Elastomers peroxide-curing

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. 

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. 

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) ... 

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 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. 

Elastomeric composition for dynamic application of cross-linked E-plastomers has been made with filer-reinforced systems which contain a metal salt (typically zinc) of an alpha, beta unsaturated acid. These additives improve the tensile and tear strength of the elastomer and are cured with a peroxide cure system. These cross-linked articles are suitable for dynamic loading applications such as belting, including power transmission and flat belting. 

Peroxidic cure systems are applicable only to fluorocarbon elastomers with cure sites that can generate new stable bonds. Although peroxide-cured fluorocarbon elastomers have superior heat resistance, their difficult processing has been an obstacle to their wider use for years. Only recent improvements in chemistry and polymerization are offering more opportunities for this class of elastomers.32... 

The most common method of preparation of PMTFPS is through the base-catalyzed ring-opening polymerization of the corresponding cyclic trimer.61-62 Details are in Section 2.11.1. A specific cure site for peroxide curing is developed by incorporating 0.2 mol% of methylvinyl siloxane.63 Typically, fluorosilicone elastomers are copolymers of 90 mol% of trifluoropropylsiloxy and 10 mol% of dimethylsiloxy monomers, but the fluorosilicone content in commercial products ranges from 40 to 90 mol%.63... 

In general, most of the problems encountered in the study of the chemistry of the sulfur vulcanisation of elastomers are also encountered in the study of peroxide-curing. In comparison with sulfur vulcanisation only a limited number of spectroscopic studies on peroxide-curing have been published. 

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... 

Co-agents are multi-unsaturated compounds, which are used in the peroxide-curing of elastomers. When classical co-agents, such as triallylcyanurate (TAC), trimethylolpropanetrimethacrylate (TRIM) or diallylterephthalate (DATP), are added, the crosslinking efficiency is enhanced [98-102]. Various mechanisms for the increase of the crosslinking efficiency have been proposed. In all cases a fast reaction between the... 

Apart from the effect on the crosslinking efficiency, the use of co-agents in peroxidecuring also imparts the molecular structure of crosslinks. It has been reported that coagents with two or more unsaturated moieties can be incorporated as individual molecules between two elastomer strands to form crosslinks [103-109]. In this way the crosslink structure of peroxide-cured elastomers can be altered. Thus, apart from the expected benefits, such as improved crosslinking efficiency, decreased compound viscosity and faster cure, the use of co-agents may also provide a tool for manipulating mechanical properties. 

In order to study the role of DATP as co-agents in the peroxide-curing of EPM, various compounds of elastomer, DCP and co-agent were cured at 170 °C in a press at different time intervals and then FT-IR spectra were recorded. Furthermore, the vulcanisates were extracted with acetone to remove the unreacted co-agent and again FT-IR spectra were recorded. Typical results are illustrated in a study using DATP as a co-agent [110]. 

Vinyl Free radical cure systems crosslinked polyethylene, peroxide cured elastomers, polyesters. Polyethylene. Polypropylene. 

The comonomer diene confers sulfur vul-canizability on the elastomer. Otherwise, a peroxide cure is required for cross-linking. The polymers are readily oil-extended with 20-50 percent oil for many applications. Some uses result from the ability of these products to resist oxidation by ozone. 

The elastomeric sealing components of the metering valve are particularly critical. In those valves used with CFC propellants, the elastomeric seals have typically been formed from an acrylonitrile/butadiene rubber, which has been cured with sulfur. These rubber seals may not be fully compatible with HFA propellants hence, alternative elastomeric materials have been used. These materials include peroxide-cured acrylonitrile/ butadiene, ethylene-propylene diene monomer (EPDM), and chloroprene and thermoplastic elastomers (TPE). The elastomeric materials used to form the dynamic seals around the stem and the static gasket seal between the can and valve may differ based on the required properties of the rubber for the specific function of the seal. The most important characteristics of the elastomeric seals... 

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