide number of accelerators are
available.
 ANTIOXIDANT & ANTIOZONANT
All commercially important antioxidants fall into three classes

1. SECONDARY AMINE BODIES

2. PHENOLIC BODIES R (OH)X

3. PHOSPHITES (RO)3 P
The amine antioxidants constitute the more important group.
They are strong protective agents but discolour and stain to
various degrees. The phenolic are less effective but are
essentially non discolouring and non-staining. The phosphites
are stabalisers for SBR.

Amines

Monoamines

Diarylamines are two types

1. Phenylnapthylamine
2. Diphenylamines

Phenyl alpha napthylamines & B napthylamines are widely

used as they combines good ageing and flexing properties.
PBNA is widely used as stabiliser for NR & SBR.
The properties are as follows:

O2 ageing Good

Heat protection Medium

Flexing Medium

Antimetal Medium

Staining Poor

These a / os contains minute traces of B-nathylamine a

known carcinogen hence the use of this type a/o going down.
Diphenylamine itself is a good antioxidant but very volatile for
this reason its derivaties are preferred. The properties of this
group good o2 ageing, medium heat ageing but antimetal and
staining properties poor. (Theromo flex A, agerite )

Another derivaties of diphenylamines are octamine, polylite

type. These materials are used in pcp.

The reaction of acetone with aniline or substituted anilines

gives products having a wide variety of physical forms
And rubber behavior (TDQ type ) properties are O 2 ageing
good,heat very good, flexing medium, antimetal / staining –
fair.
 DIAMINES

There are three commercial classes of diamines, all derivaties of

p – phenylenediamine. N – n1 dipheny1 – p – phenylenediamine
is widely used in antiflex – cracking material. Its use is limited
by its rubber solubility 0.35 % in havea and 0.7% in SBR.

By substituting dinapthyl groups for both of the phenyl groups

less staining bodies are obtained ( agerite white ). but
The flexing properties are greatly reduced.

If one or both of the phenyl groups are replaced by alkyl groups

the products become good antio-zonechemical
(IPPD type)
THE PROPERTIES OF THE PPD GROUP MAY BE SUMMERISED AS FOLLOWS.

ALKYLARYL DIARYL DIALKYL

1PPD / 6PPD DPPD

O2 AGEING GOOD GOOD GOOD

HEAT AGEING GOOD GOOD GOOD

FLEXING EXCELLENT EXCELLENT EXCELLENT

ANTIMETAL VERY GOOD VG VG

STAINING VERY POOR POOR POOR

OZONE VG FAIR GIN STATIC

DUE TO MIN DYNAMIC
LIMITED
PHENOLICS

Phenolic antioxidants are basically weaker than amine a/os in

Ageing properties. Their main use in stocks requiring low degree of
staining or discolouration. The phenolic ( simple type ) are acidic
hence retard cure. For that reason the commercial phynolic a/os
are generally alkyl derivaties of these chemicals. The styrenated
phenols are used as stabiliser for SBR.

The alkylated bis phenolics offer better protection for rubber at

somewhat higher price ( santo white powder ). The phenolic sulfides
occupy position between alkylated phenolics and bisphenolies both
in price and ability ( santowhite crystals)

PHOSPHITES

The only example of this class is polygard. This material is an

excellent nonstaining stabilizer for SBR and posses heat protect
properties ( alkylated phenol phosplities ).
 AGEING
In absence of any protective agents the rate of oxidation depend on

1. The base polymer

2. The x-linking system
3. The degree of cure
After adding necessary protective agents following tests are conducted.

4. Air oven test – normally 700c recommend for nr

Normally 1000c recommend for syn. rubber

5. O2 bomb test – temp 700c + 10c

02 pressure – 21 + 1 kg cm2

Here air is replaced by o2 and this is very sensitive test for ageing caused by copper,
MN

3) Ozone Test – Test piece of 1 cm wide stretched to various

elongation. Ozone concentration are as follows

25 + 5 pphm - 300c (NR, SBR )

50 + 5pphm - 500 c ( 11 R, PCP)
1500 + 1000 pphm - 300c rubber subjected to corona discharge.
 ANTIOXIDANT
MACHANISM OF THE PROTECTION OF RUBBER

1.Free radicals are formed in rubber by heat, light, ozone.

2.These free radicals then react either with 02 or rubber to
regenerate more free radical and a degraded polymer chain.
Weakest shpot in NR is (alpha) -methylene group CH2 – CH2 with
bond 43 kcal / mol.
3.Initial attack by O2 at CH2 – CH2 group

CH3 CH3
1 1
-CH2 – C = CH – CH2 ~ + O2  CH2 – C = CH - CH
1
0
1
0
1
H
4. HYDROPEROXIDE GIVES FREE RADICAL.

I I
HC – OOH  HC - O 0
+ 0
OH(VERY REACTIVE AND IT REMOVE
I I H FROM ANOTHER ALPHA( - METHYLENS
GROUP

(A)
I . I
CH2 – OH  CH + H2 0 0

I I
(B)

5. A & B COMBINED

I I I I
CH0 CH0  CH -- CH
I I I I

6 ACTUALLY A/O DOES INTERRUPT CHAIN REACTION AND STOP THE

AUTOCATALYSIS.

I . I
CH + RH  CH2 -- R (VERY STABLE RADICAL)
I I
A/O SHOULD HAVE a) EASILY REMOVABLE H
b) HIGHLY AROMATIC STRUCTURE TO STABBLIES FREE RADICAL
A/os has little or no effect in case of butyl, hypalon, EPDM.
Silicon can be made little bit more heat resistance by
adding metal oxide. ( T1 O2 FE203 ). in case or NR,
polyisoprene over vulcanisation is very detrimental for
subsequent oxygen ageing. It is always better to have opt.
Cure or slightly under vulcanisation for these rubber . in
NR, SBR, NBR rubber thiuram cures will give best heat
resistance to the vulcanisate due to monosulphidic x- link.
The other reason is most of the thiuram gets converated
into dithiocarbmate. In presence of sulphur
dithiocarbmates acts as acclerator for rubber vulcanisation.
In absence of sulphur the dithiocarbamate acts as good
a/o. As such in thiurm cures without sulphur. The
dithiocarbamate protects the vulcanizates against heat.
 VULCANISATION SYSTEM SULPHUR BINDING ENERGY

1. C–S X –C NORMAL VUL. 1.5 PHR < 64 K CAL /MOL

2. C – S – S – C SEMI E V 0.8 – 1.5 PHR 64 K CAL / MOL

3. C–S–C EV 0.3 – 0 . 8 68 K CAL / MOL

-C–C VUL WITH 0–0.3 84 K CAL/MOL

SULPHUR DONOR
WITHOUT SULPHUR

The thermal stability of the bond can be easily recognized by means of

binding energy.

CH2 – CH 2 LINKAGE BINDING ENERGY = 43 K CAL / MOL

2. In NR polysulphidic x – links give better flex fatigue life. Normal

vulcanisate contain micro- crak 20-40 microns. During cyclic flexture
there is stress concentration at the tip of the microcrack and crack
grows. In presence of 02 crack growth is rapid. A/ o reduce the extent of
 EFFECT OF OZONE

Ozone which is formed in the atmosphere by the action of un

light on oxygen, comedown to a lower level by wind current. A
small amount of ozone present in the atmosphere have
pronounced effect on the ageing behavior of unsaturated
rubber . ozone has no visible effect on unstretched sample
because the brittle ozonide film protects the vulcanisate form
further crack.

A slight stress ( ~ 2 % ) gives rise to cracks on the surface

which grows in the direction right angles to the direction of
extension. NR, SBR, NBR, BR, most easily showing ozone
cracks. Best ozone resistance is shown in silicone, EVA,
EPDM, hypalon, NBR,/ PVC blend.
 PEPTIZER
1. Mastication necessary to bring down the molecular weight
of NR and make rubber plastic.
2. It is a mechanico – chemical reaction.
3. Peptization done using peptizers like activated
pentachlorothihenol.
4. Breaking down of chain assume to occur at weakest link,
i .e. (Alpha) – methylene groups forming free redicals.
5 When oxygen is present degradation occurs because oxygen
reacts with broken chain ends before recombination can
occur.

6 Degradation is accelerated by adding chemical peptizer

which is very active free radical acceptor and react with
broken chain ends much quicker than oxygen

7. Sulphur strongly inhibits the peptization of natural rubber .

 RETARDER

The function of a retarder is to increase the scorch safety of

compound thus, raising the processing safety at high
temperatures. Nitrosodiphenylamine type retarder is widely
used in natural rubber based compounds. The ideal
retarder should not extend the total curing time and also
should not impair the physical properties of the
vulcanisates. Benzoic acid also used as non- staining
retarder specially in compounds containing light coloured
fillers. The most effective retarder is n – cyclohexyl
thiophalimide. Such retarder is widely used in auto tyre
compounds, retreading compounds and thick rubber item
where better processing safety is required.
 PEROXIDE

Organic peroxide like dicumyl peroxide and benzoyl peroxide

can cure saturated and unsaturated rubber. Properties of
ideal peroxide cure are as under :-

1.Safe to handle in processing

2.It should be perfactly compatable with rubber
3.It should have a low volatility.
4.It should be non- toxic
5.Cheap
6.Should be effective in presence of fillers.
7.Should not cause poor ageing.
Peroxide cured compounds generally gives slightly lower ts, eb
and higher modulus than sulphur cured compounds.
DISADVANTAGES

8.Can not use for hot air cure as oxidation takes place.
9.Strong smell which gives intoxic effects.
 Model Question and Answer

a) Mention different classes of accelerator and give example

of accelerator in each class.
b) Why a DCBS more delayed action accelerator than CBS.
c) What do you mean by conventional, semi EV and EV cure
system.
d) Why higher dosage of accelerator is required to cure
synthetic rubber namely SBR, NBR etc.
e) Which antiozanant is recommended to obtain best ozone
resistance property
f) What is the function of retarder give example of a
retarder.
g) Why natural rubber need to be peptized whereas SBR,
NBR etc do not require any peptization.
 ANSWER

A) Slow type - example DPG, DOTG

Medium fast – example MBT, MBTS sulphenamides CBS TBBS etc.
Fast / Ultra - ZDC, TMTD etc.

B) DCBS bond energy is higher and it takes longer time to convert to MBT + aniline.

Sulphur Binding energy

C) C-SX-C Conv. Cure 1.5 Phr < 64 keal / Mol.
C-S-S-C Semi Ev 0.8 – 1.5 Phr 64 Keal / Mol.
-C – C Ev. System 0 – 0.3 84 Keal / Mol.
Thermal stability of bond can be easily recognized by means of binding energy.

D) Synthetic rubber namely SBR, NBR are very slow curing polymer. To improve the
cure it is absolutely necessary to increase the dosage of accelerator.

E) Best ozone resistance is obtained by using 6PPD type antiozonant.

F) The function of a retarder is to increase the scorch safety of compound thus raising the
processing safety. Most effective retarder is N- cyclohexlthiophalamine.

G) The mooney viscosity of natural rubber varies from 90 – 130. It is necessary to bring down
the molecular weight of NR and make rubber plastic.

SBR, NBR are man made synthetic rubbers and viscosity of such rubber is made as per
requirement of application. Hence it is not possible to reduce the viscosity of such rubbers by
mastication.