Rubber synthesis polymerization reactions

Uses Determining refractive index of minerals paint diluent dyed hexane is used in thermometers instead of mercury polymerization reaction medium calibrations solvent for vegetable oils alcohol denaturant chief constituent of petroleum ether, rubber solvent, and gasoline in organic synthesis. 

Catalytic conversions were experimentally studied in Russia toward the end of the nineteenth century, and especially in the twentieth century, and regularities were empirically established in a number of cases. The work of A. M. Butlerov (1878) on polymerization of olefins with sulfuric acid and boron trifluoride, hydration of acetylene to acetaldehyde over mercury salts by M. G. Kucherov (1881) and a number of catalytic reactions described by V. N. Ipatieff beginning with the turn of the century (139b) are widely known examples. S. V. Lebedev studied hydrogenation of olefins and polymerization of diolefins during the period 1908-13. Soon after World War I he developed a process for the conversion of ethanol to butadiene which is commercially used in Russia. This process has been cited as the first example of commercial application of a double catalyst. Lebedev also developed a method for the polymerization of butadiene to synthetic rubber over sodium as a catalyst. Other Russian chemists (I. A. Kondakov I. Ostromyslenskif) were previously or simultaneously active in rubber synthesis. Lebedev s students are now continuing research on catalytic formation of dienes. 

Consider the disposable diaper. The outer, waterproof layer is composed of polyethylene. The polymerization reaction that produces polyethylene is shown in Section 12.4. The diapers have elastic to prevent leaking. The elastic is made of a natural polymer, rubber. The monomer from which natural rubber is formed is 2-methyl-l,3-butadiene. The common name of this monomer is isoprene. As we will see in coming chapters, iso-prene is an important monomer in the synthesis of many natural polymers. 

Natural rubber is synthesized by a wide variety of plants. The botanic rationale for this synthesis is still a mystery. The biosynthesis of natural rubber has been studied extensively in the past [47-50], and the basic polymerization reactions have been defined. However, the full mechanism of formation of the rubber particles has still not been elucidated, although some suggestions have been made [48,50,51],... 

In the last chapter by Singh and Kaplan, vinyl polymerizations induced by oxidoreductase enzymes are described, where a mediator is normally used. The reaction is of radical-type to form a C - C bond main chain. Vitamin C-functionaUzed vinyl monomers and others were polymerized. Such in vitro reactions are unique because nature does not utilize the vinyl-type C - C bond formation reaction except for natural rubber synthesis via polycondensation. 

However, the synthesis process, depicted in scheme 5, is rather idealized. In reality, the chemistry appears to be quite complex, resulting in a partially cross-linked rubber and the evolution of gaseous species other than chloromethane. Dietrich et al.17 reported that the progress of the polymerization at 116°C, as measured by gas evolution and polymer molecular weight, significantly slowed at around 50% conversion. The reaction could, however, be driven further forward by increasing the temperature to > 150°C. 

Since its recognition and systematic exploration by Otto Diels and Kurt Alder in the 1920s, the Diels-Alder reaction motif (5.84b) has provided one of the most powerful tools of organic synthesis. The Diels-Alder reaction led directly to the dramatic pre-World War II development of the chemical industry for production of synthetic rubber and other polymeric materials. Today, the commercial impact of Diels-Alder methods extends to virtually all areas of agricultural, pharmaceutical, and natural-products chemistry. 

The 2-pentenenitrile, 2-methyl-3-butenenitrile, and methylglutaronitrile in Figure 1.1 are by-products of this reaction sequence. duPont is still studying the phosphines used as ligands for the nickel in an effort to find one bulky enough to favor terminal addition only.214 Reduction of the various nitriles leads to the amines in Figure 1.1, including the cyclic ones. The 2,3-dichloro-l,3-buta-diene is probably a by-product in the synthesis of 2-chloro-1,3-butadiene used to make Neoprene rubber. duPont also polymerizes acrylonitrile to prepare poly (acrylonitrile) fiber (Orion). Acetonitrile is obtained as a by-product of the ammoxidation of propylene to produce acrylonitrile (reaction 1.20). 

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