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U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 3 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 4 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 5

accelerators and
accelerator systems
Scorch Rates of Some Commonly used Accelerators ZDMC or Zinc dimethyldithiocarbamate is an ultra /secondary accelerator for ZDBCX or zinc N, N-di-n-butyldithio-
selection of ultra/secondary accelerator
system
natural and synthetic based compounds that also carbamate/di-n-butylamine complex is
Ultra/Secondary N

VULCANIZATION
Primary find uses as a primary or secondary in sulfur based an ultra-accelerator which is active at
Part II: Ultra/Secondary Accelerators
N

MATERIALS
Zn-S
Kickers latex compounds. ZDMC is very active at tempera- room temperature. It can be further
SAA-30 Faster MBT
S
tures above 100C. As a primary accelerator ZDMC activated by Z.I.X., and may also be
CuDD MBTS
S
The designation ultra is applied to accelerators that speed the rate of vulcaniza- Before selecting an ultra/secondary accelerator system for the manufacture of a particular gives a faster cure rate and higher modulus, but used as a booster for thiazoles. It may
tion to the greatest degree. Generally, smaller quantities of sulfur can be used in rubber product, the following considerations must be taken into account. DPTT ZMBT shorter scorch times which find uses in continuous be used in natural rubber and SBR for
TMTD CBTS
ultra accelerated compounds to produce optimum physical properties in a shorter cure based products such as cables, tubings and profiles. Low unsaturation content dry mixes, cements, and latex. It is of + dibutylamine complex
Expected shelf life of the compound
ZDMC BBTS
curing time than can be obtained with other classes of accelerators such as rubbers such as butyl and EPDM can be cured using ZDMC as a secondary particular value for the preparation of
TM/ETD Cure-Rite 18
thiazoles or sulfenamides. Ultra/secondary accelerators solubility in rubber accelerator. It can be used at a higher dosage to achieve faster cure rates for high transparent and translucent articles
ZDEC OMTS
Quite frequently the ultra accelerators are used in combination with primary temperature curing (CV curing for wire insulation), as well as for curing thicker from both latex and dry rubber.
OBTS
The interaction of the ultra/secondary accelerators with the primary accelerators
DPG
accelerators at which time they are sometimes called secondary accelerators. In molded parts. ZDMC with MBT provides good curing activity in EPDM formula-
Part II the two classes of ultra accelerators that will be discussed are dithiocarba- CuDD or Copper dimethyldithiocarba-
TETD DCBS
tions.
mates and thiurams. The number of processing stages the compound must undergo
DOTG
mate is especially recommended for SBR,
TDEC ZDEC or Zinc diethyldithiocarbamate can be
The level of scorch safety the compound needs EPDM, and Butyl. It is a powerful

introduction
S secondary accelerator. It is possible by
Faster cure rate for economical production of the rubber product TMTM used in the same manner as ZDMC, except that N S using CuDD with MBTS to increase cure
N

TBzTD
N
Cu-S

Slower
quantities should be increased 10% to obtain S Zn N rate while holding scorch rate constant,
ZDBC
Determination of sulfur levels needed and its effect on the levels of ultra accelerators S
Accelerators and Accelerator Systems Part I covered the meaning of vulcaniza- comparable results. or even reducing it slightly in some S

ZDBC or Zinc dibutyldithiocarbamate is


tion with respect to rheology, selection of accelerators, polymer accelerator The curing method used (.e.g. injection, compression, or transfer molding) compounds. It usually results in higher
Note: red denotes the dithiocarbamates and blue the thiuram accelerators
interaction and the primary accelerators. The focus here will be on two types of modulus, tensile strength, lower
ultra/secondary accelerators, the dithiocarbamates and thiurams and their role Maximum vulcanization temperature available used in adhesives as a stabilizer and as an compression set, and a marked plateau
By far the most popular ultra/secondary accelerators are the dithiocarbamates and antioxidant in uncured rubbers. It is also S effect on over-cures. CuDD shows a
in rubber curing systems. Cure cycle desired for the available vulcanization method, the temperature, and the thiurams. The ultra/secondary accelerators often produce scorchy, very fast curing used in combination with other accelerators N distinct advantage in curing thick
vulcanizate properties required
As mentioned in Part I, accelerators are classify by ASTM as: compounds. Their major functions are that they produce increased cure rate (i.e. to produce low compression set, good heat N
Zn-S items. Compounds designed with CuDD should contain octylated dipheny-
The interaction of the ultra/secondary accelerators with the polymer systems raise the modulus) and shorten scorch times. Quite frequently they are paired with a aging, and lower bloom in EPDM S lamine antioxidant to obtain maximum aging, especially in mineral
primary accelerator to derive maximum levels of processing safety and vulcanization compounds. It is recommended as a S filled compounds.
1. Thiazoles (Mercapto) The ultra/secondary accelerators effect on other ingredients in a compound stabilizer in hot melts.
TDEC or Tellurium diethyldithiocarba-
rates.

ZBED or Zinc Dibenzyl Dithiocarbamate


N S
2. Sulfenamides No known health hazards upon usage of a chemical and of its decomposition products
mate is the fastest for EPDM and butyl
Dithiocarbamate Types
S
on cure N S S
is an active form of Zinc rubber vulcanization. TDEC or Te
3. Guanidines No adverse effects during end-use of the rubber product (e.g. accelerators used in Dithiocarbamate, which can be modified TDEC/Thiuram combinations with MBT S
S N
Dithiocarbamates are so powerful that they are rarely used alone except in such S
the manufacturing of the rubber articles intended for food contact, surgical use, etc.) by MBT or MBTS, etc. It is non-staining, are used extensively in butyl innerliner
4. Dithiocarbamates specialty applications as spread goods (fabric covered with a rubber coating: e.g.
non-discoloring and achieves safer tube production and other applications S N
Easy to handle and dust suppressed physical form hospital sheeting) cured in air at or slightly above room temperature. Usually they processing than Zinc Dibutyl requiring rapid cures.
are paired with thiazole or sulfenamide accelerators to adjust the cure rate of a stock. Dithiocarbamate. In latex it is less likely N

SAA-30 or 2, 2-dithiodiethylammo-
5. Thiurams Zn
S
Selection of the proper ultra/secondary accelerator is very important to a compounder. It can A typical curing system with natural rubber might be 0.5 parts of zinc dimethyldithio- to cause pre-cure at room temperature S S
S
6. Specialty Accelerators. affect the number of cycle times one can run. The ultra/secondary levels in a compound can carbamate (ZMDC), 0.75 parts of thiazole accelerator, and 2.0 parts of sulfur. With than other dithiocarbamates. However, N nium-bis-dibenzyldithiocarbamate is
determine the amount of storage time (shelf-life) a compound can withstand. The correct SBR stocks the system might be 0.6 ZMDC, 0.75 parts of thiazole, 1.8 parts of sulfur. ZBED is a typical ultra-accelerator at an ultra-fast accelerator in a polymeric
Other ways to classify accelerators are (a) organic or inorganic, (b) acidic or selection of ultra/secondary accelerators in combination with a delayed action accelerator (e.g. Non-staining dithiocarbamates are versatile accelerators that can be used in IIR normal curing temperatures. It is also binder that is nitrosamine safe. For
basic, (c) chemical type, (d) by acceleration speed such as slow, medium, sulfenamide) will allow sufficient scorch delay before the onset of vulcanization and high (butyl), and EPDM. Dithiocarbamates have good tensile and resiliency. They have useful as a secondary accelerator for the reference sake picture ZBED, but instead of a Zn salt, the dithiocarbamate is
semi-ultra and ultra. torque after the start of vulcanization. One must select ultra/secondary accelerators that work slightly lower modulus than the thiurams. Popular members of this class are the zinc continuous vulcanization of butyl rubber strongly activated by a thioamine. SAA-30 gives powerful acceleration at low
in a synergistic manner with other ingredients in a compound. The next section will give you methyl, ethyl and butyl dithiocarbamates. Salts of bismuth, copper, and tellurium extrusions. levels. EPDM bloom is not a problem as it is with many accelerators. SAA-30
important information on each type of ultra/secondary accelerator and some applications also are used. utilizes sulfur very efficiently to create good cures in formulas with lower levels
where they are utilized. of sulfur.
U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 3 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 4 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 5

accelerators and
accelerator systems
Scorch Rates of Some Commonly used Accelerators ZDMC or Zinc dimethyldithiocarbamate is an ultra /secondary accelerator for ZDBCX or zinc N, N-di-n-butyldithio-
selection of ultra/secondary accelerator
system
natural and synthetic based compounds that also carbamate/di-n-butylamine complex is
Ultra/Secondary N

VULCANIZATION
Primary find uses as a primary or secondary in sulfur based an ultra-accelerator which is active at
Part II: Ultra/Secondary Accelerators
N

MATERIALS
Zn-S
Kickers latex compounds. ZDMC is very active at tempera- room temperature. It can be further
SAA-30 Faster MBT
S
tures above 100C. As a primary accelerator ZDMC activated by Z.I.X., and may also be
CuDD MBTS
S
The designation ultra is applied to accelerators that speed the rate of vulcaniza- Before selecting an ultra/secondary accelerator system for the manufacture of a particular gives a faster cure rate and higher modulus, but used as a booster for thiazoles. It may
tion to the greatest degree. Generally, smaller quantities of sulfur can be used in rubber product, the following considerations must be taken into account. DPTT ZMBT shorter scorch times which find uses in continuous be used in natural rubber and SBR for
TMTD CBTS
ultra accelerated compounds to produce optimum physical properties in a shorter cure based products such as cables, tubings and profiles. Low unsaturation content dry mixes, cements, and latex. It is of + dibutylamine complex
Expected shelf life of the compound
ZDMC BBTS
curing time than can be obtained with other classes of accelerators such as rubbers such as butyl and EPDM can be cured using ZDMC as a secondary particular value for the preparation of
TM/ETD Cure-Rite 18
thiazoles or sulfenamides. Ultra/secondary accelerators solubility in rubber accelerator. It can be used at a higher dosage to achieve faster cure rates for high transparent and translucent articles
ZDEC OMTS
Quite frequently the ultra accelerators are used in combination with primary temperature curing (CV curing for wire insulation), as well as for curing thicker from both latex and dry rubber.
OBTS
The interaction of the ultra/secondary accelerators with the primary accelerators
DPG
accelerators at which time they are sometimes called secondary accelerators. In molded parts. ZDMC with MBT provides good curing activity in EPDM formula-
Part II the two classes of ultra accelerators that will be discussed are dithiocarba- CuDD or Copper dimethyldithiocarba-
TETD DCBS
tions.
mates and thiurams. The number of processing stages the compound must undergo
DOTG
mate is especially recommended for SBR,
TDEC ZDEC or Zinc diethyldithiocarbamate can be
The level of scorch safety the compound needs EPDM, and Butyl. It is a powerful

introduction
S secondary accelerator. It is possible by
Faster cure rate for economical production of the rubber product TMTM used in the same manner as ZDMC, except that N S using CuDD with MBTS to increase cure
N

TBzTD
N
Cu-S

Slower
quantities should be increased 10% to obtain S Zn N rate while holding scorch rate constant,
ZDBC
Determination of sulfur levels needed and its effect on the levels of ultra accelerators S
Accelerators and Accelerator Systems Part I covered the meaning of vulcaniza- comparable results. or even reducing it slightly in some S

ZDBC or Zinc dibutyldithiocarbamate is


tion with respect to rheology, selection of accelerators, polymer accelerator The curing method used (.e.g. injection, compression, or transfer molding) compounds. It usually results in higher
Note: red denotes the dithiocarbamates and blue the thiuram accelerators
interaction and the primary accelerators. The focus here will be on two types of modulus, tensile strength, lower
ultra/secondary accelerators, the dithiocarbamates and thiurams and their role Maximum vulcanization temperature available used in adhesives as a stabilizer and as an compression set, and a marked plateau
By far the most popular ultra/secondary accelerators are the dithiocarbamates and antioxidant in uncured rubbers. It is also S effect on over-cures. CuDD shows a
in rubber curing systems. Cure cycle desired for the available vulcanization method, the temperature, and the thiurams. The ultra/secondary accelerators often produce scorchy, very fast curing used in combination with other accelerators N distinct advantage in curing thick
vulcanizate properties required
As mentioned in Part I, accelerators are classify by ASTM as: compounds. Their major functions are that they produce increased cure rate (i.e. to produce low compression set, good heat N
Zn-S items. Compounds designed with CuDD should contain octylated dipheny-
The interaction of the ultra/secondary accelerators with the polymer systems raise the modulus) and shorten scorch times. Quite frequently they are paired with a aging, and lower bloom in EPDM S lamine antioxidant to obtain maximum aging, especially in mineral
primary accelerator to derive maximum levels of processing safety and vulcanization compounds. It is recommended as a S filled compounds.
1. Thiazoles (Mercapto) The ultra/secondary accelerators effect on other ingredients in a compound stabilizer in hot melts.
TDEC or Tellurium diethyldithiocarba-
rates.

ZBED or Zinc Dibenzyl Dithiocarbamate


N S
2. Sulfenamides No known health hazards upon usage of a chemical and of its decomposition products
mate is the fastest for EPDM and butyl
Dithiocarbamate Types
S
on cure N S S
is an active form of Zinc rubber vulcanization. TDEC or Te
3. Guanidines No adverse effects during end-use of the rubber product (e.g. accelerators used in Dithiocarbamate, which can be modified TDEC/Thiuram combinations with MBT S
S N
Dithiocarbamates are so powerful that they are rarely used alone except in such S
the manufacturing of the rubber articles intended for food contact, surgical use, etc.) by MBT or MBTS, etc. It is non-staining, are used extensively in butyl innerliner
4. Dithiocarbamates specialty applications as spread goods (fabric covered with a rubber coating: e.g.
non-discoloring and achieves safer tube production and other applications S N
Easy to handle and dust suppressed physical form hospital sheeting) cured in air at or slightly above room temperature. Usually they processing than Zinc Dibutyl requiring rapid cures.
are paired with thiazole or sulfenamide accelerators to adjust the cure rate of a stock. Dithiocarbamate. In latex it is less likely N

SAA-30 or 2, 2-dithiodiethylammo-
5. Thiurams Zn
S
Selection of the proper ultra/secondary accelerator is very important to a compounder. It can A typical curing system with natural rubber might be 0.5 parts of zinc dimethyldithio- to cause pre-cure at room temperature S S
S
6. Specialty Accelerators. affect the number of cycle times one can run. The ultra/secondary levels in a compound can carbamate (ZMDC), 0.75 parts of thiazole accelerator, and 2.0 parts of sulfur. With than other dithiocarbamates. However, N nium-bis-dibenzyldithiocarbamate is
determine the amount of storage time (shelf-life) a compound can withstand. The correct SBR stocks the system might be 0.6 ZMDC, 0.75 parts of thiazole, 1.8 parts of sulfur. ZBED is a typical ultra-accelerator at an ultra-fast accelerator in a polymeric
Other ways to classify accelerators are (a) organic or inorganic, (b) acidic or selection of ultra/secondary accelerators in combination with a delayed action accelerator (e.g. Non-staining dithiocarbamates are versatile accelerators that can be used in IIR normal curing temperatures. It is also binder that is nitrosamine safe. For
basic, (c) chemical type, (d) by acceleration speed such as slow, medium, sulfenamide) will allow sufficient scorch delay before the onset of vulcanization and high (butyl), and EPDM. Dithiocarbamates have good tensile and resiliency. They have useful as a secondary accelerator for the reference sake picture ZBED, but instead of a Zn salt, the dithiocarbamate is
semi-ultra and ultra. torque after the start of vulcanization. One must select ultra/secondary accelerators that work slightly lower modulus than the thiurams. Popular members of this class are the zinc continuous vulcanization of butyl rubber strongly activated by a thioamine. SAA-30 gives powerful acceleration at low
in a synergistic manner with other ingredients in a compound. The next section will give you methyl, ethyl and butyl dithiocarbamates. Salts of bismuth, copper, and tellurium extrusions. levels. EPDM bloom is not a problem as it is with many accelerators. SAA-30
important information on each type of ultra/secondary accelerator and some applications also are used. utilizes sulfur very efficiently to create good cures in formulas with lower levels
where they are utilized. of sulfur.
U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 3 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 4 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 5

accelerators and
accelerator systems
Scorch Rates of Some Commonly used Accelerators ZDMC or Zinc dimethyldithiocarbamate is an ultra /secondary accelerator for ZDBCX or zinc N, N-di-n-butyldithio-
selection of ultra/secondary accelerator
system
natural and synthetic based compounds that also carbamate/di-n-butylamine complex is
Ultra/Secondary N

VULCANIZATION
Primary find uses as a primary or secondary in sulfur based an ultra-accelerator which is active at
Part II: Ultra/Secondary Accelerators
N

MATERIALS
Zn-S
Kickers latex compounds. ZDMC is very active at tempera- room temperature. It can be further
SAA-30 Faster MBT
S
tures above 100C. As a primary accelerator ZDMC activated by Z.I.X., and may also be
LURAPReVTZMfVaZAn= XfdMoAVeAMbbXVRPAfaAMOORXRdMfadeAfUMfAebRRPAfURAdMfRAaSAh= XOMZVmMC CuDD MBTS
S
Before selecting an ultra/secondary accelerator system for the manufacture of a particular gives a faster cure rate and higher modulus, but used as a booster for thiazoles. It may
fVaZAfaAfURATdRMfRefAPRTdRRDAERZRdMXXlBAeY MXXRdAc= MZfVfVReAaSAe= XS= dAOMZANRA= eRPAVZ rubber product, the following considerations must be taken into account. DPTT ZMBT shorter scorch times which find uses in continuous
= XfdMAMOORXRdMfRPAOaY ba= ZPeAfaAbdaP= ORAabfVY = Y AbUl eVOMXAbdabRdfVReAVZAMAeUadfRd
be used in natural rubber and SBR for
TMTD CBTS cure based products such as cables, tubings and profiles. Low unsaturation content + dibutylamine complex
O= dVZTAfVY RAfUMZAOMZANRAaNfMVZRPAi VfUAafURdAOXMeeReAaSAMOORXRdMfadeAe= OUAMe
Expected shelf life of the compound dry mixes, cements, and latex. It is of
ZDMC BBTS
fUVMmaXReAadAe= XSRZMY VPReDA
rubbers such as butyl and EPDM can be cured using ZDMC as a secondary particular value for the preparation of
TM/ETD Cure-Rite 18
I = VfRASdRc= RZfXl AfURA= XfdMAMOORXRdMfadeAMdRA= eRPAVZAOaY NVZMfVaZAi VfUAbdVY Mdl
Ultra/secondary accelerators solubility in rubber accelerator. It can be used at a higher dosage to achieve faster cure rates for high transparent and translucent articles
ZDEC OMTS
MOORXRdMfadeAMfAi UVOUAfVY RAfURl AMdRAeaY RfVY ReAOMXXRPAneROaZPMdl oAMOORXRdMfadeDAFZ
temperature curing (CV curing for wire insulation), as well as for curing thicker from both latex and dry rubber.
OBTS
The interaction of the ultra/secondary accelerators with the primary accelerators
GMdfAFFAfURAfi aAOXMeeReAaSA= XfdMAMOORXRdMfadeAfUMfAi VXXANRAPVeO= eeRPAMdRAPVfUVaOMdNMC DPG
molded parts. ZDMC with MBT provides good curing activity in EPDM formula-
CuDD or Copper dimethyldithiocarba-
Y MfReAMZPAAfUV= dMY eDA TETD DCBS
tions.
The number of processing stages the compound must undergo
DOTG
mate is especially recommended for SBR,
TDEC ZDEC or Zinc diethyldithiocarbamate can be
The level of scorch safety the compound needs EPDM, and Butyl. It is a powerful

introduction
S secondary accelerator. It is possible by
Faster cure rate for economical production of the rubber product TMTM used in the same manner as ZDMC, except that N S using CuDD with MBTS to increase cure
N

TBzTD
N
Cu-S

Slower
quantities should be increased 10% to obtain S Zn N rate while holding scorch rate constant,
ZDBC
Determination of sulfur levels needed and its effect on the levels of ultra accelerators S
Accelerators and Accelerator Systems Part I covered the meaning of vulcaniza- comparable results. or even reducing it slightly in some S

ZDBC or Zinc dibutyldithiocarbamate is


tion with respect to rheology, selection of accelerators, polymer accelerator The curing method used (.e.g. injection, compression, or transfer molding) compounds. It usually results in higher
Note: red denotes the dithiocarbamates and blue the thiuram accelerators
interaction and the primary accelerators. The focus here will be on two types of modulus, tensile strength, lower
ultra/secondary accelerators, the dithiocarbamates and thiurams and their role Maximum vulcanization temperature available used in adhesives as a stabilizer and as an compression set, and a marked plateau
By far the most popular ultra/secondary accelerators are the dithiocarbamates and antioxidant in uncured rubbers. It is also S effect on over-cures. CuDD shows a
in rubber curing systems. Cure cycle desired for the available vulcanization method, the temperature, and the thiurams. The ultra/secondary accelerators often produce scorchy, very fast curing used in combination with other accelerators N distinct advantage in curing thick
vulcanizate properties required
As mentioned in Part I, accelerators are classify by ASTM as: compounds. Their major functions are that they produce increased cure rate (i.e. to produce low compression set, good heat N
Zn-S items. Compounds designed with CuDD should contain octylated dipheny-
The interaction of the ultra/secondary accelerators with the polymer systems raise the modulus) and shorten scorch times. Quite frequently they are paired with a aging, and lower bloom in EPDM S lamine antioxidant to obtain maximum aging, especially in mineral
primary accelerator to derive maximum levels of processing safety and vulcanization compounds. It is recommended as a S filled compounds.
1. Thiazoles (Mercapto) The ultra/secondary accelerators effect on other ingredients in a compound stabilizer in hot melts.
TDEC or Tellurium diethyldithiocarba-
rates.

ZBED or Zinc Dibenzyl Dithiocarbamate


N S
2. Sulfenamides No known health hazards upon usage of a chemical and of its decomposition products
mate is the fastest for EPDM and butyl
Dithiocarbamate Types
S
on cure N S S
is an active form of Zinc rubber vulcanization. TDEC or Te
3. Guanidines No adverse effects during end-use of the rubber product (e.g. accelerators used in Dithiocarbamate, which can be modified TDEC/Thiuram combinations with MBT S
S N
Dithiocarbamates are so powerful that they are rarely used alone except in such S
the manufacturing of the rubber articles intended for food contact, surgical use, etc.) by MBT or MBTS, etc. It is non-staining, are used extensively in butyl innerliner
4. Dithiocarbamates specialty applications as spread goods (fabric covered with a rubber coating: e.g.
non-discoloring and achieves safer tube production and other applications S N
Easy to handle and dust suppressed physical form hospital sheeting) cured in air at or slightly above room temperature. Usually they processing than Zinc Dibutyl requiring rapid cures.
are paired with thiazole or sulfenamide accelerators to adjust the cure rate of a stock. Dithiocarbamate. In latex it is less likely N

SAA-30 or 2, 2-dithiodiethylammo-
5. Thiurams Zn
S
Selection of the proper ultra/secondary accelerator is very important to a compounder. It can A typical curing system with natural rubber might be 0.5 parts of zinc dimethyldithio- to cause pre-cure at room temperature S S
S
6. Specialty Accelerators. affect the number of cycle times one can run. The ultra/secondary levels in a compound can carbamate (ZMDC), 0.75 parts of thiazole accelerator, and 2.0 parts of sulfur. With than other dithiocarbamates. However, N nium-bis-dibenzyldithiocarbamate is
determine the amount of storage time (shelf-life) a compound can withstand. The correct SBR stocks the system might be 0.6 ZMDC, 0.75 parts of thiazole, 1.8 parts of sulfur. ZBED is a typical ultra-accelerator at an ultra-fast accelerator in a polymeric
Other ways to classify accelerators are (a) organic or inorganic, (b) acidic or selection of ultra/secondary accelerators in combination with a delayed action accelerator (e.g. Non-staining dithiocarbamates are versatile accelerators that can be used in IIR normal curing temperatures. It is also binder that is nitrosamine safe. For
basic, (c) chemical type, (d) by acceleration speed such as slow, medium, sulfenamide) will allow sufficient scorch delay before the onset of vulcanization and high (butyl), and EPDM. Dithiocarbamates have good tensile and resiliency. They have useful as a secondary accelerator for the reference sake picture ZBED, but instead of a Zn salt, the dithiocarbamate is
semi-ultra and ultra. torque after the start of vulcanization. One must select ultra/secondary accelerators that work slightly lower modulus than the thiurams. Popular members of this class are the zinc continuous vulcanization of butyl rubber strongly activated by a thioamine. SAA-30 gives powerful acceleration at low
in a synergistic manner with other ingredients in a compound. The next section will give you methyl, ethyl and butyl dithiocarbamates. Salts of bismuth, copper, and tellurium extrusions. levels. EPDM bloom is not a problem as it is with many accelerators. SAA-30
important information on each type of ultra/secondary accelerator and some applications also are used. utilizes sulfur very efficiently to create good cures in formulas with lower levels
where they are utilized. of sulfur.
U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 3 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 4 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 5

accelerators and
accelerator systems
Scorch Rates of Some Commonly used Accelerators ZDMC or Zinc dimethyldithiocarbamate is an ultra /secondary accelerator for ZDBCX or zinc N, N-di-n-butyldithio-
selection of ultra/secondary accelerator
system
natural and synthetic based compounds that also carbamate/di-n-butylamine complex is
Ultra/Secondary N

VULCANIZATION
Primary find uses as a primary or secondary in sulfur based an ultra-accelerator which is active at
Part II: Ultra/Secondary Accelerators
N

MATERIALS
Zn-S
Kickers latex compounds. ZDMC is very active at tempera- room temperature. It can be further
SAA-30 Faster MBT
S
tures above 100C. As a primary accelerator ZDMC activated by Z.I.X., and may also be
CuDD MBTS
S
The designation ultra is applied to accelerators that speed the rate of vulcaniza- Before selecting an ultra/secondary accelerator system for the manufacture of a particular gives a faster cure rate and higher modulus, but used as a booster for thiazoles. It may
tion to the greatest degree. Generally, smaller quantities of sulfur can be used in rubber product, the following considerations must be taken into account. DPTT ZMBT shorter scorch times which find uses in continuous be used in natural rubber and SBR for
TMTD CBTS
ultra accelerated compounds to produce optimum physical properties in a shorter cure based products such as cables, tubings and profiles. Low unsaturation content dry mixes, cements, and latex. It is of + dibutylamine complex
Expected shelf life of the compound
ZDMC BBTS
curing time than can be obtained with other classes of accelerators such as rubbers such as butyl and EPDM can be cured using ZDMC as a secondary particular value for the preparation of
TM/ETD Cure-Rite 18
thiazoles or sulfenamides. Ultra/secondary accelerators solubility in rubber accelerator. It can be used at a higher dosage to achieve faster cure rates for high transparent and translucent articles
ZDEC OMTS
Quite frequently the ultra accelerators are used in combination with primary temperature curing (CV curing for wire insulation), as well as for curing thicker from both latex and dry rubber.
OBTS
The interaction of the ultra/secondary accelerators with the primary accelerators
DPG
accelerators at which time they are sometimes called secondary accelerators. In molded parts. ZDMC with MBT provides good curing activity in EPDM formula-
Part II the two classes of ultra accelerators that will be discussed are dithiocarba- CuDD or Copper dimethyldithiocarba-
TETD DCBS
tions.
mates and thiurams. The number of processing stages the compound must undergo
DOTG
mate is especially recommended for SBR,
TDEC ZDEC or Zinc diethyldithiocarbamate can be
The level of scorch safety the compound needs EPDM, and Butyl. It is a powerful

introduction
S secondary accelerator. It is possible by
Faster cure rate for economical production of the rubber product TMTM used in the same manner as ZDMC, except that N S using CuDD with MBTS to increase cure
N

TBzTD
N
Cu-S

Slower
quantities should be increased 10% to obtain S Zn N rate while holding scorch rate constant,
ZDBC
Determination of sulfur levels needed and its effect on the levels of ultra accelerators S
Accelerators and Accelerator Systems Part I covered the meaning of vulcaniza- comparable results. or even reducing it slightly in some S

ZDBC or Zinc dibutyldithiocarbamate is


tion with respect to rheology, selection of accelerators, polymer accelerator The curing method used (.e.g. injection, compression, or transfer molding) compounds. It usually results in higher
Note: red denotes the dithiocarbamates and blue the thiuram accelerators
interaction and the primary accelerators. The focus here will be on two types of modulus, tensile strength, lower
ultra/secondary accelerators, the dithiocarbamates and thiurams and their role Maximum vulcanization temperature available used in adhesives as a stabilizer and as an compression set, and a marked plateau
By far the most popular ultra/secondary accelerators are the dithiocarbamates and antioxidant in uncured rubbers. It is also S effect on over-cures. CuDD shows a
in rubber curing systems. Cure cycle desired for the available vulcanization method, the temperature, and the thiurams. The ultra/secondary accelerators often produce scorchy, very fast curing used in combination with other accelerators N distinct advantage in curing thick
vulcanizate properties required
As mentioned in Part I, accelerators are classify by ASTM as: compounds. Their major functions are that they produce increased cure rate (i.e. to produce low compression set, good heat N
Zn-S items. Compounds designed with CuDD should contain octylated dipheny-
The interaction of the ultra/secondary accelerators with the polymer systems raise the modulus) and shorten scorch times. Quite frequently they are paired with a aging, and lower bloom in EPDM S lamine antioxidant to obtain maximum aging, especially in mineral
primary accelerator to derive maximum levels of processing safety and vulcanization compounds. It is recommended as a S filled compounds.
1. Thiazoles (Mercapto) The ultra/secondary accelerators effect on other ingredients in a compound stabilizer in hot melts.
TDEC or Tellurium diethyldithiocarba-
rates.

ZBED or Zinc Dibenzyl Dithiocarbamate


N S
2. Sulfenamides No known health hazards upon usage of a chemical and of its decomposition products
mate is the fastest for EPDM and butyl
Dithiocarbamate Types
S
on cure N S S
is an active form of Zinc rubber vulcanization. TDEC or Te
3. Guanidines No adverse effects during end-use of the rubber product (e.g. accelerators used in Dithiocarbamate, which can be modified TDEC/Thiuram combinations with MBT S
S N
Dithiocarbamates are so powerful that they are rarely used alone except in such S
the manufacturing of the rubber articles intended for food contact, surgical use, etc.) by MBT or MBTS, etc. It is non-staining, are used extensively in butyl innerliner
4. Dithiocarbamates specialty applications as spread goods (fabric covered with a rubber coating: e.g.
non-discoloring and achieves safer tube production and other applications S N
Easy to handle and dust suppressed physical form hospital sheeting) cured in air at or slightly above room temperature. Usually they processing than Zinc Dibutyl requiring rapid cures.
are paired with thiazole or sulfenamide accelerators to adjust the cure rate of a stock. Dithiocarbamate. In latex it is less likely N

SAA-30 or 2, 2-dithiodiethylammo-
5. Thiurams Zn
S
Selection of the proper ultra/secondary accelerator is very important to a compounder. It can A typical curing system with natural rubber might be 0.5 parts of zinc dimethyldithio- to cause pre-cure at room temperature S S
S
6. Specialty Accelerators. affect the number of cycle times one can run. The ultra/secondary levels in a compound can carbamate (ZMDC), 0.75 parts of thiazole accelerator, and 2.0 parts of sulfur. With than other dithiocarbamates. However, N nium-bis-dibenzyldithiocarbamate is
determine the amount of storage time (shelf-life) a compound can withstand. The correct SBR stocks the system might be 0.6 ZMDC, 0.75 parts of thiazole, 1.8 parts of sulfur. ZBED is a typical ultra-accelerator at an ultra-fast accelerator in a polymeric
Other ways to classify accelerators are (a) organic or inorganic, (b) acidic or selection of ultra/secondary accelerators in combination with a delayed action accelerator (e.g. Non-staining dithiocarbamates are versatile accelerators that can be used in IIR normal curing temperatures. It is also binder that is nitrosamine safe. For
basic, (c) chemical type, (d) by acceleration speed such as slow, medium, sulfenamide) will allow sufficient scorch delay before the onset of vulcanization and high (butyl), and EPDM. Dithiocarbamates have good tensile and resiliency. They have useful as a secondary accelerator for the reference sake picture ZBED, but instead of a Zn salt, the dithiocarbamate is
semi-ultra and ultra. torque after the start of vulcanization. One must select ultra/secondary accelerators that work slightly lower modulus than the thiurams. Popular members of this class are the zinc continuous vulcanization of butyl rubber strongly activated by a thioamine. SAA-30 gives powerful acceleration at low
in a synergistic manner with other ingredients in a compound. The next section will give you methyl, ethyl and butyl dithiocarbamates. Salts of bismuth, copper, and tellurium extrusions. levels. EPDM bloom is not a problem as it is with many accelerators. SAA-30
important information on each type of ultra/secondary accelerator and some applications also are used. utilizes sulfur very efficiently to create good cures in formulas with lower levels
where they are utilized. of sulfur.
U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 3 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 4 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 5

accelerators and
accelerator systems
Scorch Rates of Some Commonly used Accelerators ZDMC or Zinc dimethyldithiocarbamate is an ultra /secondary accelerator for ZDBCX or zinc N, N-di-n-butyldithio-
selection of ultra/secondary accelerator
system
natural and synthetic based compounds that also carbamate/di-n-butylamine complex is
Ultra/Secondary N

VULCANIZATION
Primary find uses as a primary or secondary in sulfur based an ultra-accelerator which is active at
Part II: Ultra/Secondary Accelerators
N

MATERIALS
Zn-S
Kickers latex compounds. ZDMC is very active at tempera- room temperature. It can be further
SAA-30 Faster MBT
S
tures above 100C. As a primary accelerator ZDMC activated by Z.I.X., and may also be
CuDD MBTS
S
The designation ultra is applied to accelerators that speed the rate of vulcaniza- Before selecting an ultra/secondary accelerator system for the manufacture of a particular gives a faster cure rate and higher modulus, but used as a booster for thiazoles. It may
tion to the greatest degree. Generally, smaller quantities of sulfur can be used in rubber product, the following considerations must be taken into account. DPTT ZMBT shorter scorch times which find uses in continuous be used in natural rubber and SBR for
TMTD CBTS
ultra accelerated compounds to produce optimum physical properties in a shorter cure based products such as cables, tubings and profiles. Low unsaturation content dry mixes, cements, and latex. It is of + dibutylamine complex
Expected shelf life of the compound
ZDMC BBTS
curing time than can be obtained with other classes of accelerators such as rubbers such as butyl and EPDM can be cured using ZDMC as a secondary particular value for the preparation of
TM/ETD Cure-Rite 18
thiazoles or sulfenamides. Ultra/secondary accelerators solubility in rubber accelerator. It can be used at a higher dosage to achieve faster cure rates for high transparent and translucent articles
ZDEC OMTS
Quite frequently the ultra accelerators are used in combination with primary temperature curing (CV curing for wire insulation), as well as for curing thicker from both latex and dry rubber.
OBTS
The interaction of the ultra/secondary accelerators with the primary accelerators
DPG
accelerators at which time they are sometimes called secondary accelerators. In molded parts. ZDMC with MBT provides good curing activity in EPDM formula-
Part II the two classes of ultra accelerators that will be discussed are dithiocarba- CuDD or Copper dimethyldithiocarba-
TETD DCBS
tions.
mates and thiurams. The number of processing stages the compound must undergo
DOTG
mate is especially recommended for SBR,
TDEC ZDEC or Zinc diethyldithiocarbamate can be
The level of scorch safety the compound needs EPDM, and Butyl. It is a powerful

introduction
S secondary accelerator. It is possible by
Faster cure rate for economical production of the rubber product TMTM used in the same manner as ZDMC, except that N S using CuDD with MBTS to increase cure
N

TBzTD
N
Cu-S

Slower
quantities should be increased 10% to obtain S Zn N rate while holding scorch rate constant,
ZDBC
Determination of sulfur levels needed and its effect on the levels of ultra accelerators S
Accelerators and Accelerator Systems Part I covered the meaning of vulcaniza- comparable results. or even reducing it slightly in some S

ZDBC or Zinc dibutyldithiocarbamate is


tion with respect to rheology, selection of accelerators, polymer accelerator The curing method used (.e.g. injection, compression, or transfer molding) compounds. It usually results in higher
Note: red denotes the dithiocarbamates and blue the thiuram accelerators
interaction and the primary accelerators. The focus here will be on two types of modulus, tensile strength, lower
ultra/secondary accelerators, the dithiocarbamates and thiurams and their role Maximum vulcanization temperature available used in adhesives as a stabilizer and as an compression set, and a marked plateau
By far the most popular ultra/secondary accelerators are the dithiocarbamates and antioxidant in uncured rubbers. It is also S effect on over-cures. CuDD shows a
in rubber curing systems. Cure cycle desired for the available vulcanization method, the temperature, and the thiurams. The ultra/secondary accelerators often produce scorchy, very fast curing used in combination with other accelerators N distinct advantage in curing thick
vulcanizate properties required
As mentioned in Part I, accelerators are classify by ASTM as: compounds. Their major functions are that they produce increased cure rate (i.e. to produce low compression set, good heat N
Zn-S items. Compounds designed with CuDD should contain octylated dipheny-
The interaction of the ultra/secondary accelerators with the polymer systems raise the modulus) and shorten scorch times. Quite frequently they are paired with a aging, and lower bloom in EPDM S lamine antioxidant to obtain maximum aging, especially in mineral
primary accelerator to derive maximum levels of processing safety and vulcanization compounds. It is recommended as a S filled compounds.
1. Thiazoles (Mercapto) The ultra/secondary accelerators effect on other ingredients in a compound stabilizer in hot melts.
TDEC or Tellurium diethyldithiocarba-
rates.

ZBED or Zinc Dibenzyl Dithiocarbamate


N S
2. Sulfenamides No known health hazards upon usage of a chemical and of its decomposition products
mate is the fastest for EPDM and butyl
Dithiocarbamate Types
S
on cure N S S
is an active form of Zinc rubber vulcanization. TDEC or Te
3. Guanidines No adverse effects during end-use of the rubber product (e.g. accelerators used in Dithiocarbamate, which can be modified TDEC/Thiuram combinations with MBT S
S N
Dithiocarbamates are so powerful that they are rarely used alone except in such S
the manufacturing of the rubber articles intended for food contact, surgical use, etc.) by MBT or MBTS, etc. It is non-staining, are used extensively in butyl innerliner
4. Dithiocarbamates specialty applications as spread goods (fabric covered with a rubber coating: e.g.
non-discoloring and achieves safer tube production and other applications S N
Easy to handle and dust suppressed physical form hospital sheeting) cured in air at or slightly above room temperature. Usually they processing than Zinc Dibutyl requiring rapid cures.
are paired with thiazole or sulfenamide accelerators to adjust the cure rate of a stock. Dithiocarbamate. In latex it is less likely N

SAA-30 or 2, 2-dithiodiethylammo-
5. Thiurams Zn
S
Selection of the proper ultra/secondary accelerator is very important to a compounder. It can A typical curing system with natural rubber might be 0.5 parts of zinc dimethyldithio- to cause pre-cure at room temperature S S
S
6. Specialty Accelerators. affect the number of cycle times one can run. The ultra/secondary levels in a compound can carbamate (ZMDC), 0.75 parts of thiazole accelerator, and 2.0 parts of sulfur. With than other dithiocarbamates. However, N nium-bis-dibenzyldithiocarbamate is
determine the amount of storage time (shelf-life) a compound can withstand. The correct SBR stocks the system might be 0.6 ZMDC, 0.75 parts of thiazole, 1.8 parts of sulfur. ZBED is a typical ultra-accelerator at an ultra-fast accelerator in a polymeric
Other ways to classify accelerators are (a) organic or inorganic, (b) acidic or selection of ultra/secondary accelerators in combination with a delayed action accelerator (e.g. Non-staining dithiocarbamates are versatile accelerators that can be used in IIR normal curing temperatures. It is also binder that is nitrosamine safe. For
basic, (c) chemical type, (d) by acceleration speed such as slow, medium, sulfenamide) will allow sufficient scorch delay before the onset of vulcanization and high (butyl), and EPDM. Dithiocarbamates have good tensile and resiliency. They have useful as a secondary accelerator for the reference sake picture ZBED, but instead of a Zn salt, the dithiocarbamate is
semi-ultra and ultra. torque after the start of vulcanization. One must select ultra/secondary accelerators that work slightly lower modulus than the thiurams. Popular members of this class are the zinc continuous vulcanization of butyl rubber strongly activated by a thioamine. SAA-30 gives powerful acceleration at low
in a synergistic manner with other ingredients in a compound. The next section will give you methyl, ethyl and butyl dithiocarbamates. Salts of bismuth, copper, and tellurium extrusions. levels. EPDM bloom is not a problem as it is with many accelerators. SAA-30
important information on each type of ultra/secondary accelerator and some applications also are used. utilizes sulfur very efficiently to create good cures in formulas with lower levels
where they are utilized. of sulfur.
U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d / U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 0 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 8 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 10

Fi ures 19a:6 9b: compares the cure rate of dithiocarbamates4 The Thiurams Types TM/ETD is a combination of Tetramethylthiuram disulfide/Tetraethylthiuram Fi ure 29a:6 9b: compares the cure rate of thiurams4 The formula is SBR based4

summary
formula is SBR based4
SBR 100.0 phr
Like the dithiocarbamates, thiuram are ultra-accelerators. They are made from disulfide and is often used for single weighing purposes and is less liable to bloom
SBR 100 phr ZnO 5.0 phr
secondary amines and carbon disulfide. The most commonly used members of this than TMTD alone in comparable amounts.
ZnO 5 phr
The proper combination of ultra/secondary accelerators with the primary accelerators is essential
SA 2.0 phr
class are probably tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide
SA 2 phr Sulfur 1.8 phr
(TETD), and tetramethylthiuram monosulfide (TMTM). The strongest of these three 40% to the optimization of a cure system. Fortunately there are enough ultra/secondary accelerator
60%
Sulfur 1.8 phr Thiurams 1.0 phr
is the TMTD, followed by TETD and then TMTM. TMTD is too scorchy to be used grades to meet most compound needs. Many factors, such as primary accelerator, cure rate,
S
Dithiocarbamate 1.0 phr
S temperature, multiple processing steps, and target physical properties can limit the type and
alone. TETD is about the same, but TMTM can be used with care. If TETD is
substituted for TMTD, about 10% more TETD should be used. Like the dithiocarba- S N N S amount of ultra/secondary accelerator that can be utilized. Sometimes after a primary and an
N S S N ultra/secondary accelerator has been chosen, more adjustments of the cure system may be
ZDEC mates, the thiuram sulfides can be used in light colored stocks without staining.
18
80
8.
8.0
S
27
70
7.0
necessary. This is when a .specialty acceleratorL may be used. The topic of specialty accelerators
S
16.0
16
16. 0
The thiurams are especially useful in cure systems containing low or no elemental
24.0
24
24.0
0
will be covered in Part III.
14.
14
4.00
SA
SAA
SAAA -3
-30
30 21.0
21
21.0
0
sulfur. However, the monosulfide is not strong enough to cure satisfactorily without
DPTT or Dipentamethylene thiuram tetrahexasulfide is a sulfur bearing accelerator
ZDMC

ORQUE
QUE
E
18
1 8.0
8.0
ORQUE
QUE
E

12
12.
12.00

TORQU
added sulfur. The most common use of the thiuram is as a secondary accelerator to
TORQU

ORQ
DP
DPTT
D PTT
TT
T
ORQ

OR
15.0
15
50
OR

10.0
10
10. 0
thiazole or sulfenamide accelerated compounds. For example EPDM stock might that finds special compounding applications. It has 25% available sulfur for vulcan- 12.0
12
2.0
TETD
TE TD
D
80
8.
8.0 ZDBC
ZD
ZDBC
DBBC
BC
have a cure system of 1.5 parts of sulfur, 1.25 parts of thiazole, and 1.5 parts of ization as compared to 13% and 11 % respectively for TMTD and TETD. DPTT is used 90
9.0
60
6.
6.0
TMTD. as a sulfur donor to increase heat resistance in NR and SBR compounds. It also 60
6.0
40
4.0
functions as an acelerator for Hypalon. TB
T BzTD
TD
2.0
2
2. 0 30
3.0

TMTM or Tetramethylthiuram
0.00
00
0 0.00
00
0

1.00 2.00 3.00 4.00 5.00 S 1.00 2.00 3.00 4.00 5.00

Figure 1a: monosulfide is not a sulfur donor. It must S S Figure 2a: TIME
TIME
Cure Rate of Dithiocarbamates be used with sulfur to provide good curing N S Cure Rate of Thiurams
S S N
activity, and it has a lower scorch rate N S N
than TMTD and TETD. S

TBzTD or Tetrabenzylthiuram disulfide is a safe secondary amine accelerator. It was


TMTD or Tetramethylthiuram disulfide is an ultra fast accelerator for NR, SBR, BR, developed to replace thiurams such as TMTD, where the presence of harmful
NBR and highly unsaturated rubbers. It is the most preferred primary accelerator nitrosoamines is of concern. It gives off dibenzylnitrosoamine which is not carcino-
18
80
8.
8.0
for sulfur cured, low unsaturated content rubbers like butyl and EPDM. It contains genic, according to published literature. TBzTD is a fast curing primary or secondary 27.0
7.0
7.0

16.0
16
16. 0
approximately 13% available sulfur for cross linking, therefore it can be used in low accelerator in NR, SBR and NBR applications. In modified CR, TBzTD is a retarder 24.0
24.0
0

14.
14
4.00
TD
TDE
ECC sulfur /sulfurless EV cures of diene S when used with ETU. Compared with TMTD, TBzTD is safer processing and has longer 21.0
21.0
0

polymers. scorch resistance.

ORQUEE
QUE
18.0
1 80
8.0
ORQUE
QUE
E

12
12.
12.00 Cu
C uDD

TORQU
TORQU

ORQ
S TM
T MTD
M TD
D
ORQ

OR
15.0
15.0
5.0
N S
OR

10.0
10
10. 0
TM/ETD
TM /ETD
ETD
E TD
D

TETD or Tetraethylthiuram disulfide is a


80
8.
8.0 ZBE
ZB
ZBED
ED
ED 12.0
12.0
2.0

60
6.
6.0
S 90
9.
9.0

sulfur bearing ultra accelerator and sulfur S 60


6.0
40
4.0 Included with its product literature and upon the request of its customers, Akrochem provides product specifications and evaluations, suggested formulations and recommendations and
TM
T MT
TM
M
2.0
2
2. 0
donor. It is used extensively in heat resistant N S 3.0
3
3. 0 other technical assistance, both orally and in writing (collectively the JTechnical InformationL). Although Akrochem believes all Technical Information to be true and correct, it makes no
S 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
compound design for sulfurless and low S N 0.00
00
0 the Technical Information. Akrochem will not be liable for any cost, loss or damage, in tort, contract or otherwise, arising from customerIs use of Akrochem products or Technical
0.00
00
0 Information.
2.00 3.00 4.00 5.00
1.00 2.00 3.00 4.00 5.00 sulfur cures. It also activates the thiazoles S S
1.00
It is the customers sole responsibility to test the products and any Technical Information provided to determine whether they are suitable for the customers needs. Before working with any
Figure 1b: N N Figure 2b:
TIME and sulfenamides. S TIME product, the customer must read and become familiar with available information concerning its hazards, proper use, storage and handling, including all health, safety and hygiene
Cure Rate of Dithiocarbamates Cure Rate of Thiurams precautions recommended by the manufacturer.

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,
S method or process. No license is implied or granted by Akrochem as to any such product, method or process. The names/brand names appearing throughout this literature are believed to
be either brand names or registered or unregistered trademarks.

A ROCHEM CORPORATION DISCLAIMS AN, AND ALL WARRANTIES, EXPRESS AND IMPLIED, INCLUDING WITHOUT LIMITATION, WARRANTIES OR MERCHANTABILIT, AND FITNESS
FOR AN, PARTICULAR PURPOSE, RELATED TO AN, PRODUCTS OR TECHNICAL INFORMATION PROVIDED B, A ROCHEM.
U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d / U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 0 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 8 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 10

Fi ures 19a:6 9b: compares the cure rate of dithiocarbamates4 The Thiurams Types TM/ETD is a combination of Tetramethylthiuram disulfide/Tetraethylthiuram Fi ure 29a:6 9b: compares the cure rate of thiurams4 The formula is SBR based4

summary
formula is SBR based4
SBR 100.0 phr
Like the dithiocarbamates, thiuram are ultra-accelerators. They are made from disulfide and is often used for single weighing purposes and is less liable to bloom
SBR 100 phr ZnO 5.0 phr
secondary amines and carbon disulfide. The most commonly used members of this than TMTD alone in comparable amounts.
ZnO 5 phr
The proper combination of ultra/secondary accelerators with the primary accelerators is essential
SA 2.0 phr
class are probably tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide
SA 2 phr Sulfur 1.8 phr
(TETD), and tetramethylthiuram monosulfide (TMTM). The strongest of these three 40% to the optimization of a cure system. Fortunately there are enough ultra/secondary accelerator
60%
Sulfur 1.8 phr Thiurams 1.0 phr
is the TMTD, followed by TETD and then TMTM. TMTD is too scorchy to be used grades to meet most compound needs. Many factors, such as primary accelerator, cure rate,
S
Dithiocarbamate 1.0 phr
S temperature, multiple processing steps, and target physical properties can limit the type and
alone. TETD is about the same, but TMTM can be used with care. If TETD is
substituted for TMTD, about 10% more TETD should be used. Like the dithiocarba- S N N S amount of ultra/secondary accelerator that can be utilized. Sometimes after a primary and an
N S S N ultra/secondary accelerator has been chosen, more adjustments of the cure system may be
ZDEC mates, the thiuram sulfides can be used in light colored stocks without staining.
18
80
8.
8.0
S
27
70
7.0
necessary. This is when a .specialty acceleratorL may be used. The topic of specialty accelerators
S
16.0
16
16. 0
The thiurams are especially useful in cure systems containing low or no elemental
24.0
24
24.0
0
will be covered in Part III.
14.
14
4.00
SA
SAA
SAAA -3
-30
30 21.0
21
21.0
0
sulfur. However, the monosulfide is not strong enough to cure satisfactorily without
DPTT or Dipentamethylene thiuram tetrahexasulfide is a sulfur bearing accelerator
ZDMC

ORQUE
QUE
E
18
1 8.0
8.0
ORQUE
QUE
E

12
12.
12.00

TORQU
added sulfur. The most common use of the thiuram is as a secondary accelerator to
TORQU

ORQ
DP
DPTT
D PTT
TT
T
ORQ

OR
15.0
15
50
OR

10.0
10
10. 0
thiazole or sulfenamide accelerated compounds. For example EPDM stock might that finds special compounding applications. It has 25% available sulfur for vulcan- 12.0
12
2.0
TETD
TE TD
D
80
8.
8.0 ZDBC
ZD
ZDBC
DBBC
BC
have a cure system of 1.5 parts of sulfur, 1.25 parts of thiazole, and 1.5 parts of ization as compared to 13% and 11 % respectively for TMTD and TETD. DPTT is used 90
9.0
60
6.
6.0
TMTD. as a sulfur donor to increase heat resistance in NR and SBR compounds. It also 60
6.0
40
4.0
functions as an acelerator for Hypalon. TB
T BzTD
TD
2.0
2
2. 0 30
3.0

TMTM or Tetramethylthiuram
0.00
00
0 0.00
00
0

1.00 2.00 3.00 4.00 5.00 S 1.00 2.00 3.00 4.00 5.00

Figure 1a: monosulfide is not a sulfur donor. It must S S Figure 2a: TIME
TIME
Cure Rate of Dithiocarbamates be used with sulfur to provide good curing N S Cure Rate of Thiurams
S S N
activity, and it has a lower scorch rate N S N
than TMTD and TETD. S

TBzTD or Tetrabenzylthiuram disulfide is a safe secondary amine accelerator. It was


TMTD or Tetramethylthiuram disulfide is an ultra fast accelerator for NR, SBR, BR, developed to replace thiurams such as TMTD, where the presence of harmful
NBR and highly unsaturated rubbers. It is the most preferred primary accelerator nitrosoamines is of concern. It gives off dibenzylnitrosoamine which is not carcino-
18
80
8.
8.0
for sulfur cured, low unsaturated content rubbers like butyl and EPDM. It contains genic, according to published literature. TBzTD is a fast curing primary or secondary 27.0
7.0
7.0

16.0
16
16. 0
approximately 13% available sulfur for cross linking, therefore it can be used in low accelerator in NR, SBR and NBR applications. In modified CR, TBzTD is a retarder 24.0
24.0
0

14.
14
4.00
TD
TDE
ECC sulfur /sulfurless EV cures of diene S when used with ETU. Compared with TMTD, TBzTD is safer processing and has longer 21.0
21.0
0

polymers. scorch resistance.

ORQUEE
QUE
18.0
1 80
8.0
ORQUE
QUE
E

12
12.
12.00 Cu
C uDD

TORQU
TORQU

ORQ
S TM
T MTD
M TD
D
ORQ

OR
15.0
15.0
5.0
N S
OR

10.0
10
10. 0
TM/ETD
TM /ETD
ETD
E TD
D

TETD or Tetraethylthiuram disulfide is a


80
8.
8.0 ZBE
ZB
ZBED
ED
ED 12.0
12.0
2.0

60
6.
6.0
S 90
9.
9.0

sulfur bearing ultra accelerator and sulfur S 60


6.0
40
4.0 Included with its product literature and upon the request of its customers, Akrochem provides product specifications and evaluations, suggested formulations and recommendations and
TM
T MT
TM
M
2.0
2
2. 0
donor. It is used extensively in heat resistant N S 3.0
3
3. 0 other technical assistance, both orally and in writing (collectively the JTechnical InformationL). Although Akrochem believes all Technical Information to be true and correct, it makes no
S 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
compound design for sulfurless and low S N 0.00
00
0 the Technical Information. Akrochem will not be liable for any cost, loss or damage, in tort, contract or otherwise, arising from customerIs use of Akrochem products or Technical
0.00
00
0 Information.
2.00 3.00 4.00 5.00
1.00 2.00 3.00 4.00 5.00 sulfur cures. It also activates the thiazoles S S
1.00
It is the customers sole responsibility to test the products and any Technical Information provided to determine whether they are suitable for the customers needs. Before working with any
Figure 1b: N N Figure 2b:
TIME and sulfenamides. S TIME product, the customer must read and become familiar with available information concerning its hazards, proper use, storage and handling, including all health, safety and hygiene
Cure Rate of Dithiocarbamates Cure Rate of Thiurams precautions recommended by the manufacturer.

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,
S method or process. No license is implied or granted by Akrochem as to any such product, method or process. The names/brand names appearing throughout this literature are believed to
be either brand names or registered or unregistered trademarks.

A ROCHEM CORPORATION DISCLAIMS AN, AND ALL WARRANTIES, EXPRESS AND IMPLIED, INCLUDING WITHOUT LIMITATION, WARRANTIES OR MERCHANTABILIT, AND FITNESS
FOR AN, PARTICULAR PURPOSE, RELATED TO AN, PRODUCTS OR TECHNICAL INFORMATION PROVIDED B, A ROCHEM.
U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d / U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 0 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 8 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 10

Fi ures 19a:6 9b: compares the cure rate of dithiocarbamates4 The Thiurams Types TM/ETD is a combination of Tetramethylthiuram disulfide/Tetraethylthiuram Fi ure 29a:6 9b: compares the cure rate of thiurams4 The formula is SBR based4

summary
formula is SBR based4
SBR 100.0 phr
Like the dithiocarbamates, thiuram are ultra-accelerators. They are made from disulfide and is often used for single weighing purposes and is less liable to bloom
SBR 100 phr ZnO 5.0 phr
secondary amines and carbon disulfide. The most commonly used members of this than TMTD alone in comparable amounts.
ZnO 5 phr
The proper combination of ultra/secondary accelerators with the primary accelerators is essential
SA 2.0 phr
class are probably tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide
SA 2 phr Sulfur 1.8 phr
(TETD), and tetramethylthiuram monosulfide (TMTM). The strongest of these three 40% to the optimization of a cure system. Fortunately there are enough ultra/secondary accelerator
60%
Sulfur 1.8 phr Thiurams 1.0 phr
is the TMTD, followed by TETD and then TMTM. TMTD is too scorchy to be used grades to meet most compound needs. Many factors, such as primary accelerator, cure rate,
S
Dithiocarbamate 1.0 phr
S temperature, multiple processing steps, and target physical properties can limit the type and
alone. TETD is about the same, but TMTM can be used with care. If TETD is
substituted for TMTD, about 10% more TETD should be used. Like the dithiocarba- S N N S amount of ultra/secondary accelerator that can be utilized. Sometimes after a primary and an
N S S N ultra/secondary accelerator has been chosen, more adjustments of the cure system may be
ZDEC mates, the thiuram sulfides can be used in light colored stocks without staining.
18
80
8.
8.0
S
27
70
7.0
necessary. This is when a .specialty acceleratorL may be used. The topic of specialty accelerators
S
16.0
16
16. 0
The thiurams are especially useful in cure systems containing low or no elemental
24.0
24
24.0
0
will be covered in Part III.
14.
14
4.00
SA
SAA
SAAA -3
-30
30 21.0
21
21.0
0
sulfur. However, the monosulfide is not strong enough to cure satisfactorily without
DPTT or Dipentamethylene thiuram tetrahexasulfide is a sulfur bearing accelerator
ZDMC

ORQUE
QUE
E
18
1 8.0
8.0
ORQUE
QUE
E

12
12.
12.00

TORQU
added sulfur. The most common use of the thiuram is as a secondary accelerator to
TORQU

ORQ
DP
DPTT
D PTT
TT
T
ORQ

OR
15.0
15
50
OR

10.0
10
10. 0
thiazole or sulfenamide accelerated compounds. For example EPDM stock might that finds special compounding applications. It has 25% available sulfur for vulcan- 12.0
12
2.0
TETD
TE TD
D
80
8.
8.0 ZDBC
ZD
ZDBC
DBBC
BC
have a cure system of 1.5 parts of sulfur, 1.25 parts of thiazole, and 1.5 parts of ization as compared to 13% and 11 % respectively for TMTD and TETD. DPTT is used 90
9.0
60
6.
6.0
TMTD. as a sulfur donor to increase heat resistance in NR and SBR compounds. It also 60
6.0
40
4.0
functions as an acelerator for Hypalon. TB
T BzTD
TD
2.0
2
2. 0 30
3.0

TMTM or Tetramethylthiuram
0.00
00
0 0.00
00
0

1.00 2.00 3.00 4.00 5.00 S 1.00 2.00 3.00 4.00 5.00

Figure 1a: monosulfide is not a sulfur donor. It must S S Figure 2a: TIME
TIME
Cure Rate of Dithiocarbamates be used with sulfur to provide good curing N S Cure Rate of Thiurams
S S N
activity, and it has a lower scorch rate N S N
than TMTD and TETD. S

TBzTD or Tetrabenzylthiuram disulfide is a safe secondary amine accelerator. It was


TMTD or Tetramethylthiuram disulfide is an ultra fast accelerator for NR, SBR, BR, developed to replace thiurams such as TMTD, where the presence of harmful
NBR and highly unsaturated rubbers. It is the most preferred primary accelerator nitrosoamines is of concern. It gives off dibenzylnitrosoamine which is not carcino-
18
80
8.
8.0
for sulfur cured, low unsaturated content rubbers like butyl and EPDM. It contains genic, according to published literature. TBzTD is a fast curing primary or secondary 27.0
7.0
7.0

16.0
16
16. 0
approximately 13% available sulfur for cross linking, therefore it can be used in low accelerator in NR, SBR and NBR applications. In modified CR, TBzTD is a retarder 24.0
24.0
0

14.
14
4.00
TD
TDE
ECC sulfur /sulfurless EV cures of diene S when used with ETU. Compared with TMTD, TBzTD is safer processing and has longer 21.0
21.0
0

polymers. scorch resistance.

ORQUEE
QUE
18.0
1 80
8.0
ORQUE
QUE
E

12
12.
12.00 Cu
C uDD

TORQU
TORQU

ORQ
S TM
T MTD
M TD
D
ORQ

OR
15.0
15.0
5.0
N S
OR

10.0
10
10. 0
TM/ETD
TM /ETD
ETD
E TD
D

TETD or Tetraethylthiuram disulfide is a


80
8.
8.0 ZBE
ZB
ZBED
ED
ED 12.0
12.0
2.0

60
6.
6.0
S 90
9.
9.0

sulfur bearing ultra accelerator and sulfur S 60


6.0
40
4.0 Included with its product literature and upon the request of its customers, Akrochem provides product specifications and evaluations, suggested formulations and recommendations and
TM
T MT
TM
M
2.0
2
2. 0
donor. It is used extensively in heat resistant N S 3.0
3
3. 0 other technical assistance, both orally and in writing (collectively the JTechnical InformationL). Although Akrochem believes all Technical Information to be true and correct, it makes no
S 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
compound design for sulfurless and low S N 0.00
00
0 the Technical Information. Akrochem will not be liable for any cost, loss or damage, in tort, contract or otherwise, arising from customerIs use of Akrochem products or Technical
0.00
00
0 Information.
2.00 3.00 4.00 5.00
1.00 2.00 3.00 4.00 5.00 sulfur cures. It also activates the thiazoles S S
1.00
It is the customers sole responsibility to test the products and any Technical Information provided to determine whether they are suitable for the customers needs. Before working with any
Figure 1b: N N Figure 2b:
TIME and sulfenamides. S TIME product, the customer must read and become familiar with available information concerning its hazards, proper use, storage and handling, including all health, safety and hygiene
Cure Rate of Dithiocarbamates Cure Rate of Thiurams precautions recommended by the manufacturer.

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,
S method or process. No license is implied or granted by Akrochem as to any such product, method or process. The names/brand names appearing throughout this literature are believed to
be either brand names or registered or unregistered trademarks.

A ROCHEM CORPORATION DISCLAIMS AN, AND ALL WARRANTIES, EXPRESS AND IMPLIED, INCLUDING WITHOUT LIMITATION, WARRANTIES OR MERCHANTABILIT, AND FITNESS
FOR AN, PARTICULAR PURPOSE, RELATED TO AN, PRODUCTS OR TECHNICAL INFORMATION PROVIDED B, A ROCHEM.
U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d / U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 0 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 8 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 10

Fi ures 19a:6 9b: compares the cure rate of dithiocarbamates4 The Thiurams Types TM/ETD is a combination of Tetramethylthiuram disulfide/Tetraethylthiuram Fi ure 29a:6 9b: compares the cure rate of thiurams4 The formula is SBR based4

summary
formula is SBR based4
SBR 100.0 phr
Like the dithiocarbamates, thiuram are ultra-accelerators. They are made from disulfide and is often used for single weighing purposes and is less liable to bloom
SBR 100 phr ZnO 5.0 phr
secondary amines and carbon disulfide. The most commonly used members of this than TMTD alone in comparable amounts.
ZnO 5 phr
The proper combination of ultra/secondary accelerators with the primary accelerators is essential
SA 2.0 phr
class are probably tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide
SA 2 phr Sulfur 1.8 phr
(TETD), and tetramethylthiuram monosulfide (TMTM). The strongest of these three 40% to the optimization of a cure system. Fortunately there are enough ultra/secondary accelerator
60%
Sulfur 1.8 phr Thiurams 1.0 phr
is the TMTD, followed by TETD and then TMTM. TMTD is too scorchy to be used grades to meet most compound needs. Many factors, such as primary accelerator, cure rate,
S
Dithiocarbamate 1.0 phr
S temperature, multiple processing steps, and target physical properties can limit the type and
alone. TETD is about the same, but TMTM can be used with care. If TETD is
substituted for TMTD, about 10% more TETD should be used. Like the dithiocarba- S N N S amount of ultra/secondary accelerator that can be utilized. Sometimes after a primary and an
N S S N ultra/secondary accelerator has been chosen, more adjustments of the cure system may be
ZDEC mates, the thiuram sulfides can be used in light colored stocks without staining.
18
80
8.
8.0
S
27
70
7.0
necessary. This is when a .specialty acceleratorL may be used. The topic of specialty accelerators
S
16.0
16
16. 0
The thiurams are especially useful in cure systems containing low or no elemental
24.0
24
24.0
0
will be covered in Part III.
14.
14
4.00
SA
SAA
SAAA -3
-30
30 21.0
21
21.0
0
sulfur. However, the monosulfide is not strong enough to cure satisfactorily without
DPTT or Dipentamethylene thiuram tetrahexasulfide is a sulfur bearing accelerator
ZDMC

ORQUE
QUE
E
18
1 8.0
8.0
ORQUE
QUE
E

12
12.
12.00

TORQU
added sulfur. The most common use of the thiuram is as a secondary accelerator to
TORQU

ORQ
DP
DPTT
D PTT
TT
T
ORQ

OR
15.0
15
50
OR

10.0
10
10. 0
thiazole or sulfenamide accelerated compounds. For example EPDM stock might that finds special compounding applications. It has 25% available sulfur for vulcan- 12.0
12
2.0
TETD
TE TD
D
80
8.
8.0 ZDBC
ZD
ZDBC
DBBC
BC
have a cure system of 1.5 parts of sulfur, 1.25 parts of thiazole, and 1.5 parts of ization as compared to 13% and 11 % respectively for TMTD and TETD. DPTT is used 90
9.0
60
6.
6.0
TMTD. as a sulfur donor to increase heat resistance in NR and SBR compounds. It also 60
6.0
40
4.0
functions as an acelerator for Hypalon. TB
T BzTD
TD
2.0
2
2. 0 30
3.0

TMTM or Tetramethylthiuram
0.00
00
0 0.00
00
0

1.00 2.00 3.00 4.00 5.00 S 1.00 2.00 3.00 4.00 5.00

Figure 1a: monosulfide is not a sulfur donor. It must S S Figure 2a: TIME
TIME
Cure Rate of Dithiocarbamates be used with sulfur to provide good curing N S Cure Rate of Thiurams
S S N
activity, and it has a lower scorch rate N S N
than TMTD and TETD. S

TBzTD or Tetrabenzylthiuram disulfide is a safe secondary amine accelerator. It was


TMTD or Tetramethylthiuram disulfide is an ultra fast accelerator for NR, SBR, BR, developed to replace thiurams such as TMTD, where the presence of harmful
NBR and highly unsaturated rubbers. It is the most preferred primary accelerator nitrosoamines is of concern. It gives off dibenzylnitrosoamine which is not carcino-
18
80
8.
8.0
for sulfur cured, low unsaturated content rubbers like butyl and EPDM. It contains genic, according to published literature. TBzTD is a fast curing primary or secondary 27.0
7.0
7.0

16.0
16
16. 0
approximately 13% available sulfur for cross linking, therefore it can be used in low accelerator in NR, SBR and NBR applications. In modified CR, TBzTD is a retarder 24.0
24.0
0

14.
14
4.00
TD
TDE
ECC sulfur /sulfurless EV cures of diene S when used with ETU. Compared with TMTD, TBzTD is safer processing and has longer 21.0
21.0
0

polymers. scorch resistance.

ORQUEE
QUE
18.0
1 80
8.0
ORQUE
QUE
E

12
12.
12.00 Cu
C uDD

TORQU
TORQU

ORQ
S TM
T MTD
M TD
D
ORQ

OR
15.0
15.0
5.0
N S
OR

10.0
10
10. 0
TM/ETD
TM /ETD
ETD
E TD
D

TETD or Tetraethylthiuram disulfide is a


80
8.
8.0 ZBE
ZB
ZBED
ED
ED 12.0
12.0
2.0

60
6.
6.0
S 90
9.
9.0

sulfur bearing ultra accelerator and sulfur S 60


6.0
40
4.0 Included with its product literature and upon the request of its customers, Akrochem provides product specifications and evaluations, suggested formulations and recommendations and
TM
T MT
TM
M
2.0
2
2. 0
donor. It is used extensively in heat resistant N S 3.0
3
3. 0 other technical assistance, both orally and in writing (collectively the JTechnical InformationL). Although Akrochem believes all Technical Information to be true and correct, it makes no
S 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
compound design for sulfurless and low S N 0.00
00
0 the Technical Information. Akrochem will not be liable for any cost, loss or damage, in tort, contract or otherwise, arising from customerIs use of Akrochem products or Technical
0.00
00
0 Information.
2.00 3.00 4.00 5.00
1.00 2.00 3.00 4.00 5.00 sulfur cures. It also activates the thiazoles S S
1.00
It is the customers sole responsibility to test the products and any Technical Information provided to determine whether they are suitable for the customers needs. Before working with any
Figure 1b: N N Figure 2b:
TIME and sulfenamides. S TIME product, the customer must read and become familiar with available information concerning its hazards, proper use, storage and handling, including all health, safety and hygiene
Cure Rate of Dithiocarbamates Cure Rate of Thiurams precautions recommended by the manufacturer.

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,
S method or process. No license is implied or granted by Akrochem as to any such product, method or process. The names/brand names appearing throughout this literature are believed to
be either brand names or registered or unregistered trademarks.

A ROCHEM CORPORATION DISCLAIMS AN, AND ALL WARRANTIES, EXPRESS AND IMPLIED, INCLUDING WITHOUT LIMITATION, WARRANTIES OR MERCHANTABILIT, AND FITNESS
FOR AN, PARTICULAR PURPOSE, RELATED TO AN, PRODUCTS OR TECHNICAL INFORMATION PROVIDED B, A ROCHEM.
U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d / U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 0 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 8 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 2 U LT R A / S E C O N D A R Y A C C E L E R AT O R S : c o n t i n u e d 10

Fi ures 19a:6 9b: compares the cure rate of dithiocarbamates4 The Thiurams Types TM/ETD is a combination of Tetramethylthiuram disulfide/Tetraethylthiuram Fi ure 29a:6 9b: compares the cure rate of thiurams4 The formula is SBR based4

summary
formula is SBR based4
SBR 100.0 phr
Like the dithiocarbamates, thiuram are ultra-accelerators. They are made from disulfide and is often used for single weighing purposes and is less liable to bloom
SBR 100 phr ZnO 5.0 phr
secondary amines and carbon disulfide. The most commonly used members of this than TMTD alone in comparable amounts.
ZnO 5 phr
The proper combination of ultra/secondary accelerators with the primary accelerators is essential
SA 2.0 phr
class are probably tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide
SA 2 phr Sulfur 1.8 phr
(TETD), and tetramethylthiuram monosulfide (TMTM). The strongest of these three 40% to the optimization of a cure system. Fortunately there are enough ultra/secondary accelerator
60%
Sulfur 1.8 phr Thiurams 1.0 phr
is the TMTD, followed by TETD and then TMTM. TMTD is too scorchy to be used grades to meet most compound needs. Many factors, such as primary accelerator, cure rate,
S
Dithiocarbamate 1.0 phr
S temperature, multiple processing steps, and target physical properties can limit the type and
alone. TETD is about the same, but TMTM can be used with care. If TETD is
substituted for TMTD, about 10% more TETD should be used. Like the dithiocarba- S N N S amount of ultra/secondary accelerator that can be utilized. Sometimes after a primary and an
N S S N ultra/secondary accelerator has been chosen, more adjustments of the cure system may be
ZDEC mates, the thiuram sulfides can be used in light colored stocks without staining.
18
80
8.
8.0
S
27
70
7.0
necessary. This is when a .specialty acceleratorL may be used. The topic of specialty accelerators
S
16.0
16
16. 0
The thiurams are especially useful in cure systems containing low or no elemental
24.0
24
24.0
0
will be covered in Part III.
14.
14
4.00
SA
SAA
SAAA -3
-30
30 21.0
21
21.0
0
sulfur. However, the monosulfide is not strong enough to cure satisfactorily without
DPTT or Dipentamethylene thiuram tetrahexasulfide is a sulfur bearing accelerator
ZDMC

ORQUE
QUE
E
18
1 8.0
8.0
ORQUE
QUE
E

12
12.
12.00

TORQU
added sulfur. The most common use of the thiuram is as a secondary accelerator to
TORQU

ORQ
DP
DPTT
D PTT
TT
T
ORQ

OR
15.0
15
50
OR

10.0
10
10. 0
thiazole or sulfenamide accelerated compounds. For example EPDM stock might that finds special compounding applications. It has 25% available sulfur for vulcan- 12.0
12
2.0
TETD
TE TD
D
80
8.
8.0 ZDBC
ZD
ZDBC
DBBC
BC
have a cure system of 1.5 parts of sulfur, 1.25 parts of thiazole, and 1.5 parts of ization as compared to 13% and 11 % respectively for TMTD and TETD. DPTT is used 90
9.0
60
6.
6.0
TMTD. as a sulfur donor to increase heat resistance in NR and SBR compounds. It also 60
6.0
40
4.0
functions as an acelerator for Hypalon. TB
T BzTD
TD
2.0
2
2. 0 30
3.0

TMTM or Tetramethylthiuram
0.00
00
0 0.00
00
0

1.00 2.00 3.00 4.00 5.00 S 1.00 2.00 3.00 4.00 5.00

Figure 1a: monosulfide is not a sulfur donor. It must S S Figure 2a: TIME
TIME
Cure Rate of Dithiocarbamates be used with sulfur to provide good curing N S Cure Rate of Thiurams
S S N
activity, and it has a lower scorch rate N S N
than TMTD and TETD. S

TBzTD or Tetrabenzylthiuram disulfide is a safe secondary amine accelerator. It was


TMTD or Tetramethylthiuram disulfide is an ultra fast accelerator for NR, SBR, BR, developed to replace thiurams such as TMTD, where the presence of harmful
NBR and highly unsaturated rubbers. It is the most preferred primary accelerator nitrosoamines is of concern. It gives off dibenzylnitrosoamine which is not carcino-
18
80
8.
8.0
for sulfur cured, low unsaturated content rubbers like butyl and EPDM. It contains genic, according to published literature. TBzTD is a fast curing primary or secondary 27.0
7.0
7.0

16.0
16
16. 0
approximately 13% available sulfur for cross linking, therefore it can be used in low accelerator in NR, SBR and NBR applications. In modified CR, TBzTD is a retarder 24.0
24.0
0

14.
14
4.00
TD
TDE
ECC sulfur /sulfurless EV cures of diene S when used with ETU. Compared with TMTD, TBzTD is safer processing and has longer 21.0
21.0
0

polymers. scorch resistance.

ORQUEE
QUE
18.0
1 80
8.0
ORQUE
QUE
E

12
12.
12.00 Cu
C uDD

TORQU
TORQU

ORQ
S TM
T MTD
M TD
D
ORQ

OR
15.0
15.0
5.0
N S
OR

10.0
10
10. 0
TM/ETD
TM /ETD
ETD
E TD
D

TETD or Tetraethylthiuram disulfide is a


80
8.
8.0 ZBE
ZB
ZBED
ED
ED 12.0
12.0
2.0

60
6.
6.0
S 90
9.
9.0

sulfur bearing ultra accelerator and sulfur S 60


6.0
40
4.0 Included with its product literature and upon the request of its customers, Akrochem provides product specifications and evaluations, suggested formulations and recommendations and
TM
T MT
TM
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2.0
2
2. 0
donor. It is used extensively in heat resistant N S 3.0
3
3. 0 other technical assistance, both orally and in writing (collectively the JTechnical InformationL). Although Akrochem believes all Technical Information to be true and correct, it makes no
S 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
compound design for sulfurless and low S N 0.00
00
0 the Technical Information. Akrochem will not be liable for any cost, loss or damage, in tort, contract or otherwise, arising from customerIs use of Akrochem products or Technical
0.00
00
0 Information.
2.00 3.00 4.00 5.00
1.00 2.00 3.00 4.00 5.00 sulfur cures. It also activates the thiazoles S S
1.00
It is the customers sole responsibility to test the products and any Technical Information provided to determine whether they are suitable for the customers needs. Before working with any
Figure 1b: N N Figure 2b:
TIME and sulfenamides. S TIME product, the customer must read and become familiar with available information concerning its hazards, proper use, storage and handling, including all health, safety and hygiene
Cure Rate of Dithiocarbamates Cure Rate of Thiurams precautions recommended by the manufacturer.

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,
S method or process. No license is implied or granted by Akrochem as to any such product, method or process. The names/brand names appearing throughout this literature are believed to
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A ROCHEM CORPORATION DISCLAIMS AN, AND ALL WARRANTIES, EXPRESS AND IMPLIED, INCLUDING WITHOUT LIMITATION, WARRANTIES OR MERCHANTABILIT, AND FITNESS
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