Peroxide curing

The mechanism of peroxide crosslinking of elastomers is much less intricate than that of sulfur vulcanisation. Crosslinking is initiated by the thermal decomposition of a peroxide, which is the overall cure rate determining step. Next, the active radicals thus formed abstract hydrogen from elastomer chains to form macroradicals. Finally, crosslinking results either from the combination of two macroradicals or from the addition of a macroradical to an unsaturated moiety of another primary elastomer chain. 

In view of the abundance of unsaturation in polydiene elastomers it may be expected that this type of elastomers can be cured very efficiently with peroxides. This section will show that a very high crosslinking efficiency (= moles of crosslinks formed per mole of peroxide decomposed) can indeed be obtained. However, the substitution pattern of the unsaturation plays a major role in the actual efficiency found. 

The industrial relevance of peroxide-curing of elastomers is by far larger for main-chain saturated elastomers, such as silicone elastomers, acrylic elastomers, fluoro elastomers 

EPDM is first mixed with fillers and oil on two-roll mills or batch kneaders, and next the crosslinking chemicals are added at moderate temperatures. Then the EPDM compound may be shaped and crosslinked in a hot ( 160°C) press or calendered into a foil, and cured in a steam autoclave. EPDM strips and profiles may be continuously extruded and subsequently crosslinked in a hot-air oven, a salt bath, or an ultrahigh-frequency radiation unit. 

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Peroxide curing systems Peroxide decomposers Peroxide initiators Peroxides... 

Organofunctional silanes are used to promote polymer-to-filler bonding with clay or siHca fillers. Vinyl silanes are used in peroxide-cured wire insulation to promote stronger bonding with calcined clay fillers. Mercapto silanes are used to treat kaolin clay in sulfur-cured compounds. 

FluorosiHcones (FVMQ) have exceUent low temperature flexibUity properties coupled with good oil, fuel, and solvent resistance and exceUent aging properties. The materials are compounded and reinforced with fine particle fiUers, especiaUy sUica. The materials are mixed and processed on especiaUy clean equipment and are peroxide-cured. 

Heat resistance is iafluenced by both the type and extent of cure. The greater the strength of the chemical bonds ia the cross-link, the better is the compound s heat resistance. Peroxide cure systems, which result ia carbon—carbon bonds, result ia a range of sulfur cross-links varyiag from 1 to > 30 sulfur atoms per cross-link, and heat resistance improves as the number of more thermally stable short cross-links predominates. This is an important factor ia designing the desired cure system. 

Peroxides decompose when heated to produce active free radicals which ia turn react with the mbber to produce cross-links. The rate of peroxide cure is coatroUed by temperature and selection of the specific peroxide, based on half-hfe considerations (see Initiators, free-RADICAL Peroxy compounds, organic). Although some chemicals, such as bismaleimides, triaHyl isocyanurate, and diaHyl phthalate, act as coagents ia peroxide cures, they are aot vulcanisation accelerators. lastead they act to improve cross-link efftcieacy (cross-linking vs scissioa), but aot rate of cross-link formatioa. 

EPDM is a terpolymer of ethylene, propylene, and a small amount (<10%) of an unsaturated diene third monomer to provide a cure site. Unlike the elastomers previously discussed, the unsaturation in EPDM is not in the main chain, but it is pendent to the chain. Peroxide cure gives superior aging resistance and low compression set. 

In contrast, antioxidants can have an opposite effect when peroxide curing. Because peroxide cross-linking involves a free-radical mechanism, and antioxidants are designed to scavenge free radicals, it is obvious that peroxide efficiency can be compromised by the addition of antioxidants. Thus the decomposition products of the ppds were acting as accelerators (29). 

Peroxide curing systems are generally the same for CSM as for other elastomers but large amounts of acid acceptor must be present to complete the cure. A small amount of a polyfunctional alcohol, ie, pentaerythritol (PER) in the compound significantly reduces the amount of base required by acting as a solubiHzer. TriaHyl cyanurate [101-37-17 is an additional cure promoter and leads to higher cross-link density. 

A new family of peroxide-cured dipolymers was introduced in 1991. The peroxide cure provides copolymers that cure faster and exhibit good compression set properties without a postcure. The removal of the cure-site has also made the polymer less susceptible to attack from amine-based additives. By varying the methyl acrylate level in the dipolymer, two offerings in this family have been synthesized, VAMAC D and its more oil-resistant... 

Post-Curing. Whenever production techniques or economics permit, it is recommended that compounds based on terpolymer grades be post-cured. Relatively short press cures can be continued with an oven cure in order to develop full physical properties and maximum resistance to compression set. Various combinations of time and temperature may be used, but a cycle of 4 h at 175°C is the most common. The post-cure increases modulus, gready improves compresson set performance, and stabilizes the initial stress/strain properties, as chemically the polymer goes from an amide formation to a more stable imide formation. Peroxide-cured dipolymer compounds need not be post-cured. 

The most widely used plasticizers are paraffinic oils. Por appHcations that specify high use temperatures, or for peroxide cures, paraffinic oils of low volatihty are definitely recommended. However, since paraffinic oils exude at low temperatures from EPDM vulcanizates, or from high ethylene EPDMs, they are often blended with naphthenic oils. On the other hand, naphthenic oils interfere with peroxide cures. Aromatic oils reduce the mechanical properties of vulcanizates, and they also interfere with peroxide cures. Therefore, they are not recommended for EPM/EPDM. 

The resistance to heat and aging of optimized EPM/EPDM vulcanizates is better than that of SBR and NR. Peroxide-cured EPM can, for instance, be exposed for 1000 h at 150°C without significant hardening. Particularly noteworthy is the ozone resistance of EPM/EPDM vulcanizates. Even after exposure for many months to ozone-rich air of 100 pphm, the vulcanizates will not be seriously harmed. EPM/EPDM vulcanizates have an excellent resistance to chemicals, such as dilute acids, alkaUes, alcohol, etc. This is in contrast to the resistance to aUphatic, aromatic, or chlorinated hydrocarbons. EPM/EPDM vulcanizates swell considerably in these nonpolar media. 

Bromine- and iodine-containing fluoroolefins have been copolymerized with the above monomers in order to allow peroxide cure (14—21). The peroxide cure system does not requite dehydrofluorination of the polymer backbone, resulting in an elastomer that shows improved properties after heat and fluid aging. 

Internal mixing is widely used with fluorocarbon elastomers. Gumstocks and compounds that are particularly successful fall in the viscosity ranges discussed earlier, and use both incorporated bisphenol-type and peroxide cure systems. A typical internal mix cycle mns 6—8 min with a drop temperature of 90—120°C. The typical formulations in Tables 4 and 7 are readily mixed in an internal mixer. 

Properties and Applieations. Aryloxyphosphazene elastomers using phenoxy and J-ethylphenoxy substituents have found interest in a number of appHcations involving fire safety. This elastomer has a limiting oxygen index of 28 and contains essentially no halogens. It may be cured using either peroxide or sulfur. Peroxide cures do not require the allyhc cute monomer. Gum physical properties are as follows (17) ... 

There are no known practical peroxide cure systems for the PO—AGE polymers. Apparentiy the peroxide attacks the polymer backbone at a rate that is unfavorably competitive with the cross-linking rate. A typical sulfur cure system consists of zinc oxide [1314-13-2] tetramethylthiuram mono sulfide (TMTM), 2-2-mercaptobenzothiazole [149-30-4] (MBT), and sulfur. A sulfur donor cure system is zinc oxide, di-o-tolylguanidine [97-39-2] (DOTG) and tetramethylthiuram hexasulftde. 

Interestingly, later grades of Vamac to become available did not employ the cure site monomer, using instead a peroxide-curing system. Some of these copolymers also contained higher levels of methyl acrylate (up to 69%) to enhance the oil resistance. 

As with the amine systems such systems still suffered the disadvantage that water was split out during cure. This led to the availability in the late 1970s of peroxide-curable materials containing a cure site of enhanced receptivity to attack by aliphatic radicals. These peroxide-cured elastomers are claimed to have superior resistance to steam, hot water and mineral acids than the earlier systems. 

The polyester alkyd moulding compositions are also based on a resin similar to those used for laminating. They are prepared by blending the resin with cellulose pulp, mineral filler, lubricants, pigments and peroxide curing agents on... 

The early 1980s saw considerable interest in a new form of silicone materials, namely the liquid silicone mbbers. These may be considered as a development from the addition-cured RTV silicone rubbers but with a better pot life and improved physical properties, including heat stability similar to that of conventional peroxide-cured elastomers. The ability to process such liquid raw materials leads to a number of economic benefits such as lower production costs, increased ouput and reduced capital investment compared with more conventional rubbers. Liquid silicone rubbers are low-viscosity materials which range from a flow consistency to a paste consistency. They are usually supplied as a two-pack system which requires simple blending before use. The materials cure rapidly above 110°C and when injection moulded at high temperatures (200-250°C) cure times as low as a few seconds are possible for small parts. Because of the rapid mould filling, scorch is rarely a problem and, furthermore, post-curing is usually unnecessary. 

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