Advanced Rubber Compounding

7- Vulcanization (Sulfur & Non-Sulfur)

Instructor:
Kylie Knipp & Nicki Hershberger
Akron Rubber Development Laboratory

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 Vulcanization
Sulfur Based Cure
Systems

2
Contents
• Vulcanization
• Sulfur based cures
• Sulfur
• Sulfur donors
• Accelerators
• Accelerators types
• Activators
• Pre-vulcanization inhibitors
• Retarders
• Vulcanization effects on rubber
• Vulcanization tests

3
 Vulcanization

• ASTM defines vulcanization as an irreversible process during which a

rubber compound through a change in its chemical structure (for
example, cross-linking), becomes less plastic and more resistant to
swelling by organic liquids while elastic properties are conferred,
improved, or extended over a greater range of temperature.
• In the rubber industry the vulcanization bridge or crosslink is
generally some type of sulfur crosslink.
• Sulfur vulcanization is a slow inefficient process and accelerators and
activators are added to speed up the vulcanization process.
• The vulcanization system may include sulfur, sulfur donors,
accelerators, activators, scorch inhibitors or non-sulfur curatives.

4
 Vulcanization

• The curing system plays a major role in determining the

physical properties of a compound.

• Tensile strength, hardness, abrasion resistance, and

similar properties are primarily governed by the nature
and proportions of fillers, plasticizers and polymers.

• The curing system has a significant effect on the aging

properties of the compound.

5
 Sulfur Based Cure
Systems
Polymers typically cured with sulfur based cures systems are:
EPDM, BR, SBR, NR, IR, IIR, BIIR, CIIR, NBR, HNBR

6
 Components of a Sulfur Based Cure
• Sulfur based cure systems are based on either sulfur or
sulfur containing accelerators or sulfur donors reacting
with the double bonds or unsaturation in polymer
backbone.

• The components of a sulfur based cure system are:

• Sulfur or a sulfur donor
• Primary and/or secondary accelerators
• Activators such as zinc oxide and stearic acid
• Optional pre-vulcanization inhibitor or retarder

7
 Sulfur

• Sulfur used in the rubber industry comes in

two different forms:
• Rhombic or crystalline sulfur
• Amorphous non-crystalline sulfur

8
 Rhombic Crystalline Sulfur
• Sulfur naturally occurs as S8 rings in a crystalline structure.
• It is often referred to as rubbermaker’s sulfur or rhombic sulfur.
• It is also referred to as soluble sulfur which means it is soluble in
carbon disulfide or toluene.
• It has good solubility in rubber at elevated temperatures such as
processing temperatures but has limited solubility in rubber at
ambient temperatures.
• So the term soluble sulfur – soluble in carbon disulfide or toluene
but limited solubility in rubber – confusing?
• Sulfur bloom is quite often seem in rubber left to cool and this
bloom can interfere with compound tack and adhesion.
• It is an economical form of sulfur.

9
 Amorphous Non-crystalline Sulfur
• Amorphous, non-crystalline sulfur is often referred to as
Crystex after the trade name from the supplier Eastman
Chemical.
• It is also called insoluble sulfur because it is not soluble
in carbon disulfide or toluene.
• The ASTM procedure for determining the amount of
insoluble sulfur is D4578.
• Amorphous sulfur is very soluble in rubber and does not
bloom like rhombic, crystalline sulfur.
• Amorphous, non-crystalline sulfur is used in compounds
where sulfur bloom cannot be tolerated.

10
 Conversion of Amorphous Sulfur
• Amorphous non-crystalline sulfur (Crystex) will convert
to rhombic crystalline sulfur after 10-20 minutes at
230°F (110°C).
• Amorphous sulfur will convert slowly to rhombic sulfur
at temperatures as low as 104°F (40°C).
• At storage temperatures of 86°F (30°C) insoluble sulfur
will revert to rhombic sulfur at a rate of 1% or less per
month so inventories of insoluble should be first in first
out.
• Alkaline or basic materials such as amines will rapidly
convert amorphous to rhombic sulfur in a matter of
days especially in the presence of moisture.

11
 Amorphous Sulfur & Other Chemicals

• Basic materials that should not be pre-

blended with amorphous sulfur include:
• Calcium silicate
• Calcium oxide
• Clay or talc
• All of the items listed on the next slide

12
 Amorphous Sulfur & Other Chemicals
• Materials that should not be pre-blended or even
stored next to amorphous sulfur in a warehouse:
• Amine antidegradants such as p-phenylene diamines,
diamines, etc.
• Amine crosslink agents such as HMT, HMMM
• Guanidine basic accelerators such as DPG, DOTG
• Sulfenamide accelerators such as TBBS, DCBS, CBS
• Sulfur donor DTDM
• It is easier to just store amorphous sulfur in a
separate warehouse area than remember what it
cannot be stored next to.

13
 Amorphous Sulfur Mixing
• There are two major problems in mixing amorphous sulfur
into a rubber compound:
1) Amorphous sulfur is much more difficult to disperse into rubber than
standard rhombic sulfur.
2) The mixing temperatures of a compound with amorphous sulfur must
be kept low so as to not convert it to rhombic sulfur. Below is a chart
showing the maximum mix temperature that can be used with
amorphous sulfur in combination with the following accelerators:
o TMTD 94°C (201°F)
o CBS/DPG 99°C (210°F)
o TBBS/MBTS 108°C (226°F)
o DCBS/TMTM 110°C (230°F)
• Eastman, the manufacturer of Crystex amorphous sulfur
recommends low mix temperatures, slow mix speeds which
means a longer mix time.
Reference: Precautions Needed to Compound Insoluble Sulfur by Byron To and Arie De Hoog of
Flexsys, Rubber and Plastics News Technical Notebook, September 23, 2002

14
Sulfur Donors

15
 Sulfur Donors
• These materials are used to replace part or all of
the elemental sulfur normally used in order to
produce vulcanized products containing fewer
sulfur atoms per crosslink.
• Sulfur donors tend to produce mono-sulfidic
crosslinks that improve thermal and oxidative
aging resistance of the compound.
• Used as partial replacements for sulfur in semi-EV
cure systems or as total replacement for sulfur in
EV cure systems.

16
 Common Sulfur Donors
DPTT
Dipentamethylenethiuram tetrasulfide S S
|| ||
Medium scorch safety, N - C - (S) - C - N
Medium to fast cure rate 4
High cross link density

CH2 - CH 2 CH2 - CH 2
DTDM Morphorline disulfide O N - S - S -N O
Slow cure rate, excellent scorch safety CH2 - CH 2 CH2 - CH 2

TETD Tetraethyl thiuram disulfide C2H 5 S S C2H 5

|| ||
Scorchy, fast cure rate, N-C-S-S-C-N
High cross link density C2H 5 C2H 5

TMTD Tetramethyl thiuram disulfide S S

CH3 || || CH3
Scorchy, fast cure rate, N-C-S-S-C-N
High cross link density CH3 CH3

17
 Common Sulfur Donors
TBzTD Tetrabenzyl thiuram disulfide S S
Medium scorch safety & cure rate || ||
High cross link densities N-C-S-S-C-N
Non-regulated nitrosamine generating
OH OH

Alkylphenol disulfide polymer H S-S H

Scorchy, medium cure rate
Provides some antioxidant protection
Aids in processing
Non-nitrosamine R R
n
O O
DTDC Dithiocaprolactum CH - CH -C C-CH2 - CH
Good scorch safety, slow cure rate 2 2 2
H2C N - S - S -N CH2
Non-nitrosamine CH2 - CH 2 CH2 - CH 2

18
Accelerators
Chemical Mechanism
& Types of Accelerators

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 Accelerators Selection
• Accelerators are usually sulfur containing chemicals or are very
basic chemicals that are used to speed up the sulfur cure system.
Some of the factors to consider in choosing accelerators are:
• Time delay before vulcanization begins or scorch safety
• Speed of the vulcanization reaction after it is initiated or cure rate
• Extent of the vulcanization (tensile, modulus, hardness, etc.)
• Type of cross linking that occurs (mono-, di- or poly-sulfidic)
• Other factors such as tack, fiber or steel adhesion
• Environmental or regulatory concerns such as nitrosamine generation
• Economic considerations

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Sulfur & Accelerator
Cure Mechanism
Credit:
Merton Studebaker
Phillips Chemical
Slides 22 - 31

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 Sulfur Cure Mechanism
• Polymers and their vulcanizing ingredients are a dynamic system.
• The sulfur-sulfur (S-S) bond has the ability to form chains as in poly-sulfidic
crosslinks: R-S-S-S-S-R.
• The S-S bond is highly polarizable.
• The approach of a negative ion (anion) causes a migration of electrons away from
the negative charge of the incoming ion causing the bond to become positively
polarized and weaker so that it is more readily broken.
• In the poly-sulfidic crosslink the weakest bonds (the most readily polarized) are
the two S-S bonds.
• The longer the chain of sulfur atoms, the less stable the S-S bonds and the more
readily sulfur is liberated by heat or ionic attack.
• If these bonds are broken thermally, radicals are formed such as the following:
• R-S-S-S
• R-S-S
• R-S

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 Sulfur Cure Mechanism
• The R-S-S-S and R-S-S radicals are the most unstable
and tend to liberate reactive sulfur atoms, S, and di-
radicals S-S, etc.
• These are potent dehydrogenating agents.
• They react quite readily with the readily available
hydrogen atoms on the polymer chains.
• This attack is predominately on a hydrogen atom that is
in the α-position relative to the double bonds of the
polymer.
• The result is a dehydrogenated hydrocarbon chain as
shown on the next slide:

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 Cure Mechanism – Sulfur Only
Cure Mechanism - Sulfur Only

.
CH - CH = CH + R-Sx .
sulfur
CH - CH = CH
|
dehydrogenated
hydrocarbon chain radical R
|
Sx
|
CH - CH = CH
crosslinked
polymer

24
 Anions Attack of the S-S Bond
• The mercaptobenzothiazole and dithiocarbamyl anions are very
similar in structure.
• These two anions readily attack the S-S bond in S8 - sulfur rings.
• The S8 - sulfur ring has thermal stability but it is readily attacked
by the anions that rupture the ring and form a host of reactive
species such as below:

S
C-S
_
+ ..
Sx
S
N
C - S - Sx
_
,
N

S
_
C - S - S x-1 , etc.

S S S
CH3
CH3
||
N-C -S
_
+ ..
Sx
CH3
CH3
||
N - C - S - Sx
_
, CH3
CH3
|| _
N - C - S - S x-1 ,
etc.

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 Polysulfide Anions
• These accelerator terminated polysulfide anions are
very reactive and thermally unstable and readily give
up sulfur in reactive form or add to the double bonds
in unsaturated polymers forming unsymmetrical
polysulfides as shown below:
CH2 - CH - CH - CH2 CH2 - CH - CH - CH2
| |
S S
| |
Sx Sx
| |
S S
| |
C C=S
N S |
N
CH CH3
3
26
The accelerator anions then attack the S - S bonds in the unsymmetrical
polysulfides, stripping sulfur from them. The zinc ions from the zinc oxide cause
further reaction forming symmetrical, elastic polysulfides as shown below:
unsymmetrical anions unsymmetrical anions
CH2 - CH - CH - CH2 and/or CH2 - CH - CH - CH2
| |
S S
| |
Sx Sx
| |
S S
| |
C C=S
N S |
N
CH CH3
3
+ accelerator anions
accelerator anions S
N _ CH3 || _
and/or N - C - S - Sx
C - S - Sx CH3
S

Zn++

crosslinked polymer
CH2 - CH - CH2 - CH2
| + ZnS
Sx
|
CH2 - CH - CH2 - CH2

27
 Accelerator Summary
• This combined attack converts the unsymmetrical,
dangling polysulfide to symmetrical, elastically
crosslinked polymer.
• It also reduces the quantity of sulfur in the sulfur
crosslink which gives a more stable crosslink.
• In summary an accelerator does the following:
• Increases the sulfur cross linking reaction
• Reduces the number of sulfur atoms in the crosslink
• Decreases the cure time

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29
Accelerator Types
Amines & Aldehyde Amines
Dithiocarbamates
Dithiophosphates
Guanidines
Sulfenamides & Sulfenimides
Thiazoles
Thioureas
Thiurams
Xanthantes

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 Amines & Aldehyde-Amines
• Aldehyde-amines and amines are classified as primary
accelerators but can also be used as activators.
• They are generally scorchy and have slow cure rates.
• Amine accelerators and antidegradants help to make the zinc
oxide more soluble and require very little fatty acids.
• Amines are basic in chemical nature and can act as powerful
activators.
• When a thiazole and an amine are used with a fatty acid the
onset of vulcanization is delayed but total curing time is not
affected.
EXAMPLE:

- CH = CH - CH = N - (CH2 ) 6 - N = CH - CH = CH -

N, N'-dicinnamylidene-1,6-hexanediamine

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 Aldehyde Amines
• Acetaldehyde-butyraldehyde-aniline reaction product
• Butyraldehyde-aniline reaction product
• Aldehyde-amine reaction products
• Butyladehyde-butylamine reaction product
• N,N’-dicinnamylidene-1,6-hexanediamine
• Ethyl chloride-formaldehyde-reaction product
• Alph-ethyl, beta-propyacrolein-aniline reaction product
• Heptaldehyde-aniline reaction product

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 Amines
• Butylamine
• Cumene diamine with
m-phenylenediamine
• Cyclohexylamine
• Hexamehtylenetetramine (HMT)
• Isopropylamine
• Dibenzylamines

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 Dithiocarbamates
• The dithiocarbamates are alkyl/aryl derivatives of
dithiocarbamate acid.
• The metallic salt can be from zinc, copper, sodium,
lead, nickel or selenium.
EXAMPLE:
S

( )
CH 3 ||
N-C -S Zn
CH 3
2
ZDMC
zinc dimethyldithiocabamate

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 Dithiocarbamates
• Bismuth dimethyldithiocarbamate (BDMC) • Selenium diethyldithiocarbamate (SeEDC)
• Cadmium diethyldithiocarbamate • Potassium di-methyldithiocarbamate
• Copper dibutyldithiocarbamate (CDBC) • Selenium dimethyldithiocarbamate (SeDMC)
• Copper dimethyldithiocarbamate (CDMC) • Sodium cyclohexylethyldithiocarbamate
• Cyclohexylethylammonium & cyclohexyl • Sodium dibenzyldithiocarbamate (SBEC)
ethyldithiocarbamate • Sodium dibutyldithiocarbamate (SDBC)
• Dimethylcyclohexylammonium • Sodium diethyldithiocarbamate (SDEC)
dibutyldithiocarbamate
• Sodium dimethyldithiocarbamate (SDMC)
• Dimethylammonium dimethyldithiocarbamate
• Tellurium diethyldithiocarbamate (TDEC)
• Lead diamyldithiocarbamate
• Zinc diamyldithiocarbamate
• Lead dimethyldithiocarbamate (PDMC)
• Zinc dibenzyldithiocarbamate (ZBEC)
• Nickel di-isobutyl dithiocarbamate
• Zinc dibutyldithiocarbamate (ZDBC)
• Nickel dibutyldithiocarbamate (NDBC)
• Zinc diisobutyldithiocarbamate
• Nickel dimethyldithiocarbamate (NDMC)
• Zinc diethyldithiocarbamate (ZDEC)
• N-oxydiethylenethiocarbamoyl-N’-
oxydiethylenesulfenamide • Zinc dimethyldithiocarbamate (ZDMC)
• Piperidinium pentamethylene dithiocarbamate

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 Dithiocarbamates Cure Properties
• Used as primary or secondary accelerators.
• Generally scorchy with fast cure rates.
• Produce predominately mono-sulfidic crosslinks.
• Produce high crosslink densities.
• Zinc dithiocarbamates do not require as much zinc oxide and
stearic acid as activators.
• Higher molecular weight dithiocarbamates have better scorch
safety and slower cure rates.
• The type of metal salt effects cure rate shown below (from fast to
slow):
• Bismuth > tellurium > copper > zinc = nickel
• BDMC >TDEC > CDMC > CDBC > ZDMC > ZDEC > ZDBC = NDBC
>ZDBC > ZEPC > ZBEC (from fast to slow)

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 Dithiocarbamate Synergisms
• Dithiocarbamates are synergistic with thiazoles and are
often used as secondary accelerators to boost the
performance of thiazoles.
• Thioureas activate dithiocarbamates, especially ETU and
DPTU.
• Thiurams at 0.05 - 0.1 phr level, can be used with
dithiocarbamates to slow down the cute rate and improve
scorch safety.
• MBTS can also be used as a retarder with dithiocarbamates.

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 Dithiocarbamate Applications
• Dithiocarbamates are often used as secondary accelerators for thiazoles and
thiurams in curing slow curing polymers such as EPDM.
• One of the largest EPDM markets is weather stripping for vehicles.
• Dithiocarbamates are often used as fast curing systems for latex.
• Because of their fast cure rate, dithiocarbamates are often used in injection
molded goods.
• Dithiocarbamate promote predominately monosulfidic crosslinks densities that
are good for heat aging resistance and low compression set.
• Dithiocarbamates also have some antidegradant properties in rubber. The most
often used dithiocarbamate antidegradant is NDBC.
• Some zinc salts of dithiocarbamates, especially ZDBC are used as high
temperature processing stabilizers, antioxidants and light stabilizers in plastics
applications.
• Sodium dithiocarbamates are used for the treatment of waste water containing
heavy metals.
• Dithiocarbamates are also used as additives for lubricants, hydraulic fluids and
fuels. They provide resistance to wear, friction and oxidation.
• Dithiocarbamates have also been used as pesticides.

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 Dithiophosphates
• Used as primary or secondary accelerators.
• Generally scorchy with fast cure rates.
• Produce predominately mono-sulfidic crosslinks.
• They reduce compression set.

Example:
ZBPD Zinc-O-,O-di-N-butylphosphorodithioate

C4H9 – O S S O – C4H9
P P
C4H9 – O S-Zn-S O – C4H9

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 Dithiophosphates

• Copper diisopropyl dithiophosphate

• Dialkyl dithiphosphate polysulfide
• Zinc-amine-dithiophosphate (ZADT)
• Zinc dialkyl dithiophosphate (ZDT)
• Zinc-O,O-di-N-butylphosphorodithioate (ZBPD)

40
Dithiophosphate Synergisms & Applications
• Dithiophosphates are synergistic with thiazoles and sulfenamides.
• PVI can be used to increase the scorch safety.
• Used in non-nitrosamine cure systems.
• They are good for OTR tires, tubes, dock fenders, rollers and thick articles
that receive long cures.
• Gives improved aging properties to vulcanizates.
• Used in natural rubber for improving reversion and aging resistance.
• Non-blooming accelerator for EPDM cures. More soluble in EPDM than
thiurams or dithiocarbamates.
• Can also be used in other synthetic polymer systems.

41
 Guanidines
• Used as secondary accelerators.
• Generally scorchy with a medium cure rate.
• Produce predominately poly-sulfidic crosslinks.
• Have slow development of total crosslink density.
• Fatty acids have a retarding effect on guanidines.
• DPG has less scorch safety than DOTG.
• Need slightly more DPG than DOTG to get the same state of cure.
Example: DOTG Diorthotoyl Guanidine

CH 3 NH CH 3
| || |
- NH - C - NH -

42
Guanidines Synergisms & Applications
• Guanidines are very basic and work well with mineral filled
(silica, clay, calcium carbonate) compounds.
• Non-nitrosamine secondary accelerator used with thiazoles
and sulfenamides.
• Slow primary accelerator for NR but too slow for most
synthetic polymers.
• Excellent accelerators for curing thick rubber articles.
• Excellent compounds that need high tear & flex crack
resistance.
• Can be used in combination with diamines in curing ACM and
AEM polymers.

43
 Sulfenamides
• Sulfenamides are s-amine substituted derivatives of 2-
mercaptobenzothiazole.
• Used as primary accelerators.
• Unique accelerators that give long scorch delay with fast cure rates.
Referred to as delayed-action accelerators.
• Produce a balance between poly-, di- and mono-sulfidic crosslinks.
• Sulfenamides have a short shelf-life and chemically degrade into
MBTS and amines resulting in poorer scorch safety.
• The more basic the amine contained within the sulfenamide the
faster the cure rate and shorter the scorch safety.

44
 Sulfenamides (continued)
• Higher molecular weights generally are slower.
• Stearically hindered amines give longer scorch delays and slower
cure rates.
• Rate of Cure: CBS > TBBS > OTOS > MOR

Example: CBS N-cyclohexyl-2-benzothiazylsulfenamide

N
C - S - NH -
S

45
 Sulfenamides
• N-t-butyl-2-benzothiazole sulfenamide (TBBS)
• N-cyclohexyl-2-benzothiazole sulfenamide (CBS)
• N,N-dicyclohexyl-2-benzothiazole sulfenamide (DCBS)
• N,N-diisopropyl-w-benzothiazole sulfenamide
• N,N-diethyl-2-benzothiazole sulfenamide
• 2-(4-morpholinothio)-benzothiazole (MBS)
• N-isopropyl-2-benzothiazyl-sulfenamide (NIBS)

46
 Sulfenaminde
Synergisms & Applications
• Synergistic with dithiocarbamates, dithiophosphates,
guanidines and thiurams.
• Sulfenamides are used widely in the rubber industry in
tires, mechanical goods, injection molded goods, belts,
hoses, seals and many other rubber applications.
• Vulcanizates cured with sulfenamides have a good
balance between good tear/flex crack resistance and
good aging resistance.

47
 Sulfenimides
• The sulfenimides are compounds containing two divalent thiol moieties attached
to an amine nitrogen and are derived from primary amines.
• Sulfenimides based on pyridine offer the best overall balance between scorch
delay, extent of cure, cure rate and reversion resistance.
• They offer longer scorch delay with faster cure rates.
• The sulfenimides are considered primary accelerators and give a good balance
between mono-, di- and poly-sulfidic crosslinks.
EXAMPLE:

N
C -S CH3
S |
N - C - CH3
N |
C -S CH3
S
TBSI
N-t-butyl-2-benzothiazole sulfenimide
48
 Thiazoles
• Used as primary or secondary accelerators.
• Some scorch delay with fast cure rates.
• Faster curing and less scorch safety than sulfenamides.
• Produce a balance between poly-, di- and mono-sulfidic
crosslinks.
• Very activated by other basic accelerators such as HMT and basic
compounding ingredients.
• Scorch safety and cure rate depends on the following factors:
• Higher molecular weights generally are slower.
• The more basic the amine contained within the thiazole the
faster the cure rate and shorter the scorch safety.
• Stearically hindered amines give longer scorch delays and
slower cure rates.
• Rate of Cure: MBT > ZMBT = CMBT > MBTS

49
 Thiazoles
Example, Synergisms, Applications
• Synergistic with dithiocarbamates, dithiophosphates, guanidines
and thiurams.
• Vulcanizates cured with thiazoles have a good balance between
good tear/flex crack resistance and good aging resistance.
• Very good in NBR, EPDM and butyl based compounds.
• Thiazoles are used widely in the rubber industry in tires,
mechanical goods, injection molded goods, belts, hoses, seals
and many other rubber applications.
Example: MBTS 2-Mercaptobenzothiazole disulfide
N N
C-S-S-C
S S
50
 Thiazoles

• Benzothiazole disulfide (MBTS)

• Copper 2-mercaptobenzothiazole (CMBT)
• 2-mercaptobenzothiazole (MBT)
• 4-morpholinyl-2-benzothiazole disulfide
• Zinc 2-mercaptobenzothiazole (ZMBT)

51
 Thioureas
• Used as primary accelerators with polychloroprene and
secondary accelerators with NR, EPDM and SBR.
• Ultra fast cure rate.
• Gives primarily poly-sulfidic crosslinks.
• Cure rate (fast to slow): ETU > DETU > DBTU > DPTU.
• Non-nitrosamine.

Example: DBTU Dibutylthiourea

S
||
H 9 C 4- NH - C - NH - C H4 9

52
 Thiourea Applications
• Used primarily to cure polychloroprene rubber but also
used as a secondary accelerator with dithiocarbamates .
• Vulcanizates cured with thioureas have good tear
resistance and flex crack resistance.
• Applications include shoe soles, wire, cable jackets, hose
tubes, belts and sponge compounds.
• The alkyl-thioureas such as DETU and DBTU are also
used as corrosion inhibitors.

53
 Thioureas
• Dibutylthiourea (DBTU)
• N,N’-diphenylthiourea (DPTU)
• Diethylthiourea (DETU)
• Ethylenethiourea (ETU)
• 3-methyl-thiazolidine-thion-2
• Trimethylthiourea

54
 Thiurams
• Used as a secondary accelerator with dithiocarbamates, sulfenamides or thiazoles.
• Thiurams with two or more bridged sulfurs functions as sulfur donors.
• They give a high crosslink density.
• The thiurams are very activated by basic materials.
• Fast cure rate with high crosslink densities.
• Thiurams have a tendency to bloom.
• Higher molecular weight thiurams have slower cure rates and shorter scorch
safety, rate of cure (fast to slow):
• TMTD > TETD > DPTT > TMTM

TMTD Tetramethylthiuram Disulfide

S S
CH3 || || CH3
N-C-S-S-C-N
CH3 CH3

55
 Thiuram Synergisms & Applications
• Very synergistic with thiazoles and sulfenamides, used as a secondary
accelerator to boost the performance of these accelerators.
• Used as a secondary accelerator with dithiocarbamates to delay scorch.
• MBTS, a thiazole, is very good at delaying the scorch of thiurams.
• Thiuram cured vulcanizates have high crosslink densities and primarily
mono-sulfidic crosslinks which results in products with high heat
resistance, good aging properties and low compression set.
• Thiurams with more than one sulfur in the center bridge can partially or
totally replace sulfur in semi-EV and EV cure systems.
• Used to cure polymers with low unsaturation such as EPDM.
• Applications include automotive parts such as hoses, belts, and weather
stripping.

56
 Thiurams
• N,N’-dimethyl-N,N’-diphenylthiuram disulfide (DDTS)
• Tetrabenzylthiuram disulfide (TBzTD)
• Dipentamethylenethiuram tetrasulfide (DPTT)
• Tetrabutylthiuram disulfide (TBTD)
• Tetraethylthiuram disulfide (TETD)
• Tetraisobutylthiuram disulfide (TIsoBTD)
• Tetramethylthiuram disulfide (TMTD)
• Tetramethylthiuram monosulfide (TMTM)

57
 Xanthates
• The xanthates are primary accelerators.
• They are very fast ultra accelerators that are used for room
temperature cures used in natural rubber and latex compounding.
• They also have limited use as secondary accelerators in non-
nitrosamine cure systems.

EXAMPLE:
S S
|| ||
C4H 9 - O - C - S - S - C - O - C4H 9
CPB
dibutyl-xanthogen disulfide

58
 Xanthates

• Dibutyl xanthogen disulfide (BIX)

• Diisopropyl xanthogen
• Zinc isopropyl xanthate (ZIX)
• Zinc dibutyl xanthogen disulfide (ZBX)

59
Miscellaneous Accelerators
• surface activated urea
• tetrachloro-p-benzoquinone
• trallyl cyanurate
• zinc laurate
• carbon disulfide-methylene dipiperdine reaction
products
• anhydroformaldehyde-p-toluidine
• zinc chloride and benzothiazyl disulfide complex
• di-o-tolyguanidine salt of dicatechol borate
• dimethyl ammonium hydrogen isophthalate
• activated thiadiazine
• disulfide of 1,3,5 triazine
• activated disulfide
• complex oxadiazine thione
60
 Activators for
Sulfur Cure Systems

61
 Activators
• The performance of most organic accelerators are
enhanced by the addition of inorganic and organic
activators.
• Zinc oxide is the most common inorganic activator
but other metallic oxides such as magnesium oxide
and lead oxide can be used.
• The most frequent organic activators are fatty acids.
• Weak amines, polyalcohols and amino-alcohols also
can be used as organic activators.
• The inorganic and organic activators work together
to form complexes with the organic accelerators as
explained below.

62
 History
Effect of ZnO
of Additives oninCure
Rubber
Time of Rubber
(Credit: Hydro Technologies)

100 NR 100 NR
400 8 Sulfur 100 NR 3 Sulfur
Cure Time @ 140 C

8 Sulfur 5 Zinc Oxide

5 ZnO 1 Stearic Acid
300 1 Accelerator
110
200

100

0
Credit: Zinc Oxide Used in Rubber Compounding, presentation by Hydro Technologies (Canada) Inc., E.
Daniel Butkus/Dan Fornier

63
 Zinc Activators
• Zinc has the ability to form complexes with accelerators containing
oxygen, sulfur, and nitrogen.
• Molecular weight and structure of the fatty acid have a significant
effect on the activation properties of crosslinking agents.
• Chain length, branching and aromaticity of the carboxylic acid affect
activation properties.
• In most compounds the zinc ion is made available by the
neutralization reaction of stearic acid with zinc oxide. This reaction
takes place at about 120°C and occurs during the mixing and curing
of the compound to produce zinc stearate and water.
• The concentration of zinc stearate controls the yield, length, and
destruction of crosslinks.
• The addition of zinc oxide and stearic acid activators will increase the
rate of vulcanization and increase the number of crosslinks.

64
Three Main Types of Zinc Oxide
Manufacturing Processes

• American Process

• French Process

• Precipitation Process

65
 American Process ZnO
• The American process produces zinc oxide directly
from roasted zinc sulfide ore concentrate with a
single pass through a traveling grate.
• The ore concentrate is heated with carbon (coke)
forming zinc vapor which is burned in air to form
zinc oxide.
• It is an economical manufacturing process.
• It produces acicular and spherulite crystals.
• Contains more impurities than French Process ZnO.

66
 French Process ZnO
• French process zinc oxide is prepared by isolating Zn
metal from concentrate.
• The metal is then vaporized and burned in an electric
arc furnace at >1900ºC.
• The metal used can be scrap zinc primary, zinc metal
or purified zinc metal.
• It produces particles that are mostly acicular.
• It produces finer particles sizes with higher surface
areas and greater uniformity.
• Higher purity than American Process zinc oxide.

67
 Precipitation Process ZnO
• The precipitation process is sometimes referred to as
the wet process.
• Zinc metal is converted to dust and is dissolved in acidic
water.
• The zinc solution is treated with caustic solution which
precipitates Zn(OH)2.
• The Zn(OH)2 converts to ZnO during the drying process.
• Precipitated ZnO has particle shape and uniformity
similar to the French Process ZnO but its particles are
more agglomerated.
• Smaller particles size can made, up to 50 m2/g.

68
 Zinc Oxide
• Finer particle size zinc oxides increase the viscosity of
compounds. Finer particle size zinc oxides prolong the
scorch time considerably without appreciably affecting
the rate of vulcanization. Finer particulate zinc oxides
are active even at low dosages, where they are more
effective than coarse zinc oxides.
• Lead contamination in zinc oxides may cause
discoloration of light-colored compounds.
• Zinc oxide is an activator for organic accelerators and a
filler for white colored compounds. Zinc oxide also
helps heat aging properties in natural rubber
compounds and is used in 5 phr or higher levels in OTR
and truck tire compounds for heat resistance.

69
 Improved Heat Resistance With
Zinc Oxide
• Zinc oxide improves heat aging resistance of rubber compounds,
especially under cyclic flexing because
• it acts as a heat sink due to its high thermal capacity
• it transfers heat from a rubber compound because of its high
thermal conductivity
• Zinc oxide has two times the heat capacity and thermal conductivity
of carbon black
• Zinc oxide has almost two times the heat capacity of rubber and five
times the thermal conductivity of rubber
• Loadings of at least 5 phr of ZnO are needed in the rubber
compound to improve the heat resistance.

70
 ZnO Protection Against
Ultraviolet Light
• Zinc oxide absorbs ultraviolet light
• It prevents ultraviolet light from penetrating into the rubber and
degrading/discoloring the rubber
• This is due to zinc oxide’s opaqueness
• The table below shows the UV % transmission @ 3600 A.U. through
a pigment layer of 0.0009 mm thickness

Pigment % Transmission
Zinc Oxide 0
Titanium Dioxide (anatase) 18
Calcium Carbonate 68
Asbestine 90

71
 Zinc Fatty Acids
• Some compounders use zinc salts of the fatty acids instead of
using fatty acids and zinc oxides but this results in higher cost.
• However, using zinc fatty acids can give some improvements in
the vulcanization reaction:
• Improved reversion resistance
• Reduced plasticity
• Improved dynamic properties
• Reduced carbon black incorporation time
• Lower accelerator amounts
• Increase in modulus
• Lower hysteresis
• The zinc salts of the fatty acids are decomposed by strong acids
or bases. Silica in the compound has an acidic enough surface
to interchange and forms a zinc silicate and zinc soap silicate on
the surface of the filler.

72
 Fatty Acids
• In rubber compounds stearic acid acts as an activator in sulfur based
cure systems.
• Stearic acid also can function as a process aid in rubber.
• Stearic acid is used in combination with zinc oxide in rubber
compounds. When the rubber compound reaches about 120°C it
forms zinc stearate by the zinc oxide reacting with the stearic acid.
The newly formed zinc stearate is actually the activator.
• Rubber grade stearic acid is a mixture of fatty acids some of which is
stearic.
• These fatty acids range from C8 to C18 in carbon length.
• The makeup of the fatty acid depends on its source.
• Fatty acids can be either tallow (animal fat based) or vegetable based.

73
 Fatty Acid Tests
• Acid Value (Neutralization Value): The number of milligrams of potassium hydroxide
required to neutralize one gram of sample. Higher acid number will slow down the cure
rate.
• Carbon Chain Composition: The carbon chain composition, based on weight percent,
usually determined by gas chromatography. Fatty acids with higher chain lengths give
slower cure rates.
• Iodine Value: A measure of the degree of unsaturation of a product, expressed as
centigrams of iodine absorbed per gram of sample. Higher iodine values give slower cure
rates.
• Saponification Value: Number of milligrams of potassium hydroxide necessary to convert
all saponifiable constituents into potassium soap. Measures the combined and free fatty
acids present, and allows for the calculation of average molecular weight. Roughly higher
saponification numbers mean higher molecular weights (longer carbon chains) and slower
cure rate.
• Titer: Solidification point of fatty acids or acids resulting from hydrolysis of the glyceride. It
is a function of the chain length and the degree of saturation of the component acids, and
is commonly expressed in degrees C. Higher titer values would result in a slower cure rate.
• Unsaponifiable Matter: Measurement of the non-fatty matter present in the product,
other than moisture and insolubles. Higher saponifiable number would mean less fatty
acids and perhaps a slower cure rate.

74
 Polymers and Stearic Acid
• Natural rubber contains some natural fatty acids so they
require less stearic acid added to the compound.
• Synthetic polymers produced by the emulsion process,
such as emulsion SBR have 5-7% residual fatty acids and
require less stearic acid added to the compound.
• Polymers produced by the solution process (solution
SBR, EPDM, polyisoprene, butyl) have no fatty acids in
them and require more stearic acid in the compound.

75
 Miscellaneous Activators
• Glycols: used to neutralize acid effect on cures from silica based fillers
• Triethanolamine: used to neutralize acid effect on cures from silica
based fillers
• Magnesium stearate: used in CR and butyl cures
• Surface treated urea: activator for thiazoles, thiurams and
dithiocarbamates
• Type W Neoprene (CR): activator for bladder curing resins
• Halobutyls: activator for bladder curing resins
• Stannous chloride: activator for bladder curing resins
• Calcium hydroxide
• Zinc sulfide and barium sulfate
• Amines such as HMT and zinc diamine diisocyanoate

76
 Pre-Vulcanization Inhibitors
• Prevulcanization inhibitors are compounds that increase the scorch
safety without altering the final state of cure.
• MBT is one of the reaction products produced during the breakdown
of organic accelerators and tends to further catalyze the breakdown
process.
• PVI or CTPI (N-cyclohexylthiophthalimide) acts by slowing the
formation of MBT thus increasing the scorch safety.
• PVI can lengthen scorch time in dithiophosphates cure systems.
O
||
C
N-S-
C
||
O
77
 Retarders
• Retarders are compounds that increase the scorch safety but also
alter the final state of cure. Retarders include the following:
• benzoic acid
• phthalic anhydride
• salicylic acid
• treated aromatic sulfonamide
• magnesium oxide
• stannous chloride
• N-diphenylnitrosoamine
• Diphenylnitrosoamine
• N-phenyl-N-phenyl-N-trichloromethylfulfenylbenzene
solfonamide

78
 Question #12:
What of the follow items have an effect on a
sulfur based cure system?
a) Sulfur or sulfur donor level
b) Accelerator type
c) Activators such as stearic acid and
zinc oxide
d) The pH (basic or acidic) of the
ingredient
e) All of the above.

79
Vulcanization Effects
on Rubber Properties

80
 Introduction
• Rubber vulcanizate properties are highly
dependent on the crosslink density and the
type of crosslinks (mono-, di-, poly-sulfidic).

• The crosslink density and type of the

vulcanizate can be varied by the type of
accelerator used and the sulfur/accelerator
ratio.

81
 Crosslink Density
• Crosslink density falls as cure temperature is increased and also the rate of
reversion increases with increasing temperature.
• This is more evident in NR compounds but is also seen with SBR/BR compounds.
• Cure times well beyond optimum crosslink density values plateau out,
particularly at temperatures in excess of 160°C.
• Therefore, cure temperature is more important than cure time in determining
the crosslink density achieved for compounds that are over cured.
• As the cure temperature increases, the tendency is toward more di- and mono-
sulfidic crosslinks versus polysulfidic crosslinks.
• In general when compounds are over cured at high temperature, it can be
concluded that:
a) Crosslink density is drastically reduced
b) Essentially monosulfidic crosslinks are obtained
c) There is a large increase in main chain modifications
• Of these factors, the most important in determining initial physical properties of
compounds is the crosslink density.

82
 Crosslink Density
• To maintain crosslink density at elevated cure temperatures, it is necessary
to increase curative levels or go with a more semi-EV or EV type cure system.
• Crosslink density (or degree of cross linking) will have a major influence on:
• modulus
• tensile
• hardness
• elongation at break
• tear resistance
• compression set
• tension set (creep)
• fatigue resistance
• swelling resistance.
• Crosslink density has only a minor effect on:
• abrasion resistance
• gas permeability
• glass transition temperature
• electrical conductivity
• chemical stability.

83
Reference: High Temperature Curing of Radial Passenger Tires by Lloyd
Walker and William Helt, III of Monsanto, Rubber Division ACS, October 1985 84
 Crosslink Density & Physical Properties
• Increasing crosslink density will increase fatigue resistance, tensile
strength and tear strength to a point then decreases these properties.
• Increasing crosslink density decreases hysteresis, permanent set and
creep.
• Increasing crosslink density will slightly decrease the permeability of
rubber.
• Increasing crosslink density increases both elastic and dynamic
modulus.
• The diagram on the next slide describes the relationship between
vulcanizate properties and crosslinks density.

Reference (slides 77-79): High Temperature Curing of Radial Passenger Tires by Lloyd Walker and William
Helt, III of Monsanto, Rubber Division ACS, October 1985

85
 Graph: Credit Monsanto (Flexsys)
V
u
l Elastic
c Modulus
Fatigue Resistance
a Tear Strength
Dynamic
n Modulus
Toughness
i Hardness
z
a
t Tensile Strength
e

P
r Creep
o Hysteresis
p Permanant Set
e Elongation
r Dry Friction Coefficient
t
y
Crosslink Density
Reference: High Temperature Curing of Radial Passenger Tires by Lloyd Walker and
William Helt, III of Monsanto, Rubber Division ACS, October 1985
86
 Crosslink Density Summary
• Best at Vulcanization Optimum
• Tensile
• Modulus
• Aging resistance
• Abrasion resistance
• Best When Crosslink Density is Slightly Excessive
• Rebound resilience
• Compression set
• Dynamic damping
• Hysteresis
• Low temperature flexibility
• Ozone resistance in SBR

Reference: High Temperature Curing of Radial Passenger

Tires by Lloyd Walker and William Helt, III of Monsanto,
Rubber Division ACS, October 1985
87
 Types of Cure Systems

• Conventional Cure System

• Semi-Efficient Cure System (Semi-EV)

• Efficient Cure System (EV)

88
 Conventional Cure System

• A conventional cure system is mostly sulfur

with only small amounts of accelerator.

• This type of cure system gives mostly poly-

sulfidic crosslinks (approximately 70%),
pendant groups and cyclic sulfide crosslinks.

89
 Semi-Efficient Cure System (Semi-EV)
• Semi-EV cure systems can be created by partially
replacing sulfur by a sulfur donor or by
increasing the accelerator/sulfur ratio.
• A semi-EV cure system produces mono-di- and
poly-sulfidic crosslinks and is a good
compromise for aging/reversion resistance
versus fatigue properties.
• A semi-EV cure system produces slightly higher
mono-di-sulfidic crosslinks than a conventional
cure system.

90
 Efficient Cure System (EV)
• EV cure system is created by total replacement of sulfur by a
sulfur donor or by the use of very high ratios of accelerator to
sulfur.
• Usually the amount of free sulfur used is less than 0.50 phr.
• Most EV cure systems use TMTD up to its solubility level (to
avoid bloom) and a non-blooming sulfur donor such as di-
morpholine disulfide to reach the total sulfur donor level
required.
• EV cure systems give almost exclusively mono- and di-sulfidic
crosslinks.
• EV systems give good aging and reversion resistance but have
poor fatigue properties.
• An EV system produces 90% plus mono-sulfidic crosslinks.

91
 Crosslink Type
• The type of crosslink that is generated by a vulcanization system
can have a great influence on the vulcanizate and its aging
properties.
• The types of crosslinks are greatly influenced by
• the relative amounts sulfur and accelerator used
• the type of accelerator used
• the cure time/temperature
• Crosslinks can be classified into the following groups:
• Polysulfidic
• Di-sulfidic
• Mono-sulfidic
• Carbon-carbon bonds

92
 SULFUR CROSSLINKS

mono- S di-
S
poly- Sx
S
polymer chains

S cyclic mono or di sulfides

S-S

ACC-Sy
pendant sulfide groups
terminated by accelerator

Type of Crosslink Bond Energy (kJ/mole)

poly-sulfidic: -C-Sx-C- (x>2) <268
di-sulfidic: -C-S2-C- 268
mono-sulfidic: -C-S-C- 285
carbon bonds: -C-C- 352

Credit: Crosslink Structure and Elastomer Properties by Bayer Mobay 93

 Mono- and Di-sulfidic Crosslinks
• Mono- and di-sulfidic crosslinks are relatively stable because of their
higher bond energies.
• Because of this stability they give good aging and reversion resistance
but have poor fatigue properties.
• Mono- and di-sulfidic crosslinks because of their stability do not
rearrange like poly-sulfidic crosslinks to relieve highly localized
stresses associated with a flaw.
• In general these types of crosslinks are the best for the following
rubber properties:
• Low permanent set
• Low compression set at elevated temperatures
• Low hysteresis
• Good heat stability
• Good resistance to reversion

94
 Poly-sulfidic, Pendant Groups
and Cyclic Sulfides
• These types of crosslinks are chemically and thermally unstable
and undergo further reactions as the vulcanizate ages.
• Because these crosslinks can rearrange, they can relieve local
stresses and provide good fatigue resistance.
• In general these types of crosslinks are best for the following
rubber properties:
• High tensile strength
• Rebound resilience (in natural rubber only)
• Abrasion resistance
• Fatigue crack resistance
• Mold tear resistance
• Tear resistance
• Cut/chip resistance
95
 Accelerator Effects on Crosslink Type
• As mentioned before, the type accelerators used in the cure
system has a great effect on the type of crosslinks generated.
• In general the following is true of accelerator classes and the type
of crosslinks they generate:
• Mono-di-sulfidic Balanced Mono-di-polysulfidic Poly-sulfidic
Dithiocarbamates Sulfenamides Guanidines
Thiurams Sulfenimides Thioureas
Sulfur donors Thiazoles Amine types
Low sulfur Moderate sulfur High sulfur

• Mono-di-sulfidic Balanced Mono-di-polysulfidic Poly-sulfidic

Heat Resistant Seal Tires Shoe Soles

96
 Summary of Crosslink Types
Di- or mono-sulfidic or Polysulfidic
carbon-carbon • High tensile strength
• Low permanent set • Rebound resilience
• Low compression (in natural rubber
set at elevated only)
temperatures • Abrasion resistance
• Low hysteresis • Fatigue crack
• Good heat stability resistance
• Good resistance to • Mold tear resistance
reversion • Tear resistance
• Cut/chip resistance

97
 Non-curative Effects on Vulcanization
(Polymer)
• Sulfur curing requires double bonds (unsaturation) in the
polymer.
• Polymers with a high degree of unsaturation such as BR and NR
cure faster than polymers such as SBR and NBR that have less
double bonds.
• Hence, polymers with less double bonds require more
accelerator and/or sulfur.
• For example low unsaturated EPDM takes about three times as
much TMTD accelerator as NR to give the same crosslink
density.
• Completely saturated polymers require peroxides, resin cures,
metallic oxide cures, amine cures, etc.

98
Non-curative Effects on Vulcanization
(Fillers)
• Silica
• Additional amounts of accelerators and activators may be
required with silicas due to silica's slightly acidic nature which
retards the cure.
• Silica also tends to absorb accelerators on its surface.
• Carbon Black
• Carbon blacks promote accelerators because they act as a
basic catalyst with a source of electrons which polarize sulfur-
sulfur bonds as in TMTD or in the sulfur rings.

99
 Non-curative Effects on Vulcanization
(Oils & Anti-degradants)
• Petroleum Oil
• Petroleum oils decrease the amount of crosslinks that are
formed. Oils, especially non-aromatic types such as paraffinic
and naphthenic compete with the polymer for the curing agents.
• Anti-degradants
• Paraphenylene diamine and amine type antidegradants promote
acceleration because they are basic.

100
Non-curative Effects on Vulcanization
(Other Ingredients)
• Basic Materials
• Any materials that are basic in nature will accelerate the cure.
• Acidic Materials
• Any materials that are acidic in nature will retard the cure.
• Process Aids
• Process Aids such as zinc salts of fatty acids tend to increase
the crosslink density because they act as activators much like
the combination of zinc oxide and stearic acid.

101
 Solubility Levels of
Accelerators in Various
Polymers

102
 Solubility Levels
From Dr. Joachim Graf’s Work at Rhein Chemie

Polymer TMTD TbzTD CBS TBBS MBT MBTS TBzTD ZBEC ZDBC DTDM DTDC
EPDM < 0.5 phr <0.5 phr < 2.0 phr < 2.0 phr < 1.0 phr < 1.0 phr <0.5 phr < 0.5 phr < 2.5 phr < 1.5 phr < 1.0 phr
Natural Rubber <0.5 phr <2.0 phr > 5.0 phr < 0.5 phr < 2.0 phr < 0.5 phr < 2.0 phr < 2.5 phr < 3.0 phr < 2.5 phr < 0.5 phr
SBR <0.5 phr < 0.5 phr < 1.0 phr < 0.5 phr < 1.5 phr < 0.5 phr < 0.5 phr < 0.5 phr < 2.5 phr >5.0 phr < 1.0 phr
NBR <3.0 phr > 5.0 phr > 5.0 phr > 5.0 phr < 1.0 phr < 1.0 phr < 5.5 phr < 3.5 phr > 5.0 phr > 5.0 phr < 0.5 phr

Methyl or diethyl Dibutyl

Insoluble Thiurams Thiurams
Polymer Sulfur Sulfur Dithiocarbamates Dithiocarbamates DPTT
EPDM < 1.5 phr < 0.5 phr <0.8 phr 1.0-1.2 phr No bloom
Natural Rubber < 3.0 phr < 0.5 phr
SBR < 3.0 phr < 0.5 phr
NBR < 1.0 phr < 2.0 phr

103
 Solubility Levels
From Rhein Chemie, Steven Monthey’s paper given at the
Akron Rubber Group, January 2004
EPDM NBR SBR NR
TMTD <0.5 <0.5 <0.5 <0.5
TBzTD <0.5 <2.0 <0.5 <0.5
DTDC <1.0 <0.5 <1.0 <0.5
CBS <2.0 <5.0 <1.0 <5.0
TBBS <2.0 <0.5 <0.5 <5.0
MBTS <1.0 <0.5 <0.5 <1.0
ZBEC <0.5 <2.5 <0.5 <3.5
ZDBC <2.5 <3.0 <2.5 <5.0
TP <6.0 <1.5 <6.0 <7.0 zinc dibutyldithiphosphate
ZABOP <6.0 <5.5 <6.0 <7.0
ZDT <6.0 <5.5 <6.0 <7.0 zinc dialkyldithiophosphate
ZAT <3.0 <7.7 <7.0 <7.1 zinc dithioate complex
ZADT <5.5 <5.5 <5.5 <5.5 zinc-O-O-di-N-butylphosphorodithioate
SDT <7.0 <6.5 <6.0 <5.5 phosphoryl polysulfide
Sulfur <1.5 <3.0 <3.0 <6.0

104
Substituting Accelerators

105
Suggestions on Replacing Accelerators
• First look at the type of crosslink (mono/di vs. polysulfidic) that the
accelerator you want to replace generates. Try replacing with an
accelerator that generates similar crosslink types. If you start this
way you have a better chance that your compound physical
properties are not changed much.
• Start substitution of one accelerator for another first based on equal
molar sulfur levels. This will help keep your state of cure similar and
again help match the control compound for physical properties. The
next slide gives an example.
• Rarely, is there a direct drop in replacement for accelerators, so
adjustments of other accelerators in the cure system or addition of
a scorch inhibitor or kicker may be needed.
• Keep in mind the general rule: higher molecular weight = lower
sulfur level and slower cure rate.

106
 Example Molar Sulfur Accelerator Replacement
Calculation: TBBS for CBS
CH3
CBS N
C - S - NH - TBBS
N |
C - S - NH - C - CH3
S S |
CH3

• Molecular weight 264 • Molecular weight 238

• Sulfur, 2 molecules x 32 MW • Sulfur, 2 molecules X 32 MW
of sulfur = 64 of sulfur = 64
• Molar sulfur 64/264 = 0.242 • Molar sulfur 64/238 = 0.269
• So if the compound has 2 phr of CBS I have 2 phr x 0.242 sulfur or 0.484
molar sulfur
• So TBBS at 0.269 molar substituted for CBS is 0.484 total sulfur/0.269
molar sulfur % of TBBS = 1.80.
• So you need only 1.80 phr TBBS to replace the 2 phr of CBS at an equal
molar sulfur level.

107
Vulcanization Tests
Rheometer
Mooney Viscometer

108
 Rheometer Vulcanization Curve
SCHEMATIC REPRESENTATION OF RUBBER VULCANIZATION

Scorch Undercure Optimum Cure

Marching Modulus
Torque Plateau (Preferred)
(Lb.-in.)

Reversion (Overcure)

Time (minutes)

109
 Rheometer Measurement Properties
• Rheometer Minimum Torque (ML): This is a measure of the viscosity of the stock
at the test temperature. The Rheometer minimum torque is proportional to
Mooney Viscosity when both tests are run at the same temperature.
• Rheometer Maximum Torque (MH): This maximum torque is a measure of shear
modulus or stiffness at the test temperature. It is also an effective measure of
changes in tensile modulus and crosslink density.
• Rheometer Induction Time (usually t2): At normal rheometer temperatures (i.e.
at or above curing temperature), the induction time is a measure of the time
available for mold flow. At lower temperatures, t2 is a processability measure
similar to Mooney Scorch. If both tests are run at the same temperature, a close
relationship exists between Rheometer t2 and Mooney t5.
• Rheometer Cure Time (usually t90): The time for torque to increase to 90% of its
maximum – frequently referred to as optimum cure time.
• Rheometer Cure Rate Index (100/(t90 - t2): The cure rate index is proportional
to the average slope of the cure rate curve in the steep regions. It is a measure
of the speed of the vulcanization reaction once it begins.

110
Mooney Viscosity/Scorch Curve

Credit: ASTM
111
 References
• A New Nitrosamine-Free Accelerator; Mixland+ TBP 75 GA by Pierre Lugez, MLPC, presented at ACS
Rubber Division Meeting, Cleveland, OH, October 2007
• Accelerator Systems for the Vulcanization of Chlorobutyl Elastomer -- Cruz, Sharma, Rodgers of
ExxonMobil Chemical Co., presented at the ACS Rubber Division Meeting, Cleveland, OH, October
2011
• Avoiding Potentially Hazardous Emissions in Rubber Compounding and Processing by Steven
Monthey, Dr Martin Saewe, Scott Zemanek of Rhein Chemie, presented at ACS Rubber Division
Meeting, Pittsburgh, PA, October 2009
• High Performance 'Safe' Nitrosamine Cure Systems for Elastomers -- Virdi, Chakroborty, Bowen of
Robinson Brothers Limited, presented at the ACS Rubber Division Meeting, Orlando, FL, October
1993
• Nitrosamines, from problem to challenge -- Verhelst, Seeberger, Endstra of Akzo Chemicals,
presented at ACS Rubber Division Meeting, Orlando, FL, October 1993
• Some forgotten Accelerators, The Thiophosphates-helpful in the Design of nitrosamine-free
Accelerator Systems -- Graf, Johansson of Rhein Chemie, presented at ACS Rubber Division,
Orlando, FLE October 1993
• Nitrosamines A New Generation of cure Systems to Eliminate Carcinogenic N-Nitrosamines by
[Link], [Link], Thomas J. Leo of Rhein Chemie, presented at the ACS Rubber Division Meeting,
Nashville, TN

112
 References
• Nitrosamines in Tires Why They Form and Who Cares by Dwight W. Chasar of BFGoodrich, presented
at ITEC, September 1994
• Nitrosamines The Hidden Enemy by Anders Johansson of Rhein Chemie, Technical bulletin
• Seminar on Nitrosamines by Robert Ohm of Uniroyal Chemical
• Practical Strategies to Avoid Hazardous N-nitrosamines in the Vulcanization of Elastomers by [Link]
of Rhein Chemie presented at the DKG (German Rubber Society) conference, Wurzburg, Germany,
October 1992
• Review and the Latest Update of N-Nitrosamines in the Rubber Industry; the Regulated, the
Potentially Regulated, and Compounding to Eliminate Nitrosamine Formation by [Link] Jr.,
[Link], [Link] of Rhein Chemie, presented at ACS Rubber Division Meeting, Pittsburgh, PA,
2005
• Realistic Strategies to Prevent Carcinogenic N-Nitrosamines in Rubber by [Link], [Link] of
Rhein Chemie presented at ACS Rubber Division Meeting, October 1993
• Modern Rubber Additives to Avoid Hazardous Substances by Harald Kleinknecht of Rhein Chemie
presented at Automotive Days Poland, October 2011
• Robac Chemicals Nitrosamine Solutions, technical bulletin
• Thiophosphates Helpful in the Design of Nitrosamine-free Accelerator Systems by [Link] and
[Link] of Rhein Chemie published in Rubber World, August 1995

113
 References
• Using Dithiophosphates to Develop Synergistic Accelerator Packages That Achieve Total
Performance Solutions for Non-nitrosamine Formulations by Steven Monthey of Rhein Chemie
• Vulcanization, Vulcanizate Structure and Properties – An Overview by [Link], presented at
ACS Rubber Division Meeting, Toronto, Ontario, May 1983
• The Vulcanization of Rubber by Bob Ohm and Russ Mazzeo presented at Rhode Island Rubber &
Plastics Group, Providence, RI, April 2001
• Review of Vulcanization Chemistry by Fred Ignatz-Hoover, Flexsys published in Rubber World,
August 1999
• Vulcanization by Merton Studebaker of Phillips Petroleum Co. and [Link] of [Link]
presented at ACS Rubber Division Meeting, Boston, MA, April 1972
• Vulcanization and Vulcanizing Agents by Werner Hofmann, published by Palmerton Publishing
Co., Inc.
• Rubber Curing and Properties by Jean-Maurice Vergnaud, Iosif-Daniel Rosca, published by CRC
Press
• Vulcanization of Elastomers by Michael Fath of Elastomer Technology, Inc. published in Rubber
World, October 1993
• Zinc Dithiphosphates Application in Sulfur Cure Polymers by Jon Nienaber of Rhein Chemie,
presented at ACS Rubber Division Meeting, Cincinnati, OH October 2012

114
 References
• Vulkalent E, An Examination of its Usefulness as Retarder and Accelerator of Sulfur Vulcanization
by [Link] of Bayer, presented at ACS Rubber Division Meeting, Cleveland, OH, October 1997
• Discussion and the Resistance to Reversion of Natural Rubber with the Help of Thiphosphate Cure
Systems by H.J. Graf, [Link], Rhein Chemie, presented at ACS Rubber Division, Montreal,
May 1996
• Tetrabenzylthiuram Disulfide-A Secondary Accelerator for Stable Crosslink Systems in Tire
Applications -- Ferrandino, Sanders, Hong of Uniroyal Chemical Co., presented at ACS Rubber
Division Meeting, Philadelphia, PA, May 1995
• Formulation Suggestion for Replacing DOTG in AEM Compounds by Edward McBride, Klaus
Kammerer, Laurent Lefebvre of DuPont, presented at ACS Rubber Division Meeting, Milwaukee,
WI, October 2010.
• Compounding Parameters to Control the Iridescent Bloom in EPDM Body Sealing Applications by
Eric Jourdain, Exxon Chemical Co., presented at ACS Rubber Division Meeting, Montreal, May
1996
• An Effective DOTG Replacement Accelerator for Both High Performance and General Elastomer by
Jennifer Forgue of [Link] Co., presented at ACS Rubber Division Meeting, Cleveland, OH,
October 2011
• Designing alternate Cure Systems to Eliminate Restricted Substances for ECO, ACM and AEM
Polymer by Christina Bergmann, Martin Saewe, Steven Monthey of Rhein Chemie, presented at
ACS Rubber Division Meeting, Louisville, KY, October 2008

115
 References

• Xanathate Accelerators in the Vulcanization of Isobutylene-based Elastomers by Nitin Tambe,

Scott Solis, Brendan Rodgers, Bharat Sharma, Walter Waddell of ExxonMobil Chemical Co.,
presented at ACS Rubber Division, Pittsburgh, PA, November 2005
• A New Approach to Activating Dithiocarbamates in EPDM by [Link] of Rhein Chemie,
presented at ACS Rubber Division Meeting, Pittsburgh, PA, October 2009
• Alkylphenol Disulfide Polymer Accelerators and the Vulcanization of Isobutylene Based
Elastomers by Brendan Rodgers, Nitin Tambe, Scott Solis and Bharat Sharma of ExxonMobil
Chemical Co., presented at ACS Rubber Division Meeting, Cleveland, OH, October 2007
• Better Thermal and Thermal Oxidative Aging Resistance by Byron To and Fredrick Ignatz-Hoover,
Gilbert Anthoine of Flexsys, published in Rubber & Plastics News, October 16, 2006
• New Thiophosphate Generation – Advantages in Nitrosamine-free Vulcanization Systems by
[Link] of Rhein Chemie, presented at IRC, Orlando, FL, October 1993
• Precautions Needed to Compound Insoluble Sulfur by Byron To and Arie De Hoog of Flexsys,
Rubber and Plastics News Technical Notebook, September 23, 2002
• High Temperature Curing of Radial Passenger Tires by Lloyd Walker and William Helt, III of
Monsanto, Rubber Division ACS, October 1985

116
 References
• Vulcanization Chapter by A.Y. Coran of Monsanto Industrial Chemicals from the book Science and Technology of
Rubber, Academic Press 1978
• Peroxide Vulcanization of Elastomers by Peter Dluzneski of GEO Specialty Chemicals
• A Review of Fast-Cure Systems for Vamac® Elastomers, Doc. Ref. VAM020507_2, v.1, May 2002,
• Vamac® Polymer and Performance Review, DuPont Vamac Web Site
• Rubber Technology Handbook by Werner Hofmann, Hanser Publishers
• Advancure,A New Curative for Vamac, [Link], Rubber Division ACS, October 2006
• Cure Activators to Improve both ECO-Balance and Economics of a Cure System by Martin Saewe, Steven Monthey
of Rhein Chemie, presented at ACS Rubber Division, Pittsburgh, PA, October 2009
• [Link], Kunststoffe 50 (1960), p. 623
• [Link], [Link], [Link], Kautschuk Gummi Kunstst, 49 (1996), p. 340
• [Link], [Link], Kautschuk Fummi Kunstst, 33 (1980), p. 696
• [Link], K..S. Reinartz, Kautschik Gummi Kinstst, 53 (2000), p. 419
• An Original Anti-reversion Nitrosamine-free Curing Agent as an Alternative to TMTD by Pierre Luge of MLPC,
presented at ACS Rubber Division Meeting, Pittsburgh, PA, October 2009
• Zinc Dithipohosphates Applications in Sulfur Cured Polymers by Jon Nienaber of Rhein Chemie, presented at the
ACS Rubber Division Meeting, Cincinnati, OH, Oct. 2012

117
 References

• Zinc Dithipohosphates Applications in Sulfur Cured Polymers by Jon Nienaber of Rhein

Chemie, presented at the ACS Rubber Division Meeting, Cincinnati, OH, Oct. 2012

118
Regulatory Issues with Curatives

ETU and Replacements

Guanidines and Replacements
Nitrosamine Generating Accelerators and Replacements

119
Replacing ETU

120
 ETU, Ethylene Thiourea

• ETU is classified as a CMR substance (carcinogenic,

mutagenic and toxic for reproduction)
• ETU is used in cure systems for CR (polychloroprene)
and ECO (epichlorohydrine copolymer)

121
 ETU Replacements
• In ECO Rhein Chemie suggests a combination of
• Rhenogran HPCA-50 (aminic co-activator and
antioxidant)
• Rhenogran Triazine TM-70 (2,4,6-trimercapto-s-
triazine)
• Retarder E80 (sulfonamide derivative)
• Rhenogran TP-50 (zinc dialkyldithiophosphate)
• In ECO Rhein Chemie also suggests using MTT to
replace ETU

122
Replacing Guanidines

123
 Guanidines
• Under R.E.A.C.H. regulations, guanidines such as
DOTG and DPG are being targeted for restriction and
perhaps elimination.
• O-toluidine is presented in trace amounts in DOTG and
additional amounts of o-toluidine can also be
liberated during the decomposition of guanidine
accelerators during the rubber curing process.
• O-toluidine is classified as a carcinogen by IARC, NTP,
OSHA and ACGIH.
• German studies have observed low levels of o-
toluidine in rubber plants and also in blood/urine
samples of workers.

124
 Guanidine Replacements
• In AEM, DuPont studies show that 2 phr of Rhein
Chemie Vulcofac ACT 55 (diazobicyclo undecene,DBU)
can replace DOTG
• In ACM, Zeon studies show that Rhein Chemie Vulcofac
ACT 55 (diazobicyclo undecene,DBU) and Rhenocure
XLA-60 (a proprietary activated amine with retarder)
can replace DOTG
• In AEM and ACM, Rhein Chemie studies show that
Rhenocure XLA-60 (a proprietary activated amine with
retarder) can replace DOTG

125
 Guanidine Replacements
• In AEM and ACM, [Link] studies show that Vanax 107
(proprietary mixture of aliphatic amines and alicyclic amine) is a
drop replacement for DOTG
• In CR, [Link] studies show that Vanax 107 works as a
replacement for DOTG in a zinc cure system
• In NR, [Link] studies show that Vanax 107 can replace
DOTG
• In SBR/BR (mostly silica filled), Rhein Chemie studies show it is
possible to replace DPG in a sulfenamide/sulfur cure with the
different levels of the following:
• Rhenogran SDT-50 (Phosphoryl polysulfide)
• Rhenocure XLA-60 (a proprietary activated amine with retarder)
• Arginin
• Lysin

126
Nitrosamines & Accelerators

127
 Regulated Nitrosamines
• Most rubber manufacturers refer to a non-nitrosamine
cure system as not containing chemicals that will
generate any of the nitrosamines on the list adopted by
Germany.
• Higher molecular weight nitrosamines are not included
on this list because the secondary amines needed to
generate these nitrosamines are not volatile enough to
get airborne at ambient temperatures.
• However, some manufacturers of pharmaceutical rubber
parts require a complete non-nitrosamine cure system
that does not generate any secondary amines of any
kind.

128
Nitrosamines on the German Regulated List
• N-nitrosodi-n-butylamine (NDBA)
• N-nitrosodiethylamine (NDEA)
• N-nitrosodi-i-propylamine
• N-nitrosodiethanolamine
• N-nitrosodimethylamine (NDMA)
• N-nitrosodi-n-prolylamine
• N-nitrosoethylphenylamine (NEPhA)
• N-nitrosomethylphenylamine (NMPhA)
• N-nitrosopiperidine
• N-nitrosomethylethylamine
• N-nitrosomorpholine (NMOR)
• N-nitrosopyrolidine (NPVR)

129
 Amine Type and Nitrosamine Formation
• Not all amine compounds form nitrosamine amines – only secondary amines
have the potential of forming a stable nitrosamine.
• Chemicals that form primary amines decompose to nitrogen and alcohols that
are not toxic.
• Chemicals that form tertiary amines do not react to form nitrosamines.
Primary Amine Tertiary Amine
H R1
R-N R -N
3
H R2
Does not form nitrosamines
Decomposes in the reaction with NOx with N2 elimination

H
R-N + ON - OH R - N - N - OH + H2 O
H unstable diazonium
hydroxide

R - N - N - OH R - OH + N2
unstable diazonium
hydroxide

130
 Formation of Nitrosamines
• Nitrosamines are formed by the reaction between secondary
amines that are split off from the rubber curatives and oxides of
nitrogen that are in the air.
Nitrosamine Mechanism
R1
. R1
N + NOx N - NO
R R2
2
Secondary-amine + nitrogen oxide = nitrosamine
(NO = NO, N O , NO2 )
2 3

131
 Nitrosamine Sources
• Chemicals that are nitrosamines and can split off NO, such as N,N-
dinitroso pentamethylenetramine (a blowing agent) and
nitrosodiphenylamine (a retarding agent).
• Rubber chemicals that have absorbed NOx on their surface. These include
carbon blacks, light-colored fillers such as silica and metal oxides with large
surface areas formed at high temperatures in the presence of air.
• Mixtures of molten salt consisting of alkali nitrates and nitrites used with
salt bath vulcanization systems.
• Oxides of nitrogen, at increased concentration, in the atmosphere. This is
caused by fork-lift trucks and other machinery run by internal combustion
engines.
• Common foods and beverages such as bacon and beer usually contain
much higher levels of nitrosamines than the average rubber plant worker
is exposed to.

132
Chemical Structure Nitrosamine Generation
• The formation of nitrosamines is dependent on the secondary
amine given off by the break-up of the rubber accelerator being
volatile enough to come out of the rubber compound and react
with NOx in the air.
• Secondary amines with lower boiling points are more volatile.
• The boiling point of the secondary amine is dependent on the
chemical structure of its -R groups:
• Secondary amines based on lower molecular weight -R
groups are more volatile and come out the compound more
readily and at a faster rate than higher molecular weight
secondary amines.
• Stearic hindrance and branching within the -R groups also
affect the boiling point of the secondary amine

133
 Nitrosamine Accelerators
• Some of the curatives that are used in the rubber industry split off secondary
amines and can therefore produce carcinogenic nitrosamines.
• These include accelerators from the thiuram, dithiocarbamate and
morpholine compound families as shown below:
Thiurams Dithiocarbamate
R1 R1 R1
N - C - Sx - C - N R1
|| || N - C - S - Me - C - N
R2 R2 R2 || ||
R2
S S S S
S-amine S-amine
group group S-amine S-amine
group group

Morpholine Compounds
CH 2 - CH2
O N - S - R3
CH2 - CH2
S-amine
group

134
 High Molecular Weight Curatives
• Some thiurams and dithiocarbamates generate higher
molecular weight secondary amine groups that are not
very volatile and do not form carcinogenic
nitrosamines. The following are examples:
N-methyl-piperazinyl-thiuramdisulfide
CH2 - CH2 CH2 - CH2
CH3 - N N - C - S -S - C -N N - CH
CH2 - CH2 || ||
CH2 - CH2 3
High Molecular Weight
S S
High Molecular Weight
s-amine Group s-amine Group

Zn-dibenzyldithiocarbamate (ZBEC)
- CH2 CH 2 -
N - C - Zn - S - C - N
- CH2 || || CH 2 -
S S
High Molecular Weight High Molecular Weight
s-amine Group s-amine Group

135
 Common Secondary Amines Formed By
Rubber Accelerators vs. Boiling Point
400
Nitrosamine concern Not volatile enough to generate nitrosamines

350
Would generate low levels of nitrosamines

Decomposes
300
Higher volatility and higher measurable nitroamines
Boiling Point (Deg.C)

250

200

150

100

50

0
Di- Di- Di- Methyl- Ethyl- Di- Di- Di- Pentyl- Di- Di-
methyl ethyl iso- phenyl phenyl morpholine butyl amyl methyl cyclo benzyl
propyl hexyl
136
Secondary Amine
 Thiurams are a good group of accelerators to look at
the effects of structure on the formation of nitrosamines.

S S CH3 CH3
CH3 || || CH3
N-C-S-S-C-N NH N-NO
CH3 CH3
CH3 CH3
TMTD N-nitrosodimethylamine
Dimethylamine
B.P. 7.4°C
S S C2H5
C2H 5 || || C2H 5 C2H5 N-NO
N-C-S-S-C-N NH C2H5
C2H 5 C2H 5 C2H5
TETD N-nitrosodiethylamine
Diethylamine
B.P. 56°C
C4H9 S S C4H9 C4H9
|| || C4H9
N-C-S-S-C NH N-NO
C4H9 C4H9
C4H9 -N C4H9
TBTD N-nitrosodibutylamine
Dibutylamine
B.P. 159°C
-H2C
S S
-H2C || || CH2- -H2C N-NO
N-C-S-S-C NH -H2C
-H2C CH2-
-N -H2C
TBzTD N-nitrosodibenzylamine
Dibenzylamine
137
B.P. 300°C
 Nitrosamines & Curatives
Curative Type Nitrosamine Generating Non-nitrosamine Generating
Amines HMT, CEA, DBA, PEP, TCT BAA, DBzA
Dithiocabamates ZDMC, NaDMC, ZDEC, NaDEC, ZBEC
ZDBC, NaDBC, ZPEC, PPC,
SeDMC, TeDMC, CdDMD,
CuDMB, BiDMC Z5BC, Cd5MC
TDEC
Dithiophosphates ZDBP, CulDP
Guanidines DPG, DOTG, OTBG
Retarders NDPA CTP, PTA, BES
Sulfenamides DIBS, CBBS, MBS, MBSS, CBS, DCBS, TBBS
NIBS, OTOS, OTTES
Sulfenimides TBSI
Sulfur Donors DTDM, DPTT, MBSS, TMTD, CLD, Vultacs
DPTT
Thiazoles MBT, ZMBT, MBTS, CMBT
Thioureas ETU, DETU, DBTU, DPTU
Thiurams TMTD, TMTM, TEDT, DPTT TBzTD
Xanthates BIZ, NaIX, ZBX 138
Plant Areas With Measurable Nitrosamine
Concentrations
• Injection molding units
• Salt bath vulcanization and testing equipment
• Vulcanization units such as curing presses
• Warehouses
• Compound mixing areas

139
Some Accelerators Used in
Non-nitrosamine Cure
Systems

140
Summary of Nitrosamine Substitutes
• Alkyphenol Disulfides can allow improvement in scorch
resistance and aging properties
• Dithiophosphates show good reversion resistance, good
heat aging and high temperature curing
• Higher molecular weight thioureas (like DBTU) have
excellent reversion resistance
• Xanthates can be used in low temperature cure systems
and as ultra accelerators to kick the cure system
• Higher molecular weight and stearically hindered
thiurams and dithiocarbamates (ZBEC, ZiBDC, TBzTD,
TiBTD)

141
 Dithiocarbamates
(only common ones included)

Nitrosamine Generating Non-nitrosamine

• BDMC, Bismuth • ZBEC, Zinc dibenzyldithiocarbamate
dimethyldithiocarbamate
• ZiBDC, Zinc
• CDBC, Copper diisobutyldithiocarbamate
dibutyldithiocarbamate
• CDMC, Copper • Robac SAA-30 PM 50 is 2,2’-
dimethyldithiocarbamate dithiodi(theylammonium) –
bis(dibezyldithiocarbamate)
• TDEC, Tellurium
diethyldithiocarbamate
• ZDBC, Zinc dibutyldithiocarbamate
• ZDEC, Zinc diethyldithiocarbamate
• ZDMC, Zinc
dimethyldithiocarbamate

142
 ZBEC
Nitrosamine Safe Alternative
• ZBEC, tetrabenzyldithiocarbamte is considered a safe nitrosamine
alternative because the benzyl secondary amine it forms is large,
has a high boiling point and does not volatilize easily. Also, the
nitrosamine it forms is not listed as carcinogenic. Therefore it can
be used in nitrosamine safe cure systems.
• ZBEC is one of the fastest non-nitrosamine accelerators but
compared to other dithiocarbamates, especially low weight
dithiocarbamates based on ethyl or methyl groups, it is slow.
Because of its high molecular weight it is also low in sulfur content,
so you need more of it to generate the same state of cure.
• ZBEC also has limited solubility in EPDM (<0.5 phr) which limits its
use.

143
 ZBEC
Nitrosamine Safe Alternative
• The dithiocarbamtes are ultra accelerators and most often used in
EPDM because its low unsaturation.
• The dithiocarbamates are often used in combination with thiurams
and/or DTDM which also generate nitrosamine.
• Replacing all these nitrosamine accelerators becomes problematic
when you are only using ZBEC and the TBzTD nitrosamine safe
thiuram.
• It just becomes impossible from both a solubility standpoint and a
cost standpoint.
• This is why many EPDM compounds use ZBEC and TBzTD along
with dithiophosphates and amine kickers in EPDM.

144
 ZiBDC
Low Nitrosamine Alternative
• ZiBDC, zinc diisobutyl dithiocarbamate is considered a low
nitrosamine alternative because the isbutyl secodary amine
it forms is stearically hindered, has a high boiling point and
does not volatilize easily. It is used in small amounts in
nitrosamine safe systems because not enough nitrosamine
are generated usually to be detected and the
isobutylnitrosamine is not on the German regulated list.
• The advantage that ZiBDC has over ZBEC is greater solubility
in most elastomers, it has a higher sulfur content and it is
faster.

145
 Sulfur Donors
Nitrosamine Generating Nitrosamine Safe or Low
• DPTT, Dipentamethylenethiuram • TBzTD Tetrabenzyl thiuram disulfide
tetrasulfide (fast cure rate) (fast cure rate but slower the TETD
and TMTD)
• DTDM Morphorline disulfide (slow
cure rate) • TiBTD, Tetraisobutyl thiuram disulfide
(fast)
• TETD Tetraethyl thiuram disulfide
(fast cure rate) • Alkylphenol disulfide polymer
(medium cure rate but scorchy)
• TMTD Tetramethyl thiuram disulfide
(fast cure rate) • DTDC Dithiocaprolactum (slow cure
rate)
• DDTS, N,N’-dimethyl-N,N’-
diphenylthiuram disulfide
• [Link] disulfide

146
Structure of Alkylphenol Disulfide Polymers

Alkylphenol Disulfide Polymer Accelerators and the Vulcanization of Isobutylene Based

Elastomers by Brendan Rodgers, Nitin Tambe, Scott Solis and Bharat Sharma of ExxonMobil
Chemical Co., presented at ACS Rubber Division Meeting, Cleveland, OH, October 2007

147
 Alkylphenol Disulfide
Non-nitrosamine Alternative
• The alkyl phenol disulfides are most often known by their popular trade
name, Vultac.
• They can be used with adjustments to the sulfur and/or accelerator types.
• The adjustments usually involves a cure system revamp but good results
can be had.
• Generally, alkyl phenol disulfides generate a laid back rheometer curve
(slow cure but short scorch). This is in contrast to the more vertical slopes
seen with the thiurams (TETD and TMTD).
• The alkylphenol disulfide can replace DTDM with other adjustments in the
cure system. DTDM has more scorch safety and builds higher torque.
• The alkylphenol disulfides are resins and they must be melted to get good
dispersion in the rubber matrix.
• The alkylphenol disulfides have an added benefit in that they act as process
aids and weak antioxidants.

148
 TBzTD – Safe Nitrosamine Alternative
• TBzTD, tetrabenzyl thiuram disulfide is considered a safe nitrosamine alternative
because the benzyl secodary amine it forms is large, has a high boiling point and
does not volatilize easily. Also, the nitrosamine it forms is not listed as
carcinogenic. Therefore it can be used in nitrosamine safe cure systems.
• Compared to the other non-nitrosamine sulfur donors, it is relatively fast but not
as fast as TETD and TMTD.
• TBzTD is used a lot with adjustments in other accelerators to replace TETD, TBTD
and TMTD. Quite often if TBzTD is used to replace TETD, TBTD or TMTD and if the
cure system also has a sulfenamide, some of it is replaced by faster thiazoles. If
MBTS (a thiazole) is currently be being used it is sometimes shifted to faster MBT.
• In EPDM cure systems, TBzTD is used in combination with ZBEC (a
dithiocarbamate) to replace nitrosamine generating thiurams and
dithiocarbamates. Dithiophosphates may also be used.
• TBzTD has limited solubility in some rubbers, such as EPDM, so care must taken to
stay below the solubility limits.

149
 TiBTD – Low Nitrosamine Alternative
• TiBTD, tetraisobutylothiuram disulfide is considered a low
nitrosamine alternative because the isbutyl secodary amine it
forms is stearically hindered, has a high boiling point and does
not volatilize easily. It is used in small amounts in nitrosamine
safe systems because not enough nitrosamines are generated
usually to be detected.
• The advantage that TiBTD has over TBzTD is greater solubility in
most elastomers, it has a higher sulfur content and it is faster.
• Follow some of the same development paths suggested with
TBzTD shown on the previous slide but keep in mind the
differences listed above.

150
 Thiurams
Nitrosamine Generating Nitrosamine Safe
• N,N’-dimethyl-N,N’-diphenylthiuram • Tetrabenzylthiuram disulfide (TBzTD)
disulfide (DDTS)
• Tetraisobutylthiuram disulfide
• Dipentamethylenethiuram (TIsoBTD)
tetrasulfide (DPTT)
• Tetrabutylthiuram disulfide (TBTD)
• Tetraethylthiuram disulfide (TETD)
• Tetramethylthiuram disulfide (TMTD)
• Tetramethylthiuram monosulfide
(TMTM)

151
 DTDC – Non-nitrosamine Alternative
• DTDC, Dithiocaprolactum is very slow and quite
expensive
• It is a sulfur donor
• It is most often used to replace the slower DTDM
sulfur donor

152
 Dithiophosphates vs. Dithiocarbamate
Chemical Structures
• ZBPD zinc, O,O-dibutylphosphorodithioate and ZDBC, zinc
dibutyldithiocarbamate chemical structures are similar. Basically the nitrogen in
ZDBC is replaced with phosphorus in ZBPD. There is no nitrogen in ZBPD to
form a secondary amine and hence a nitrosamine.
• The nitrogen in ZDBC and other dithiocarbamates makes these chemicals more
polar, causing them to be less compatible with non-polar polymer such as
EPDM. This leads to limited solubility levels and blooming issues.
• The phosphorus in the ZBPD gives a less polar molecule and higher solubility in
non-polar polymers like EPDM.
Credit: Zinc Dithipohosphates Applications in Sulfur Cured Polymers by Jon Nienaber of Rhein Chemie, presented at
the ACS Rubber Division Meeting, Cincinnati, OH, Oct. 2012

153
 EPDM Cure Systems Using
Dithiophosphates
• As mentioned before, replacing a typical EPDM cure system with
nitrosamine generating dithiocarbamates, thiurams and perhaps
DTDM becomes problematic. It is just not practical to do it with
the current nitrosamine safe or free alternatives such as ZBEC
and TBzTD from both a solubility or cost standpoint.
• For nitrosamine safe or free cure systems, the industry has
turned to dithiophosphates in combination with ZBEC, TBzTD,
thiazoles or sulfenamides and sometimes amine complexes as
the acceleration package.
• The dithiophosphates have an advantage over dithiocarbamates
and thiurams because they have high solubility levels in EPDM.

154
Dithiophosphate Combinations
Rheometer Curves

Modern Rubber Additives to Avoid Hazardous Substances by Harald Kleinknecht of Rhein

Chemie presented at Automotive Days Poland, October 2011

155
 Replacements

Modern Rubber Additives to Avoid Hazardous Substances by Harald Kleinknecht of

Rhein Chemie presented at Automotive Days Poland, October 2011

156
 References
• A New Nitrosamine-Free Accelerator; Mixland+ TBP 75 GA by Pierre Lugez, MLPC, presented at ACS
Rubber Division Meeting, Cleveland, OH, October 2007
• Accelerator Systems for the Vulcanization of Chlorobutyl Elastomer -- Cruz, Sharma, Rodgers of
ExxonMobil Chemical Co., presented at the ACS Rubber Division Meeting, Cleveland, OH, October
2011
• Avoiding Potentially Hazardous Emissions in Rubber Compounding and Processing by Steven
Monthey, Dr Martin Saewe, Scott Zemanek of Rhein Chemie, presented at ACS Rubber Division
Meeting, Pittsburgh, PA, October 2009
• High Performance 'Safe' Nitrosamine Cure Systems for Elastomers -- Virdi, Chakroborty, Bowen of
Robinson Brothers Limited, presented at the ACS Rubber Division Meeting, Orlando, FL, October
1993
• Nitrosamines, from problem to challenge -- Verhelst, Seeberger, Endstra of Akzo Chemicals,
presented at ACS Rubber Division Meeting, Orlando, FL, October 1993
• Some forgotten Accelerators, The Thiophosphates-helpful in the Design of nitrosamine-free
Accelerator Systems -- Graf, Johansson of Rhein Chemie, presented at ACS Rubber Division, Orlando,
FLE October 1993
• Nitrosamines A New Generation of cure Systems to Eliminate Carcinogenic N-Nitrosamines by
[Link], [Link], Thomas J. Leo of Rhein Chemie, presented at the ACS Rubber Division Meeting,
Nashville, TN

157
 References
• Nitrosamines in Tires Why They Form and Who Cares by Dwight W. Chasar of BFGoodrich, presented
at ITEC, September 1994
• Nitrosamines The Hidden Enemy by Anders Johansson of Rhein Chemie, Technical bulletin
• Seminar on Nitrosamines by Robert Ohm of Uniroyal Chemical
• Practical Strategies to Avoid Hazardous N-nitrosamines in the Vulcanization of Elastomers by [Link]
of Rhein Chemie presented at the DKG (German Rubber Society) conference, Wurzburg, Germany,
October 1992
• Review and the Latest Update of N-Nitrosamines in the Rubber Industry; the Regulated, the
Potentially Regulated, and Compounding to Eliminate Nitrosamine Formation by [Link] Jr.,
[Link], [Link] of Rhein Chemie, presented at ACS Rubber Division Meeting, Pittsburgh, PA,
2005
• Realistic Strategies to Prevent Carcinogenic N-Nitrosamines in Rubber by [Link], [Link] of
Rhein Chemie presented at ACS Rubber Division Meeting, October 1993
• Modern Rubber Additives to Avoid Hazardous Substances by Harald Kleinknecht of Rhein Chemie
presented at Automotive Days Poland, October 2011
• Robac Chemicals Nitrosamine Solutions, technical bulletin
• Thiophosphates Helpful in the Design of Nitrosamine-free Accelerator Systems by [Link] and
[Link] of Rhein Chemie published in Rubber World, August 1995

158
 References
• Using Dithiophosphates to Develop Synergistic Accelerator Packages That Achieve Total
Performance Solutions for Non-nitrosamine Formulations by Steven Monthey of Rhein
Chemie
• Vulcanization, Vulcanizate Structure and Properties – An Overview by [Link],
presented at ACS Rubber Division Meeting, Toronto, Ontario, May 1983
• The Vulcanization of Rubber by Bob Ohm and Russ Mazzeo presented at Rhode Island
Rubber & Plastics Group, Providence, RI, April 2001
• Review of Vulcanization Chemistry by Fred Ignatz-Hoover, Flexsys published in Rubber
World, August 1999
• Vulcanization by Merton Studebaker of Phillips Petroleum Co. and [Link] of
[Link] presented at ACS Rubber Division Meeting, Boston, MA, April 1972
• Vulcanization and Vulcanizing Agents by Werner Hofmann, published by Palmerton
Publishing Co., Inc.
• Rubber Curing and Properties by Jean-Maurice Vergnaud, Iosif-Daniel Rosca, published
by CRC Press
• Vulcanization of Elastomers by Michael Fath of Elastomer Technology, Inc. published in
Rubber World, October 1993
• Zinc Dithiphosphates Application in Sulfur Cure Polymers by Jon Nienaber of Rhein
Chemie, presented at ACS Rubber Division Meeting, Cincinnati, OH October 2012

159
 References
• Vulkalent E, An Examination of its Usefulness as Retarder and Accelerator of Sulfur
Vulcanization by [Link] of Bayer, presented at ACS Rubber Division Meeting,
Cleveland, OH, October 1997
• Discussion and the Resistance to Reversion of Natural Rubber with the Help of
Thiphosphate Cure Systems by H.J. Graf, [Link], Rhein Chemie, presented at ACS
Rubber Division, Montreal, May 1996
• Tetrabenzylthiuram Disulfide-A Secondary Accelerator for Stable Crosslink Systems in
Tire Applications -- Ferrandino, Sanders, Hong of Uniroyal Chemical Co., presented at
ACS Rubber Division Meeting, Philadelphia, PA, May 1995
• Formulation Suggestion for Replacing DOTG in AEM Compounds by Edward McBride,
Klaus Kammerer, Laurent Lefebvre of DuPont, presented at ACS Rubber Division
Meeting, Milwaukee, WI, October 2010.
• Compounding Parameters to Control the Iridescent Bloom in EPDM Body Sealing
Applications by Eric Jourdain, Exxon Chemical Co., presented at ACS Rubber Division
Meeting, Montreal, May 1996
• An Effective DOTG Replacement Accelerator for Both High Performance and General
Elastomer by Jennifer Forgue of [Link] Co., presented at ACS Rubber Division
Meeting, Cleveland, OH, October 2011
• Designing alternate Cure Systems to Eliminate Restricted Substances for ECO, ACM and
AEM Polymer by Christina Bergmann, Martin Saewe, Steven Monthey of Rhein Chemie,
presented at ACS Rubber Division Meeting, Louisville, KY, October 2008

160
 References

• Xanathate Accelerators in the Vulcanization of Isobutylene-based Elastomers by Nitin Tambe, Scott

Solis, Brendan Rodgers, Bharat Sharma, Walter Waddell of ExxonMobil Chemical Co., presented at
ACS Rubber Division, Pittsburgh, PA, November 2005
• A New Approach to Activating Dithiocarbamates in EPDM by [Link] of Rhein Chemie, presented
at ACS Rubber Division Meeting, Pittsburgh, PA, October 2009
• Alkylphenol Disulfide Polymer Accelerators and the Vulcanization of Isobutylene Based Elastomers
by Brendan Rodgers, Nitin Tambe, Scott Solis and Bharat Sharma of ExxonMobil Chemical Co.,
presented at ACS Rubber Division Meeting, Cleveland, OH, October 2007
• Better Thermal and Thermal Oxidative Aging Resistance by Byron To and Fredrick Ignatz-Hoover,
Gilbert Anthoine of Flexsys, published in Rubber & Plastics News, October 16, 2006
• New Thiophosphate Generation – Advantages in Nitrosamine-free Vulcanization Systems by [Link]
of Rhein Chemie, presented at IRC, Orlando, FL, October 1993
• Precautions Needed to Compound Insoluble Sulfur by Byron To and Arie De Hoog of Flexsys, Rubber
and Plastics News Technical Notebook, September 23, 2002
• High Temperature Curing of Radial Passenger Tires by Lloyd Walker and William Helt, III of
Monsanto, Rubber Division ACS, October 1985

161
 References

• Vulcanization Chapter by A.Y. Coran of Monsanto Industrial Chemicals from the book Science and Technology of
Rubber, Academic Press 1978
• Peroxide Vulcanization of Elastomers by Peter Dluzneski of GEO Specialty Chemicals
• A Review of Fast-Cure Systems for Vamac® Elastomers, Doc. Ref. VAM020507_2, v.1, May 2002,
• Vamac® Polymer and Performance Review, DuPont Vamac Web Site
• Rubber Technology Handbook by Werner Hofmann, Hanser Publishers
• Advancure,A New Curative for Vamac, [Link], Rubber Division ACS, October 2006
• Cure Activators to Improve both ECO-Balance and Economics of a Cure System by Martin Saewe, Steven
Monthey of Rhein Chemie, presented at ACS Rubber Division, Pittsburgh, PA, October 2009
• [Link], Kunststoffe 50 (1960), p. 623
• [Link], [Link], [Link], Kautschuk Gummi Kunstst, 49 (1996), p. 340
• [Link], [Link], Kautschuk Fummi Kunstst, 33 (1980), p. 696
• [Link], K..S. Reinartz, Kautschik Gummi Kinstst, 53 (2000), p. 419
• An Original Anti-reversion Nitrosamine-free Curing Agent as an Alternative to TMTD by Pierre Luge of MLPC,
presented at ACS Rubber Division Meeting, Pittsburgh, PA, October 2009
• Zinc Dithipohosphates Applications in Sulfur Cured Polymers by Jon Nienaber of Rhein Chemie, presented at the
ACS Rubber Division Meeting, Cincinnati, OH, Oct. 2012

162
Some Common
Non-sulfur Cure
Systems
Phenol formaldehyde resins
Metal oxides
P-quinonedioxime
Peroxides
Diamine
Bisphenol

163
 Resol phenol-
formaldehyde resin cure

164
 Resol Phenol-formaldehyde
• Resol type phenol-formaldehyde resins can be used to cure butyl
polymers.
• In addition to the resin, zinc oxide is also needed. Ratio is usually
2 resin: 1 ZnO.
• It is best to grind the resin and zinc oxide together to get fine
particle size on the resin.
• A halogen donor, usually 5 phr of CR (Neoprene W) is used to
activate the cure with straight butyl polymers. Bromobutyl and
chlorobutyl are halogenated so they do not need the CR added.
Stannous chloride can also be used to activate the cure.
• Resin cured butyl vulcanizates have excellent high temperature
degradation resistance.
• This cure system is most often used in curing bags and bladders
for curing presses.

165
 Resol Phenol-formaldehyde Resin Cure
OH OH OH O
| | heat | || CH2
HOCH2- - R' - - CH2OH HOCH2- - R' -
| -H 0 | |
| 2
R R R R

OH O CH3
|
| || CH2
HOCH2- - R' - + CH2- C = CH - CH 2 CH 2 CH3
| | C
R R
O CH - CH
OH | 2
| CH Chroman ring
HOCH - - R' - 2
2
| |
R R

CH3
- H2 O |
CH2- C = CH - CH 2

Crosslinked
Polymer

Credit: Phenol-Formaldehyde Resins by Bonnie Stuck of Sovereign Chemical Co., Rubber Division ACS, Education Symposium #42, May 1997

166
 Metallic Oxide Cures
• Polychloroprene rubber (CR) or chlorosulfonated polyethylene (CSM) is most often cured with a
combination of magnesium oxide and zinc oxide.
• Lead oxides have also been used but have limited use because of regulation issues.
• A thiourea (typically ETU) is sometimes used to speed up the reaction.
• The zinc oxide actually acts as the curing agent but some excess zinc chloride is formed.
• The magnesium oxide acts as a stabilizer, neutralizing the zinc chloride to maintain scorch safety.

Credit: Robert P. Kane, DuPont, Vanderbilt Rubber Handbook

167
P-quinonedioxime
Cure System

168
 P-quinonedioxime Cure System
• P-quinonedioxime combined with an oxidizing
agent can be used to cure butyl polymers.
• P-quinoenioxime oxidizes to p-dinitrosobenzene,
which is the actual cure agent.
• These cure systems are fast and give crosslinks
that are thermally stable.
• The next slide shows the reaction.

169
P-quinonedioxime Cure System

Credit: Isobutylene Based Elastomers: A Review by Ilan Duvdevani, Glenn

Jones, Donal Tracey, Andrew Tisler of Exxon Chemical Company, Rubber
Division ACS, Education Symposium No. 46, April 1999

170
Peroxide Cure Systems

171
 Peroxide Cures
• Polymers with and without double bonds can be vulcanized with peroxides to
form carbon-carbon bonds.
• The C-C bonds are very stable, resulting in vulcanizates with the following
properties:
• Low creep
• Low permanent set
• High heat resistance
• High chemical resistance
• Poor tear and flex crack resistance
• Peroxides are compounds containing an oxygen-oxygen bond (O-O).
• The O-O bond is unstable, so peroxides tend to decompose during storage.
• Peroxides crosslink by a chain free radical mechanism initiated by the
hemolytic cleavage of the O-O bond.

172
 What polymers can be peroxide cured?
Rubber Peroxide Rubber Peroxide
Cured Cured
ACM, acrylic rubber Yes EPM, ethylene propylene rubber Yes
BR, butadiene rubber Yes BR, butadiene rubber Yes
IIR, butyl rubber No EPDM, ethylene propylene diene Yes
BIIR, bromobutyl rubber No EVA, ethylene vinylaceate Yes
CIIR, chlorobutyl rubber No NR, IR, polyisoprene rubber Yes
CR, Chloroprene rubber Yes NBR, nitrile, butadiene Yes
CSM, chlorosulfonated Yes acrylonitirle rubber
polyethylene PB, polybutene Yes
CPE, chlorinated polyethylene Yes MQ, silicone rubber Yes
CO, epichlorohydrine rubber No AU/EU, polyurethane rubber Yes
ECO, epichlorohydrine No T, polysulfide rubber Yes
copolymer

173
 Peroxide Cure of a Saturated Polymer
Initiation:
R - O - O -R
Peroxide
2R-O
Free Radical
.
Propogation: CH3 CH3

2R-O . +
|
CH -CH2- CH2 ROH + .|
C -CH2 - CH2
Polymer Chain

Termination:
CH3
|
CH3 C -CH2 - CH2
2 .|
C -CH2 - CH2
|
C -CH2 - CH2
|
CH3

Crosslinked Polymer
Credit: Vulcanization Chapter by A.Y. Coran of Monsanto Industrial Chemicals from the
book Science and Technology of Rubber, Academic Press 1978

174
 Classes of Peroxides
Diacyl, half-life 21-75°C Peroxyketals, half-life 92-112°C

O O R" OO - (tert R)
C
R - C - OO - C - R R' OO - (tert R)
Dialkyl, half-life 115-131°C
(tert R’) – OO (tert R”)
Peroxydicarbonates, half-life 49-51°C
O O
(tert-Alkyl hydroperoxides),
(tert R) - OOH
RO - C - OO - C - OR

Ketone peroxides
T-Alkyl peroxyesters, half-life 38-107°C
R' R'
O I I
HOO - C - OO - C - OOH
R - C - OO - (tert R)
I I
R R 175
2,4-dimethyl-2,5-di(t-butyperoxy)-3-hexyne

• EPDM, EPM, PE, NBR

• Half-life
• 0.1 hr: 173°C
• 1 hr.: 147°C
• 10 hr.: 124°C
• Safe process temp.
• T90@12’: 150°C
• Scorch:
• 150°C: 20’
• 180°C: 5’

176
DCP, Dicumyl Peroxide
• NR, IR, SBR, BR, NBR, EPDM,
CR, PE, EPM, MQ, EVA
• Half-life
• 0.1 hr: 155°C
• 1 hr.: 128°C
• 10 hr.: 105°C
• Safe process temp.
• T90@12’: 121°C
• Scorch:
• 150°C: 5’
• 180°C: 3’

177
Dibenzoyl Peroxide
• NR, IR, SBR, BR, NBR, EPDM,
CR, PE, EPM, MQ, EVA
• Half-life
• 0.1 hr: 155°C
• 1 hr: 128°C
• 10 hr: 107°C
• Safe process temp.
• T90@12’: 123°C
• Scorch:
• 150°C: 5’
• 180°C: 5’

178
Bis (p-chlorobenzoyl) Peroxide
• NR, IR, SBR, BR, NBR, EPDM,
CR, PE, EPM, MQ, EVA
• Half-life
• 0.1 hr: 155°C
• 1 hr.: 128°C
• 10 hr.: 108°C
• Safe process temp.
• T90@12’: 124°C
• Scorch:
• 150°C: 5’
• 180°C: 6’

179
 Bis (2,4-chlorobenzol) Peroxide

• NR, IR, SBR, BR, NBR,

EPDM, CR, PE, EPM, MQ,
EVA
Cl O Cl • Half-life
O
|| || • 0.1 hr: 155°C
Cl - -C-O-O-C- - Cl • 1 hr.: 128°C
• 10 hr.: 108°C
Bis (2,4 -dichlorobenzoyl) Peroxide
• Safe process temp.
• T90@12’: 124°C
• Scorch:
• 150°C: 5’
• 180°C: 6’

180
T-Butyl Cumyl Peroxide
• NR, EPM, EPDM, EVA , olefins, silicones
and other synthetic rubbers. Gives low
compression set and good heat
resistance.
• Half-life
• 0.1 hr: 160°C
• 1 hr.: 131°C
• 10 hr.: 105°C
• Safe process temp.
• T90@12’: 130°C
• Scorch:
• 150°C: 7’
• 180°C: 3’

181
Di-t-Butyl Peroxide
• Polymerization agent for ethylene and
styrene. Vulcanizing agent for vinyl
silicon rubber, curing agent for
unsaturated polyester resin at
temperatures above 120°C
• Half-life
• 0.1 hr: 162°C
• 1 hr.: 136°C
• 10 hr.: 113°C
• Safe process temp.
• T90@12’: 140°C
• Scorch:
• 150°C: 14’
• 180°C: 4’

182
2,5-Dimethyl-2,5-di(t-butylperoxy)hexane
2,5-Bis-(t-butylperoxy)-2,5-dimethylhexane
• Used with polyolefins, EPDM, EPM, PE,
NBR, NR, SBR, EVA and fluoroelastomers.
FDA approved. Gives high tensile
strength and hardness, low elongation
and compression set. Can stand higher
temperature of normal mixing equipment
without scorching.
• Half-life
• 0.1 hr: 159°C
• 1 hr.: 132°C
• 10 hr.: 108°C
• Safe process temp.
• T90@12’: 130°C
• Scorch:
• 180°C: 3’

183
1,1-Bis-(t-butylperoxy)-3,3,5-
trimethylcyclohexane
• Used with SBR, EPR, EPDM, EPM, CPE, PE,
EVA and silicones.
• Half-life
• 0.1 hr: 129°C
• 1 hr.: 104°C
• 10 hr.: 83°C
• Safe process temp.
• T90@12’: 110°C
• Scorch:
• 150°C: 3’
• 180°C: 1.5’

184
Ethyl-3,3-di(t-butylperoxy) butylrate

• Used with SBR, NBR, EPDM,

CPE and silicones at low
processing temperatures.

185
Cyclohexylidene bis (1,1-dimethylethyl) Peroxide

• Used with SBR, EPR, EPDM,

EPM, CPE, PE, EVA and
silicones.
• Used in shrink-film
applications.
• Recommended curing
temperature 275°F-350°F.

186
 Benzoyl Peroxide

• Used for all types of silicone

and fluorosilicone rubbers.
O O • Good for thin molding
|| ||
H-C -O -O -C - applications.
• Very effect in continuous
Benzoyl Peroxide
steam vulcanization (CV),
continuous curing tower and
autoclave methods of curing.

187
Bis-(t-butylperoxyisopropyl)benzene
CH3 H 3C
O O
(CH3 )3 C O C(CH 3)
O 3
CH3 H 3C

Bis-(t-butylperoxyisopropyl)benzene

• Used for NR, synthetic ruber and • Scorch:

various olefin copolymers. Less
objectionable odor than dicumyl • 150°C: 8’
peroxide and offers more scorch- • 180°C: 3’
safety. Will bloom at high dosage.
• Half-life
• 0.1 hr: 160°C
• 1 hr.: 133°C
• 10 hr.: 101°C

188
 Butyl-4,4-bis(t-butylperoxy) valerate

• Functions at 300F. Used with BR, CPE and

EPDM.
• Half-life
C(CH3 ) 3
• 0.1 hr: 1143°C
O
O
• 1 hr.: 122°C
O
H 3C
||
O (CH3 ) - CH3
3
• 10 hr.: 103°C
O • Safe process temp.
O • T90@12’: 140°C
C(CH3 ) 3
• Scorch:
Butyl 4,4-bis(t-butylperoxy) valerate
• 150°C: 4’, 180°C: 2’

189
t-Butyl Peroxybenzoate
• Functions at 300F. Used with BR, CPE and
EPDM.
• Half-life
• 0.1 hr: 146°C
• 1 hr.: 122°C
• 10 hr.: 101°C
• Safe process temp.
• T90@12’: 140°C
• Scorch:
• 150°C: 3.5’, 180°C: 1.5’

190
Butyl 4,4-bis(tert-butyldioxy)valerate

• Used for NR and synthetic

rubber.
• Good for adhesives and
sealants.

191
 Peroxides and Co-agents
• Coagents are often used with peroxide cure systems.
• Coagents are multi-functional vinyl monomers which are reactive
towards free radicals.
• Trimethylolpropane triacrylate (TMPTA)
• Trimetholopropane (TMPTMA)
• N,N’-m-phenylene dimaleimide (HVA-2)
• 1,2-polybutadiene
• Diallyl phthalate (DAP)
• Triallyl isocyanurate (TAIC)
• Triallyl cyanurate (TAC)

• Coagents are used to improve the processability of the peroxide

cured polymers and also to modify the physical properties of the
polymers.
• The addition of a coagent can improve the following vulcanizate
properties:
• Improved heat aging
• Higher modulus
• High tensile strength
• High tear strength
• Higher hardness
• Increased abrasion resistance
• Improved compression set
• Lower Mooney viscosity
• Improve rubber/metal adhesion
Credit: Peroxide Vulcanization of Elastomers by Peter Dluzneski of GEO Specialty Chemicals 192
 Peroxide Cure Incompatibles
• Fillers
• Avoid acidic fillers such as channel blacks, clays and acidic silicas
• These will cause ionic decomposition of the peroxides and a
reduction in the state of cure
• Use treated fillers to reduce acidity
• Oils
• Aromatic oils can react with peroxide radicals, reducing the state
of cure
• Naphthenic oils with lower aromatic content can be used
• Paraffinic oils or ester type plasticizers are preferred

193
 Peroxide Cure Incompatibles
• Antidegradants
• Avoid hindered phenols especially
• Avoid amines such as p-phenylene diamines
• Diphenylamines can sometime be used in small amounts
• Quinoline types such as TDQ (TMQ) are preferred
• Resins
• Novolak phenolic reinforcing and tackifying resins should not
be used

194
 Question #13:
Can phenolic antioxidants be used with
peroxide cure systems?
a) Yes
b) No

195
Diamine Cure System

196
 Diamine Cure Systems
• AEM and FKM polymers are often cured with a diamines such as
hexamethylenediamine carbamate (HMDC) or
hexamethylenediamine (HMDA).
• FKMs can be cured with HMDC, HMDA but also dicinnamylidene
hexamethlyene diamine or triethylene tetra amine (TETA)
• Guanidines (DPG and DOTG) are often used with the diamines
when curing AEM.
• Metal oxide such as MgO, CaO, or PbO are used as acid acceptors
in cure systems with diamines when curing FKM polymers.
• The next few slides show how AEM (Vamac) can be cured with
either HMDC or HMDA.

Credits :
• A Review of Fast-Cure Systems for Vamac® Elastomers, Doc. Ref. VAM020507_2, v.1, May 2002,
• Vamac® Polymer and Performance Review, DuPont Vamac Web Site
• Rubber Technology Handbook by Werner Hofmann, Hanser Publishers
• Advancure,A New Curative for Vamac, [Link], Rubber Division ACS, October 2006

197
 HMDC Conversion to HMDA
H2N-(CH2)6NH-C-OH + heat / moisture CO2 + H2N-(CH2)6-NH2
||
(HMDC) O (HMDA)
Hexamethylenediamine Hexamethylenediamine
carbamate

 The HMDC during the heat/moisture in the curing process break downs into
HMDA.
 The HMDA is the actual curative whether starting with HMDC or HMDA.
 Carbon dioxide is given off during the curing process when HMDC is used but
not when HMDA is used.

Credits :
A Review of Fast-Cure Systems for Vamac® Elastomers, Doc. Ref. VAM020507_2, v.1, May 2002,
Vamac® Polymer and Performance Review, DuPont Vamac Web Site
Rubber Technology Handbook by Werner Hofmann, Hanser Publishers
Advancure,A New Curative for Vamac, [Link], Rubber Division ACS, October 2006

198
 Hexamethlyenediamine Cure Mechanism

Credits :
A Review of Fast-Cure Systems
for Vamac® Elastomers, Doc. Ref.
VAM020507_2, v.1, May 2002,
Vamac® Polymer and
Performance Review, DuPont
Vamac Web Site
Rubber Technology Handbook by
Werner Hofmann, Hanser
Publishers
Advancure,A New Curative for
Vamac, [Link], Rubber Division
ACS, October 2006

199
Bisphenol Cure System

200
 Bisphenol Cure System
• Bisphenol cures are often used to cure FKM
• Developed in the 1960s
• They are based on two parts – an accelerator and a
curative
• Accelerator is benzyl tri-phenyl phosphonium
chloride (BTPPC)
• Curative (Bisphenol AF) is
hexafluoroisopropylidenediphenol

201
Benzyl tri-phenyl phosphonium chloride (BTPPC)

202
 Bisphenol AF
hexafluoroisopropylidenediphenol

203
 References
• Rubber Technology edited by John Dick, Chapter 14, p.367, “Ester Plasticizers and Processing
Additives by R.R. Stone
• Struktol Rubber Additives Website – product datasheets
• Eastman Chemical Tackifiers Website
• Further Advances in Use of Polymer Process Aids to Reduce Material Cost by Chandrasekaran,
[Link], Hari Chandra, Krish Chandran of Quantum Polymer presented at the ACS Rubber
Division Meeting, Cleveland, OH, 2011
• Changing Elastomer Properties with Zinc Soaps by John Vander Kooi, Jerry Sherritt of Struktol
and [Link], [Link] of Schill and Seilacher, presented at ACS Rubber Division, Orlando,
FL, October 1993
• Improved Natural Rubber Processing and Physical Properties by Use of Selected Compounding
Additives by Colin Clarke, Manfred Hensel of Schill + Seilacher, presented at the ACS Rubber
Division, Pittsburgh, KY, October 2009

204