Rubbers accelerated-sulfur vulcanization

The accelerated sulfur vulcanization of general-purpose diene rubbers (e.g., NR, styrene-butadiene rubber [SBR], and butadiene rubber [BR]) by sulfur in the presence of organic accelerators and other rubbers, which are vulcanized by closely related technology (e.g., ethylene-propylene-diene monomer [EPDM] mbber, butyl rubber [HR], halobutyl mbber [XIIR], nitrile rubber [NBR]) comprises more than 90% of all vulcanizations. 

FIGURE 14.3 Development of accelerated sulfur vulcanization of natural rubber (NR). (From A.Y. Coran, Chem. Tech., 23, 106, 1983.)... 

Most accelerators used in the accelerated sulfur vulcanization of other high diene rubbers are not applicable to the metal oxide vulcanization of CR. An exception is the use of so-called mixed-curing system for CR, in which metal oxide and accelerated sulfur vulcanization are combined. Along with the metal oxides, TMTD, DOTG, and sulfur are used. This is a good method to obtain high resilience and dimensional stability. 

G. Heideman, R.N. Datta, J.W.M. Noordermeer, and B. van Barle, Activators in accelerated sulfur vulcanization. Rubber Chemistry and Technology, 77(3), 512-541, 2004. 

Polydiene rubbers can also be crosslinked by heating with p-dinitrosobenzene, phenolic resins, or maleimides [Coran, 1978 Gan and Chew, 1979 Gan et al., 1977, 1978 Sullivan, 1966]. The crosslinking mechanism is similar to that for accelerated sulfur vulcanization, for example, for vulcanization by p-dinitrosobenzene... 

The new absorptions in the spectra of crosslinked rubber are assigned on the basis of 13C solution NMR chemical shifts for a variety of model compounds, such as pentenes and mono-, di- and tri-sulfidic compounds, by using the 13C chemical shift substituent effect. From the calculated values for particular structural units, the experimental spectra of a sulfur vulcanized natural rubber 194,195,106), natural rubber cured by accelerated sulfur vulcanization 197 y-irradiation crosslinked natural rubber198 and peroxide crosslinked natural rubber and cis-polybutadiene 193 1991 are assigned. 

By using this method, the chemical shifts of the resonances in the spectra of a sulfur vulcanized natural rubber (Fig. 32 expanded aliphatic region in shown in Fig. 33 [top]) are assigned to various units of the polymer network, which arise from structural modifications induced by the vulcanization 194,196 200). Different sulfidic structures are found for unaccelerated and accelerated sulfur vulcanizations, respectively. With increasing amount of accelerator (as compared to the sulfur), the network structure exhibits less crosslinking, fewer main chain structural modifications, and fewer cyclic sulfide structures 197). 

Manik, S.P. Banerjee, S. Sulfenamide accelerated sulfur vulcanization of natural rubber in presence and absence of dicumyl peroxide. Rubber Chem. Technol. 1970, 40, 1311. 

A comparison of polychloroprene and natural rubber or polyisoprene molecular structures shows close similarities. However, while the methyl groups activates the double bond in the polyisoprene molecule, the chlorine atom has the opposite effect in polychloroprene. Thus polychloroprene is less prone to oxygen and ozone attack than natural rubber is. At the same time accelerated sulfur vulcanization is also not a feasible proposition, and alternative vulcanization or curing systems are necessary. 

FIGURE 7.10 Improvements in the accelerated-sulfur vulcanization of natural rubber. 

Accelerated-Sulfur Vulcanization of Various Unsaturated Rubbers... 

Over the years, much of the research on accelerated-sulfur vulcanization was done by using natural rubber as a model substrate. Natural rubber was the first elastomer and therefore the search for the understanding of vulcanization originated with work on natural rubber. Most of the work cited in the previous sections is related to natural rubber. However, some rather early studies have been directed to the vulcanization of butadiene 1,4-polymers (Skinner and Watson, 1969 Wolfe et al, 1329 Gregg and Katrenick, 1970). More recent is the work of Pellicioli and coworkers. Early basic work on the vulcanization of ethylene-propylene-diene-monomer rubber (EPDM) has been carried out (van den Berg et al., 1984a,b). Recently, Kuno and coworkers did basic work on EPDM networks. They found that, essentially, the vulcanizate properties depend only on the crosslink density, not on the type of curing system (Dijkhuis et al., 2009). 

The attack upon rubber molecules by the vulcanization system Can be visualized in a way similar to that which was postulated for the sulfurization of the rubber molecules by the action of accelerated-sulfur vulcanization systems. Reaction schemes for these two types of vulcanization can be written as follows ... 

This is another example of what has variously been called a pseudo-Diels-Alder, ene, or no-mechanism reaction (Hoffmann, 1969). It is similar to the reaction written for the attack of rubber molecules by phenolic curatives or the in situ formed nitroso derivative of the quinoid (e.g., benzoquinonedioxime) vulcanization system. It is also closely related to the sulfurization scheme written for accelerated-sulfur vulcanization. Comparisons between accelerated sulfur, phenolic, quinoid, and maleimide vulcanization can then be visualized as follows ... 

Accelerated-sulfur vulcanization is the most widely used method. For many applications, it is the only rapid crossUnking technique that can, in a practical manner, give the delayed action required for processing, shaping, and forming before the formation of the intractable vulcanized network. It is used to vulcanize natural rubber (NR), synthetic isoprene rubber (IR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), butyl rubber (HR), chlorobutyl rubber (ClIR), bromobutyl rubber (BUR), and ethylene-propylene-diene-monomer rubber (EPDM). The reactive moiety for all of these elastomers can be represented by... 

TTie chemistry of the accelerated vulcanization of BR, SBR, and EPDM appears to have much in common with the vulcanization of natural rubber Before the formation of crosshnks, the rubber is first sulfurated by accelerator-derived polysulfides (Ac-S -Ac) to give macromolecular, polysul-fidic intermediates (rubber-Sx-Ac). However, whereas in the case of MBTS-or benzothiazolesulfenamide-accelerated sulfur vulcanization of natural rubber, MBT is given off during the formation of rubber-Sx-BT from the attack of rubber by BT-S -BT, in the case of BR and SBR, MBT is not eliminated and remains unextractable presumably because it becomes bound as the macromolecular thioether rubber-S-BT. (BT is a 2-benzothiazolyl group.) As in the case of natural rubber, the average length of a crosslink (its sulfidic rank, the value of x in the crosslink, rubber-Sx-rubber) increases with the ratio of sulfur concentration to accelerator concentration (S/Ac) used in the... 

Contemporary science considers SA an effective activator (along with ZnO) of sulto vulcanization of non-saturated rubbers. With regards to the mechanism accelerated sulfur vulcanization, most of the presently proposed hypotheses suggest that at the conditions of the process a... 

Tipova, N. PhD Thesis Investigation of Zinc Stearate as Activator of the Accelerated Sulfur Vulcanization with a view to Zinc Reducing in the Rubber Compoimds , 2006, University of Chemical Technology and Metallurgy, Sofia (in Bulgarian). 

Accelerated-Sulfur Vulcanization of Various Unsaturated Rubbers. Over the years, much of the research on accelerated-sulfur vulcanization was done by using natural... 

Most accelerators for accelerated-sulfur vulcanization do not work for the metal oxide vulcanization of neoprene rubbers. An exception to this is in the use of the so-called mixed curing system for CR, in which metal oxide vulcanization is combined with accelerated-sulfur vulcanization. In this case, along with the metal oxides, accelerators such as tetram-ethylthiuram disulfide(TMTD) or N,N -di-o-tolylguanidine (DOTG) are used with sulfur. This may be desirable for high resihence or for good dimensional stability. 

Diatomite (Kieselguhr). Diatomaceous earth (as it is also called) is chemically ineit, but it has high adsorptive power. This can account for adsorption of curing ingredients that interfere with accelerated-sulfur vulcanization. However, diatomite is used as a filler in silicone rubber. Because of its high adsorptive capacity, it is used as a process aid in high-oU rubber compounds. 

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