IJSRD - International Journal for Scientific Research & Development| Vol.

1, Issue 3, 2013 | ISSN (online): 2321-0613

Replacing TMTD with Nitrosamine Free TBzTD- Accelerator in Curing

of Rubber

Parin Sheth1 Prof. Rupande N. Desai2

1, 2
L. D. College Of Engineering, Ahmedabad, Gujarat, INDIA

Abstract—Nitrosamines are generated during the mixing,

II. WHY BUTYL RUBBER
vulcanisation and storage of rubber articles. The major
source of Nitrosamine in Rubber products is amine Main Application of IIR (Butyl Rubber) includes
containing accelerators. TMTD is very widely used as a  Automobile Tubes
primary and sulphur donor-standalone accelerator in  Pharmaceutical Elastomeric Components
traditional sulphur curing systems. Due to secondary amine  Medical and Surgical Tubing
contents in TMTD, it produces Nitrosamine during its use.  Human exposure to these products are very wide and
TBzTD is again of same thiuram group accelerator but some time in very critical conditions.
without secondary amine, which results into Nitrosamine
free cure. The experiment to replace TMTD from III. BUTYL RUBBER (IIR)

conventional Butyl rubber recipe was carried out to study
and compare various physical properties of the Vulcanisate. Copolymer of Isobutylene with small amount of
Isoprene.
Keywords: Nitrosamine, Curing of Rubber, TMTD, TBzTD  Isoprene provides double bonds which allow rubber to
be vulcanised with Sulphur and other vulcanising
I. INTRODUCTION agents.
To date, Germany leads the world in legislation and the  Level of unsaturation (double bonds) is usually quoted
elimination of nitrosamines in the work place. In its in mol% i.e. numbers of unsaturated sites for every
hundred monomer units in chain.

“Technical Rules for Dangerous Substances” (TRGS 522),
eight suspected carcinogenic nitrosamines are listed that are Commercial butyl rubber have 0.5% to 3.0% of
commonly used in cure systems by the rubber industry unsaturation in contrast to unsaturation of NR and BR
(Table 1).4 Additionally, the TRGS 522 sets the following (100%),SBR(86%),and NBR (70% in 30%ACN
content)

restrictions;
 2.5 μg/m3 for vulcanization / following production steps / This requires less quantity of curatives but more of
warehousing of technical rubber goods. efficiency (Ultra-fast).
 1.0 μg/m3 for production steps before vulcanization and
warehouses. IV. CURING SYSTEMS FOR BUTYL
Slowly, the United States and Canada are Most widely adopted: Sulphur and Sulphur donor Curing
beginning to regulate nitrosamines. Two of the “Big Three” systems.
companies have set Engineering Specifications limiting, or There are four classes of common rubber
eliminating, their use in automotive rubber parts. Both have accelerators that during the curing process form reactive
published specifications that require a supplier to list the intermediate structures that contain secondary amines. If
level of nitrosamines present in the rubber parts. these intermediates react with nitrosating agents,
Table shows a list of countries that have set limits nitrosamines can be formed. These four classes of rubber
in the amount (measured in ppb) of nitrosamines and their accelerators are:
precursors that can be extracted from baby bottle nipples  Dithiocarbamates
and pacifiers.  Sulfenamides
 Sulfur Donors

Nitrosamin
Country es (ppb Precursors (ppb max) Thiurams
max.)
Canada 10 Not regulated Quinoid systems: Very fast curing used for wire insulation
Germany 10 200 in continues vulcanization.
Netherlands 1 20
U.S.A. 20 Not regulated Resin Curing systems: Dimethylol Phenol Resins systems
Table 1: Nitrosamine limits are very slow and require very high curing temperatures.
Considering these rapidly developing standards rubber
chemist need to develop more and more tools. The Sulphur Curing Systems for Butyl:

 Conventional Acceleration system used for sulphur or

purpose of this paper is to provide options for the
production of rubber products, with testing and
evaluating the TBzTD as a compounding alternative that sulphur donor curing of butyl rubber includes ultra-
eliminate the production of nitrosamines. In particular, accelerators like
for replacement of TMTD.

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 Replacing TMTD with Nitrosamine Free TBzTD- Accelerator in Curing of Rubber
(IJSRD/Vol. 1/Issue 3/2013/0033)

a) Thiurams: slabs to be molded. This was accomplished by using the

The thiurams are secondary accelerators used in a rubber procedure as outlined in ASTM D3182. The ASTM
formulation at low phr levels to “tweak” the cure system to a Standard tests that were performed on each compound are
desired rate of cure. Although the thiurams are not as fast as identified in below table.
the dithiocarbamates, thiurams act as both an accelerator and Test ASTM Method
as a sulfur donor. Examples of common thiurams include Rheology (ODR with 1.5º arc@180 ºC for 15
DPTT, TBTB, TETD, TMTD, and TMTM D 5289
minutes
Mooney viscosity, MS 1+4 (121 ºC) D 1646
b) Sulphenamides: Mooney viscosity, MS 1+T5 (121 ºC) D 1646
Hardness, Shore A D 2240
The sulfenamides are primary accelerators that are used at Tensile, Elongation and Modulus D 412
low phr levels in a rubber compound and can influence not Table. 2: Physical Test and ASTM Methods
only the rate of cure, but also the scorch safety of the
compound. The specimens were also subjected to chemical testing for
Due to this nature, the sulfenamides have been Nitrosamine generation and identifications.
termed fast-delayed action accelerators. A feature of the The instrument used for these analyses, the
sulfenamides is that three of them are based on morpholine GC/TEA (gas chromatograph/thermal energy analyzer), is
and can generate the regulated nitroso-morpholine. They are specifically designed to detect only N-nitrosamines and to
MBSS, OBTS and OTOS (Cure-Rite® 18). However, there omit the signals produced by other types of compounds that
are three sulfenamides that do not produce regulated may interfere with the analysis. The GC/TEA (Thermo
nitrosamines. These include CBS, DCBS and TBBS. Scientific, USA) is more practical for volatile N-
nitrosamines. The volatile N-nitrosamines are of most
c) Dithiocarbamates: concern to the rubber industry and are the focus of the
German regulation.
The dithiocarbamates are secondary accelerators that are
used at low phr levels in a rubber compound to “tweak” the
cure system to a desired rate of cure. Examples of VII. EXPERIMENTAL FORMULATIONS OF BUTYL
dithiocarbamates include ZDBC, ZDMC, ZEPC, Z5MC, RUBBER
SDMC, LDMC, NDBC, BDMC, CDMC, ZDEC, TDEC, Recipe 1.0 1.1 1.2 1.3
etc. Almost every dithiocarbamate has the ability to form a Butyl Rubber 1675N 100 100 100 100
Zinc Oxide 4.0 4.0 4.0 4.0
regulated nitrosamine in the presence of a nitrosating agent. Kaolin 100 100 100 100
Paraffinic oil P-25 5.0 5.0 5.0 5.0
Suggested Thiuram for Nitrosamine free curing: Titanium Dioxide 4.0 4.0 4.0 4.0
Carbon HAF 0.5 0.5 0.5 0.5
TBzTD: Tetrabenzylthiuram disulphide TMTD (Lanxess) 1.0 0.0 0.0 0.0
MBT (Lanxess) 0.5 0.0 0.25 0.5
Sulphur 1.5 1.5 1.5 1.5
TBzTD (Robac) 0.0 1.5 1.5 1.5
Physical Properties Analysis:
Recipe 1.0 1.1 1.2 1.3 1.4
Compound
Viscosity ML 79 78 79 78 78
1+4 (100c)
Mooney scorch
Fig. 1: TBzTD ML 1+t5 @125c 12 >25 >25 >25 >25
(min)
V. EXPERIMENTAL WORK Rheometer
12.24 12.39 12.30 12.35 12.38
Cure@180c ML

 Design and Process various compositions.

Methodology Rheometer
29.22 31.28 28.68 29.34 29.25
Cure@180c MH
 Testing and Evaluation of various Physical and Rheometer
Cure@180c t5 140 360 240 200 210
Chemical Properties of the Vulcanisate formed using (sec)
Nitrosamine Free TBzTD Accelerators Systems and Rheometer
compare the physical properties of Vulcanisate with Cure@180c t90 360 720 460 420 440
(sec)
conventional TMTD based recipe.
 Scope in this paper is limited to accelerators useful for
Curing at 170c
5 6 6 6 6
(min)
Butyl rubber i.e. TBzTD. Hardness Shore A
42 38 39 40 40
, 3”
Modulus @100%
VI. COMPOUNDING AND TESTING 1.8 1 1.1 1.3 1.2
elongation (MPa)
A rubber compound was created with each test formulation Modulus @300%
2.4 1 1 1.1 1.1
by adding the corresponding cure system into a master batch elongation (MPa)
Tensile Strength
on a two roll mill. End passes and cross cuts were (MPa)
9 7 7.2 7.7 7.5
performed. Following mixing, several physical tests were Ultimate
790 910 885 900 900
performed on the rubber compound. Some tests required elongation (%)
Cured @170c for 10 12 12 12 12

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 Replacing TMTD with Nitrosamine Free TBzTD- Accelerator in Curing of Rubber
(IJSRD/Vol. 1/Issue 3/2013/0033)

Compression set related laws become easy and purposeful. Considering the
(min) above facts rubber technologist will require more and more
Set 24h at 100c
(%)
33 50 46 40 40 tools in future to meet the stringent environmental and
Set 70h at 70c health risk related guidelines. TMTD, which is widely used
36 50 45 40 40
(%) in Butyl Rubber curing accelerator systems, can be replaced
Table. 3: Physical Property Analysis with TBzTD and ZAT type accelerators with a slight tweak
in secondary accelerator type and level in the curing system.
Physical Properties of This review of accelerator systems will provide insights of
Nitrosamine formation and possible alternative to
Vulcanisates conventional butyl rubber curing systems. Future works on
1000 secondary accelerator and its synergy with the thiophosphate
and thiurams other booster chemicals need to be carrying
900 out to collect more date to provide more alternatives.
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