Select Accelerators for Rubbers

Accelerators are added in small amounts to speed up the curing of adhesives by reducing the cure time and temperature of elastomers,
particularly latex systems. The selection of an accelerator will depend on the specific vulcanizing system and curing properties.

Explore the classification of accelerators, the checklist to select the right accelerator based on the specific vulcanizing systems and
curing properties.
 O v er vie w
o Function of Accelerators
o Classification of Accelerators for Rubbers
o Selecting the Right Vulcanizing Agents
o Checklist to Select an Accelerator
o Selecting the Right Accelerator for Your System

Function of Accelerators
Accelerators are materials that are added in small amounts to speed up the curing of adhesives. The first accelerators were used in the
19th century. In that period, mostly oxides and hydroxides of inorganic compounds like lead, zinc, magnesium and calcium were brought to
use. These days organic compounds are majorly used as accelerators.

Accelerators have made elastomers particularly latex systems, viable adhesives by reducing their cure time and temperature. Accelerators
have also been found to be beneficial as a crosslinking agent in influencing final performance properties.

Definition of Accelerators

An accelerator is a material that, when mixed with a catalyst or a resin, speeds the chemical reaction between the catalyst and the resin.
Therefore, accelerators are not usually employed alone, but they are used within a cure package.

The accelerator itself does not usually become part of the final molecular structure, but it may cause physical or chemical changes in the
reactant molecules that increase the speed at which they react. The accelerator concentration may or may not be fully consumed by the
reaction.

Usually, the accelerator does not contribute directly to changes in the final physical or chemical properties of the formulation. However, it
could indirectly affect properties by controlling the speed and order of side reactions in the polymerization process. Accelerators will also
affect practical, rate-related properties such as storage life, working life, gel time, set time and so forth. Therefore, accelerators should be
used in adhesive or sealant formulation only when they are needed to control the cure rate and after their full effect on the final properties is
determined.
The term "accelerator" is very appropriate in that it succinctly describes the function of the additive. However, there is often confusion
resulting from misuse or overuse of the term.

An accelerator has the following unique properties.

o It is used along with a catalyst, curing agent or hardener to increase the rate of reaction, to lower the polymerization
temperature, or to improve the efficiency of the reaction.
o It does not become part of the final molecule and does not directly affect the final chemical or physical properties of the
formulation. However, it may indirectly affect these properties by controlling the rate or order of competing reaction that
occurs within the polymerizing system.
o It is used in small concentrations, and the concentration of accelerator to other ingredients in the formula is usually of no
consequence.
o Accelerators can be completely consumed by the polymerization reaction or there may be an accelerator leftover
depending on the formulation and polymerization conditions.

Accelerators are often confused with curing agents, hardeners, and catalysts.

Term Definition

o An accelerator is a material that, when mixed with a catalyst and resin, speeds
up the chemical reaction between the catalyst and the resin (usually in the
Accelerator polymerizing of resin or vulcanization of rubbers).
o Accelerators are also known as promoters when used with polyester resins and
vulcanizing agents when used with rubbers.

o An inhibitor or retarder is sometimes incorporated into an adhesive formulation

Inhibitor, retarder
to de- accelerate the curing rate.

Activator o Activators (e.g., zinc oxide and stearic acid) are used to help initiate the cure.

Curing agent, hardener, o A curing agent is a substance added to an adhesive to promote the curing
vulcanizing agent reaction by taking part in it. These affect cure by chemically combining with the
 base resin and becoming part of the final polymer molecule. They are
specifically chosen to react with a certain resin.
o Curing agents will have a significant effect on the curing characteristics and on
the ultimate properties of the adhesive system. Concentrations can be large and
variations in concentration can be used to adjust properties.

o Catalysts remain unchanged in the curing reaction, causing the primary resin to
crosslink and solidify. Acids, bases, salts, sulfur compounds and peroxides are
Catalysts commonly used. Only small quantities are usually required to influence curing.
Unlike hardeners, the amount of catalyst used is critical, and poor bond
strengths can result when resins are over or under catalyzed.
Definitions of Some Additives that Control Curing Mechanism in Polymeric Systems

Classification of Accelerators for Rubbers

Elemental sulfur is the predominant vulcanizing agent for general-purpose rubbers. It is used in combination with one or more accelerators
and an activator system comprising zinc oxide and a fatty acid (normally stearic acid).

The most popular accelerators are delayed-action sulfenamides, thiazoles, thiuram sulfides, dithocarbamates and guanidines.

Part or all of the sulfur may be replaced by an accelerator that is also a sulfur donor such as a thiuram disulfide. The accelerator determines
the rate of vulcanization, whereas the accelerator to sulfur ratio dictates the efficiency of vulcanization and, in turn, the thermal stability of the
resulting vulcanizate.

Certain elastomers such as chloroprene can be vulcanized by the action of metal oxides such as zinc oxide as well as sulfur. As a result,
several of the same accelerators that are used with sulfur vulcanization systems can be used with zinc oxide/neoprene systems. Because
there are so many, accelerators are generally classified by chemical family.

Accelerators are also classified as being primary or secondary.

o Primary accelerators are relatively slow and have a delayed onset of cure. These are used primarily to build physical
properties.
o Secondary accelerators are fast and mainly used to affect the cure rate.
The table below provides a summary of the major accelerator families and specific types within a family.

Family Common Types General Characteristics

o They are the condensation products of aldehydes

and amines.
o Their accelerating effect is majorly decided by the
aldehyde type, and a mole ratio of aldehyde Á
amine used in the reaction mixture.
o Hexamethylene tetramine is an inexpensive
secondary accelerator.
o Cyclohexylethylamine
o Primary accelerator for natural and synthetic
Hexamethylene tetramine
rubbers.
Amines and (HMT)
o Used as secondary accelerators with
aldehyde-amines o Ethyldiene aniline (EA)
dithiocarbamates, and in combination with
o Butyraldehyde dianiline (BA)
sulfenamides and thiazoles.
condensation product
o Cyclohexylethylamine has a strong secondary
acceleration effect with dithiocarbamates for
adhesives solutions and zinc n-ethylphenyl
dithiocarbamate is used in combination with
cyclohexylethylamine.
o Some amines are used as activators for active silica
fillers.

o Less important as individual accelerators because

of lower vulcanizing speed.
o Diphenyl guanidine
o Important secondary accelerators for thiazoles and
o DPG Di-o-tolyl guanidine
thiurams.
Guanidines (DOTG)
o Can be used as an activator of sulfenamides to
o DOTG Triphenyl guanidine
increase the reaction rate.
(TPG)
o Slow development of crosslink density.
o Fatty acids have a retarding effect.
 o Synergistic with thiazoles, sulfenamides, and
thiurams.
o Presence of ZnO is necessary.

o Tetramethyl thiuram disulfide o Faster onset of cure and more complete cure than
(TMTD) thiazoles.
o Tetraethyl thiuram disulfide o Especially good for isoprene and chloroprene.
(TETD) o At high dosages (2-5%) can eliminate sulfur.
o Tetramethyl thiuram o Good corrosion resistance to metals.
Thiurams
monosulfide (TMTM) o Good heat resistance in vulcanizate.
o Dipentamethylene thiuram o Used as a secondary accelerator with
tetrasulfate (DPTS) dithiocarbamates, sulfenamides, or thiazole.
o Dipentaethylene thiuram o Higher molecular weight have slower cure rates.
(DPTT) o Rate of cure: TMTD>TETD>DPTT>TMTM

o Zinc diethyl dithiocarbamate

(ZDEC)
o N-dimethyl dithiocarbamate
o Delayed action.
(ZDMC)
o Zinc compounds are used most frequently.
o Zinc N-dibutyl
o Low-temperature vulcanization in the shortest time.
dithiocarbamate (ZDBC)
Dithiocarbamates o Used in lattices and solution cements.
o Piperdiene pentamethylene
o Primary accelerator for natural and synthetic
dithiocarbamate (PPD)
rubbers.
o Sodium diethyl
o Higher molecular weights have slower cure rates.
dithiocarbamate (SDC)
o Zinc ethyl phenyl
dithiocarbamate

o 2-Mercaptobenzothiazole o Zinc salt (ZMBT) is used mainly with latex

(MBT) compounds.
Thiazoles o 2,2’-Dithiobenzothiazole o Relatively long activation time.
(mercapto (MBTS) o Good resistance to aging.
compounds) o Sodium salt of MBT o Used alone or in combination with others (premixed
o 2,4-dinitrophenyl products are available).
mercaptobezothiazole (DMB) o Very fast with basic accelerators such as HMT.
 o Zinc mercaptobenzothiazole o All combinations are synergistic.
(ZMBT) o In CR, MBT and MBTS act as retarders. Rate of
o 2- cure: MBT>ZMBT >MBTS
morpholinochiobenzothiaxole
(MBS)

o Largest class of accelerator in terms of quantity and

value.
o Delayed onset of cure.
o N-cyclohexyl benzothiazole-
o Sulfenamides are generally used alone, but the rate
2-sulfenamide (CBS)
can be increased by secondary accelerators (e.g.,
o N-1-butylbenzothiazole-2-
Sulfenamides thiurams).
sulfenamide (TBBS)
o Higher molecular rate generally gives slower cure
o N-dicyclohexylbenzothiazole-
rates.
2-sulfenamice (DCBS)
o Provide good resistance to reversion.
o Limited shelf life (1 yr) under controlled conditions.
o Rate of cure: CBS>TBBS

o Mainly used during vulcanization of chloroprene

rubbers.
o High crosslink density when used with zinc oxide.
o Used mainly for vulcanization of chloroprene and
o Ethylenethiourea (ETU) EPDM.
Thioureas o Diethlyenethiourea (DETU) o Thiazoles can be used as retarders.
o Diphenylthiourea (DPTU) o Use is decreasing because of health concerns (dust
is an issue).
o Primary accelerator with polychloroprene and
secondary with NR, EPDM, and SBR.
o Cure rate: ETU>DETU>DPTU

o They are generally used with other accelerators.

o They show an optimum accelerating effect when
Dithiophosphates o Zinc dithiophosphate used in combination with thiazoles.
o Fast cure rates.
o Higher molecular weight reduces the cure rate.
 o Used mainly in crosslinking of EPDM.
o Used in combination with thiazoles, sulfenamides
and dithiocarbamates.

o Zinc isopropyl xanthate (ZIX)

o Similar to dithiocarbamates.
o Sodium isopropyl xanthate
Xanthates o Sometimes used for self-vulcanizing adhesives
(SIX)
solutions and lattices.
o Zinc butyl xanthate (ZBX)

Common Types & General Characteristics of Accelerator Families

Selecting the Right Vulcanizing Agents

The chemistry of rubber cure or rubber vulcanization is complex. There are several rubber vulcanization systems possible based on reactions
with different chemicals. The selection of an accelerator will depend on the specific vulcanizing system.

Sulfur vulcanization processes are the most common, but peroxide and metal oxide systems are also used in the adhesives industry.

Check out the vulcanization systems generally used with common elastomers below.

Elastomer Sulfur Zinc oxide Peroxide Phenolic Diamines Diisocyanates

Polyurethane ✔ ✔

Polychloroprene ✔ ✔ ✔

Natural rubber ✔ ✔

Styrene butadiene
copolymers ✔ ✔

Silicone ✔
 Ethylene propylene
diene monomer ✔ ✔

Acrylonitrile-butadiene
copolymer ✔ ✔

Butyl rubber ✔ ✔

Isoprene ✔

Polysulfide ✔

Natural rubber and many synthetic rubbers, contain unsaturated molecules (i.e., molecules that contain double bonds providing sites for the
vulcanization or crosslinking reaction). It is through these double bonds that vulcanization occurs.

The most common curing systems for rubber vulcanization are based on sulfur. While sulfur alone will cure unsaturated rubbers on heating,
the process is slow and inefficient. The mechanisms of sulfur curing are not well understood, but it is thought to include, among other things,
the formation of sulfide or disulfide links between chains and the abstraction of protons from adjacent chains with the chains crosslinking at
the remaining unshared electrons.

To speed the vulcanization process, accelerators are used. These are usually complex organic compounds, often of proprietary composition.
They include:

o Sulfur-containing compounds such as thiocarbamates, thiazoles, sulfenamides, and thiuram sulfide

o A few non-sulfur types such as phenols, guanidines, and amines.

Except for the fact that accelerators contribute to vulcanization little is known about their specific action in speeding up vulcanization.
Optimizing Properties for Rubber Vulcanization

It is the responsibility of the formulator to optimize the desired properties for the finished adhesive. This can be done by manipulating the
levels of crosslinkers, activators, and accelerators. Typical vulcanization systems for several sulfur-cured elastomers are provided in the table
below. Generally, the optimum components and concentrations are determined by trial and error.

In rubber, an accelerator to sulfur ratio typically of 1:5 is called a conventional vulcanizing system. It gives a crosslinked network. The same
principles apply to synthetic rubbers, although the optimum accelerator to sulfur ratio may not be the same as in natural rubber.

Acrylonitrile-
Styrene butadiene Ethylene propylene
Natural rubber butadiene Butyl rubber
copolymers diene monomer
copolymer

Sulfur 2.5 2.0 1.5 2.0 1.5

Zinc oxide 5.0 5.0 5.0 3.0 5.0

Stearic acid 2.0 2.0 1.0 2.0 1.0

Sulfenamide (CBS) 0.6 1.0

Thiazole (MBTS) 1.5 0.5

Thiazole (MBT) 1.5

Thiuram (TMTD) 1.0 0.5

Dithiocarbamate (ZDBC) 1.5

Vulcanization Systems for Several Sulfur-Cured Elastomers
Solvent-borne Vulcanizable Natural Rubber Adhesive Formulation

Vulcanized adhesives are usually supplied in two parts that are mixed together at the time of use. One part contains sulfur and no
accelerator, and the other part contains accelerator and no sulfur. The mixed adhesives are stable for about 8 hrs after mixing and cure
completely in about 2 weeks.

The table below provides an example of a starting formulation for a solvent-borne vulcanizable natural rubber adhesive using dithiocarbamate
as an accelerator. It is used for bonding leather, fabric, paper, and elastomers.

Component Ingredients Parts by Weight

Natural rubber 10

Zinc oxide 1

Part A Antioxidant 0.1

Sulfur 0.1

Solvent 80
Dithiocarbamate
Part B accelerator 4
(10% solution)
Starting Formulation of a Solvent-Borne Vulcanizable Natural Rubber Adhesive

Checklist to Select an Accelerator

Selecting an accelerator system is one of the most difficult problems in compounding. A number of factors must be considered while selecting
an accelerator. Selection of the proper accelerator and the amount to be used for any application depends on:
 o The resin
o The temperature at which the resin is to be cured
o Properties such as working life, shelf life, etc.

With the choices narrowed down to several products, questions of purely an economic or practical nature will probably determine the final
choice of an accelerator. Sometimes no single accelerator is available that can meet all the requirements. Therefore, a combination of
accelerators or catalysts and accelerators must be used to obtain the optimum results.

Since accelerators are used at a very small weight or volume percentage in a formulation, losses should be avoided in mixing. These losses
could be due to dusting and escape of the accelerator if the accelerator is solid. For even dispersion in the formulation, the accelerator should
be preferably in a powder or liquid form.

Accelerators also should be added last in the formulation. This helps to avoid the loss of the accelerator due to premature reactions with the
system's chemistry. Important compounding or handling properties include the following:

o Free-flowing for automatic weighing and bulk handling systems

o No caking in transit and storage
o Supply forms need to resist abrasion and break-up
o Particle uniformity to prevent separation of blends in bulk storage
o Dust-free to meet industrial hygiene standards
o Improved processing and dispersion to shorten mixing cycles
o High purity to target specific reaction sites
o High activity to prevent undesirable side effects
o Shelf-life stability

The list below offers a questionnaire that may be useful for selecting an accelerator or in discussing the formulator's needs with the
accelerator supplier.

☑ What are the base polymers, curing agents, catalysts and other components in the adhesive or sealant formulation?

☑ What commercial accelerators have been commonly used with the base polymer?

☑ What is the solubility of the accelerator in the adhesive or sealant system?

☑ What form is required for the accelerator (solid or liquid)? How is it to be incorporated into the formulation?

☑ What is the main reaction process (heat cure, moisture cure, UV cure, etc.) and what are the various processing stages?

☑ What are the curing conditions required (temperature, time, etc.) and what is the expected variance in production?

☑ Is the product to be a one-component or a two-component system?

☑ What is the expected shelf life of the final formulation?

☑ What is the expected working life (or pot life) of the final formulation?

☑ What is the known safety or health hazards for formulating the catalyst into an adhesive or sealant system and what are the known
hazards to the end-user in applying the system?

☑ What are possible adverse effects on other properties of the adhesive or sealant formulation (uncured as well as cured)?

Selecting the Right Accelerator for Your System

Selection According to Your Elastomer

When a compounder sets out to develop a new curing system, he or she proceeds in two steps:

o A base system is selected which will work with the base polymer chemistry and provide a level of performance requirements.
o It will be necessary to refine that system to meet both the curing characteristics needed and the final physical properties.
The table below will help you select the accelerator according to the chosen elastomer.

Primary or
Accelerator Onset of Crosslinking Water Recommended
Secondary Cure Rate Form
Family Cure Density Solubility Elastomer
Accelerator

Aldehyde- o Polyurethane
amines and Slow to Liquid o Polychloroprene
Secondary Short Medium Soluble
amines medium o Polysulfide

o Polyurethane
Guanidines Secondary Slow to Small to Slightly o Polychloroprene
Moderate Solid
medium medium soluble o SBC

o Polychloroprene
Generally o EPDM
Thiurams Secondary Very fast Short High Solid
insoluble o ACN
o Isoprene

o Polychloroprene
Liquid o Natural Rubber
Generally
Dithiocarbamates Both Ultra-fast Very short High and o SBC
insoluble
solid o EPDM
o Isoprene

o Natural Rubber
Generally o SBC
Thiazoles Both Moderate Moderate High Solid
insoluble o EPDM
o Isoprene

o Natural Rubber
Moderate to Generally o SBC
Sulfenamides Primary Fast Long Solid
High Insoluble o EPDM
o Butyl Rubber
 Solid o Polychloroprene
Thioureas Secondary Ultra-fast Short High Soluble and o Natural Rubber
Liquid o EPDM

o Polychloroprene
o Natural Rubber
Slow to
Xanthates Secondary Short Medium Soluble Liquid o SBC
Medium
o EPDM
o Isoprene
Accelerator Families & Properties Recommended for Certain Elastomers

Selection According to Curing Properties of your System

The selection of an accelerator family will also depend on:
o The various cure properties (cure rate, speed of cure onset, crosslink density)
o The convenience of compounding (solubility and form) that is provided by the accelerator.
These parameters are summarized for the main accelerator families in the table below.

Primary or
Accelerator Onset of Crosslinking Water
Secondary Cure Rate Form
Family Cure Density Solubility
Accelerator

Aldehyde-amines Slow to
Secondary Short Medium Soluble Liquid
and amines medium

Guanidines Secondary Slow to Small to

Moderate Slightly soluble Solid
medium medium

Generally
Thiurams Secondary Very fast Short High Solid
insoluble

Generally Solid and

Dithiocarbamates Both Ultra-fast Very short High insoluble Liquid

Generally
Thiazoles Both Moderate Moderate High Solid
insoluble

Moderate to Generally
Sulfenamides Primary Fast Long Solid
High Insoluble

Thioureas Ultra-fast Solid and

Secondary Short High Soluble
Liquid

Dithiophosphates Both Fast Short High Insoluble Liquid

Xanthates Secondary Ultra-fast Short High Soluble Solid

Property Parameters for Accelerator Families