Sulfur without accelerator, vulcanization

Initially, vulcanization was accomplished by heating elemental sulfur at a concentration of 8 parts per 100 parts of rubber (phr) for 5 h at 140°C. The addition of zinc oxide reduced the time to 3 h. Accelerator in concentrations as low as 0.5 phr have since reduced time to 1-3 min. As a result, elastomer vulcanization by sulfur without accelerator is no longer of commercial significance. An exception is the use of about 30 or more phr of sulfur, with httle or no accelerator, to produce molded products of hard mbber called ebonite. 

While free radical attack in step (i) is by no means confined to carbon atom 4, the products obtained in the reactions involving the lower polyisoprenes indicate that this process is the dominant one. Likewise in step (ii) sulfur may frequently add at carbon atom 4 rather than at atom 2. Addition in the manner shown is indicated, however, by infrared spectra, which reveal the formation of —CH=CH— groups during vulcanization. The scheme accounts also for the observed constancy of the C/H ratio during vulcanization and for the relatively low efficiency of utilization of sulfur in the formation of cross-linkages in the absence of accelerators. A preponderance of the sulfur is involved in addition without formation of cross-linkages a considerable fraction of the thus-combined sulfur may occur in five- and six-membered heterocyclic rings formed by the mechanisms indicated. 

The vulcanization of polychloroprene (Neoprene) is carried out in different ways. Vulcanization by sulfur, even with an accelerator, is not practiced to a large extent. Vulcanizations by metal oxides (without diamine), either alone or in combination with sulfur (sometimes together with an accelerator), give the best physical properties for the crosslinked product. Halogenated butyl rubber is crosslinked in a similar manner. The mechanism for crosslinking by metal oxide alone is not established [Stewart et al., 1985 Vukov, 1984]. 

Use Vulcanization agent without added sulfur, or as a primary or secondary accelerator with sulfur. 

Liquid polybutadienes without functional groups may be vulcanized on double bonds of the diene part of the polymeric chain in the presence of a sulfur-accelerating, redox, or peroxide system. However, only the sulfur-accelerating system is able to provide the maximal durability values. Sulfur also has other advantages such as low price, availability, and so on. The amount of involved sulfur in the system depends on the desired properties of the product. For hard RubCon, this is 47-55 mass parts per 100 mass parts of rubber. 

The hypothesis of a sulfur/asphalt chemical reaction without release of hydrogen sulfide has been put forward by certain writers (3, 4) who have used vulcanization accelerating agents to reduce the maturing time to a few hours. After the chemical determinations of dissolved sulfur, this laboratory agrees that a sulfur/asphalt chemical reaction occurs. 

The second example of a polymer reaction is the industrial cross-linking of rubber by vulcanization sketched in Fig. 3.50. The process was invented already in 1839 by C. N. Goodyear without knowledge of its chemical stracture. Natural rubber is cis-poly(l-methyl-1-butenylene) or polyisoprene with a low glass transition temperature of about 210 K. Its structure and those of other rubbers are given in Fig. 1.15. The addition of sulfur in the form of Sg rings and heating causes the vulcanization. Of the listed cross-hnks in Fig. 3.50, only the left example is an efficient network former. The sulfur introduces about 1 cross-link for each of 50 S-atoms used. Modem vulcanization involves activators and accelerators for increased efficiency. The detailed mechanism is rather complicated and not fully understood. 

CO and ECO are vulcanized without sulfur. Rather, they are generally cured by the action of thioureas or triazines in the presence of acid acceptors such as MgO or dibasic lead phosphite. The terpolymers can be cured by accelerated sulfur or peroxide curing systems as well as by the action of thioureas, and so on. 

The undesirable premature cross-linking of pol5uner chains in the processing step is called scorch the ability of the vulcanization system to withstand the heat of processing without premature cross-linking is called scorch safety. This attribute of delayed action (scorch safety) with fast cure is imique to accelerated sulfur vulcanization, and allows for safe and rapid mixing and fabrication of rubber compounds and parts coupled with rapid cure. 

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