Synthetic rubber polymerization

A relatively small percentage of the total stearic acid produced is used by the rubber industry as an activator. Also, some stearic acid is used to make soap emulsions to polymerize synthetic rubber such as SBR and NBR. Most of the stearic acid produced is used to make various stearates used as soaps and dispersing agents that are used by the coatings, plastics, and cosmetic industries. 

The revolutionary development of stereospecific polymerization by the Ziegler-Natta catalysts also resulted ia the accomplishment ia the 1950s of a 100-year-old goal, the synthesis of i7j -l,4-polyisoprene (natural mbber). This actually led to the immediate termination of the U.S. Government Synthetic Rubber Program ia 1956 because the technical problem of dupHcating the molecular stmcture of natural mbber was thereby solved, and also because the mbber plantations of the Far East were again available. 

Chemical Reactivity - Reactivity with Water Reacts slowly to form flammable hydrogen gas, which can accumulate in closed area Reactivity with Common Materials Corrosive to natural rubber, some synthetic rubbers, some greases and some lubricants Stability During Transport Stable Neutralizing Agents for Acids and Caustics Flush with 3% aqueous ammonia solution, then with water. Methyl alcohol may also be used Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

When polymerizing dienes for synthetic rubber production, coordination catalysts are used to direct the reaction to yield predominantly 1,4-addition polymers. Chapter 11 discusses addition polymerization. The following reviews some of the physical and chemical properties of butadiene and isoprene. 

Butadiene is by far the most important monomer for synthetic rubber production. It can be polymerized to polybutadiene or copolymerized with styrene to styrene-butadiene rubber (SBR). Butadiene is an important intermediate for the synthesis of many chemicals such as hexa-methylenediamine and adipic acid. Both are monomers for producing nylon. Chloroprene is another butadiene derivative for the synthesis of neoprene rubber. 

Block copolymers are formed hy reacting two different prepolymers, which are obtained by polymerizing the molecules of each monomer separately. A block copolymer made of styrene and butadiene is an important synthetic rubber ... 

Cationic polymerizations work better when the monomers possess an electron-donating group that stabilizes the intermediate carbocation. For example, isobutylene produces a stable carbocation, and usually copolymerizes with a small amount of isoprene using cationic initiators. The product polymer is a synthetic rubber widely used for tire inner tubes ... 

Polystyrene (PS) is the fourth big-volume thermoplastic. Styrene can be polymerized alone or copolymerized with other monomers. It can be polymerized by free radical initiators or using coordination catalysts. Recent work using group 4 metallocene combined with methylalumi-noxane produce stereoregular polymer. When homogeneous titanium catalyst is used, the polymer was predominantly syndiotactic. The heterogeneous titanium catalyst gave predominantly the isotactic. Copolymers with butadiene in a ratio of approximately 1 3 produces SBR, the most important synthetic rubber. 

Polychloroprene is the oldest synthetic rubber. It is produced by the polymerization of 2-chloro-1,3-butadiene in a water emulsion with potassium sulfate as a catalyst ... 

A number of different synthetic rubbers are produced commercially by diene polymerization. Both cis- and frrms-polyisoprene can be made, and the synthetic rubber thus produced is similar to the natural material. Chloroprene (2-chloro-l,3-butadiene) is polymerized to yield neoprene, an excellent, although expensive, synthetic rubber with good weather resistance. Neoprene is used in the production of industrial hoses and gloves, among other things. 

About half of the styrene produced is polymerized to polystyrene, an easily molded, low-cost thermoplastic that is somewhat brittle. Foamed polystyrene can be made by polymerizing it in the presence of low-boiling hydrocarbons, which cause bubbles of gas in the solid polymer after which it migrates out and evaporates. Modification and property enhancement of polystyrene-based plastics can be readily accomplished by copolymerization with other substituted ethylenes (vinyl monomers) for example, copolymerization with butadiene produces a widely used synthetic rubber. 

Natural rubber latex, obtained from rubber trees, is converted to its final form by a process known as vulcanization, first discovered by Charles Goodyear in 1839. Vulcaiuzation is basically a crosslinking reaction of double bonds in the latex structure with sulfur. The polymerization of butadiene with itself or with other vinyl monomers results in a material that like natural latex, still contains double bonds. Thus, synthetic rubber made from butadiene can be processed and vulcanized just like natural rubber. 

When many molecules combine the macromolecule is termed a polymer. Polymerization can be initiated by ionic or free-radical mechanisms to produce molecules of very high molecular weight. Examples are the formation of PVC (polyvinyl chloride) from vinyl chloride (the monomer), polyethylene from ethylene, or SBR synthetic rubber from styrene and butadiene. 

Anionic polymerization of polystyrene takes place very rapidly- much faster than free radical polymerization. When practiced on a large scale, this gives rise to heat transfer problems and limits its commercial practice to special cases, such as block copolymerization by living reactions. We employ anionic polymerization to make tri-block copolymer rubbers such as polystyrene-polybutadiene-polystyrene. This type of synthetic rubber is widely used in the handles of power tools, the soft grips of pens, and the elastic side panels of disposable diapers. 

The rubber may be natural, in which case the latex is produced by the rubber tree. Latex of the main synthetic rubbers is produced by the technique of emulsion polymerisation. The term latex has been broadened in recent years and a general definition is now a stable dispersion of a polymeric substance in an aqueous medium . Latices may be classified as natural (from trees and plants), synthetic (by emulsion polymerisation) and artificial (by dispersion of the solid polymer in an aqueous medium). They may also be classified according to the chemical nature of the polymer, e.g., SBR, nitrile, polychloroprene, etc. 

Polybutadiene and polyisoprene are produced and used mainly as synthetic rubber on an industrial scale by using transition metal catalysts, especially titanium- and nickel-based ones. By contrast, only minor attention has been paid to the palladium-catalyzed polymerization of butadiene. A mixture of 1,2-polybutadiene and trans- and c/s-l, 4-polybutadiene was obtained by using PdCl2 as a catalyst (7, 2). 

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. 

Alfin An obsolete process for making synthetic rubber by polymerizing butadiene in pentane solution. The catalyst was an insoluble aggregate of sodium chloride, sodium iso-propoxide, and allyl sodium. The name is actually the name of the catalyst, derived from alcohol, used to make the sodium Aopropoxide, and olefin, referring to the propylene used to make the allyl sodium. 

Buna [Butadien natrium] The name has been used for the product, the process, and the company VEB Chemische Werke Buna. A process for making a range of synthetic rubbers from butadiene, developed by IG Farbenindustrie in Leverkusen, Germany, in the late 1920s. Sodium was used initially as the polymerization catalyst, hence the name. Buna S was a copolymer of butadiene with styrene Buna N a copolymer with acrylonitrile. The product was first introduced to the pubhc at the Berlin Motor Show in 1936. Today, the trade name Buna CB is used for a polybutadiene rubber made by Bunawerke Hiils using a Ziegler-Natta type process. German Patent 570, 980. 

GRS A process for making a synthetic rubber by co-polymerizing styrene and butadiene. 

Diene polymers refer to polymers synthesized from monomers that contain two carbon-carbon double bonds (i.e., diene monomers). Butadiene and isoprene are typical diene monomers (see Scheme 19.1). Butadiene monomers can link to each other in three ways to produce ds-1,4-polybutadiene, trans-l,4-polybutadi-ene and 1,2-polybutadiene, while isoprene monomers can link to each other in four ways. These dienes are the fundamental monomers which are used to synthesize most synthetic rubbers. Typical diene polymers include polyisoprene, polybutadiene and polychloroprene. Diene-based polymers usually refer to diene polymers as well as to those copolymers of which at least one monomer is a diene. They include various copolymers of diene monomers with other monomers, such as poly(butadiene-styrene) and nitrile butadiene rubbers. Except for natural polyisoprene, which is derived from the sap of the rubber tree, Hevea brasiliensis, all other diene-based polymers are prepared synthetically by polymerization methods. 

In 1866 AD a polymeric product was formed from styrene and sulphuric acid. Another breakthrough was the production of synthetic rubber from butadiene by using metallic sodium or potassium by German scientists during 1911 -22. In 1929, Ziegler reported polymerisation of vinyl monomers using butyllithium. 

Hermann Staudinger, on developing a new and simple preparation of the monomer, studied the polymerization of isoprene as early as 1910 (42). Stimulated by the differences in physical properties between his synthetic rubber and natural rubber, he turned his full attention to the study of polymers. 

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