Peroxide cure mechanism

Peroxide cured rubbers are the most difficult to bond to metal with conventional adhesives. This is because the free radical peroxide cure mechanism competes with the curative in the adhesive for reactive sites on the rubber backbone. 

The coagent, the most efficient one being TAIC, is essential for the peroxide-cure mechanism. Indeed, it permits the reaction of crosslinking and improves the compression set resistance. 

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). 

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. 

Figure 8 shows the SEM images with a low level of strain (50%). It is clear that even with a low-strain level defects are initiated in the sulfur cured system with the formation of large cracks at the boundary layer between the two phases. However, in the peroxide cured system the mechanism of crack initiation is very different. In the latter case the NR-LDPE interface is not the site for crack initiation. In this case, stress due to externally applied strains is distributed throughout the matrix by formation of fine crazes. Furthermore, such crazes are developed in the continuous rubber matrix in a direction... 

Influences of the different methacrylates and 1,2-polybutadiene as coagents on the mechanical and rheological properties of the peroxide-cured PP/EPDM TPVs were reported by Rishi and Noordermeer [39, 40]. They interpreted the results in terms of solubility parameter and cure kinetics. The effects of coagents on both processing and properties of the compound depend on the nature of the polymer, type of peroxide, and other compounding ingredients. Among the methacrylate... 

The free-radical cure mechanism of the vinyl ester resins is well understood. In most respects, it is similar to that of the unsaturated polyester resins. To initiate the curing process, it is necessary to generate free radicals within Ike resm mass. Organic peroxides are tlie most common source of free radicals. These peroxides will decompose under the influence of elevated temperatures or chemical promoters, e.g., organometallics or tertiary amines, to form free radicals. Generation of free radicals also can be effected by ultraviolet or high-energy radiation applied directly to the resin system. The free radicals thus formed react to open the double bond... 

In more recent studies from Gonzalez and co-workers [88-90] it was concluded from dynamic mechanical analysis of peroxide-cured NR that a non-uniform crosslinked network results if a large amount of peroxide is used. This result seems to be in line with the optical spectroscopy studies discussed. 

Based on the literature reports discussed, a rough scheme for the peroxide-curing of EPDM is proposed (Figure 6.7). This scheme is identical to the mechanism that was proposed based on the results of rheometer studies [11]. 

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 efforts to come to a better understanding of the action of co-agents, the reactions of some classical co-agents in peroxide-curing of amorphous EPDM have been studied in the absence of fillers and oils, using FT-IR spectroscopy as the major tool for the elucidation of the cure mechanism. 

Network structure and reaction mechanisms in high pressure vulcanisation (HPV) and peroxide vulcanisation of BR was studied by 13C solid-state NMR [43]. Different samples of polybutadiene (51% trans, 38% cis, and 11 % vinyl) were peroxide cured with dicumyl peroxide on a silica carrier and by the HPV conditions of 250 °C and 293 MPa. The 13C NMR spectra from peroxide and HPV cures were compared to a control samples heated to 250 °C for 6 minutes under atmospheric pressure. Although no new isolated strong peaks were detected in either the peroxide or HPV vulcanisations, small increases in both spectra were observed at 29.5, 36.0, 46.5, and 48.0 ppm. These peaks compare favourably with calculated shifts from structures that arise from main chain radical addition to the pendent vinyl groups. These assignments are further reinforced by the observation that the vinyl carbon concentration is substantially reduced during vulcanisation in both peroxide and HPV curing. Two peaks at 39.5 and 42.5 ppm appear only in the peroxide spectrum. Cis-trans isomerisation was absent in both cures. 

Cross-Linking by Free Radical Mechanism (Peroxide Cure)... 

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