240-87 NitrosaminesSSPRINT.

fh8 10/13/03 8:24 AM Page 1

NITROSAMINES: c o n t i n u e d 2 NITROSAMINES: c o n t i n u e d 3 NITROSAMINES: c o n t i n u e d 4

Detection of NAs is relatively easy with the use of some sophisticated analytical equipment.
High Performance Liquid Chromatography (HPLC), Gas Chromatography (GC), Mass
nitrosamines R
N H + NOx
R
N N = O Spectroscopy (MS) and Thermal Energy Analyzer (TEA) can detect NAs as low as 0.1 ug/kg.
The equipment listed can also determine different types of NAs, safe and regulated NAs.
solutions to the nitrosamine issue
To combat the NA issue a compounder has three options or a combination of options:

VULCANIZATION
Nitrosamines (NAs) are a family of chemical compounds discovered over 100 years R R

MATERIALS
ago. It was not until the 1950s that these compounds received worldwide attention. Secondary Amine Nitrogen Oxides Nitrosamine (NA) • Avoid compounds that produce NAs completely
In the 1950s, two British scientists, Barnes and Magee discovered that dimethylnitrosamine • Use only safe non-regulated NA-generating additives
As stated above, secondary amines (R2- NH) are of most concern. Primary amines (R1- NH2 ) do
is a powerful carcinogen in laboratory animals. This finding led to massive studies
involving NAs in many industries throughout the years. Due to the advent of more form NAs, but they are very unstable and quickly decompose. Tertiary amines (R3- N) typically do accelerators with regulated NAs • Use an inhibitor to absorb NAs
reliable, sophisticated testing equipment developed in the early 1980s, over 250 different not form NAs. For these reasons, secondary amines have been extensively investigated by the FDA Unfortunately, the most utilized families of accelerators incorporated into cure systems In addition to the options above and whether NAs are an issue or not, proper
nitrosamine (NA) compounds have tested positive as mutagens (chemicals that change and BGA (Germany). These agencies have found that most secondary amines produce harmful for elastomers produce “regulated” or harmful nitrosamines. These families include: environmental measures must be practiced. Education and training of all employees,
DNA) and carcinogens. NA compounds tend to target organs such as the liver, kidney, general good manufacturing practices, the use of fresh air ventilation and proper
lungs, skin and eyes.
or regulated NAs. Some secondary amines do produce safe or non-regulated NAs. Further discussion dithiocarbamates, sulfenamides, thiurams and some sulfur donors. Again, these chemistries
on these NAs will follow. or chemical compounds break down and form secondary amines that are nitrosatable by respirators and protective clothing are essential to any manufacturing process. These
Industries in which NAs are typically found are: Rubber, Food, Metal, Leather oxides of nitrogen. controls may not eliminate NAs, but will greatly reduce the exposure of employees to
and Chemical. Products and manufacturing facilities common to NA development NAs are produced mostly during the curing and post-curing process of rubber components. Therefore NAs, especially in curing and post-curing operations. Within the cured product, NAs
are: tobacco, cured meats, beer, pesticides, tanneries and rubber articles that are the air quality leading to exposure of workers to NAs in manufacturing facilities is very important. R S S R R S N R are still available to migrate during storage, in operation and/or be extracted. Also, it
vulcanized with very common, traditional accelerators. Particular rubber parts In addition, NAs migrate to the surface on rubber parts after cure during storage and use. Some should be mentioned that factory processes, i.e., salt bath curing when using nitrogen-
N C Sx C N N C S Me S N
with NA concerns are baby teats (nipples) and soothers (pacifiers), potable water major tire companies have detected substantial NA levels in tire warehouses and have implemented containing salts could produce harmful NAs. First let’s consider accelerators that do
R R R S R
components, pharmaceutical articles, condoms and gloves. Also, and just as important, ventilation equipment in these facilities. Primary routes of exposure are ingestion, inhalation and not produce any NAs.
Thiurams Dithiocarbamates Sulfenamides
any rubber facility’s air quality is of major NA concern for the safety of the workers dermal (skin) contact. All types of potential exposures have been and will be further addressed by
regulatory agencies. Non-Nitrogen-Containing Accelerators:
when utilizing accelerators that produce NAs. Thiurams are secondary accelerators or “kickers” used at very small quantities to fine-tune Xanthogens (AS-100, ZIX), phosphates (Accelerator VS), peroxides and resin cures
the cure system. All the most commonly utilized thiurams are secondary amines that readily are products of non-nitrogen-containing curatives. Peroxides and resin cures are
The focus of this Solutions insert will be NAs in the Rubber Industry with major
form regulated NAs. These include: TMTM, TMTD, TETD, TBTD and DPTT. certainly viable options if the function of the part and physical properties permit.
emphasis on dry rubber compounding techniques. This literature discusses the
chemistry and formation of NAs, current regulations, cure systems contributing regulations Dithiocarbamates, like thiurams, are secondary accelerators used at very small quantities to Not all elastomers can be resin- or peroxide-cured. Resin cures are utilized in niche
to the formation of NAs and alternative cure systems and additives to reduce, After the detection of over 300 ppb (parts per billion) of NAs was discovered in baby teats and soothers, fine-tune the cure system. These kickers are slightly faster and more active than the thiurams. situations where certain properties are required (steam resistance - butyl curing bags).
inhibit or eliminate NAs in rubber products. many countries set maximum permitted NA levels on these products: Also, dithiocarbamates are extensively used in latex cure systems. All the major accelerators Peroxide cures are typically used in situations where excellent compression set and
in this group produce regulated nitrosamines including: MZ (ZMDC), EZ (ZEDC), BZ (ZBDC), heat resistance are required. Peroxide-cured products can be difficult to process and
ZPD, TDEC, CuDD and BiDD. have limited physical properties. The use of peroxide curatives is growing every year,
chemistry Country
Australia
Nitrosamines (ppb max.1)
20
Nitrosatables (ppb max.)
400
but sulfur/accelerator systems still dominate the rubber industry.
To understand NA formation, a brief explanation of amine chemistry is required. Sulfenamides are delayed-reaction primary accelerators used extensively to produce scorch
Denmark 5 100 safety and fast cure rates. When considering NAs in an elastomeric formulation, the selection Accelerator VS is an interesting, traditional option. This is a zinc salt of dibutyl
Amines are chemical compounds derived from ammonia (NH 3 ). By substituting one
Netherlands 1 100 of sulfenamides is a little more forgiving than the chemistries above. About half of the phosphorodithioate (liquid) on a silica carrier (62% active solid). It does not contain
or all the hydrogens (H) in ammonia with a carbon-containing group (-R), primary,
Canada 10 each – 60 total nr industrially important sulfenamides do not produce regulated NAs: BBTS (TBBS), CBTS (CBS) any nitrogen and therefore cannot generate NAs. Accelerator VS is typically used in
secondary and tertiary amines are created. The substitution of one hydrogen atom
Switzerland 10 200 and DCBS. The other half, OBTS, MBSS and OTOS (Cure-Rite ® 18) are based on morpholine EPDM and NR compounds. This accelerator tends to be scorchy, but certainly is a viable
with one carbon-containing group produces a primary amine. The substitution of
Germany 10 200 and produce the regulated nitrosamine nitroso-morpholine. This nitrosamine derivative is alternative.
two or three hydrogen atoms with two of three carbon-containing groups produces
UK 10 each – 30 total 100 considered one of the most potent NA carcinogens tested in laboratory animals.
secondary and tertiary amines, respectively. Accelerator ZIX is a very fast accelerator and chemically known as zinc iso-propylxanthate.
USA 10 each – 60 total nr
1 Another commonly used accelerator that generates a harmful nitrosamine is Accelerator R Due to its very scorchy nature, this accelerator has a very limited but important use
extractions in artificial saliva or dichloromethane (US, Canada), nr-not regulated
H H R H R R R R in the rubber formulations. Typically, ZIX is used in very low or room temperature cure
(DTDM). This accelerator is also based on morpholine. It is selected as a powerful sulfur donor
N R N N N Currently in Germany, workplace atmospheric concentration of NAs is regulated at 1 ug/m 3. In the systems for adhesive cements, tank linings, coatings, patching compounds, etc.
to create mono- and di-sulfur crosslinks to improve the heat aging and compression set
H H H R
US and Canada, workplace atmospheric concentration of NAs is not regulated to date. Agencies and resistance characteristics of rubber compounds. Other accelerators that produce regulated NAs
unions in the US and Canada and other countries are monitoring, documenting and reporting NA Robac® AS-100 is a new alternative, primary accelerator used globally in dry elastomers
Ammonia Primary Amine Secondary Amine Tertiary Amine are amines and thioureas (ETU, DETU, etc.). and latex. This compound is diisopropyl xanthogen polysulfide, which does not contain
levels in rubber facilities to petition their governments for restrictive limits. Interesting to note that
NAs are formed by secondary amines reacting with oxides of nitrogen. Very common the German regulation (1 ug/m 3) now includes the cabin space of automotive vehicles. This is Fortunately, Akrochem has a full line of accelerators, some traditional and some new chemistry, any nitrogen, phosphorus or metallic components and donates about 10% sulfur. AS-
accelerators such as dithiocarbamates, sulfenamides and thiurams break down and causing automotive suppliers, especially window and door sealant manufacturers, to reformulate to offer that do not produce regulated NAs or any type of amine. The latter are compounds 100 has FDA approval per FDA 21 CFR. 177.2600 and has been selected as the primary
produce secondary amines. Oxides of nitrogen are formed by heating any compound compounds with accelerators that do not produce regulated NAs. In the future, baby teats and that do not contain any nitrogen, thus eliminating the NA issue completely. or secondary accelerator of choice in such rubber articles as: baby soothers and teats,
containing nitrogen, even air (atmospheric oxides). This reaction is called nitrosation: soothers NA regulations will be implemented to include toy balloons, condoms and possibly balloons, condoms, gloves and other elastomeric vulcanizates. Other interesting
pharmaceutical articles. Even warehouse facilities of cured elastomer articles are being investigated characteristics of AS-100 are: completely consumed during cure, highly soluble in
for NA levels. rubbers (non-blooming), free from copper staining and taste and easily dispersible.
SEVEN DECADES OF SUPERIOR SERVICE
240-87 NitrosaminesSSPRINT.fh8 10/13/03 8:24 AM Page 1

NITROSAMINES: c o n t i n u e d 2 NITROSAMINES: c o n t i n u e d 3 NITROSAMINES: c o n t i n u e d 4

Detection of NAs is relatively easy with the use of some sophisticated analytical equipment.
High Performance Liquid Chromatography (HPLC), Gas Chromatography (GC), Mass
nitrosamines R
N H + NOx
R
N N = O Spectroscopy (MS) and Thermal Energy Analyzer (TEA) can detect NAs as low as 0.1 ug/kg.
The equipment listed can also determine different types of NAs, safe and regulated NAs.
solutions to the nitrosamine issue
To combat the NA issue a compounder has three options or a combination of options:

VULCANIZATION
Nitrosamines (NAs) are a family of chemical compounds discovered over 100 years R R

MATERIALS
ago. It was not until the 1950s that these compounds received worldwide attention. Secondary Amine Nitrogen Oxides Nitrosamine (NA) • Avoid compounds that produce NAs completely
In the 1950s, two British scientists, Barnes and Magee discovered that dimethylnitrosamine • Use only safe non-regulated NA-generating additives
As stated above, secondary amines (R2- NH) are of most concern. Primary amines (R1- NH2 ) do
is a powerful carcinogen in laboratory animals. This finding led to massive studies
involving NAs in many industries throughout the years. Due to the advent of more form NAs, but they are very unstable and quickly decompose. Tertiary amines (R3- N) typically do accelerators with regulated NAs • Use an inhibitor to absorb NAs
reliable, sophisticated testing equipment developed in the early 1980s, over 250 different not form NAs. For these reasons, secondary amines have been extensively investigated by the FDA Unfortunately, the most utilized families of accelerators incorporated into cure systems In addition to the options above and whether NAs are an issue or not, proper
nitrosamine (NA) compounds have tested positive as mutagens (chemicals that change and BGA (Germany). These agencies have found that most secondary amines produce harmful for elastomers produce “regulated” or harmful nitrosamines. These families include: environmental measures must be practiced. Education and training of all employees,
DNA) and carcinogens. NA compounds tend to target organs such as the liver, kidney, general good manufacturing practices, the use of fresh air ventilation and proper
lungs, skin and eyes.
or regulated NAs. Some secondary amines do produce safe or non-regulated NAs. Further discussion dithiocarbamates, sulfenamides, thiurams and some sulfur donors. Again, these chemistries
on these NAs will follow. or chemical compounds break down and form secondary amines that are nitrosatable by respirators and protective clothing are essential to any manufacturing process. These
Industries in which NAs are typically found are: Rubber, Food, Metal, Leather oxides of nitrogen. controls may not eliminate NAs, but will greatly reduce the exposure of employees to
and Chemical. Products and manufacturing facilities common to NA development NAs are produced mostly during the curing and post-curing process of rubber components. Therefore NAs, especially in curing and post-curing operations. Within the cured product, NAs
are: tobacco, cured meats, beer, pesticides, tanneries and rubber articles that are the air quality leading to exposure of workers to NAs in manufacturing facilities is very important. R S S R R S N R are still available to migrate during storage, in operation and/or be extracted. Also, it
vulcanized with very common, traditional accelerators. Particular rubber parts In addition, NAs migrate to the surface on rubber parts after cure during storage and use. Some should be mentioned that factory processes, i.e., salt bath curing when using nitrogen-
N C Sx C N N C S Me S N
with NA concerns are baby teats (nipples) and soothers (pacifiers), potable water major tire companies have detected substantial NA levels in tire warehouses and have implemented containing salts could produce harmful NAs. First let’s consider accelerators that do
R R R S R
components, pharmaceutical articles, condoms and gloves. Also, and just as important, ventilation equipment in these facilities. Primary routes of exposure are ingestion, inhalation and not produce any NAs.
Thiurams Dithiocarbamates Sulfenamides
any rubber facility’s air quality is of major NA concern for the safety of the workers dermal (skin) contact. All types of potential exposures have been and will be further addressed by
regulatory agencies. Non-Nitrogen-Containing Accelerators:
when utilizing accelerators that produce NAs. Thiurams are secondary accelerators or “kickers” used at very small quantities to fine-tune Xanthogens (AS-100, ZIX), phosphates (Accelerator VS), peroxides and resin cures
the cure system. All the most commonly utilized thiurams are secondary amines that readily are products of non-nitrogen-containing curatives. Peroxides and resin cures are
The focus of this Solutions insert will be NAs in the Rubber Industry with major
form regulated NAs. These include: TMTM, TMTD, TETD, TBTD and DPTT. certainly viable options if the function of the part and physical properties permit.
emphasis on dry rubber compounding techniques. This literature discusses the
chemistry and formation of NAs, current regulations, cure systems contributing regulations Dithiocarbamates, like thiurams, are secondary accelerators used at very small quantities to Not all elastomers can be resin- or peroxide-cured. Resin cures are utilized in niche
to the formation of NAs and alternative cure systems and additives to reduce, After the detection of over 300 ppb (parts per billion) of NAs was discovered in baby teats and soothers, fine-tune the cure system. These kickers are slightly faster and more active than the thiurams. situations where certain properties are required (steam resistance - butyl curing bags).
inhibit or eliminate NAs in rubber products. many countries set maximum permitted NA levels on these products: Also, dithiocarbamates are extensively used in latex cure systems. All the major accelerators Peroxide cures are typically used in situations where excellent compression set and
in this group produce regulated nitrosamines including: MZ (ZMDC), EZ (ZEDC), BZ (ZBDC), heat resistance are required. Peroxide-cured products can be difficult to process and
ZPD, TDEC, CuDD and BiDD. have limited physical properties. The use of peroxide curatives is growing every year,
chemistry Country
Australia
Nitrosamines (ppb max.1)
20
Nitrosatables (ppb max.)
400
but sulfur/accelerator systems still dominate the rubber industry.
To understand NA formation, a brief explanation of amine chemistry is required. Sulfenamides are delayed-reaction primary accelerators used extensively to produce scorch
Denmark 5 100 safety and fast cure rates. When considering NAs in an elastomeric formulation, the selection Accelerator VS is an interesting, traditional option. This is a zinc salt of dibutyl
Amines are chemical compounds derived from ammonia (NH 3 ). By substituting one
Netherlands 1 100 of sulfenamides is a little more forgiving than the chemistries above. About half of the phosphorodithioate (liquid) on a silica carrier (62% active solid). It does not contain
or all the hydrogens (H) in ammonia with a carbon-containing group (-R), primary,
Canada 10 each – 60 total nr industrially important sulfenamides do not produce regulated NAs: BBTS (TBBS), CBTS (CBS) any nitrogen and therefore cannot generate NAs. Accelerator VS is typically used in
secondary and tertiary amines are created. The substitution of one hydrogen atom
Switzerland 10 200 and DCBS. The other half, OBTS, MBSS and OTOS (Cure-Rite ® 18) are based on morpholine EPDM and NR compounds. This accelerator tends to be scorchy, but certainly is a viable
with one carbon-containing group produces a primary amine. The substitution of
Germany 10 200 and produce the regulated nitrosamine nitroso-morpholine. This nitrosamine derivative is alternative.
two or three hydrogen atoms with two of three carbon-containing groups produces
UK 10 each – 30 total 100 considered one of the most potent NA carcinogens tested in laboratory animals.
secondary and tertiary amines, respectively. Accelerator ZIX is a very fast accelerator and chemically known as zinc iso-propylxanthate.
USA 10 each – 60 total nr
1 Another commonly used accelerator that generates a harmful nitrosamine is Accelerator R Due to its very scorchy nature, this accelerator has a very limited but important use
extractions in artificial saliva or dichloromethane (US, Canada), nr-not regulated
H H R H R R R R in the rubber formulations. Typically, ZIX is used in very low or room temperature cure
(DTDM). This accelerator is also based on morpholine. It is selected as a powerful sulfur donor
N R N N N Currently in Germany, workplace atmospheric concentration of NAs is regulated at 1 ug/m 3. In the systems for adhesive cements, tank linings, coatings, patching compounds, etc.
to create mono- and di-sulfur crosslinks to improve the heat aging and compression set
H H H R
US and Canada, workplace atmospheric concentration of NAs is not regulated to date. Agencies and resistance characteristics of rubber compounds. Other accelerators that produce regulated NAs
unions in the US and Canada and other countries are monitoring, documenting and reporting NA Robac® AS-100 is a new alternative, primary accelerator used globally in dry elastomers
Ammonia Primary Amine Secondary Amine Tertiary Amine are amines and thioureas (ETU, DETU, etc.). and latex. This compound is diisopropyl xanthogen polysulfide, which does not contain
levels in rubber facilities to petition their governments for restrictive limits. Interesting to note that
NAs are formed by secondary amines reacting with oxides of nitrogen. Very common the German regulation (1 ug/m 3) now includes the cabin space of automotive vehicles. This is Fortunately, Akrochem has a full line of accelerators, some traditional and some new chemistry, any nitrogen, phosphorus or metallic components and donates about 10% sulfur. AS-
accelerators such as dithiocarbamates, sulfenamides and thiurams break down and causing automotive suppliers, especially window and door sealant manufacturers, to reformulate to offer that do not produce regulated NAs or any type of amine. The latter are compounds 100 has FDA approval per FDA 21 CFR. 177.2600 and has been selected as the primary
produce secondary amines. Oxides of nitrogen are formed by heating any compound compounds with accelerators that do not produce regulated NAs. In the future, baby teats and that do not contain any nitrogen, thus eliminating the NA issue completely. or secondary accelerator of choice in such rubber articles as: baby soothers and teats,
containing nitrogen, even air (atmospheric oxides). This reaction is called nitrosation: soothers NA regulations will be implemented to include toy balloons, condoms and possibly balloons, condoms, gloves and other elastomeric vulcanizates. Other interesting
pharmaceutical articles. Even warehouse facilities of cured elastomer articles are being investigated characteristics of AS-100 are: completely consumed during cure, highly soluble in
for NA levels. rubbers (non-blooming), free from copper staining and taste and easily dispersible.
SEVEN DECADES OF SUPERIOR SERVICE
240-87 NitrosaminesSSPRINT.fh8 10/13/03 8:24 AM Page 1

NITROSAMINES: c o n t i n u e d 2 NITROSAMINES: c o n t i n u e d 3 NITROSAMINES: c o n t i n u e d 4

Detection of NAs is relatively easy with the use of some sophisticated analytical equipment.
High Performance Liquid Chromatography (HPLC), Gas Chromatography (GC), Mass
nitrosamines R
N H + NOx
R
N N = O Spectroscopy (MS) and Thermal Energy Analyzer (TEA) can detect NAs as low as 0.1 ug/kg.
The equipment listed can also determine different types of NAs, safe and regulated NAs.
solutions to the nitrosamine issue
To combat the NA issue a compounder has three options or a combination of options:

VULCANIZATION
Nitrosamines (NAs) are a family of chemical compounds discovered over 100 years R R

MATERIALS
ago. It was not until the 1950s that these compounds received worldwide attention. Secondary Amine Nitrogen Oxides Nitrosamine (NA) • Avoid compounds that produce NAs completely
In the 1950s, two British scientists, Barnes and Magee discovered that dimethylnitrosamine • Use only safe non-regulated NA-generating additives
As stated above, secondary amines (R2- NH) are of most concern. Primary amines (R1- NH2 ) do
is a powerful carcinogen in laboratory animals. This finding led to massive studies
involving NAs in many industries throughout the years. Due to the advent of more form NAs, but they are very unstable and quickly decompose. Tertiary amines (R3- N) typically do accelerators with regulated NAs • Use an inhibitor to absorb NAs
reliable, sophisticated testing equipment developed in the early 1980s, over 250 different not form NAs. For these reasons, secondary amines have been extensively investigated by the FDA Unfortunately, the most utilized families of accelerators incorporated into cure systems In addition to the options above and whether NAs are an issue or not, proper
nitrosamine (NA) compounds have tested positive as mutagens (chemicals that change and BGA (Germany). These agencies have found that most secondary amines produce harmful for elastomers produce “regulated” or harmful nitrosamines. These families include: environmental measures must be practiced. Education and training of all employees,
DNA) and carcinogens. NA compounds tend to target organs such as the liver, kidney, general good manufacturing practices, the use of fresh air ventilation and proper
lungs, skin and eyes.
or regulated NAs. Some secondary amines do produce safe or non-regulated NAs. Further discussion dithiocarbamates, sulfenamides, thiurams and some sulfur donors. Again, these chemistries
on these NAs will follow. or chemical compounds break down and form secondary amines that are nitrosatable by respirators and protective clothing are essential to any manufacturing process. These
Industries in which NAs are typically found are: Rubber, Food, Metal, Leather oxides of nitrogen. controls may not eliminate NAs, but will greatly reduce the exposure of employees to
and Chemical. Products and manufacturing facilities common to NA development NAs are produced mostly during the curing and post-curing process of rubber components. Therefore NAs, especially in curing and post-curing operations. Within the cured product, NAs
are: tobacco, cured meats, beer, pesticides, tanneries and rubber articles that are the air quality leading to exposure of workers to NAs in manufacturing facilities is very important. R S S R R S N R are still available to migrate during storage, in operation and/or be extracted. Also, it
vulcanized with very common, traditional accelerators. Particular rubber parts In addition, NAs migrate to the surface on rubber parts after cure during storage and use. Some should be mentioned that factory processes, i.e., salt bath curing when using nitrogen-
N C Sx C N N C S Me S N
with NA concerns are baby teats (nipples) and soothers (pacifiers), potable water major tire companies have detected substantial NA levels in tire warehouses and have implemented containing salts could produce harmful NAs. First let’s consider accelerators that do
R R R S R
components, pharmaceutical articles, condoms and gloves. Also, and just as important, ventilation equipment in these facilities. Primary routes of exposure are ingestion, inhalation and not produce any NAs.
Thiurams Dithiocarbamates Sulfenamides
any rubber facility’s air quality is of major NA concern for the safety of the workers dermal (skin) contact. All types of potential exposures have been and will be further addressed by
regulatory agencies. Non-Nitrogen-Containing Accelerators:
when utilizing accelerators that produce NAs. Thiurams are secondary accelerators or “kickers” used at very small quantities to fine-tune Xanthogens (AS-100, ZIX), phosphates (Accelerator VS), peroxides and resin cures
the cure system. All the most commonly utilized thiurams are secondary amines that readily are products of non-nitrogen-containing curatives. Peroxides and resin cures are
The focus of this Solutions insert will be NAs in the Rubber Industry with major
form regulated NAs. These include: TMTM, TMTD, TETD, TBTD and DPTT. certainly viable options if the function of the part and physical properties permit.
emphasis on dry rubber compounding techniques. This literature discusses the
chemistry and formation of NAs, current regulations, cure systems contributing regulations Dithiocarbamates, like thiurams, are secondary accelerators used at very small quantities to Not all elastomers can be resin- or peroxide-cured. Resin cures are utilized in niche
to the formation of NAs and alternative cure systems and additives to reduce, After the detection of over 300 ppb (parts per billion) of NAs was discovered in baby teats and soothers, fine-tune the cure system. These kickers are slightly faster and more active than the thiurams. situations where certain properties are required (steam resistance - butyl curing bags).
inhibit or eliminate NAs in rubber products. many countries set maximum permitted NA levels on these products: Also, dithiocarbamates are extensively used in latex cure systems. All the major accelerators Peroxide cures are typically used in situations where excellent compression set and
in this group produce regulated nitrosamines including: MZ (ZMDC), EZ (ZEDC), BZ (ZBDC), heat resistance are required. Peroxide-cured products can be difficult to process and
ZPD, TDEC, CuDD and BiDD. have limited physical properties. The use of peroxide curatives is growing every year,
chemistry Country
Australia
Nitrosamines (ppb max.1)
20
Nitrosatables (ppb max.)
400
but sulfur/accelerator systems still dominate the rubber industry.
To understand NA formation, a brief explanation of amine chemistry is required. Sulfenamides are delayed-reaction primary accelerators used extensively to produce scorch
Denmark 5 100 safety and fast cure rates. When considering NAs in an elastomeric formulation, the selection Accelerator VS is an interesting, traditional option. This is a zinc salt of dibutyl
Amines are chemical compounds derived from ammonia (NH 3 ). By substituting one
Netherlands 1 100 of sulfenamides is a little more forgiving than the chemistries above. About half of the phosphorodithioate (liquid) on a silica carrier (62% active solid). It does not contain
or all the hydrogens (H) in ammonia with a carbon-containing group (-R), primary,
Canada 10 each – 60 total nr industrially important sulfenamides do not produce regulated NAs: BBTS (TBBS), CBTS (CBS) any nitrogen and therefore cannot generate NAs. Accelerator VS is typically used in
secondary and tertiary amines are created. The substitution of one hydrogen atom
Switzerland 10 200 and DCBS. The other half, OBTS, MBSS and OTOS (Cure-Rite ® 18) are based on morpholine EPDM and NR compounds. This accelerator tends to be scorchy, but certainly is a viable
with one carbon-containing group produces a primary amine. The substitution of
Germany 10 200 and produce the regulated nitrosamine nitroso-morpholine. This nitrosamine derivative is alternative.
two or three hydrogen atoms with two of three carbon-containing groups produces
UK 10 each – 30 total 100 considered one of the most potent NA carcinogens tested in laboratory animals.
secondary and tertiary amines, respectively. Accelerator ZIX is a very fast accelerator and chemically known as zinc iso-propylxanthate.
USA 10 each – 60 total nr
1 Another commonly used accelerator that generates a harmful nitrosamine is Accelerator R Due to its very scorchy nature, this accelerator has a very limited but important use
extractions in artificial saliva or dichloromethane (US, Canada), nr-not regulated
H H R H R R R R in the rubber formulations. Typically, ZIX is used in very low or room temperature cure
(DTDM). This accelerator is also based on morpholine. It is selected as a powerful sulfur donor
N R N N N Currently in Germany, workplace atmospheric concentration of NAs is regulated at 1 ug/m 3. In the systems for adhesive cements, tank linings, coatings, patching compounds, etc.
to create mono- and di-sulfur crosslinks to improve the heat aging and compression set
H H H R
US and Canada, workplace atmospheric concentration of NAs is not regulated to date. Agencies and resistance characteristics of rubber compounds. Other accelerators that produce regulated NAs
unions in the US and Canada and other countries are monitoring, documenting and reporting NA Robac® AS-100 is a new alternative, primary accelerator used globally in dry elastomers
Ammonia Primary Amine Secondary Amine Tertiary Amine are amines and thioureas (ETU, DETU, etc.). and latex. This compound is diisopropyl xanthogen polysulfide, which does not contain
levels in rubber facilities to petition their governments for restrictive limits. Interesting to note that
NAs are formed by secondary amines reacting with oxides of nitrogen. Very common the German regulation (1 ug/m 3) now includes the cabin space of automotive vehicles. This is Fortunately, Akrochem has a full line of accelerators, some traditional and some new chemistry, any nitrogen, phosphorus or metallic components and donates about 10% sulfur. AS-
accelerators such as dithiocarbamates, sulfenamides and thiurams break down and causing automotive suppliers, especially window and door sealant manufacturers, to reformulate to offer that do not produce regulated NAs or any type of amine. The latter are compounds 100 has FDA approval per FDA 21 CFR. 177.2600 and has been selected as the primary
produce secondary amines. Oxides of nitrogen are formed by heating any compound compounds with accelerators that do not produce regulated NAs. In the future, baby teats and that do not contain any nitrogen, thus eliminating the NA issue completely. or secondary accelerator of choice in such rubber articles as: baby soothers and teats,
containing nitrogen, even air (atmospheric oxides). This reaction is called nitrosation: soothers NA regulations will be implemented to include toy balloons, condoms and possibly balloons, condoms, gloves and other elastomeric vulcanizates. Other interesting
pharmaceutical articles. Even warehouse facilities of cured elastomer articles are being investigated characteristics of AS-100 are: completely consumed during cure, highly soluble in
for NA levels. rubbers (non-blooming), free from copper staining and taste and easily dispersible.
SEVEN DECADES OF SUPERIOR SERVICE
240-87 NitrosaminesSSPRINT.fh8 10/13/03 8:24 AM Page 1

NITROSAMINES: c o n t i n u e d 2 NITROSAMINES: c o n t i n u e d 3 NITROSAMINES: c o n t i n u e d 4

Detection of NAs is relatively easy with the use of some sophisticated analytical equipment.
High Performance Liquid Chromatography (HPLC), Gas Chromatography (GC), Mass
nitrosamines R
N H + NOx
R
N N = O Spectroscopy (MS) and Thermal Energy Analyzer (TEA) can detect NAs as low as 0.1 ug/kg.
The equipment listed can also determine different types of NAs, safe and regulated NAs.
solutions to the nitrosamine issue
To combat the NA issue a compounder has three options or a combination of options:

VULCANIZATION
Nitrosamines (NAs) are a family of chemical compounds discovered over 100 years R R

MATERIALS
ago. It was not until the 1950s that these compounds received worldwide attention. Secondary Amine Nitrogen Oxides Nitrosamine (NA) • Avoid compounds that produce NAs completely
In the 1950s, two British scientists, Barnes and Magee discovered that dimethylnitrosamine • Use only safe non-regulated NA-generating additives
As stated above, secondary amines (R2- NH) are of most concern. Primary amines (R1- NH2 ) do
is a powerful carcinogen in laboratory animals. This finding led to massive studies
involving NAs in many industries throughout the years. Due to the advent of more form NAs, but they are very unstable and quickly decompose. Tertiary amines (R3- N) typically do accelerators with regulated NAs • Use an inhibitor to absorb NAs
reliable, sophisticated testing equipment developed in the early 1980s, over 250 different not form NAs. For these reasons, secondary amines have been extensively investigated by the FDA Unfortunately, the most utilized families of accelerators incorporated into cure systems In addition to the options above and whether NAs are an issue or not, proper
nitrosamine (NA) compounds have tested positive as mutagens (chemicals that change and BGA (Germany). These agencies have found that most secondary amines produce harmful for elastomers produce “regulated” or harmful nitrosamines. These families include: environmental measures must be practiced. Education and training of all employees,
DNA) and carcinogens. NA compounds tend to target organs such as the liver, kidney, general good manufacturing practices, the use of fresh air ventilation and proper
lungs, skin and eyes.
or regulated NAs. Some secondary amines do produce safe or non-regulated NAs. Further discussion dithiocarbamates, sulfenamides, thiurams and some sulfur donors. Again, these chemistries
on these NAs will follow. or chemical compounds break down and form secondary amines that are nitrosatable by respirators and protective clothing are essential to any manufacturing process. These
Industries in which NAs are typically found are: Rubber, Food, Metal, Leather oxides of nitrogen. controls may not eliminate NAs, but will greatly reduce the exposure of employees to
and Chemical. Products and manufacturing facilities common to NA development NAs are produced mostly during the curing and post-curing process of rubber components. Therefore NAs, especially in curing and post-curing operations. Within the cured product, NAs
are: tobacco, cured meats, beer, pesticides, tanneries and rubber articles that are the air quality leading to exposure of workers to NAs in manufacturing facilities is very important. R S S R R S N R are still available to migrate during storage, in operation and/or be extracted. Also, it
vulcanized with very common, traditional accelerators. Particular rubber parts In addition, NAs migrate to the surface on rubber parts after cure during storage and use. Some should be mentioned that factory processes, i.e., salt bath curing when using nitrogen-
N C Sx C N N C S Me S N
with NA concerns are baby teats (nipples) and soothers (pacifiers), potable water major tire companies have detected substantial NA levels in tire warehouses and have implemented containing salts could produce harmful NAs. First let’s consider accelerators that do
R R R S R
components, pharmaceutical articles, condoms and gloves. Also, and just as important, ventilation equipment in these facilities. Primary routes of exposure are ingestion, inhalation and not produce any NAs.
Thiurams Dithiocarbamates Sulfenamides
any rubber facility’s air quality is of major NA concern for the safety of the workers dermal (skin) contact. All types of potential exposures have been and will be further addressed by
regulatory agencies. Non-Nitrogen-Containing Accelerators:
when utilizing accelerators that produce NAs. Thiurams are secondary accelerators or “kickers” used at very small quantities to fine-tune Xanthogens (AS-100, ZIX), phosphates (Accelerator VS), peroxides and resin cures
the cure system. All the most commonly utilized thiurams are secondary amines that readily are products of non-nitrogen-containing curatives. Peroxides and resin cures are
The focus of this Solutions insert will be NAs in the Rubber Industry with major
form regulated NAs. These include: TMTM, TMTD, TETD, TBTD and DPTT. certainly viable options if the function of the part and physical properties permit.
emphasis on dry rubber compounding techniques. This literature discusses the
chemistry and formation of NAs, current regulations, cure systems contributing regulations Dithiocarbamates, like thiurams, are secondary accelerators used at very small quantities to Not all elastomers can be resin- or peroxide-cured. Resin cures are utilized in niche
to the formation of NAs and alternative cure systems and additives to reduce, After the detection of over 300 ppb (parts per billion) of NAs was discovered in baby teats and soothers, fine-tune the cure system. These kickers are slightly faster and more active than the thiurams. situations where certain properties are required (steam resistance - butyl curing bags).
inhibit or eliminate NAs in rubber products. many countries set maximum permitted NA levels on these products: Also, dithiocarbamates are extensively used in latex cure systems. All the major accelerators Peroxide cures are typically used in situations where excellent compression set and
in this group produce regulated nitrosamines including: MZ (ZMDC), EZ (ZEDC), BZ (ZBDC), heat resistance are required. Peroxide-cured products can be difficult to process and
ZPD, TDEC, CuDD and BiDD. have limited physical properties. The use of peroxide curatives is growing every year,
chemistry Country
Australia
Nitrosamines (ppb max.1)
20
Nitrosatables (ppb max.)
400
but sulfur/accelerator systems still dominate the rubber industry.
To understand NA formation, a brief explanation of amine chemistry is required. Sulfenamides are delayed-reaction primary accelerators used extensively to produce scorch
Denmark 5 100 safety and fast cure rates. When considering NAs in an elastomeric formulation, the selection Accelerator VS is an interesting, traditional option. This is a zinc salt of dibutyl
Amines are chemical compounds derived from ammonia (NH 3 ). By substituting one
Netherlands 1 100 of sulfenamides is a little more forgiving than the chemistries above. About half of the phosphorodithioate (liquid) on a silica carrier (62% active solid). It does not contain
or all the hydrogens (H) in ammonia with a carbon-containing group (-R), primary,
Canada 10 each – 60 total nr industrially important sulfenamides do not produce regulated NAs: BBTS (TBBS), CBTS (CBS) any nitrogen and therefore cannot generate NAs. Accelerator VS is typically used in
secondary and tertiary amines are created. The substitution of one hydrogen atom
Switzerland 10 200 and DCBS. The other half, OBTS, MBSS and OTOS (Cure-Rite ® 18) are based on morpholine EPDM and NR compounds. This accelerator tends to be scorchy, but certainly is a viable
with one carbon-containing group produces a primary amine. The substitution of
Germany 10 200 and produce the regulated nitrosamine nitroso-morpholine. This nitrosamine derivative is alternative.
two or three hydrogen atoms with two of three carbon-containing groups produces
UK 10 each – 30 total 100 considered one of the most potent NA carcinogens tested in laboratory animals.
secondary and tertiary amines, respectively. Accelerator ZIX is a very fast accelerator and chemically known as zinc iso-propylxanthate.
USA 10 each – 60 total nr
1 Another commonly used accelerator that generates a harmful nitrosamine is Accelerator R Due to its very scorchy nature, this accelerator has a very limited but important use
extractions in artificial saliva or dichloromethane (US, Canada), nr-not regulated
H H R H R R R R in the rubber formulations. Typically, ZIX is used in very low or room temperature cure
(DTDM). This accelerator is also based on morpholine. It is selected as a powerful sulfur donor
N R N N N Currently in Germany, workplace atmospheric concentration of NAs is regulated at 1 ug/m 3. In the systems for adhesive cements, tank linings, coatings, patching compounds, etc.
to create mono- and di-sulfur crosslinks to improve the heat aging and compression set
H H H R
US and Canada, workplace atmospheric concentration of NAs is not regulated to date. Agencies and resistance characteristics of rubber compounds. Other accelerators that produce regulated NAs
unions in the US and Canada and other countries are monitoring, documenting and reporting NA Robac® AS-100 is a new alternative, primary accelerator used globally in dry elastomers
Ammonia Primary Amine Secondary Amine Tertiary Amine are amines and thioureas (ETU, DETU, etc.). and latex. This compound is diisopropyl xanthogen polysulfide, which does not contain
levels in rubber facilities to petition their governments for restrictive limits. Interesting to note that
NAs are formed by secondary amines reacting with oxides of nitrogen. Very common the German regulation (1 ug/m 3) now includes the cabin space of automotive vehicles. This is Fortunately, Akrochem has a full line of accelerators, some traditional and some new chemistry, any nitrogen, phosphorus or metallic components and donates about 10% sulfur. AS-
accelerators such as dithiocarbamates, sulfenamides and thiurams break down and causing automotive suppliers, especially window and door sealant manufacturers, to reformulate to offer that do not produce regulated NAs or any type of amine. The latter are compounds 100 has FDA approval per FDA 21 CFR. 177.2600 and has been selected as the primary
produce secondary amines. Oxides of nitrogen are formed by heating any compound compounds with accelerators that do not produce regulated NAs. In the future, baby teats and that do not contain any nitrogen, thus eliminating the NA issue completely. or secondary accelerator of choice in such rubber articles as: baby soothers and teats,
containing nitrogen, even air (atmospheric oxides). This reaction is called nitrosation: soothers NA regulations will be implemented to include toy balloons, condoms and possibly balloons, condoms, gloves and other elastomeric vulcanizates. Other interesting
pharmaceutical articles. Even warehouse facilities of cured elastomer articles are being investigated characteristics of AS-100 are: completely consumed during cure, highly soluble in
for NA levels. rubbers (non-blooming), free from copper staining and taste and easily dispersible.
SEVEN DECADES OF SUPERIOR SERVICE
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NITROSAMINES: c o n t i n u e d 5 NITROSAMINES: c o n t i n u e d 6 NITROSAMINES: c o n t i n u e d 7 NITROSAMINES: c o n t i n u e d 8

Below is data pertaining to a sulfurless cure system utilizing AS-100: There is a lot of literature published concerning the more traditional accelerators like MBT, The rheologies above show the cure characteristics of SAA-30 in the following test compound: Accelerator ZBED is a popular choice to replace other dithiocarbamates to lower or eliminate regulated NA levels.
MBTS, CBTS, BBTS, DPG, etc. Therefore, let’s focus on some interesting, non-traditional, safe SMR CV-100 phr, zinc oxide-5, stearic acid-1, antioxidant-1, N762 carbon black-5, calcium This ultra accelerator, is chemically, zinc dibenzyl dithiocarbamate. It acts like a typical dithiocarbamate
Cure System TS 2 T50 T90 MH Hardness Mod. 500% TS EB NA-generating accelerators such as: Robac® SAA-30, Cure-Rite® IBM, Cure-Rite® IBT and ZBED. carbonate-50, sulfur-1.2 and accelerator-0.5. This accelerator produces fast cures, i.e. short secondary accelerator by decreasing scorch times and cure rate while increasing cure states. ZBED does produce
mins. mins. mins. lb-in pts. psi psi %
scorch and rate of cure. The state of cure in most cases is comparable to thiurams. Also, note the non-regulated N-nitrosodibenzylamine and is used effectively with sulfenamides, thiazoles and thiurams.
TMTD 1.37 3.26 7.28 45.0 48 1204 3422 700 Robac® SAA-30 PM 50 is a new, interesting, ultra-fast accelerator chemically known as 2,2 -
when compared to other safe NA-generating accelerators, SAA-30 produces a fast cure rate with ZBED has a high molecular weight relative to other more common dithiocarbamates like MZ, EZ and BZ;
AS-100 1.46 2.34 4.52 27.4 30 493 2132 890 dithiodi(ethylammonium) - bis (dibenzyldithiocarbamate). This product is available as a 50%
the highest state of cure. SAA-30 in natural rubber produces some very interesting and favorable therefore about 1.5 times more ZBED is needed to replace common dithiocarbamates. Typical cure systems
TBZTD/AS-100 2.00 3.27 6.21 39.0 43 798 3089 890 rubber-bound dispersion in cylindrical pellet form. SAA-30 functions as an accelerator, which
physical, aging and dynamic properties when compared to other traditional dithiocarbamates. using ZBED to obtain low NA levels are:
can replace conventional dithiocarbamates (MZ, EZ, BZ, etc.) and thiurams (TMTM, TMTD, etc.).
Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, N762-5, CaCO 3-50, Accelerator-3. Cure: 160C/T95
Below are some results utilizing SAA-30 as a primary accelerator:
AS-100’s rheological data shows that it’s marginally less scorchy, but considerably Cure System Hard. TS EB Hard.1 TS1 EB1 Fatigue 2 NR or SBR EPDM BUTYL
tors
c e l e ra pts. psi % pts. psi % cycles x 100
faster than TMTD. The state of cure of the compound utilizing AS-100 is lower than o f ac Sulfur 2.0 - 2.5 Sulfur 1.5 - 2.0 Sulfur 1.0 - 2.0
TMTD. This is easily corrected by the addition of Accelerator TBzTD (thiuram, safe ses EZ 44 3248 840 35 2393 680 509 ZBED 0.5 - 1.5 ZBED 1.5 - 2.0 ZBED 0.5 - 1.5
cl as
nitrosamine generator) working synergistically with AS-100. Accelerator AS-100 also er SAA-30 50 3698 780 50 3205 680 1039 BBTS 1.5 - 2.5 MBT 1.5 - 2.0 BBTS 1.0 - 1.5

h
works well in combination with sulfenamides to produce low compression set, ZBED 37 2146 980 32 1900 830 836 MBTS 0.5 - 1.5 CBTS 1.0 - 2.5 IBT 0.7 - 1.2

ot
vs.
sulfurless EV cure systems (below). Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, N762 carbon black-5, CaCO3-50, sulfur-2.5, accel.-0.6.

-30
1
45
heat aged: 168 hrs./70C, 2fatigue to failure: JIS ave. 100% extension. Inhibitors:

SAA
TMTD CBTS
Cure System Hard. Mod. 300% TS EB Comp.Set Comp.Set NAs Rubber compounders have incorporated the use of NA inhibitors into formulations, but typically as a last resort
pts. psi psi % 24hr/70C,% 24hr/100C,% ug/kg
40 When SAA-30 is used as a primary accelerator and compared to accelerator EZ (table above),
and in combination with the accelerators discussed above. It is believed that NA inhibitors disable nitrogen oxides
SAA-30 produces higher initial properties and superior heat-aged and dynamic performance.
A - traditional 56 1494 3234 509 9 15 ˜ 200
35
preventing them from reacting with secondary amines. The concern with these inhibitors is that they are not
SAA-30 SAA-30’s values also outperform the safe NA generating accelerator ZBED.
B - safer 54 1378 3219 529 10 15 ND 30 EZ always effective in eliminating or reducing levels of NAs. Chemicals that have been tested and in some cases

Torque (in-lb)
Heat aging A +1 -15 -25 -5 - - - 25 Cure System Hard. TS EB Hard.1 TS1 EB1 Fatigue 2 found to reduce NA levels are: ascorbic acid (vitamin C), -tocopherol (vitamin E), calcium oxide
Heat aging B +3 -2 -17 -5 - - - MBT pts. psi % pts. psi % cycles x 100 (Akrocal 90) and alkyl phenol formaldehyde resins (Akrochem P-101).
20
Compound: SMR CV-100, ZnO-5, S.Acid-2, AO-1.0, N550-45, CaCO 3-50, Paraffinic oil-4, Wax-3, AOz-3,
TMTD/CBTS 55 3843 630 55 2378 470 792
15
Accelerator-3. Cure Systems: A-Accelerator R-1.0, OBTS-1.0, TMTD-1.0. B-AS-100-1.2, TBZTD-2.2, BBTS-1.0 SAA-30/CBTS 56 3698 620 55 2552 480 840
Cure: 160C/T95, Heat Aging: 168 hrs./100C, ND—none detected 10

5
Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, c.black-5, CaCO3-50, sulfur-1.25, CBTS-1.6, TMTD/SAA-30-0.3.
1
heat-aged: 70 hrs./100C, 2fatigue to failure: JIS ave. 100% extension.
conclusion
The data reflects that AS-100 used in combination with TB zTD and BBTS can create 0 2.5 5 7.5 10 The Nitrosamine issue has been under investigation for many decades. Both US and German environmental
a compound very close to the performance of the traditional Accelerator R, OBTS Very comparable results were obtained substituting SAA-30 for TMTD as the secondary accelerator and health-related government agencies have imposed limitations on the use of substances that create nitrosamines
and TMTD system used for low compression set and good heat aging. The obvious
Minutes at 160° C in the above natural rubber test formulation. Again, the heat-aged and dynamic properties are in the Rubber Industry. More countries in the near future will also impose regulations. More notably, these
favorable utilizing the SAA-30.
benefit to the AS-100 cure system is the low levels of NAs. BBTS and TB zTD both rators current regulations are being reviewed and will be altered in the future to stricter standards. For example, in
g en e
produce NAs, but of the non-regulatory type. In contrast, Accelerator R and OBTS As Cure-Rite® IBM and Cure-Rite® IBT are non-staining ultra accelerators that produce approximately Germany the latest regulation permits a maximum atmospheric concentration of regulated NAs of only 1 ug/m 3.
N
produce N-nitroso-morpholine and TMTD produces N-nitrosodimethylamine, both fe This amendment includes the cabin space in automobiles. Therefore, automotive suppliers are placing increased
sa 100 times less NAs than common thiurams like TMTM and TMTD. IBM is a mono-sulfide thiuram
regulated NAs. interest on the Nitrosamine issue especially in door and window seals. This interest will trickle over to non-
.

and IBT is a di-sulfide thiuram. Although IBM and IBT were developed to replace TMTM and
vs

automotive rubber industries and components. Realistically, NAs are far more potent in rubber factories’
0

TMTD, respectively, both have found applications to replace DPTT, TETD and the pricey TB zTD.
A -3

Non-Regulated or Safe NA-Producing Accelerators: atmosphere during curing or post-curing of rubber. Currently in the US, unions and special interest groups
SA

Below is a listing of accelerators that produce non-regulated, safe NAs or cannot 40 Two additional characteristics have been discovered with the use of these accelerators. First, both
IBM and IBT provided much more scorch safety and shorter cure times than TMTM and TMTD. are placing increasing pressure on the EPA and OSHA to set nitrosamine restrictions, not only in the factories,
produce any type of NAs because they do not contain secondary amines or any but also in storage facilities. Akrochem offers rubber manufacturers a variety of safe and non-nitrosamine-
35 SAA-30 In fact, in certain formulations, IBM provided increased scorch safety beyond that of a sulfenamide
nitrogen: producing accelerators, as well as some nitrosamine inhibitors. Further details and information are available
30
DPG (delayed-reaction accelerator) used alone. Second, both accelerators deliver much less reversion
from Akrochem. Please contact your Technical Salesperson or the Technical Department at Akrochem.
Chemical Family No/Safe NAs Replace ZBED in natural rubber compounds than comparable accelerators. The increased scorch resistance
Torque (in-lb)

25
Sulfenamides DCBS, CBTS, BBTS OBTS, OMTS, MBSS, OTOS and cure rate combined with reduced reversion translates to shorter cure cycles or increased
TBZTD Robac® - Robinson Brothers Limited, Cure-Rite® - Noveon Incorporated
Thiazoles MBT, MBTS, ZMBT 20 safety of hard-to-process compounds.
Guanidines DPG, DOTG
Thiurams TBzTD, TETD, TMTM, TMTD, 15 Zn Dithiophosphate Being a higher molecular weight accelerator, more IBM by weight should be used if replacing
other thiurams (1.6 x TMTD phr; 1.85 x TMTM; 1.33x TETD). The exception is the replacement SEVEN DECADES OF SUPERIOR SERVICE
IBT1, IBM1 DPTT, TBTD 10
of TBzTD would require only 0.70 as much IBM. IBT also is a higher molecular weight accelerator, Included with its product literature and upon the request of its customers, Akrochem provides product specifications and evaluations, suggested formulations and recommendations and other technical assistance, both orally and in writing (collectively the
Dithiocarbamates SAA-30, Arbestab Z. MZ, EZ, BZ, CuDD, ZPD, “Technical Information”). Although Akrochem believes all Technical Information to be true and correct, it makes no warranty, either express or implied, as to the accuracy, completeness or fitness of the Technical Information for any intended use, or the
results which may be obtained by any person using the Technical Information. Akrochem will not be liable for any cost, loss or damage, in tort, contract or otherwise, arising from customer's use of Akrochem products or Technical Information.
5 therefore a good starting point to replace other thiurams should be (1.7 x TMTD phr; 2.0 x
ZBED TDEC, BiDD 0 2.5 5 7.5 10
It is the customer’s sole responsibility to test the products and any Technical Information provided to determine whether they are suitable for the customer’s needs. Before working with any product, the customer must read and become familiar with available
TMTM; 1.4 x TETD). The exception is the replacement of TBzTD would require only 0.75 as information concerning its hazards, proper use, storage and handling, including all health, safety and hygiene precautions recommended by the manufacturer.

Non-Nitrogen AS-100, ZIX, VS DTDM Nothing in the Technical Information is intended to be a recommendation to use any product, method or process in violation of any intellectual property rights governing such product, method or process. No license is implied or granted by Akrochem as to
Minutes at 160° C much IBT. any such product, method or process. The names/brandnames appearing throughout this literature are believed to be either brandnames or registered or unregistered trademarks.
1
very low levels of NAs AKROCHEM CORPORATION DISCLAIMS ANY AND ALL WARRANTIES, EXPRESS AND IMPLIED, INCLUDING WITHOUT LIMITATION, WARRANTIES OR MERCHANTABILITY AND FITNESS FOR ANY PARTICULAR PURPOSE, RELATED TO ANY PRODUCTS
OR TECHNICAL INFORMATION PROVIDED BY AKROCHEM.
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NITROSAMINES: c o n t i n u e d 5 NITROSAMINES: c o n t i n u e d 6 NITROSAMINES: c o n t i n u e d 7 NITROSAMINES: c o n t i n u e d 8

Below is data pertaining to a sulfurless cure system utilizing AS-100: There is a lot of literature published concerning the more traditional accelerators like MBT, The rheologies above show the cure characteristics of SAA-30 in the following test compound: Accelerator ZBED is a popular choice to replace other dithiocarbamates to lower or eliminate regulated NA levels.
MBTS, CBTS, BBTS, DPG, etc. Therefore, let’s focus on some interesting, non-traditional, safe SMR CV-100 phr, zinc oxide-5, stearic acid-1, antioxidant-1, N762 carbon black-5, calcium This ultra accelerator, is chemically, zinc dibenzyl dithiocarbamate. It acts like a typical dithiocarbamate
Cure System TS 2 T50 T90 MH Hardness Mod. 500% TS EB NA-generating accelerators such as: Robac® SAA-30, Cure-Rite® IBM, Cure-Rite® IBT and ZBED. carbonate-50, sulfur-1.2 and accelerator-0.5. This accelerator produces fast cures, i.e. short secondary accelerator by decreasing scorch times and cure rate while increasing cure states. ZBED does produce
mins. mins. mins. lb-in pts. psi psi %
scorch and rate of cure. The state of cure in most cases is comparable to thiurams. Also, note the non-regulated N-nitrosodibenzylamine and is used effectively with sulfenamides, thiazoles and thiurams.
TMTD 1.37 3.26 7.28 45.0 48 1204 3422 700 Robac® SAA-30 PM 50 is a new, interesting, ultra-fast accelerator chemically known as 2,2 -
when compared to other safe NA-generating accelerators, SAA-30 produces a fast cure rate with ZBED has a high molecular weight relative to other more common dithiocarbamates like MZ, EZ and BZ;
AS-100 1.46 2.34 4.52 27.4 30 493 2132 890 dithiodi(ethylammonium) - bis (dibenzyldithiocarbamate). This product is available as a 50%
the highest state of cure. SAA-30 in natural rubber produces some very interesting and favorable therefore about 1.5 times more ZBED is needed to replace common dithiocarbamates. Typical cure systems
TBZTD/AS-100 2.00 3.27 6.21 39.0 43 798 3089 890 rubber-bound dispersion in cylindrical pellet form. SAA-30 functions as an accelerator, which
physical, aging and dynamic properties when compared to other traditional dithiocarbamates. using ZBED to obtain low NA levels are:
can replace conventional dithiocarbamates (MZ, EZ, BZ, etc.) and thiurams (TMTM, TMTD, etc.).
Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, N762-5, CaCO 3-50, Accelerator-3. Cure: 160C/T95
Below are some results utilizing SAA-30 as a primary accelerator:
AS-100’s rheological data shows that it’s marginally less scorchy, but considerably Cure System Hard. TS EB Hard.1 TS1 EB1 Fatigue 2 NR or SBR EPDM BUTYL
tors
c e l e ra pts. psi % pts. psi % cycles x 100
faster than TMTD. The state of cure of the compound utilizing AS-100 is lower than o f ac Sulfur 2.0 - 2.5 Sulfur 1.5 - 2.0 Sulfur 1.0 - 2.0
TMTD. This is easily corrected by the addition of Accelerator TBzTD (thiuram, safe ses EZ 44 3248 840 35 2393 680 509 ZBED 0.5 - 1.5 ZBED 1.5 - 2.0 ZBED 0.5 - 1.5
cl as
nitrosamine generator) working synergistically with AS-100. Accelerator AS-100 also er SAA-30 50 3698 780 50 3205 680 1039 BBTS 1.5 - 2.5 MBT 1.5 - 2.0 BBTS 1.0 - 1.5

h
works well in combination with sulfenamides to produce low compression set, ZBED 37 2146 980 32 1900 830 836 MBTS 0.5 - 1.5 CBTS 1.0 - 2.5 IBT 0.7 - 1.2

ot
vs.
sulfurless EV cure systems (below). Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, N762 carbon black-5, CaCO3-50, sulfur-2.5, accel.-0.6.

-30
1
45
heat aged: 168 hrs./70C, 2fatigue to failure: JIS ave. 100% extension. Inhibitors:

SAA
TMTD CBTS
Cure System Hard. Mod. 300% TS EB Comp.Set Comp.Set NAs Rubber compounders have incorporated the use of NA inhibitors into formulations, but typically as a last resort
pts. psi psi % 24hr/70C,% 24hr/100C,% ug/kg
40 When SAA-30 is used as a primary accelerator and compared to accelerator EZ (table above),
and in combination with the accelerators discussed above. It is believed that NA inhibitors disable nitrogen oxides
SAA-30 produces higher initial properties and superior heat-aged and dynamic performance.
A - traditional 56 1494 3234 509 9 15 ˜ 200
35
preventing them from reacting with secondary amines. The concern with these inhibitors is that they are not
SAA-30 SAA-30’s values also outperform the safe NA generating accelerator ZBED.
B - safer 54 1378 3219 529 10 15 ND 30 EZ always effective in eliminating or reducing levels of NAs. Chemicals that have been tested and in some cases

Torque (in-lb)
Heat aging A +1 -15 -25 -5 - - - 25 Cure System Hard. TS EB Hard.1 TS1 EB1 Fatigue 2 found to reduce NA levels are: ascorbic acid (vitamin C), -tocopherol (vitamin E), calcium oxide
Heat aging B +3 -2 -17 -5 - - - MBT pts. psi % pts. psi % cycles x 100 (Akrocal 90) and alkyl phenol formaldehyde resins (Akrochem P-101).
20
Compound: SMR CV-100, ZnO-5, S.Acid-2, AO-1.0, N550-45, CaCO 3-50, Paraffinic oil-4, Wax-3, AOz-3,
TMTD/CBTS 55 3843 630 55 2378 470 792
15
Accelerator-3. Cure Systems: A-Accelerator R-1.0, OBTS-1.0, TMTD-1.0. B-AS-100-1.2, TBZTD-2.2, BBTS-1.0 SAA-30/CBTS 56 3698 620 55 2552 480 840
Cure: 160C/T95, Heat Aging: 168 hrs./100C, ND—none detected 10

5
Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, c.black-5, CaCO3-50, sulfur-1.25, CBTS-1.6, TMTD/SAA-30-0.3.
1
heat-aged: 70 hrs./100C, 2fatigue to failure: JIS ave. 100% extension.
conclusion
The data reflects that AS-100 used in combination with TB zTD and BBTS can create 0 2.5 5 7.5 10 The Nitrosamine issue has been under investigation for many decades. Both US and German environmental
a compound very close to the performance of the traditional Accelerator R, OBTS Very comparable results were obtained substituting SAA-30 for TMTD as the secondary accelerator and health-related government agencies have imposed limitations on the use of substances that create nitrosamines
and TMTD system used for low compression set and good heat aging. The obvious
Minutes at 160° C in the above natural rubber test formulation. Again, the heat-aged and dynamic properties are in the Rubber Industry. More countries in the near future will also impose regulations. More notably, these
favorable utilizing the SAA-30.
benefit to the AS-100 cure system is the low levels of NAs. BBTS and TB zTD both rators current regulations are being reviewed and will be altered in the future to stricter standards. For example, in
g en e
produce NAs, but of the non-regulatory type. In contrast, Accelerator R and OBTS As Cure-Rite® IBM and Cure-Rite® IBT are non-staining ultra accelerators that produce approximately Germany the latest regulation permits a maximum atmospheric concentration of regulated NAs of only 1 ug/m 3.
N
produce N-nitroso-morpholine and TMTD produces N-nitrosodimethylamine, both fe This amendment includes the cabin space in automobiles. Therefore, automotive suppliers are placing increased
sa 100 times less NAs than common thiurams like TMTM and TMTD. IBM is a mono-sulfide thiuram
regulated NAs. interest on the Nitrosamine issue especially in door and window seals. This interest will trickle over to non-
.

and IBT is a di-sulfide thiuram. Although IBM and IBT were developed to replace TMTM and
vs

automotive rubber industries and components. Realistically, NAs are far more potent in rubber factories’
0

TMTD, respectively, both have found applications to replace DPTT, TETD and the pricey TB zTD.
A -3

Non-Regulated or Safe NA-Producing Accelerators: atmosphere during curing or post-curing of rubber. Currently in the US, unions and special interest groups
SA

Below is a listing of accelerators that produce non-regulated, safe NAs or cannot 40 Two additional characteristics have been discovered with the use of these accelerators. First, both
IBM and IBT provided much more scorch safety and shorter cure times than TMTM and TMTD. are placing increasing pressure on the EPA and OSHA to set nitrosamine restrictions, not only in the factories,
produce any type of NAs because they do not contain secondary amines or any but also in storage facilities. Akrochem offers rubber manufacturers a variety of safe and non-nitrosamine-
35 SAA-30 In fact, in certain formulations, IBM provided increased scorch safety beyond that of a sulfenamide
nitrogen: producing accelerators, as well as some nitrosamine inhibitors. Further details and information are available
30
DPG (delayed-reaction accelerator) used alone. Second, both accelerators deliver much less reversion
from Akrochem. Please contact your Technical Salesperson or the Technical Department at Akrochem.
Chemical Family No/Safe NAs Replace ZBED in natural rubber compounds than comparable accelerators. The increased scorch resistance
Torque (in-lb)

25
Sulfenamides DCBS, CBTS, BBTS OBTS, OMTS, MBSS, OTOS and cure rate combined with reduced reversion translates to shorter cure cycles or increased
TBZTD Robac® - Robinson Brothers Limited, Cure-Rite® - Noveon Incorporated
Thiazoles MBT, MBTS, ZMBT 20 safety of hard-to-process compounds.
Guanidines DPG, DOTG
Thiurams TBzTD, TETD, TMTM, TMTD, 15 Zn Dithiophosphate Being a higher molecular weight accelerator, more IBM by weight should be used if replacing
other thiurams (1.6 x TMTD phr; 1.85 x TMTM; 1.33x TETD). The exception is the replacement SEVEN DECADES OF SUPERIOR SERVICE
IBT1, IBM1 DPTT, TBTD 10
of TBzTD would require only 0.70 as much IBM. IBT also is a higher molecular weight accelerator, Included with its product literature and upon the request of its customers, Akrochem provides product specifications and evaluations, suggested formulations and recommendations and other technical assistance, both orally and in writing (collectively the
Dithiocarbamates SAA-30, Arbestab Z. MZ, EZ, BZ, CuDD, ZPD, “Technical Information”). Although Akrochem believes all Technical Information to be true and correct, it makes no warranty, either express or implied, as to the accuracy, completeness or fitness of the Technical Information for any intended use, or the
results which may be obtained by any person using the Technical Information. Akrochem will not be liable for any cost, loss or damage, in tort, contract or otherwise, arising from customer's use of Akrochem products or Technical Information.
5 therefore a good starting point to replace other thiurams should be (1.7 x TMTD phr; 2.0 x
ZBED TDEC, BiDD 0 2.5 5 7.5 10
It is the customer’s sole responsibility to test the products and any Technical Information provided to determine whether they are suitable for the customer’s needs. Before working with any product, the customer must read and become familiar with available
TMTM; 1.4 x TETD). The exception is the replacement of TBzTD would require only 0.75 as information concerning its hazards, proper use, storage and handling, including all health, safety and hygiene precautions recommended by the manufacturer.

Non-Nitrogen AS-100, ZIX, VS DTDM Nothing in the Technical Information is intended to be a recommendation to use any product, method or process in violation of any intellectual property rights governing such product, method or process. No license is implied or granted by Akrochem as to
Minutes at 160° C much IBT. any such product, method or process. The names/brandnames appearing throughout this literature are believed to be either brandnames or registered or unregistered trademarks.
1
very low levels of NAs AKROCHEM CORPORATION DISCLAIMS ANY AND ALL WARRANTIES, EXPRESS AND IMPLIED, INCLUDING WITHOUT LIMITATION, WARRANTIES OR MERCHANTABILITY AND FITNESS FOR ANY PARTICULAR PURPOSE, RELATED TO ANY PRODUCTS
OR TECHNICAL INFORMATION PROVIDED BY AKROCHEM.
240-87 NitrosaminesSSPRINT.fh8 10/13/03 8:24 AM Page 2

NITROSAMINES: c o n t i n u e d 5 NITROSAMINES: c o n t i n u e d 6 NITROSAMINES: c o n t i n u e d 7 NITROSAMINES: c o n t i n u e d 8

Below is data pertaining to a sulfurless cure system utilizing AS-100: There is a lot of literature published concerning the more traditional accelerators like MBT, The rheologies above show the cure characteristics of SAA-30 in the following test compound: Accelerator ZBED is a popular choice to replace other dithiocarbamates to lower or eliminate regulated NA levels.
MBTS, CBTS, BBTS, DPG, etc. Therefore, let’s focus on some interesting, non-traditional, safe SMR CV-100 phr, zinc oxide-5, stearic acid-1, antioxidant-1, N762 carbon black-5, calcium This ultra accelerator, is chemically, zinc dibenzyl dithiocarbamate. It acts like a typical dithiocarbamate
Cure System TS 2 T50 T90 MH Hardness Mod. 500% TS EB NA-generating accelerators such as: Robac® SAA-30, Cure-Rite® IBM, Cure-Rite® IBT and ZBED. carbonate-50, sulfur-1.2 and accelerator-0.5. This accelerator produces fast cures, i.e. short secondary accelerator by decreasing scorch times and cure rate while increasing cure states. ZBED does produce
mins. mins. mins. lb-in pts. psi psi %
scorch and rate of cure. The state of cure in most cases is comparable to thiurams. Also, note the non-regulated N-nitrosodibenzylamine and is used effectively with sulfenamides, thiazoles and thiurams.
TMTD 1.37 3.26 7.28 45.0 48 1204 3422 700 Robac® SAA-30 PM 50 is a new, interesting, ultra-fast accelerator chemically known as 2,2 -
when compared to other safe NA-generating accelerators, SAA-30 produces a fast cure rate with ZBED has a high molecular weight relative to other more common dithiocarbamates like MZ, EZ and BZ;
AS-100 1.46 2.34 4.52 27.4 30 493 2132 890 dithiodi(ethylammonium) - bis (dibenzyldithiocarbamate). This product is available as a 50%
the highest state of cure. SAA-30 in natural rubber produces some very interesting and favorable therefore about 1.5 times more ZBED is needed to replace common dithiocarbamates. Typical cure systems
TBZTD/AS-100 2.00 3.27 6.21 39.0 43 798 3089 890 rubber-bound dispersion in cylindrical pellet form. SAA-30 functions as an accelerator, which
physical, aging and dynamic properties when compared to other traditional dithiocarbamates. using ZBED to obtain low NA levels are:
can replace conventional dithiocarbamates (MZ, EZ, BZ, etc.) and thiurams (TMTM, TMTD, etc.).
Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, N762-5, CaCO 3-50, Accelerator-3. Cure: 160C/T95
Below are some results utilizing SAA-30 as a primary accelerator:
AS-100’s rheological data shows that it’s marginally less scorchy, but considerably Cure System Hard. TS EB Hard.1 TS1 EB1 Fatigue 2 NR or SBR EPDM BUTYL
tors
c e l e ra pts. psi % pts. psi % cycles x 100
faster than TMTD. The state of cure of the compound utilizing AS-100 is lower than o f ac Sulfur 2.0 - 2.5 Sulfur 1.5 - 2.0 Sulfur 1.0 - 2.0
TMTD. This is easily corrected by the addition of Accelerator TBzTD (thiuram, safe ses EZ 44 3248 840 35 2393 680 509 ZBED 0.5 - 1.5 ZBED 1.5 - 2.0 ZBED 0.5 - 1.5
cl as
nitrosamine generator) working synergistically with AS-100. Accelerator AS-100 also er SAA-30 50 3698 780 50 3205 680 1039 BBTS 1.5 - 2.5 MBT 1.5 - 2.0 BBTS 1.0 - 1.5

h
works well in combination with sulfenamides to produce low compression set, ZBED 37 2146 980 32 1900 830 836 MBTS 0.5 - 1.5 CBTS 1.0 - 2.5 IBT 0.7 - 1.2

ot
vs.
sulfurless EV cure systems (below). Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, N762 carbon black-5, CaCO3-50, sulfur-2.5, accel.-0.6.

-30
1
45
heat aged: 168 hrs./70C, 2fatigue to failure: JIS ave. 100% extension. Inhibitors:

SAA
TMTD CBTS
Cure System Hard. Mod. 300% TS EB Comp.Set Comp.Set NAs Rubber compounders have incorporated the use of NA inhibitors into formulations, but typically as a last resort
pts. psi psi % 24hr/70C,% 24hr/100C,% ug/kg
40 When SAA-30 is used as a primary accelerator and compared to accelerator EZ (table above),
and in combination with the accelerators discussed above. It is believed that NA inhibitors disable nitrogen oxides
SAA-30 produces higher initial properties and superior heat-aged and dynamic performance.
A - traditional 56 1494 3234 509 9 15 ˜ 200
35
preventing them from reacting with secondary amines. The concern with these inhibitors is that they are not
SAA-30 SAA-30’s values also outperform the safe NA generating accelerator ZBED.
B - safer 54 1378 3219 529 10 15 ND 30 EZ always effective in eliminating or reducing levels of NAs. Chemicals that have been tested and in some cases

Torque (in-lb)
Heat aging A +1 -15 -25 -5 - - - 25 Cure System Hard. TS EB Hard.1 TS1 EB1 Fatigue 2 found to reduce NA levels are: ascorbic acid (vitamin C), -tocopherol (vitamin E), calcium oxide
Heat aging B +3 -2 -17 -5 - - - MBT pts. psi % pts. psi % cycles x 100 (Akrocal 90) and alkyl phenol formaldehyde resins (Akrochem P-101).
20
Compound: SMR CV-100, ZnO-5, S.Acid-2, AO-1.0, N550-45, CaCO 3-50, Paraffinic oil-4, Wax-3, AOz-3,
TMTD/CBTS 55 3843 630 55 2378 470 792
15
Accelerator-3. Cure Systems: A-Accelerator R-1.0, OBTS-1.0, TMTD-1.0. B-AS-100-1.2, TBZTD-2.2, BBTS-1.0 SAA-30/CBTS 56 3698 620 55 2552 480 840
Cure: 160C/T95, Heat Aging: 168 hrs./100C, ND—none detected 10

5
Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, c.black-5, CaCO3-50, sulfur-1.25, CBTS-1.6, TMTD/SAA-30-0.3.
1
heat-aged: 70 hrs./100C, 2fatigue to failure: JIS ave. 100% extension.
conclusion
The data reflects that AS-100 used in combination with TB zTD and BBTS can create 0 2.5 5 7.5 10 The Nitrosamine issue has been under investigation for many decades. Both US and German environmental
a compound very close to the performance of the traditional Accelerator R, OBTS Very comparable results were obtained substituting SAA-30 for TMTD as the secondary accelerator and health-related government agencies have imposed limitations on the use of substances that create nitrosamines
and TMTD system used for low compression set and good heat aging. The obvious
Minutes at 160° C in the above natural rubber test formulation. Again, the heat-aged and dynamic properties are in the Rubber Industry. More countries in the near future will also impose regulations. More notably, these
favorable utilizing the SAA-30.
benefit to the AS-100 cure system is the low levels of NAs. BBTS and TB zTD both rators current regulations are being reviewed and will be altered in the future to stricter standards. For example, in
g en e
produce NAs, but of the non-regulatory type. In contrast, Accelerator R and OBTS As Cure-Rite® IBM and Cure-Rite® IBT are non-staining ultra accelerators that produce approximately Germany the latest regulation permits a maximum atmospheric concentration of regulated NAs of only 1 ug/m 3.
N
produce N-nitroso-morpholine and TMTD produces N-nitrosodimethylamine, both fe This amendment includes the cabin space in automobiles. Therefore, automotive suppliers are placing increased
sa 100 times less NAs than common thiurams like TMTM and TMTD. IBM is a mono-sulfide thiuram
regulated NAs. interest on the Nitrosamine issue especially in door and window seals. This interest will trickle over to non-
.

and IBT is a di-sulfide thiuram. Although IBM and IBT were developed to replace TMTM and
vs

automotive rubber industries and components. Realistically, NAs are far more potent in rubber factories’
0

TMTD, respectively, both have found applications to replace DPTT, TETD and the pricey TB zTD.
A -3

Non-Regulated or Safe NA-Producing Accelerators: atmosphere during curing or post-curing of rubber. Currently in the US, unions and special interest groups
SA

Below is a listing of accelerators that produce non-regulated, safe NAs or cannot 40 Two additional characteristics have been discovered with the use of these accelerators. First, both
IBM and IBT provided much more scorch safety and shorter cure times than TMTM and TMTD. are placing increasing pressure on the EPA and OSHA to set nitrosamine restrictions, not only in the factories,
produce any type of NAs because they do not contain secondary amines or any but also in storage facilities. Akrochem offers rubber manufacturers a variety of safe and non-nitrosamine-
35 SAA-30 In fact, in certain formulations, IBM provided increased scorch safety beyond that of a sulfenamide
nitrogen: producing accelerators, as well as some nitrosamine inhibitors. Further details and information are available
30
DPG (delayed-reaction accelerator) used alone. Second, both accelerators deliver much less reversion
from Akrochem. Please contact your Technical Salesperson or the Technical Department at Akrochem.
Chemical Family No/Safe NAs Replace ZBED in natural rubber compounds than comparable accelerators. The increased scorch resistance
Torque (in-lb)

25
Sulfenamides DCBS, CBTS, BBTS OBTS, OMTS, MBSS, OTOS and cure rate combined with reduced reversion translates to shorter cure cycles or increased
TBZTD Robac® - Robinson Brothers Limited, Cure-Rite® - Noveon Incorporated
Thiazoles MBT, MBTS, ZMBT 20 safety of hard-to-process compounds.
Guanidines DPG, DOTG
Thiurams TBzTD, TETD, TMTM, TMTD, 15 Zn Dithiophosphate Being a higher molecular weight accelerator, more IBM by weight should be used if replacing
other thiurams (1.6 x TMTD phr; 1.85 x TMTM; 1.33x TETD). The exception is the replacement SEVEN DECADES OF SUPERIOR SERVICE
IBT1, IBM1 DPTT, TBTD 10
of TBzTD would require only 0.70 as much IBM. IBT also is a higher molecular weight accelerator, Included with its product literature and upon the request of its customers, Akrochem provides product specifications and evaluations, suggested formulations and recommendations and other technical assistance, both orally and in writing (collectively the
Dithiocarbamates SAA-30, Arbestab Z. MZ, EZ, BZ, CuDD, ZPD, “Technical Information”). Although Akrochem believes all Technical Information to be true and correct, it makes no warranty, either express or implied, as to the accuracy, completeness or fitness of the Technical Information for any intended use, or the
results which may be obtained by any person using the Technical Information. Akrochem will not be liable for any cost, loss or damage, in tort, contract or otherwise, arising from customer's use of Akrochem products or Technical Information.
5 therefore a good starting point to replace other thiurams should be (1.7 x TMTD phr; 2.0 x
ZBED TDEC, BiDD 0 2.5 5 7.5 10
It is the customer’s sole responsibility to test the products and any Technical Information provided to determine whether they are suitable for the customer’s needs. Before working with any product, the customer must read and become familiar with available
TMTM; 1.4 x TETD). The exception is the replacement of TBzTD would require only 0.75 as information concerning its hazards, proper use, storage and handling, including all health, safety and hygiene precautions recommended by the manufacturer.

Non-Nitrogen AS-100, ZIX, VS DTDM Nothing in the Technical Information is intended to be a recommendation to use any product, method or process in violation of any intellectual property rights governing such product, method or process. No license is implied or granted by Akrochem as to
Minutes at 160° C much IBT. any such product, method or process. The names/brandnames appearing throughout this literature are believed to be either brandnames or registered or unregistered trademarks.
1
very low levels of NAs AKROCHEM CORPORATION DISCLAIMS ANY AND ALL WARRANTIES, EXPRESS AND IMPLIED, INCLUDING WITHOUT LIMITATION, WARRANTIES OR MERCHANTABILITY AND FITNESS FOR ANY PARTICULAR PURPOSE, RELATED TO ANY PRODUCTS
OR TECHNICAL INFORMATION PROVIDED BY AKROCHEM.
240-87 NitrosaminesSSPRINT.fh8 10/13/03 8:24 AM Page 2

NITROSAMINES: c o n t i n u e d 5 NITROSAMINES: c o n t i n u e d 6 NITROSAMINES: c o n t i n u e d 7 NITROSAMINES: c o n t i n u e d 8

Below is data pertaining to a sulfurless cure system utilizing AS-100: There is a lot of literature published concerning the more traditional accelerators like MBT, The rheologies above show the cure characteristics of SAA-30 in the following test compound: Accelerator ZBED is a popular choice to replace other dithiocarbamates to lower or eliminate regulated NA levels.
MBTS, CBTS, BBTS, DPG, etc. Therefore, let’s focus on some interesting, non-traditional, safe SMR CV-100 phr, zinc oxide-5, stearic acid-1, antioxidant-1, N762 carbon black-5, calcium This ultra accelerator, is chemically, zinc dibenzyl dithiocarbamate. It acts like a typical dithiocarbamate
Cure System TS 2 T50 T90 MH Hardness Mod. 500% TS EB NA-generating accelerators such as: Robac® SAA-30, Cure-Rite® IBM, Cure-Rite® IBT and ZBED. carbonate-50, sulfur-1.2 and accelerator-0.5. This accelerator produces fast cures, i.e. short secondary accelerator by decreasing scorch times and cure rate while increasing cure states. ZBED does produce
mins. mins. mins. lb-in pts. psi psi %
scorch and rate of cure. The state of cure in most cases is comparable to thiurams. Also, note the non-regulated N-nitrosodibenzylamine and is used effectively with sulfenamides, thiazoles and thiurams.
TMTD 1.37 3.26 7.28 45.0 48 1204 3422 700 Robac® SAA-30 PM 50 is a new, interesting, ultra-fast accelerator chemically known as 2,2 -
when compared to other safe NA-generating accelerators, SAA-30 produces a fast cure rate with ZBED has a high molecular weight relative to other more common dithiocarbamates like MZ, EZ and BZ;
AS-100 1.46 2.34 4.52 27.4 30 493 2132 890 dithiodi(ethylammonium) - bis (dibenzyldithiocarbamate). This product is available as a 50%
the highest state of cure. SAA-30 in natural rubber produces some very interesting and favorable therefore about 1.5 times more ZBED is needed to replace common dithiocarbamates. Typical cure systems
TBZTD/AS-100 2.00 3.27 6.21 39.0 43 798 3089 890 rubber-bound dispersion in cylindrical pellet form. SAA-30 functions as an accelerator, which
physical, aging and dynamic properties when compared to other traditional dithiocarbamates. using ZBED to obtain low NA levels are:
can replace conventional dithiocarbamates (MZ, EZ, BZ, etc.) and thiurams (TMTM, TMTD, etc.).
Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, N762-5, CaCO 3-50, Accelerator-3. Cure: 160C/T95
Below are some results utilizing SAA-30 as a primary accelerator:
AS-100’s rheological data shows that it’s marginally less scorchy, but considerably Cure System Hard. TS EB Hard.1 TS1 EB1 Fatigue 2 NR or SBR EPDM BUTYL
tors
c e l e ra pts. psi % pts. psi % cycles x 100
faster than TMTD. The state of cure of the compound utilizing AS-100 is lower than o f ac Sulfur 2.0 - 2.5 Sulfur 1.5 - 2.0 Sulfur 1.0 - 2.0
TMTD. This is easily corrected by the addition of Accelerator TBzTD (thiuram, safe ses EZ 44 3248 840 35 2393 680 509 ZBED 0.5 - 1.5 ZBED 1.5 - 2.0 ZBED 0.5 - 1.5
cl as
nitrosamine generator) working synergistically with AS-100. Accelerator AS-100 also er SAA-30 50 3698 780 50 3205 680 1039 BBTS 1.5 - 2.5 MBT 1.5 - 2.0 BBTS 1.0 - 1.5

h
works well in combination with sulfenamides to produce low compression set, ZBED 37 2146 980 32 1900 830 836 MBTS 0.5 - 1.5 CBTS 1.0 - 2.5 IBT 0.7 - 1.2

ot
vs.
sulfurless EV cure systems (below). Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, N762 carbon black-5, CaCO3-50, sulfur-2.5, accel.-0.6.

-30
1
45
heat aged: 168 hrs./70C, 2fatigue to failure: JIS ave. 100% extension. Inhibitors:

SAA
TMTD CBTS
Cure System Hard. Mod. 300% TS EB Comp.Set Comp.Set NAs Rubber compounders have incorporated the use of NA inhibitors into formulations, but typically as a last resort
pts. psi psi % 24hr/70C,% 24hr/100C,% ug/kg
40 When SAA-30 is used as a primary accelerator and compared to accelerator EZ (table above),
and in combination with the accelerators discussed above. It is believed that NA inhibitors disable nitrogen oxides
SAA-30 produces higher initial properties and superior heat-aged and dynamic performance.
A - traditional 56 1494 3234 509 9 15 ˜ 200
35
preventing them from reacting with secondary amines. The concern with these inhibitors is that they are not
SAA-30 SAA-30’s values also outperform the safe NA generating accelerator ZBED.
B - safer 54 1378 3219 529 10 15 ND 30 EZ always effective in eliminating or reducing levels of NAs. Chemicals that have been tested and in some cases

Torque (in-lb)
Heat aging A +1 -15 -25 -5 - - - 25 Cure System Hard. TS EB Hard.1 TS1 EB1 Fatigue 2 found to reduce NA levels are: ascorbic acid (vitamin C), -tocopherol (vitamin E), calcium oxide
Heat aging B +3 -2 -17 -5 - - - MBT pts. psi % pts. psi % cycles x 100 (Akrocal 90) and alkyl phenol formaldehyde resins (Akrochem P-101).
20
Compound: SMR CV-100, ZnO-5, S.Acid-2, AO-1.0, N550-45, CaCO 3-50, Paraffinic oil-4, Wax-3, AOz-3,
TMTD/CBTS 55 3843 630 55 2378 470 792
15
Accelerator-3. Cure Systems: A-Accelerator R-1.0, OBTS-1.0, TMTD-1.0. B-AS-100-1.2, TBZTD-2.2, BBTS-1.0 SAA-30/CBTS 56 3698 620 55 2552 480 840
Cure: 160C/T95, Heat Aging: 168 hrs./100C, ND—none detected 10

5
Compound: SMR CV-100, ZnO-5, S.Acid-1, AO-1, c.black-5, CaCO3-50, sulfur-1.25, CBTS-1.6, TMTD/SAA-30-0.3.
1
heat-aged: 70 hrs./100C, 2fatigue to failure: JIS ave. 100% extension.
conclusion
The data reflects that AS-100 used in combination with TB zTD and BBTS can create 0 2.5 5 7.5 10 The Nitrosamine issue has been under investigation for many decades. Both US and German environmental
a compound very close to the performance of the traditional Accelerator R, OBTS Very comparable results were obtained substituting SAA-30 for TMTD as the secondary accelerator and health-related government agencies have imposed limitations on the use of substances that create nitrosamines
and TMTD system used for low compression set and good heat aging. The obvious
Minutes at 160° C in the above natural rubber test formulation. Again, the heat-aged and dynamic properties are in the Rubber Industry. More countries in the near future will also impose regulations. More notably, these
favorable utilizing the SAA-30.
benefit to the AS-100 cure system is the low levels of NAs. BBTS and TB zTD both rators current regulations are being reviewed and will be altered in the future to stricter standards. For example, in
g en e
produce NAs, but of the non-regulatory type. In contrast, Accelerator R and OBTS As Cure-Rite® IBM and Cure-Rite® IBT are non-staining ultra accelerators that produce approximately Germany the latest regulation permits a maximum atmospheric concentration of regulated NAs of only 1 ug/m 3.
N
produce N-nitroso-morpholine and TMTD produces N-nitrosodimethylamine, both fe This amendment includes the cabin space in automobiles. Therefore, automotive suppliers are placing increased
sa 100 times less NAs than common thiurams like TMTM and TMTD. IBM is a mono-sulfide thiuram
regulated NAs. interest on the Nitrosamine issue especially in door and window seals. This interest will trickle over to non-
.

and IBT is a di-sulfide thiuram. Although IBM and IBT were developed to replace TMTM and
vs

automotive rubber industries and components. Realistically, NAs are far more potent in rubber factories’
0

TMTD, respectively, both have found applications to replace DPTT, TETD and the pricey TB zTD.
A -3

Non-Regulated or Safe NA-Producing Accelerators: atmosphere during curing or post-curing of rubber. Currently in the US, unions and special interest groups
SA

Below is a listing of accelerators that produce non-regulated, safe NAs or cannot 40 Two additional characteristics have been discovered with the use of these accelerators. First, both
IBM and IBT provided much more scorch safety and shorter cure times than TMTM and TMTD. are placing increasing pressure on the EPA and OSHA to set nitrosamine restrictions, not only in the factories,
produce any type of NAs because they do not contain secondary amines or any but also in storage facilities. Akrochem offers rubber manufacturers a variety of safe and non-nitrosamine-
35 SAA-30 In fact, in certain formulations, IBM provided increased scorch safety beyond that of a sulfenamide
nitrogen: producing accelerators, as well as some nitrosamine inhibitors. Further details and information are available
30
DPG (delayed-reaction accelerator) used alone. Second, both accelerators deliver much less reversion
from Akrochem. Please contact your Technical Salesperson or the Technical Department at Akrochem.
Chemical Family No/Safe NAs Replace ZBED in natural rubber compounds than comparable accelerators. The increased scorch resistance
Torque (in-lb)

25
Sulfenamides DCBS, CBTS, BBTS OBTS, OMTS, MBSS, OTOS and cure rate combined with reduced reversion translates to shorter cure cycles or increased
TBZTD Robac® - Robinson Brothers Limited, Cure-Rite® - Noveon Incorporated
Thiazoles MBT, MBTS, ZMBT 20 safety of hard-to-process compounds.
Guanidines DPG, DOTG
Thiurams TBzTD, TETD, TMTM, TMTD, 15 Zn Dithiophosphate Being a higher molecular weight accelerator, more IBM by weight should be used if replacing
other thiurams (1.6 x TMTD phr; 1.85 x TMTM; 1.33x TETD). The exception is the replacement SEVEN DECADES OF SUPERIOR SERVICE
IBT1, IBM1 DPTT, TBTD 10
of TBzTD would require only 0.70 as much IBM. IBT also is a higher molecular weight accelerator, Included with its product literature and upon the request of its customers, Akrochem provides product specifications and evaluations, suggested formulations and recommendations and other technical assistance, both orally and in writing (collectively the
Dithiocarbamates SAA-30, Arbestab Z. MZ, EZ, BZ, CuDD, ZPD, “Technical Information”). Although Akrochem believes all Technical Information to be true and correct, it makes no warranty, either express or implied, as to the accuracy, completeness or fitness of the Technical Information for any intended use, or the
results which may be obtained by any person using the Technical Information. Akrochem will not be liable for any cost, loss or damage, in tort, contract or otherwise, arising from customer's use of Akrochem products or Technical Information.
5 therefore a good starting point to replace other thiurams should be (1.7 x TMTD phr; 2.0 x
ZBED TDEC, BiDD 0 2.5 5 7.5 10
It is the customer’s sole responsibility to test the products and any Technical Information provided to determine whether they are suitable for the customer’s needs. Before working with any product, the customer must read and become familiar with available
TMTM; 1.4 x TETD). The exception is the replacement of TBzTD would require only 0.75 as information concerning its hazards, proper use, storage and handling, including all health, safety and hygiene precautions recommended by the manufacturer.

Non-Nitrogen AS-100, ZIX, VS DTDM Nothing in the Technical Information is intended to be a recommendation to use any product, method or process in violation of any intellectual property rights governing such product, method or process. No license is implied or granted by Akrochem as to
Minutes at 160° C much IBT. any such product, method or process. The names/brandnames appearing throughout this literature are believed to be either brandnames or registered or unregistered trademarks.
1
very low levels of NAs AKROCHEM CORPORATION DISCLAIMS ANY AND ALL WARRANTIES, EXPRESS AND IMPLIED, INCLUDING WITHOUT LIMITATION, WARRANTIES OR MERCHANTABILITY AND FITNESS FOR ANY PARTICULAR PURPOSE, RELATED TO ANY PRODUCTS
OR TECHNICAL INFORMATION PROVIDED BY AKROCHEM.