Accelerated vulcanization and

This is an activator-starved formulation and so is highly sensitive to the presence of nonmbbers that are capable of activating or accelerating vulcanization, and Table 2 illustrates the cure behavior of different grades of SMR (28). Cup lump grades show the highest state of cure and fastest rate of cure, whereas the stabilized grade, SMR CV, shows the lowest state of cure and slowest cure rate. 

There are obvious differences between accelerated vulcanization and unaccelerated vulcanization. (Greater crosslinking efficiencies and greater crosslinking rates are obtained with accelerated vulcanization.) But there are more subtle differences. Results from model reactions with curing ingredients indicate that sulfur becomes attached to the rubber hydrocarbon almost exclusively at allylic positions (Skinner, 1972). This is not the case with unaccelerated-sulfur vulcanization, thus ... 

Ammonia Cure n A modification of a hot air pressure cure for rubber, often used for curing, in which ammonia gas is used to accelerate vulcanization and to prevent the deteriorating effect of air. 

Accelerators. During sulfur vulcanization of rubber, accelerators serve to control time to onset of vulcanization, rate of vulcanization, and number and type of sulfur cross-links that form. These factors in turn play a significant role in determining the performance properties of the vulcanizate. 

Sulfenamide accelerators generally requite less fatty acid because they release an amine during the vulcanization process which acts to solubilize the zinc. Guanidines and similar amine accelerators also serve to both activate and accelerate vulcanization. 

Rubber. The mbber industry consumes finely ground metallic selenium and Selenac (selenium diethyl dithiocarbamate, R. T. Vanderbilt). Both are used with natural mbber and styrene—butadiene mbber (SBR) to increase the rate of vulcanization and improve the aging and mechanical properties of sulfudess and low sulfur stocks. Selenac is also used as an accelerator in butyl mbber and as an activator for other types of accelerators, eg, thiazoles (see Rubber chemicals). Selenium compounds are useflil as antioxidants (qv), uv stabilizers, (qv), bonding agents, carbon black activators, and polymerization additives. Selenac improves the adhesion of polyester fibers to mbber. 

The principal mbbers, eg, natural, SBR, or polybutadiene, being unsaturated hydrocarbons, are subjected to sulfur vulcanization, and this process requires certain ingredients in the mbber compound, besides the sulfur, eg, accelerator, zinc oxide, and stearic acid. Accelerators are catalysts that accelerate the cross-linking reaction so that reaction time drops from many hours to perhaps 20—30 min at about 130°C. There are a large number of such accelerators, mainly organic compounds, but the most popular are of the thiol or disulfide type. Zinc oxide is required to activate the accelerator by forming zinc salts. Stearic acid, or another fatty acid, helps to solubilize the zinc compounds. 

The Goodyear vulcanization process takes hours or even days to be produced. Accelerators can be added to reduce the vulcanization time. Accelerators are derived from aniline and other amines, and the most efficient are the mercaptoben-zothiazoles, guanidines, dithiocarbamates, and thiurams (Fig. 32). Sulphenamides can also be used as accelerators for rubber vulcanization. A major change in the sulphur vulcanization was the substitution of lead oxide by zinc oxide. Zinc oxide is an activator of the accelerator system, and the amount generally added in rubber formulations is 3 to 5 phr. Fatty acids (mainly stearic acid) are also added to avoid low curing rates. Today, the cross-linking of any unsaturated rubber can be accomplished in minutes by heating rubber with sulphur, zinc oxide, a fatty acid and the appropriate accelerator. 

Conventional crosslinking agents, such as sulphur, accelerators, and peroxide, etc., used in dynamic vulcanization and melt-mixing of two polymers is the first step in the preparation of an EA. The dynamic vulcanization is done by dynamic shear at a high temperature to activate the process. 

It has been used to some extent as an ignition promotor for Diesel fuels, in insecticides, fungicides, as an accelerator in rubber vulcanization, and as an indicator in acid titrations (Refs 10 11)... 

Fig. 89.—The total force of retraction at 25°C and dE/dL)T,v obtained from the force-temperature intercepts at constant elongation for natural rubber gum-vulcanized using an accelerator. (Wood and Roth. )...

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. 

ISO 188, Rubber, vulcanized or thermoplastic - Accelerated ageing and heat resistance tests (available in English only), 1998. 

Although sulfur vulcanization has been studied since its discovery in 1839 by Goodyear, its mechanism is not well understood. Free-radical mechanisms were originally assumed but most evidence points to an ionic reaction [Bateman, 1963]. Neither radical initiators nor inhibitors affect sulfur vulcanization and radicals have not been detected by ESR spectroscopy. On the other hand, sulfur vulcanization is accelerated by organic acids and bases as well as by solvents of high dielectric constant. The ionic process can be depicted as a chain reaction involving the initial formation of a sulfonium ion (XI) by reaction of the polymer with polarized sulfur or a sulfur ion pair. The sulfonium ion reacts with a polymer molecule by hydride... 

Sulfur vulcanization leads to a variety of cross-link structures as shown in Figure 1. All the sulfur does not result in cross-links some of it remains as pendent accelerator polysulfide groups and internal cyclic polysulfides. These alternative structures do not contribute to load bearing or strength properties and are more prevalent in unaccelerated or weakly accelerated vulcanization systems. Additional heating can also reduce the polysulfide rank of the cross-links. In some elastomers, this leads to a larger number of cross-links. However, in natural mbber or its synthetic polyisoprene equivalent, the overall result is a loss of cross-links, especially at temperatures over 160°C. 

Accelerators are second in importance only to sulphur. Their function is to accelerate the normally slow rubber-sulphur reaction, increase the rate of vulcanization, and increase productivity. Accelerators are classified into two main classes by types, namely organic and inorganic. The inorganic accelerators such as lime, litharge and other lead compounds and magnesia were employed extensively before the introduction of organic accelerators. They are still used mainly to produce hard rubber or ebonite products. Litharge is used in rubberized fabrics, insulated wires and cables and shoe compounds as well as chemical resistant rubber products... 

These were first investigated and used in rubber as accelerators. Their effect in improving the vulcanizing and ageing properties of rubber was utilized for several years. Primary diamines, primary secondary amines and aminophenols are much more active than simple primary amines. Aminophenol and phenolamine salts are effective antidegradents. 

Like their competitors in Europe and in America, the Japanese producers have focused their attention on accelerators (vulcanization activators and agents) and on antiaging agents (antiozonants, stabilizers). Their automobile exports provide a market for tires that their counterparts in other countries cannot claim to the same extent. 

Interactions with Closure Systems. Elastomeric and plastic container and closure systems release leachable compounds into the liquid dosage form, such as nitrosamines, monomers, plasticizers, accelerators, antioxidants, and vulcanizing agents [44], Each type of container and closure with different composition and/or design proposed for marketing the drug or physician s samples has to be tested and stability data should be developed. Containers should be stored upright, on their side, and inverted in order to determine if container-closure interactions affect product stability [6,45]. 

Elastomers Vulcanization accelerator Notural and synthetic rubber 411-415... 

Rubber Chemicals. Sodium nitrite is an important raw material in the manufacture of mbber processing chemicals. Accelerators, retarders, antioxidants (qv), and antiozonants (qv) are the types of compounds made using sodium nitrite. Accelerators, eg, thiuram [137-26-8] gready increase the rate of vulcanization and lead to marked improvement in mbber quality. Retarders, on the other hand (eg, N-nitrosodiphenylamine [156-10-5]) delay the onset of vulcanization but do not inhibit the subsequent process rate. Antioxidants and antiozonants, sometimes referred to as antidegradants, serve to slow the rate of oxidation by acting as chain stoppers, transfer agents, and peroxide decomposers. A commonly used antioxidant is A/,A7-disubstituted Nphenylenediamine which can employ sodium nitrite in its manufacture (see Rubber chemicals). 

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