Isoprene gutta percha

Poly(frans-isoprene), gutta percha (crossl.) 85/250 3000... 

Poly (f raws-1,4-isoprene) gutta-percha, balata... 

Poly(isoprene) occurs naturally as cis-l,4-poly(isoprene) (natural rubber) and as fraws-l,4-poly(isoprene) (gutta percha, balata). Both isomers can also be prepared synthetically. 

The polymorphism in poly(l, 4-trans-isoprene) (gutta percha) has been studied in detail. Based on a detailed analysis of chain stereochemistry Bunn (261) predicted the possibility of four different crystalline modifications of this polymer, each with a different chain structure. Two of these, crystallized solely by cooling the polymer to an appropriate temperature, have been identified and their crystal structures determined.(261-263) A third form, that crystallizes upon stretching, has also been identified.(264) However, its structure has been questioned.(264)... 

CsHg, Poly-trans-isoprene (gutta percha), 9, 359 10, 237... 

All the double bonds in rubber have the Z (or cis) con figuration A different polymer of isoprene called gutta-percha has shorter polymer chains and E (or trans) double bonds Gutta percha is a tough horn like substance once used as a material for golf ball covers ... 

Gutta percha is a natural polymer of isoprene (3-methyl-l,3-butadiene) in which the configuration around each double bond is trans. It is hard and horny and has the following formula ... 

Natural mbber (Hevea) is 100% i7j -l,4-polyisoprene, whereas another natural product, gutta-percha, a plastic, consists of the trans-1,4 isomer. Up until the mid-1900s, all attempts to polymerize isoprene led to polymers of mixed-chain stmcture. 

Condensation of isoprene (2-methyl-1,3-butadiene) either leads to a polymer in which all double bonds are trans ( natural rubber ) or in which they are cis (gutta-percha). 

As noted in the Chapter 7 Focus On, rubber is a naturally occurring polymer of isoprene, or 2-methyl-l,3-butadiene. The double bonds of rubber have Z stereochemistry, but gutta-percha, the E isomer of rubber, also occurs naturally. Harder and more brittle than rubber, gutta-percha has a variety of minor applications, including occasional use as the covering on golf balls. 

Polymers containing each of these configurations are known, the most common being the cis- A and the 1,4-isomers. The first of these, poly(c/ -l,4-isoprene), is the macromolecular constituent of natural rubber the second is the material known as gutta percha. The latter, unlike natural rubber, has no elastomeric properties, but has a leathery texture. It has been used for diverse applications such as golf-ball covers and as an insulating material for the trans-Atlantic cables of the late nineteenth century. 

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. 

A class of hydrocarbons occurring in many essential oils of plants. They can be regarded as low-molecular weight polymers of isoprene (C5I I8)n. Dipentene is a terpene, while natural rubber, gutta percha and balata have been termed polyterpenes. 

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. 

Natural rubber (Hevea brasiliensis) is as-poly-2-methyl-1,4-butadiene, and gutta-percha (Palaquium oblongi/olium) and balata (Minusops globosa) are polymers of isoprene (2-methyl-1,4-butadiene) with trans configurations. Neoprene is a polymer of 2-chloro-1,3-butadiene (chloroprene). 

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. 

Continuation of the head-to-tail addition of five-carbon units to geranyl (or neryl) pyrophosphate can proceed in the same way to farnesyl pyrophosphate and so to gutta-percha (or natural rubber). At some stage, a new process must be involved because, although many isoprenoid compounds are head-to-tail type polymers of isoprene, others, such as squalene, lycopene, and /3- and y-carotene (Table 30-1), are formed differently. Squalene, for example, has a structure formed from head-to-head reductive coupling of two farnesyl pyrophosphates ... 

In 1954, 1,4-cA-polyisoprene, the synthetic equivalent of natural rubber, was obtained in the laboratories of Goodrich-Gulf [22] by isoprene polymerisation with new catalysts developed by Natta, and later on 1,4-trans-polyisoprene, a synthetic analogue of gutta percha, was obtained by Natta et al. [23]. 

Some of the polybutadienes obtained with transition metal-based coordination catalysts have practical significance the most important is cA-1,4-polybutadiene, which exhibits excellent elastomeric properties. As regards isoprene polymers, two highly stereoregular polyisoprenes, a cA-1,4 polymer (very similar to natural rubber) and a trans- 1,4-polymer (of equal structure to that of gutta percha or balata) have been obtained with coordination catalysts. Various polymers of mixed 3,4 structure, amorphous by X-ray, were also obtained [7]. 

By contrast, cis- 1,4-polyisoprene is produced in limited amounts, since it is not price competitive with natural rubber (owing to the relatively high costs of manufacturing the isoprene monomer). The same applies to trans- 1,4-polyisoprene, which is more expensive than its natural counterparts gutta percha and balata. 

Draw a stepwise mechanism for the polymerization of isoprene to gutta-percha using (CH3)3CO—OC(CH3)3 as the initiator. 

It is obtained from latex extracted from the Hevea brasiliensis tree. There exists another structural isomer called gutta-percha formed from po y trans-1,4-isoprene), whose elastic properties differ from those of natural rubber. 

Polymers with unsaturated carbon chain backbone form another important class of macromolecules, many of the compounds from this class having properties of elastomers. The most common polymers from this class are obtained from 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene) and their derivatives. Natural rubber, which is poly(c/s-isoprene), as well as the natural polymers gutta-percha and balata also have an unsaturated carbon chain backbone. For many practical applications, the polymers from this class are subject to a process known as vulcanization, which consists of a reaction with sulfur or S2CI2, and leads to the formation of bridges between the molecular chains of the polymer. This process significantly improves certain physical properties of practical interest. A separate subclass of polymers with unsaturated carbon chain backbone is formed by polyacetylene. 

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