Vulcanization unsaturated hydrocarbon

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 coefficient of vulcanization is usually defined as the number of units of weight of sulphur combined with 100 units by weight of unsaturated hydrocarbon. Ebonites prepared from natural rubber are... 

Sulfur and selenium react with many organic molecules. For example, saturated hydrocarbons are dehydrogenated. The reaction of sulfur with alkenes and other unsaturated hydrocarbons is of enormous technical importance hot sulfurization results in the vulcanization (formation of S bridges between carbon chains) of natural and synthetic rubbers. 

In order to overcome thfe drawbadr, new types of multi-unsaturated hydrocarbon monomers have been synthedzed in recent years and their behavior in ethylene-propylene copolymerization has been extensively studied. Such mcmomers are characterized by the presence of one unconjugated double bond suitable for copolymerization and of a system of two or three cmijugated double bonds, the high reactivity of which makes them competitive with conventional diene rubbers in sulfur vulcanization despite their low concentration. 

Peroxide Vulcanization of Unsaturated Hydrocarbon Elastomers. The initiation step in peroxide-induced vulcanization is the decomposition of the peroxide to give free radicals. If the elastomer is derived from butadiene or isoprene, the next step is either the abstraction of a hydrogen atom from an allyUc position on the polymer molecule or the addition of the peroxide-derived radical to a double bond of the polymer molecule. In either case, polymeric free radicals are the result (Scheme 17). 

A weakness of many polymers is their tendency to fail at fairly low stress levels due to the impact of some hostile environments. This phenomenon is known as environmental stress cracking. Cracking occurs when the polymer is stressed for a long time under loads that are relatively small compared to the yield point of the material. A well-known example includes the failure of vulcanized natural rubber in the presence of ozone. It reacts with unsaturated hydrocarbons at the surface and, even when the elastomers are subjected to low stresses, cracks can... 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

Polymeric hydrocarbon elastomers, such as natural rubber, are cross-linked or vulcanized by the use of sulfur, which reacts with the carbon of the unsaturated bonds in polymer molecules to form a bridge between two molecules so that one polymer molecule is covalently bonded to a second polymer molecule (6). 

The properties of these elastomers are widely different. All require vulcanization. In general, sulfur is used only for unsaturated polymers, peroxides, quinones, metallic oxides, or cliisocyauates effect vulcanization with saturated types. Many are special-puipose rubbers, some can be used in tires when loaded with carbon black, others have high resistance to attack by heat and hydrocarbon oils and thus are superior to natural rubber for steam hose, gasoline and oil-loading hose. Most are available in latex form. See also Elastomers. 

Rubbers are plasticized with petroleum oils, before vulcanization, to improve processability and adhesion of rubber layers to each other and to reduce the cost and increase the softness of the final product. Large quantities of these oil-extended rubbers are used in tire compounds and related products. The oil content is frequently about 50 wt% of the styrene-butadiene rubber. The chemical composition of the extender oil is important. Saturated hydrocarbons have limited compatibility with most rubbers and may sweat-out. Aromatic oils are more compatible and unsaturated straight chain and cyclic compounds are intermediate in solvent power. 

When isoprene and similar hydrocarbons polymerize only a part of the double bonds present are involved in the union of the several molecules the rubber formed as a result is unsaturated. It shows the reactions characteristic of the derivatives of ethylene. Owing to this unsaturation it will add sulphur. This process, which is called vulcanization, was discovered by Goodyear in 1839. Vulcanization is usually effected by heating the mixture of rubber and sulphur at about 140°. Sheet rubber can be vulcanized in the cold by dipping it into a dilute solution of sulphur monochloride in a volatile solvent, such as carbon disulphide or benzene. 

Ethylene-propylene rubber is a synthetic hydrocarbon-based rubber made either from ethylene-propylene diene monomer or ethylene-propylene terpolymer. These monomers are combined in such a manner as to produce an elastomer with a completely saturated backbone and pendant unsaturation for sulfur vulcanization. As a result of this configuration, vulcanizates of EPDM elastomers are extremely resistant to attack by ozone, oxygen, and weather. 

Medium high ACN, high level of unsaturation for low dynamic hysteresis in belts and dynamic applications, sulfur or peroxide vulcanization, lower viscosity for transfer and injection molding Higher ACN content for better hydrocarbon resistance, peroxide vulcanization High ACN for fuel applications, peroxide vulcanization... 

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