Isoprene synthetic natural rubber

Stereospecific polymerization has particular significance for the preparation of stereoregular polymeric dienes. In the radical polymerization of butadiene or isoprene the molecular chains always consist of varying proportions of adjacent cis- and trans-1,4-units as well as 1,2- and 3,4- linked units, depending on the polymerization conditions but it is now possible, using particular ionic initiation systems to make a synthetic natural rubber that contains more than 90% cfs-l,4-isoprene repeating units (see Example 3-21). 

Natural rubber is a polymer of isoprene- most often cis-l,4-polyiso-prene - with a molecular weight of 100,000 to 1,000,000. Typically, a few percent of other materials, such as proteins, fatty acids, resins and inorganic materials is found in natural rubber. Polyisoprene is also created synthetically, producing what is sometimes referred to as "synthetic natural rubber". Owing to the presence of a double bond in each and every repeat unit, natural rubber is sensitive to ozone cracking. Some natural rubber sources called gutta percha are composed of trans-1,4-poly isoprene, a structural isomer which has similar, but not identical properties. Natural rubber is an elastomer and a thermoplastic. However, it should be noted that as the rubber is vulcanized it will turn into a thermoset. Most rubber in everyday use is vulcanized to a point where it shares properties of both, i.e., if it is heated and cooled, it is degraded but not destroyed. 

The isoprene unit is the most important building block for lipids, steroids, terpenoids, and a wide variety of natural products. The only chemical reaction of commercial importance (other than polymerization) is its conversion to terpenes. Isoprene is used in the manufacture of synthetic natural rubber, butyl rubber, and as a copolymer in the production of synthetic elastomers. 

New types of catalyst systems that could selectively join together monomer units in a well ordered fashion were discovered in the 1950s. Shortly after the discovery of the breakthrough Ziegler-Natta catalyst systems for the polymerization of ethylene, stereospecific catalysts were developed for the polymerization of isoprene. This enabled the production of a nearly pure cis-1,4-polymer, the so-called synthetic natural rubber. In 1962, Goodyear introduced Natsyn , a strain-crystallizable isoprene polymer with a cis-1,4-content of 98.5 percent. 

Isoprene l-s3-ipren [prob. fr. is- - - propyl -f -ene] (1860) (3-methyl-1,3-butadiene, 2-methyl-1,3-butadiene) n. CH2=C-(CH3) CH=CH2- a colorless, volatile liquid derived from propylene or from coal gases or tars, chemically similar to the mer unit of natural rubber. Its polymer of the cis-1, 4-type of polyisoprene is chemistry s nearest approach to synthesizing the natural product and it has sometimes been called synthetic natural rubber . It has a molecular weight of 68.06, a mp of—120°C, and a bp of 34°C. Ash M, Ash I (1982-1983) Encyclopedia of plastics polymers, and resins, vols 1-3. Chemical Publishing Co., New York. 

Thus by the means outlined above, it has been established that natural rubber is essentially cis-, 4-polyisoprene. The final proof in this long endeavour may be considered to have been given in 1954 when the stereospecific polymerization of isoprene was achieved and synthetic natural rubber was obtained. (See Section 18.3.)... 

Isoprene monomer is also used in the polymerization process to produce polyiso-prene rubber (IR), which is considered to be a synthetic natural rubber (which is not perfectly equivalent to natural rubber, primarily due to impurities in the latter). 

The use of alkaU metals for anionic polymerization of diene monomers is primarily of historical interest. A patent disclosure issued in 1911 (16) detailed the use of metallic sodium to polymerize isoprene and other dienes. Independentiy and simultaneously, the use of sodium metal to polymerize butadiene, isoprene, and 2,3-dimethyl-l,3-butadiene was described (17). Interest in alkaU metal-initiated polymerization of 1,3-dienes culminated in the discovery (18) at Firestone Tire and Rubber Co. that polymerization of neat isoprene with lithium dispersion produced high i7j -l,4-polyisoprene, similar in stmcture and properties to Hevea natural mbber (see ELASTOLffiRS,SYNTHETic-POLYisoPRENE Rubber, natural). 

Rubber and Elastomers Rubber and elastomers are widely used as lining materials. To meet the demands of the chemical indus-tiy, rubber processors are continually improving their products. A number of synthetic rubbers have been developed, and while none has all the properties of natural rubber, they are superior in one or more ways. The isoprene and polybutadiene synthetic rubbers are duphcates of natural. 

Isoprene may be the naturally occurring alkene with the greatest economic impact. This compound, a major component of the sap of the rubber tree, is used to make the long-chain molecules of natural rubber (polyisoprene). As we describe in Chapter 13. the synthetic rubbers that make up most of today s tires are made from other alkenes. 

Surprisingly, the idea that Collins new compound might form the basis for a synthetic rubber took several weeks to evolve. And it was not Carothers, but Stine s successor, Elmer K. Bolton, who first realized that the molecular structure of Collins mass was similar to that of isoprene, the main constituent of natural rubber. Bolton had studied in Germany and was familiar with its World War I efforts to develop an ersatz rubber for tires. 

In 1994, the worldwide consumption of rubber was approximately 14.5 million tons a year, of which about 40% consisted of natural rubber. Natural rubber is produced as latex by tropical rubber trees (Hevea brasiliensis). It is processed locally and therefore the quality of natural rubber fluctuates remarkably [ 140]. Due to increasing demand for rubbers, combined with a decreasing production capacity in Asia and a vast increase in labor costs, the price of natural rubber is still rising sharply. In 1990-1994, the average price of natural rubber was about 0.38 /lb, while in 1996 it was already over 0.80 /lb. The remaining 60% of the articles were manufactured from synthetic petroleum-based rubbers such as isoprene rubber, styrene-butadiene rubber, chloroprene rubber and polyurethanes. The quality of synthetic rubbers is constant, and their price varies between 2 and 5 US per kilogram [137-140]. 

Other polymeric binders, natural and synthetic, may be found as paints or varnishes in modern artworks and installations. Artists very easily adopt resins developed as industrial coatings or for specialized applications, and use them according to their creative needs. Natural rubber latex is a water dispersion of 1,4-ds-polyisoprene particles where pigments can be added to give coloured paints. By means of Py-GC/MS the presence of these paints can be easily assessed. As shown in Figure 12.13, the principal marker peaks in the pyrogram are those of isoprene, limonene and other cyclic dimers. 

Polymerised isoprene. Naturally-occurring polyisoprenes are natural rubber (cA-form) and gutta percha (trans- form). The use of stereo specific catalysts has made possible the manufacture of synthetic cA-polyisoprene and fraws-polyisoprene both of which are now available commercially. 

Butadiene and isoprene have two double bonds, and they polymerize to polymers with one double bond per monomeric unit. Hence, these polymers have a high degree of unsaturation. Natural rubber is a linear cis-polyisoprene from 1,4-addition. The corresponding trans structure is that of gutta-percha. Synthetic polybutadienes and polyisoprenes and their copolymers usually contain numerous short-chain side branches, resulting from 1,2-additions during the polymerization. Polymers and copolymers of butadiene and isoprene as well as copolymers of butadiene with styrene (GR-S or Buna-S) and copolymers of butadiene with acrylonitrile (GR-N, Buna-N or Perbunan) have been found to cross-link under irradiation. 

They are not found to any extent in natural products, but are produced in the destructive distillation of complex natural substances, such as coal, and are formed in large amounts in petroleum refining, particularly in the cracking process. The first member of the series is ethylene, C2H4. The dienes contain two double bonds between pairs of carbon atoms in the molecule. They are related to the complex hydrocarbons in natural rubber and are important in the manufacture of synthetic rubber and plastics. The most important members of this series are butadiene, C4H5 and isoprene, CsHg. 

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. 

C. J. Carman Earlier in your talk you showed the carbon Ti data and NOEF for partially crystalline and amorphous poly-isoprenes. Was this a natural rubber which had been allowed to crystallize to different degrees or was this a synthetic rubber ... 

Synthetic rubbers include a variety of compounds that mimic the properties of natural rubber. In 1860, Charles Greville Williams (1829-1910) isolated the monomer isoprene from rubber, showing that rubber was a polymer of isoprene ... 

RUBBER (Synthetic). Any of a group of manufactured elastomers that approximate one or more of the properties of natural rubber. Some of these aie sodium polysulfide ( Thiokol ). polychloiopiene (neoprene), butadiene-styrene copolymers (SBR), acrylonitrilebutadiene copolymers (nitril rubber), ethvlenepropylene-diene (EPDM) rubbers, synthetic poly-isoprene ( Coral, Natsyn ), butyl rubber (copolymer of isobutylene and isoprene), polyacrylonitrile ( Hycar ). silicone (polysiloranei. epichlorohy-drin, polyurethane ( Vulkollan ). 

---