3.

State of the art in hazardous substances, substitutes and

inhibitors

3.1 hazardous substances

The substance groups and individual substances under consideration with regard to the possible formation of
nitrosatable substances are listed in Table 1 . Depending on the required product characteristics, a
replacement can be more or less successful. Therefore, in some cases multiple classification (several x) is
necessary.
Sulfenamides (Group 1)
Here, primarily 2-morpholine-benzothiazole-sulfenamide (MBS) and N, N-diisopropyl-2-benzothiazole-
sulfenamide (DIBS) should be replaced by other sulfenamides (see Table 2, group E1 ) in combination with
retarders or other secondary accelerators.
However, MBS has not been interchangeable in all cases, especially in applications requiring heat resistance
and dynamic resistance (eg, certain engine mountings). In individual applications, however, these requirements
can be achieved by using a combination of CBS or TBBS with 1,6-bis (N, N-dibenzyl-thiocarbamoyl-dithio)
hexane (BDBzTH).
In the case of 2-morpholine-dithiobenzothiazole (MBSS), due to specialized use, there is insufficient knowledge
to be classified.
For the products N-oxydiethylene-thiocarbamoyl-N-oxydiethylene-sulfenamide (OTOS) and N-oxydiethylene-
thiocarbamoyl-N-tert-butyl-sulfenamide (OTTBS), the same applies as for the sulfenamides in terms of loading
and applications. In special cases (heat, dynamic stress) a replacement is not possible here. It should be noted
that in the meantime OTOS itself has been classified as carcinogenic by the manufacturer.
Dithiocarbamates (Group 2) / Thiurams (Group 3)
We are dealing here with a large number of substances that structurally contain all secondary amines. For
normal loads here offer a number of substitutes, such. Zinc dibenzyl dithiocarbamate (ZBEC), zinc (4-
methylpiperazino) dithiocarbamate (ZMP), di-isononyl dithiocarbamate (all group E2), dithiophosphates (E8),
guanidines (E6), xanthates, polyxanthogenate (both E9), silanes and diamminediisocyanato-zinc (E10).
It should be pointed out in particular that the dithiocarbamates only ever appear as components of a
crosslinking system, so that an individual evaluation is only of limited use.
A special case is the nickel dithiocarbamates, which are still used as antiozonants in dynamically stressed
special rubbers. Replacement of these products by other, more generally applicable, antiozonants is difficult
(Note: soluble nickel salts have been classified as "Category 1 carcinogens").
As at least related substitute products for the common thiurams such as tetramethylthiuram disulfide (TMTD)
come the tetrabenzyl thiuram disulfide (TBzTD), the tetraisobutyl thiuram disulfide (TiBTD) or the bis (4-methyl-
piperazino) thiuram disulfide (MPT) in question (E3), which can not be considered as a simple substitute
because of their special molecular size. Decisive factors here are the heat resistance and the low compression
set of the material, always in conjunction with a favorable technological processability of the raw mixture.
Sulfur donor (group 4)
As a substitute for the N, N'-Dithiodimorpholin (DTDM) is only the Caprolactamdisulfid (CDS) in question (E4).

3.2 Substitutes
The substitutes that are possible from the point of view of the substitution of hazardous substances ( Table 1 )
are listed in Table 2 and partly mentioned in Section 3.1 .
Additional Comments:
Dithiocarbamates (group E2) / thiurams (group E3)
Questions about the carcinogenicity of N-nitroso-4-methylpiperazine (NMPz) and N-nitroso-diisobutylamine
(NDiBA) have not yet been conclusively clarified. Work on the carcinogenicity of N-nitroso diisononylamine
(NDiNA) is not yet available. When using these products, it is currently expected that there will be less health
risk for the employees.
Thiazoles (group E5)
Thiazoles as one of the most important accelerator groups and the compounds mentioned can be used as a
basis for replacement systems.
Guanidines (group E6)
This class of substance is very important as a secondary accelerator class. The problem is the possible release
of primary aromatic amines.
Thioureas (group E7)
In principle, the thioureas are no substitute for the hazardous substances in Table 1 . However, they can have
an effect as additives in replacement systems. The toxicological profile of thioureas is not adequately
protected. 2-mercapto-imidazoline (ETU) itself is considered a teratogenic substance. For the others, mustard
oil formation (ie formation of organic isothiocyanates) is possible.
Thiophosphates (group E8)
Representatives of this class of substances can replace single dithiocarbamates. Several dithiocarbamates can
not be replaced by thiophosphates alone. However, as secondary accelerators in conjunction with thiazoles or
sulfenamides, thiophosphates can replace some dithiocarbamates or thiurams. Long chain dithiophosphates
should be preferred because they can avoid possible volatile decomposition products.
Xanthogenates (group E9)
In the construction of replacement systems, the polyxanthogenate (AS 100) plays a role, but requires the
additional activation.
Other products (Group E10)
Like the thiophosphates, diamminediisocyanato-zinc (Geniplex A) can also be used as a substitute for
individual dithiocarbamates.
3-Methyl-thiazolidin-thione-2 (Vulkacit CRV) is a special replacement for ETU in polychloroprene.
1,6-bis (N, N-dibenzyl-thiocarbamoyl-dithio) hexane (BDBzTH) is a bifunctional crosslinker to prevent
reversion. Its effect is based on the incorporation of thermodynamically stable, flexible hybrid network sites. In
addition, BDBzTH can also be used as a scorch-safe secondary accelerator.
Hexamethylenetetramine (HMT) is commonly used as a formaldehyde donor for adhesive systems, but also
acts as a secondary accelerator. The crosslinking with phenolic resins takes place according to another
mechanism. The mixing composition must be adapted to this system. The vulcanization usually takes place at
higher temperatures than the sulfur crosslinking and leads to products with good thermal but limited dynamic
properties.
Peroxides (group E11)
Since peroxides obey a completely different crosslinking mechanism, the composition of the mixture is only
partially comparable to that of sulfur crosslinking. Therefore, a new development is always necessary in their
use. The vulcanization should be done with exclusion of oxygen. The achievable vulcanization properties are
superior to those of sulfur crosslinking in terms of strength, elongation at break, tear strength and dynamic
properties, but superior in thermal resistance.

3.3 Inhibitors

3.3.1 NOx trap

The most prominent compounds of this type ("NOx inhibitors") are ascorbic acid (vitamin C), α-tocopherol
(vitamin E) and urea.
Experiments with ascorbic acid have been stopped early because of the temperature and oxidation sensitivity
of the substance. Stabilized derivatives of ascorbic acid, e.g. As ascorbyl palmitate, prove to be less effective.
The effect of α-tocopherol is known to be limited to mixtures containing Rus. However, technically more
complex measures must be taken into account.
Urea, like primary amines, could compete with secondary amines in nitrosation. There is not enough
experience for an assessment.
NOx scavengers work only in the gum itself; exiting secondary amines can react rapidly in the gas phase with
nitrosating agents to N-nitrosamines.

3.3.2 amine scavengers

Amine scavengers ("amine inhibitors") have the advantage of binding the amines released in the vulcanization,
in order to prevent or reduce the formation of the corresponding N-nitrosamines and thus also strong N-
nitrosamine emissions from the vulcanizate To reduce dimensions. Their use has proved to be effective in the
field of vulcanization presses in many cases and beyond, in contrast to the NOx scavengers, in downstream
production and storage areas as well as the customer.
The binding of the liberated amines is achieved by the use of blocked isocyanates to form the corresponding
urea derivatives. A number of commercial products are available. These non-toxic compounds are largely
stable in the mixing process and split in the vulcanization - in reversal of their formation reaction - necessary for
the amine binding, very reactive isocyanates. Unreacted (toxic) isocyanates are converted back into the
 blocked form during cooling of the vulcanizates, so that there is no danger to the employees.
In particular with carbon black-filled mixtures, an almost complete reduction of the amine or N-nitrosamine
emissions can be achieved with this procedure. Long-time proven vulcanization systems can continue to be
maintained. The use of blocked isocyanates always makes sense if no customer-accepted technical solution
based on N-nitrosamine-free crosslinker systems exists.

4. Possible limits of substitute use

With the described and other substitutes and substitute methods for reducing the formation of carcinogenic N-
nitrosamines, a positive development for occupational safety has started, but at the same time it also has
certain problems.
It proves to be particularly difficult to characterize the cases in which complete replacement is not yet
possible. Comparisons have been made of characteristic mixtures which, on the basis of the physical level,
show that the desired level could not yet be attained by conversion. Physical data does not sufficiently reflect
the behavior. Decisive are the results on the test bench and the practical behavior.
Customer requirements for the article often can not be fully met or the function of the article is impaired. This
mainly relates to aging resistance, compression set and dynamic efficiency and other special requirements.
Further obstacles to recipe changes may be requirements regarding food and drinking water applications. So
far, mixtures have only been optimized for very specific cases. Substitutes are often not approved for food
commodities.

Table 1: Hazardous substances of technical importance that can form carcinogenic N-nitrosamines cat.
1 and 2
Replacement recommendations

substance name I II
III IV
formed N- 1: 1 1: 1
new ones No
nitros without without
with losses replacement
Internat.abbreviation CAS no. EINECS no. amine loss loss

1. - sulfenamide -

N, N-diisopropyl-2-benzothiazole
1.1 DIBS 95-29-4 202-407-0 NDiPA x
sulfenamide

2-morpholin-benzothiazol
1.2 MBS 102-77-2 203-052-2 NMOR x x
sulfenamide

1.3 2-morpholin-dithiobenzothiazol MBSS 95-32-9 202-410-7 NMOR *)

N-oxydiethylene-thiocarbamoyl
1.4 OTOS 13752-51-7 237-335-9 NMOR x
N-oxydiethylene-sulfenamide

N-oxydiethylene-thiocarbamoyl-
1.5 OTTBS 68310-86-1 269-740-1 NMOR x
N-tert-butyl sulfenamide

Second - dithiocarbamates -

Copper dimethyl-
2.1 CDMC 137-29-1 205-287-8 NDMA x
dithiocarbamate

2.2 Nickel-dimethyl-dithiocarbamate NDMC 15521-65-0 239-560-8 NDMA x

2.3 Nickel-di-n-butyl-dithiocarbamate NDBC 13927-77-0 237-696-2 NdBa x

2.4 Tellurium diethyl dithiocarbamate TDEC 20941-65-5 244-121-9 NDMA x

 Zinc pentamethylene-dithiocar-
2.5 Z5MC 13878-54-1 237-643-3 NPIP x
Bamat

2.6 Zinc dibutyldithiocarbamate ZDBC 136-23-2 205-232-8 NdBa x x

2.7 Zinc diethyl dithiocarbamate ZDEC 14324-55-1 238-270-9 NDMA x x

2.8 Zinc ethylphenyl dithiocarbamate ZEPC 14634-93-6 237-677-1 NEPhA x

2.9 Zinc dimethyl-dithiocarbamate ZDMC 137-30-4 205-288-3 NDMA x x

Third - Thiurame -

Dipentamethylenthiuram- DPTT
3.1 120-54-7 204-406-0 NPIP x
hexasulfide (DPTH)

Dimethyl diphenyl-thiuram
3.2 MPhTD 53880-86-7 258-835-3 NM; Ph x
disulfide

3.3 Tetraethyl thiuram disulfide TETD 97-77-8 202-607-8 *) x

3.4 Tetramethyl thiuram disulfide TMTD 137-26-8 205-286-2 NDMA x x

3.5 Tetramethyl thiuram monosulfide TMTM 97-74-5 202-605-7 NDMA x x

4th - sulfur donor -

4.1 N, N'-Dithiodimorpholine DTDM 103-34-4 203-103-0 NMOR x

Table 2: Substitutes for the hazardous substances listed in Table 1

possible N-
substance name Internat.abbreviation CAS no. EINECS no. Comments on the product
nitrosamines

E1. - sulfenamide -

N-cyclohexyl-2-benzothiazole
E1.1 CBS 95-33-0 202-411-2 - -
sulfenamide

N, N-dicyclohexyl-2-benzothiazole
E1.2 DCBS 4979-32-2 225-625-8 NDCHA N-nitrosamine not carcinogenic *)
sulfenamide

E1.3 N-tert-butyl-2-benzothiazole sulfenamide TBBS 95-31-8 202-409-2 - -

N-tert-butyl-bis (2-benzothiazole-
E1.4 TBSI 3741-80-8 -
sulfenamide)

E2. - dithiocarbamates -

E2.1 Zinc dibenzyl-dithiocarbamate ZBEC 14726-36-4 238-778-0 NDBzA N-nitrosamine not carcinogenic *)

Zinc (4-methylpiperazino)
E2.2 ZMP 55518-81-5 NMPz Carcinogenicity assessment is pending
dithiocarbamate
 Arbestab Z; Carcinogenicity assessment
E2.3 Zinc diisononyl dithiocarbamate 84604-96-6 283-381-8 NDiNA
is pending

E3. - Thiurame -

Bis (4-methylpiperazino) -thiuram-

E3.1 MPT 20231-01-0 NMPz Carcinogenicity assessment is pending
disulfide

E3.2 Tetrabenzyl-thiuram disulfide TBzTD 10591-85-2 404-310-0 NDBzA N-nitrosamine not carcinogenic *)

E3.3 Tetraisobutyl-thiuram disulfide TiBTD 3064-73-1 221-312-5 Ndiba Carcinogenicity assessment is pending

E4. - sulfur donor -

E4.1 Caprolactam disulfide CDS 23847-08-7 245-910-0 -

E5. Thiazoles -

E5.1 2-mercaptobenzothiazole MBT 149-30-4 205-736-8 -

E5.2 Dibenzothiazol disulfide MBTS 120-78-5 204-424-9 -

E5.3 Zinc-2-mercapto-benzothiazol ZMBT 155-04-4 205-840-3 -

2 (2 ', 4'-dinitrophenylthio) benzo- releases NOx compounds that can

E5.4 4230-91-5 224-183-3 -
thiazole nitrosate amines

E6. - guanidine -

E6.1 N, N'-diphenyl guanidine DPG 102-06-7 203-002-1 - can release aniline

E7. - thioureas -

possibly mustard oil formation during

E7.1 Di-n-butyl-thiourea DBTU 109-46-6 203-674-6 -
vulcanization possible

possibly mustard oil formation during

E7.2 Diethyl-thiourea DETU 105-55-5 203-307-5 -
vulcanization possible

possibly mustard oil formation during

E7.3 Diphenyl-thiourea DPTU 102-08-09 203-004-2 -
vulcanization possible

E8. - thiophosphates -

E8.1 Zinc O, O-di-n-butyl-dithiophosphate ZBPD 6990-43-8 230-257-6 - short-chain dithiophosphate

E8.2 Zinc-O-butyl-O-hexyl-dithiophosphate 68413-49-0 270-221-7 - long-chain dithiophosphate, preferred

E8.3 Zinc O, O-diisooctyl dithiophosphate ZOPD long-chain dithiophosphate, preferred

Dodecylammonio-
E8.4 AOPD long-chain dithiophosphate, preferred
diisooctyldithiophosphat

E9. - xanthogenates -
 E9.1 Zinc O, O'-diisopropyl-bisxanthogenat 1000-90-4 213-680-0 - Robac ZIX

E9.2 Polyxanthogenat 69303-50-0 - Robac AS 100

E10. - Further products -

Geniplex A; can replace single

E10.1 Diammindiisocyanato-zinc 122012-52-6 401-610-3 -
dithiocarbamates

Vulkacit CRV; special replacement for

E10.2 3-methyl-thiazolidine-thione-2 1908-87-8 217-614-1 -
ETU in CR

E10.3 hexamethylenetetramine HMT 100-97-0 202-905-8 - forms formaldehyde

Application of the phenolic resin

E10.4 Octylphenolresol 26678-93-3 - crosslinking requires an adapted mixture
composition

Hexamethylene-1,6-bis (thiosulfate) Hybrid crosslinkers in addition to sulfur

E10.5 HTS 5719-73-3 401-320-7 -
disodium, dihydrate crosslinks

Reversible stabilizer, which can be

E10.6 1,3-bis (citraconimidomethyl) benzene BCI-MX 11946-56-5 - compensated for cross-linking, can be
planned for the overall cross-linking

Reversion-stable crosslinker, effect

1,6-bis (N, N-dibenzyl-thiocarbamoyl-
E10.7 BDBzTH 151900-44-6 through the formation of thermostable,
dithio) -hexane
flexible Carbasulfannetzstellen

E11. - peroxides -

E11.1 dicumylperoxide DCP 80-43-3 201-279-3 Application limited by specifically others

achievable rubber properties as well as

E11.2 tert-butyl cumyl peroxide TBCP 3457-61-2 222-389-8 -
through

E11.3 Di-tert-butyl peroxide DTBP 110-05-4 203-733-6 - special processing conditions

E11.4 Bis (tert-butylperoxyisopropyl) benzene 25155-25-3 246-678-3 -

2,5- (tert-butylperoxy) -2,5-

E11.5 78-63-7 201-128-1 -
dimethylhexane

1,1-di (tert-butylperoxy) -3,3,5-

E11.6 6731-36-8 229-782-3 -
trimethylcyclohexane

E11.7 dibenzoyl DBP 94-36-0 202-327-6 -

E11.8 Bis (2,4-dichlorobenzoyl) peroxide 133-14-2 205-094-9 -

E11.9 4,4-bis (tert-butylperoxy) -butylvalerat 995-33-5 213-626-6 -

2,5- (tert-butylperoxy) -2,5-

E11.10 1068-27-5 213-944-5 -
dimethylhexyne-3

E11.11 tert-butyl peroxybenzoate TBPB 614-45-9 -

Footnote § 11 GefStoffV
Note to the cross reference:
The GefStoffV was replaced on 26.11.2010 (after publication of this publication) by an amended version, the structure
of which differs in part from the here linked version. Click here for the GefStoffV .
Footnote NDiPA
N-nitroso-diisopropylamine
Footnote x
Multiple answers are given when requirements of different application areas are assessed differently.
Footnote NMOR
N-nitroso-morpholine
Footnote *)
no knowledge available
Footnote NDMA
N-nitroso-dimethylamine
Footnote NDBA
N-nitroso-di-n-butylamine
Footnote NPIP
N-nitroso-piperidine
Footnote NEPhA
N-nitroso-ethylphenylamine
Footnote NM; PhA
N-nitroso-methylphenylamino
Footnote NDCHA
N-nitroso-dicyclohexylamine
Footnote *)
see TRGS 552 number 1 paragraph 2
Footnote NDBzA
N-nitroso-dibenzylamine
Footnote NMPz
N-nitroso-4-methylpiperazine
Footnote NDiNA
N-nitroso-diisononylamine
Footnote NDiBA
N-nitroso-isobutylamine