APPLICATION BULLETIN

Basic Principles of Peroxide-Coagent Curing of Elastomers

This bulletin discusses the basic principles of peroxidecoagent curing of elastomers. It answers basic questions about the elastomer curing process using peroxide and a coagent. What is a coagent? A coagent, or more specifically a peroxide curing coagent, is a monomeric or oligomeric system that when used in a peroxide cure system enhances crosslinking. What are the names of these coagents? The most common coagents in use in the rubber industry today are esters of acrylic and methacrylic acid, although other types are used. The first three listed below are the most common. This list contains some of the coagents used in peroxide curing.
Ethylene glycol dimethacrylate 1,3 Butylene glycol dimethacrylate Trimethylolpropane trimethacrylate Difunctional Saret crosslinking agent Trifunctional Saret crosslinking agent Trifunctional Saret crosslinking agent Difunctional Saret crosslinking agent Difunctional Saret crosslinking agent Saret modified metallic diacrylate

Butadiene/styrene copolymer Methacrylate resin High vinyl butadiene homopolymers High vinyl butadiene homopolymers High vinyl butadiene homopolymers High vinyl butadiene homopolymers High vinyl butadiene homopolymers High vinyl butadiene homopolymers

Ricon 100 Ricacryl 3500 Ricon 150 Ricon 152 Ricon 153 Ricon 154 Ricon 156 Ricon 157

SR206 SR297 SR350 SR516 SR517 SR519 SR-521 SR522 SR633 SR634 Ricobond 1756

Why is a coagent used? Coagents are used with peroxide to increase the efficiency of cure, i.e., to give more crosslinks, or a tighter cure. Also, when coagents are used in quantities exceeding 1 part per hundred rubber (phr), they contribute significantly to the nature of the polymer network and cause changes in properties in addition to those associated with crosslinking efficiency. How do coagents work? To answer this, first consider a simplified schematic of the mechanism of peroxide curing. When a peroxide is heated it splits into two free radicals: R-O-O-R D 2 (R - O)*
* denotes free radical

Saret modified metallic dimethacrylate Adhesion promoter

These free radicals then typically (other side reactions can infrequently occurs) extract hydrogen from the polymer chain: R - O* + PH

P* + ROH

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Polymer radicals then react with other polymer radicals to form carbon-to-carbon crosslinks. P* + P*

PP

The presence of a coagent in this system provides more reactive sites where this reaction can occur, e.g., in the case of SR350, trimethylolpropane trimethacrylate (TMPTMA), the following reaction can occur: * R - O* + + ROH Monomer (SR350) can combine with additional monomer. * + *

Different peroxides decompose at different temperatures. The rate of thermal decomposition of a peroxide (half-life) helps determine the time and temperature for compounding, shelf life and curing. Half-life is the time necessary for 1/2 of the peroxide to thermally decompose or break down into free radicals. Peroxide tables supplied by the manufacturer typically list the half-life in time for a given peroxide and temperature. The table below shows how much peroxide has decomposed for various half-lives. Half-Life vs. Peroxide Decomposition Number of % of Original Peroxide Half-Lives Decomposed
1 2 3 4 5 6 7 8 9 10 50 75 87.5 93.8 96.9 98.4 99.2 99.6 99.8 99.9

*
(M=2 or more)

Combined monomer reacts with active polymer. P P

Thus, in the final network, polymer chains can be connected with TMPTMA molecules ranging from one to several. This increase in the length of the network chain length leads to higher elongation for a given modulus. Further improvement in elongation can be achieved with metallic coagents where ionic bonding allows for chain slippage and reforming along the hydrocarbon chain:

How is the cure time needed calculated from the half-life ? Assume 99.9% peroxide decomposition is desired. From the half-life table above, ten half-lives are needed to accomplish this. Specific half-life data supplied by the manufacturer shows the half life time for various peroxides at specific temperatures. If this table specifies a half-life time of 2 minutes at 160C then the cure time is calculated 2 X 10 (or 20) minutes. As a rule of thumb, a minimum of six half-lives should be used to calculate the time required for complete cure. Can the cure time be determined without calculation? Yes. Using the recommended cure temperature supplied by the manufacturer, run the compound on a cure meter (examples are oscillating disc rheometer and ODR) and determine the cure time, generally specified as TC90. It is generally accepted that optimum cure is achieved at 90% of the completed cure. Even if the cure time is calculated from half-life data, an ODR test should be run to confirm results. This is necessary since the rubber used can influence the cure time.
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Does coagent or peroxide dictate the cure temperature? The peroxide used dictates the cure temperature.

Do coagents effect the cure time? Sartomers monomeric coagents generally reduce cure time. Sartomers oligomeric coagents such as the Ricon, Ricacryl, and Ricobond series of products do not affect the cure time. One of the best Sartomer coagents for cure time reduction is Saret SR519. For an EPDM cure at 320F, the peroxide alone TC90 time is18 minutes. Use of 2 PHR Saret SR519 reduced this cure time to 11 minutes.
 
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Dicumyl peroxide (40% active) SR350 Saret SR517 Crosslinking Agent Mooney Data-ML @ 250F Minimum Viscosity 5 pt. rise (minutes) Physicals Durometer (Shore A) Modulus (100%) Tensile Strength (psi) Elongation (1%)

4 52 40 75 870 2170 180

4 10 37 4.5 85 2175 2400 120

4 10 36 45 85 2200 2375 115

 

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Do Saret and Ricon crosslinking agents work with all elastomers? Elastomers mentioned previously that can be peroxide cured are good candidates. In some cases Saret crosslinking agents are more efficient than in others, but in all cases retardation is shown in the 250F range and no difference occurs at curing temperatures. What elastomers can be cured with peroxide-coagent systems?
NR IR BR SBR NBR HNBR CR AU/EU CSM CM EPR/ EPDM Q BIIR FKM PE ACM/EAM

* 7.5 phr 40% active dicumyl peroxide

Dont coagents make the cure scorchy? Yes, some may, but Sartomer has corrected that problem with the use of a patented scorch retarder. Products modified with this retarder are labeled Saret. The name Saret is derived from Sartomer retarder. Sartomer has built a coagent system that is not scorchy in the processing temperature range (250F), and does not retard at curing temperatures (above 300F). Consider the following formulation and processing data: The mooney scorch at 250F with SR350 is 4 1/2 minutes, whereas, with Saret SR517 the scorch is 45 minutes, which is also greater than peroxide alone. Table 1 Processing study of a nitrile test recipe cured with three different peroxide systems.
Compound NBR (Medium ACN) FEF Black Zinc Oxide 1 100 40 5 2 100 40 5 3 100 40 5

Natural Rubber Polyisoprene Polybutadiene copolymers Styrene butadiene rubber Acrylonitrile butadiene rubber Hydrogenated butadiene acrylonitrile rubber Polychloroprene Polyurethane Hypalon Clorinated polyethylene Ethylene-Propylene co-and terpolymers Silicone Bromobutyl rubber Fluor Rubber Polyethylene Polyethene

What elastomers cannot be cured with peroxide-coagent systems?

IIR CO/ECO PPO PVC IM PB PP Butyl rubber Epichlorohydrin rubbers Polypropylene oxide rubbers Polyvinyl chloride Polyisobutene Polybutene-1 Polypropylene

What are the most common peroxides used? A table listing some of the most common peroxides is presented below. This is not a comprehensive list, but Commonly Used Peroxides
Chemical Name 2,5-Dimethyl-2,5 BIS (Tert-Butyl Peroxy)Hexyne-3 Di-Tert-Butyl Peroxide 2,5-Dimethyl-2,5 BIS (Tert-Butyl Peroxy)Hexane Tert-Butyl Cumyl Peroxide BIS(Tert-Butyl Peroxy Isopropyl) Benzene Dicumyl Peroxide 4,4-Di-Tert-Butyl Peroxy N-Butyl Valerate 1,1-Di-Tert-ButylPeroxy-3,3,5-Trimethylcyclohexane

is meant to provide some insight into the peroxide chemistries available.

Trade Name Luperox 130/Triganox 145 Triganox B/Di-t-B-Peroxide Luperox 101/Triganox 101 Luperox 801/Triganox T Luperox F/Perkadox 14/VulCup Luperox DCP/DiCup Luperox 230/Triganox 17 Luperox 231/Triganox 29

Typical Cure Temp. C 195 190 185 175 180 160 160 150

What are the Saret coagents used?

Saret SR516 Saret SR517 Saret SR519 Saret SR521 Saret SR522 Saret SR633 Saret SR634 Form Liquid Liquid Solid Liquid Solid Solid Solid Functionality 2 3 3 2 2 2 2 Property Good Scorch General Purpose Fast Cure/ Low Set Hot Tear Good Compression Set Rubber/Metal Adhesion Elongation/ Hot Tear

What are the benefits of using a coagent system?

Lower compression set Higher resilience Higher modulus Higher hardness Lower viscosity Improved resistance to oils and fuels Improved heat aging Improved rubber to metal adhesion Faster cure Improved peroxide efficiency Higher tensile strength Good room temperature & hot tear Improved dynamic flexibility (metallic coagents)

Do coagents only work with peroxides? No, coagents work in any free radical cure system. In elastomers these free radicals are generated by peroxides, but they can also be generated by other sources, e.g. UV light, beta and gamma irradiation, etc. VAZO are nitrogen compounds that break down like peroxides but at lower temperatures. What is the order of addition of materials? Coagents can be successfully added at various stages of the mixing cycle. In general, solid (metallic) coagents should be added as early into the mixing cycle as possible to insure thorough dispersion. One rule of thumb is to add the peroxide portion of the recipe last. This will allow for sufficient mixing but prevent the peroxide from prolonged sheer (and resulting temperature increase) which could prematurely activate the peroxide.
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What are the advantages /disadvantages of peroxide/coagent vs sulfur?

Advantages Excellent heat stability Excellent compression set at elevated temperature No reversion Good shelf life stability Vulcanization of saturated polymers Co-vulcanization of blends Simple compounding High temperature processing without scorch No contact discoloration Better hot tear Better dynamic properties (metallic coagents)

Disadvantages Higher cost of raw materials Interference with antidegradants Surface tackiness in presence of oxygen

Why do peroxide/coagent systems have better heat stability? In a normal sulfur cure system the crosslinks formed are a random assortment of monosulfide and disulfides, as well as polymeric sulfides. This so-called normal sulfur crosslink network requires 49 kilo calories to break the bonds. A perfect monosulfide crosslink requires 64 kilo calories to degrade. A carbon-carbon crosslink, as provided by a peroxide cure system, require 84 kilo calories for degradation to occur. This difference in caloric values for bond breakage is one of the major reasons why peroxide and peroxidecoagent cure systems are used over sulfur cure systems for improved heat aging. This is illustrated in the graph below:
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curing, they crosslink into the system and become part of the rubber matrix. Saret SR516 and Saret SR521 are effective plasticizers and upon curing give moderate hardness rubbers. Saret SR517, Ricon 153, and Ricon 154, produce high hardness rubbers. Saret SR519 is recommended for high hardness and fast cure. The relationship between hardness and Mooney viscosity versus coagent concentration is shown below for Saret SR517 in NBR.
  
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How do Sartomer coagents compare with other coagents for improved compression set? Ricon 153, Ricon154, Saret SR522 (tri-allyl isocyanurate) and Saret SR519 compare favorably to TAC. Sulfur cure is reported to give better hot tear performance than peroxide cure. How do Sartomer coagents effect hot tear? Saret SR 633 and Saret SR634 can be used with most rubbers to improve hot tear performance. Unlike conventional coagents, Saret SR633 and Saret SR634 increase tear resistance of peroxide-cured rubbers even at high hardness and high tear modulus. Saret SR634 is the best coagent available for hot tear properties. The hot tear strength of EPDM cured with peroxide and Saret SR634 versus sulfur cured EPDM at the same modulus value is illustrated below. Hot tear strength is also improved with Saret SR516 and SR521. These are liquid coagents which also lower Mooney viscosity.

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Do all the Sartomer coagents offer improved rubber to metal adhesion? The Ricobond coagents, Ricacryl 3500, Saret SR633 , and Saret SR634 offer the greatest improvement. Saret SR634 offers improved adhesion (80% of Saret SR633) with improved water resistance and higher elongation. Can Sartomer coagents be used as reactive plasticizers? Both Saret and Ricon liquid coagents behave as plasticizers to aid in processing the rubber. But upon
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Saret SR634 Saret SR516 Saret SR521 Ricacryl 3500 Ricon 150 Ricon 152 Saret SR516 Saret SR517 Saret SR519 Saret SR519 All Sarets All Sarets Ricon 150 Ricon 152 Ricon 153 Ricon 154 Ricon 157

Processability

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Fast Cure Heat Stability Scorch Resistance

Which coagents give the best elongational characteristics? Highest elongations are obtained with lower functionality coagents. The graph below shows the superiority of the Saret SR633 and Saret SR634 previously mentioned. For a given modulus, the highest elongation is obtained with Saret SR634. The trifunctional Saret SR517 and TAIC (tri-allyl isocyanurate) give lower elongations.
           
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What precautions should be taken when processing peroxide/coagent systems? Contrary to vulcanization with sulfur, zinc oxide/stearic acid is not necessary for the reaction. However, additives such as ZnO can be included to increase hardness. What materials can interface with these coagents? Beware of interference from:

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What are the Sartomer recommendations for the several properties? Sartomers recommendation for picking the right coagent for the job are:
FDA approvable Compression Set Ricon 153 Ricon 154 Saret SR519 Ricon 153 Ricon 154 Saret SR522 Saret SR633 Ricobond 1756

(Acid) Fillers Some Process Oils, Especially Aromatic Types Most Antioxidants Permanax TQ is Relatively Undetrimental at Max. 1 PHR

In what applications can coagents be used? Applications involving peroxide cure include paper rolls, O-rings, automotive seals, automotive hose, oil well packers, swab cups, golf balls, butterfly valves, diaphragms, belts, mats, shock absorbers, engine mounts, adhesives, cables, coatings, sealants, and foam packing. Acrylic coagents and Ricon butadienes are liquid systems. SR633 and SR634 are solids. Both behave as plasticizers; but upon curing these materials become part of the polymeric system.

Metal Adhesion

What products offer improved oil and fuel resistance? These coagents are acrylic-type systems, and acrylates and methacrylates have excellent resistance to virtually all oils and fluids. Therefore, by grafting these coagents to the elastomer the fluid resistance is increased, i.e., as in the case of SR350 in various NBR rubbers. Polybutadiene based coagents have especially good resistance to water-based fluids, oils, and fuels. What products yield improved aging? In a normal sulfur cure system the crosslinks formed are a random assortment of cyclic, sulfide, polymeric sulfide and mono and disulfides. This so-called normal sulfur crosslink requires 49 kilo calories to degrade. A perfect monosulfide crosslink requires 64 kilo calories to degrade. A carbon-carbon crosslink, as provided by a peroxide cure system, requires 84 kilo calories for degradation to occur. This difference in caloric values accounts for the major reason why peroxide and peroxide-coagent cure systems are used. The viscosity with coagents is very low. Exactly. This was pointed out earlier. Compared with straight peroxides the Mooney viscosity is a lot lower with coagents, but the cured hardness is higher. Dont high styrene resins do the same thing? To some extent, yes, but high styrene resins adversely affect compression set. They are thermoplastic in nature and do not crosslink. Acrylic type and high

vinyl polybutadiene resins coagents generally do not affect compression set, and in many cases actually reduce compression set. Do phenolic resins behave similarly to high styrene resins? Yes, in regard to compression set, i.e., they harden, but degrade compression set. What other benefits are obtained by using a coagent type system? Apart from increased hardness and lower viscosity without affecting compressions set, modulus is increased, oil and fuel resistance is improved, resilience is improved, heat aging is vastly improved, and there is improved tackiness before cure. What products offer improved modulus? This is very similar to hardness; as the amount of coagent is increased the modulus increases. This can result in improved abrason and wear resistance. Will Saret acrylic crosslinking agents replace all the known acrylic coagents in peroxide systems? In most applications, yes. Some applications, however, never have a scorch problem and, therefore, there is no reason for Saret products. Will Peroxide/Coagents replace sulfur curing of rubber? In most applications, yes. However, they do require different processing equipment and mixing methods to achieve superior performance properties in rubber.

The information in this bulletin is believed to be accurate but all recommendations are made without warranty, since the conditions of use are beyond SARTOMER Companys control. The listed properties are illustrative only, and not product specifications. SARTOMER Company disclaims any liability in connection with the use of the information, and does not warrant against infringement by reason of the use of its products in combination with other material or in any process.