Elastomers cross-link accelerators

A unique process for chemical stabili2ation of a ceUular elastomer upon extmsion has been shown for ethylene—propylene mbber the expanded mbber obtained by extmsion is exposed to high energy radiation to cross-link or vulcani2e the mbber and give dimensional stabUity (9). EPDM is also made continuously through extmsion and a combination of hot air and microwaves or radio frequency waves which both activate the blow and accelerate the cure. 

The role of activators in the mechanism of vulcanization is as follows. The soluble zinc salt forms a complex with the accelerator and sulfur. This complex then reacts with a diene elastomer to form a mbber—sulfur—accelerator cross-link cursor while also Hberating the zinc ion. The final step involves completion of the sulfur cross-link to another mbber diene segment (18). 

The manufacture of the majority of fluorocarbon elastomer gums includes the addition of an incorporated cure system comprising an organic onium cure accelerator, such as triphenylbenzylphosphonium chloride [1100-88-5] and a bisphenol cross-linking agent, such as... 

Rubber base adhesives can be used without cross-linking. When necessary, essentially all the cross-linking agents normally used in the vulcanization of natural rubber can be used to cross-link elastomers with internal double carbon-carbon bonds. A common system, which requires heat to work, is the combination of sulphur with accelerators (zinc stearate, mercaptobenzothiazole). The use of a sulphur-based cross-linking system with zinc dibutyldithiocarbamate and/or zinc mercaptobenzothiazole allows curing at room temperature. If the formulation is very active, a two-part adhesive is used (sulphur and accelerator are placed in two separate components of the adhesive and mixed just before application). 

The process that makes the chemistry, properties, and applications of elastomers so different from other polymers is cross-linking with sulfur, commonly called vulcanization. The modem method of cross-linking elastomers involves using a mixture of sulfur and some vulcanization accelerator. Those derived from benzothiazole account for a large part of the market today. Temperatures of 100-160°C are typical. 

The introduction of cross-links to inhibit chain slippage was discovered by Goodyear in 1839. He accomplished this through the addition of sulfur to NR. Shortly after this, an accelerator, zinc (II) oxide, was used to speed up the process. Other additives were discovered often through observation and trial-and-error so that today s elastomers have a number of important additives that allow them to perform demanding tasks. 

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. 

A good elastomer should not undergo plastic flow in either the stretched or relaxed state, and when stretched should have a memory of its relaxed state. These conditions are best achieved with natural rubber (ds-poIy-2-methyl-1,3-butadiene, ds-polyisoprene Section 13-4) by curing (vulcanizing) with sulfur. Natural rubber is tacky and undergoes plastic flow rather readily, but when it is heated with 1-8% by weight of elemental sulfur in the presence of an accelerator, sulfur cross-links are introduced between the chains. These cross-links reduce plastic flow and provide a reference framework for the stretched polymer to return to when it is allowed to relax. Too much sulfur completely destroys the elastic properties and produces hard rubber of the kind used in cases for storage batteries. 

Polypropylene (PP) in various forms (filled, unfilled, reinforced, rubber blended) finds the greatest usage of all automotive plastics. Its consumption is likely to accelerate as a result of new laws requiring recyclability, and because of the weight and cost reductions it offers. New fabrication techniques may also contribute to growth. For example, the monomaterial sandwich construction techniques developed by fabricators yield rugged and lightweight PP-based instrument and door panels. These parts consist of a sandwich of reinforced or neat PP substrate, a cross-linked PP foam, and a thermoplastic polyolefin elastomer (TPO) cover. 

Accelerated-sulfur vulcanization is the most widely used method. For many applications, it is the only rapid cross-linking 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 can be used to vulcanize natural rubber (NR), synthetic isoprene rubber (IR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), butyl rubber (HR), chlorobutyl rubber (CIIR), bromobutyl rubber (BUR), and ethylene-propylene-di-ene-monomer rubber (EPDM). The reactive moiety for all of these elastomers can be represented by... 

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