Gutta-percha, structure

These different forms Figure 4.7) take up different crystalline structures and consequently the bulk properties of the polymer differ. At room temperature gutta percha is a stiff leathery material. 

Natural rubber is known to be more elastic (deformable) than gutta-percha. Is there any obvious difference in the structures in the two strands which might lead to a difference in the properties of the real polymers ... 

This discussion of the structures of diene polymers would be incomplete without reference to the important contributions which have accrued from applications of the ozone degradation method. An important feature of the structure which lies beyond the province of spectral measurements, namely, the orientation of successive units in the chain, is amenable to elucidation by identification of the products of ozone cleavage. The early experiments of Harries on the determination of the structures of natural rubber, gutta-percha, and synthetic diene polymers through the use of this method are classics in polymer structure determination. On hydrolysis of the ozonide of natural rubber, perferably in the presence of hydrogen peroxide, carbon atoms which were doubly bonded prior to formation of the ozonide... 

Figure 13 Chemical structures of trans and cis isomers of 1,4 polyisoprene (gutta-percha and natural rubber, respectively).

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 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. 

Gutta-percha, the trans 1,4-isomer of natural rubber, is hard and brittle at room temperature. The reason for the difference in properties between the cis and trans isomers readily can be seen by inspecting molecular models. The chains with trans double bonds are able to lie along side of each other, forming a semicrystalline array, as shown in Figure 13-2. This ordered arrangement cannot be deformed easily, hence the material is hard and brittle. However, when the double bonds are cis, steric hindrance prevents the chains from assuming a similar ordered structure and the bulk of the material exists in a... 

Exercise 29-19 Ozonizations of natural rubber and gutta-percha, which are both poly-2-methyl-1,3-butadienes, give high yields of CH3COCH2CH2CHO and no CH3-COCH2CH2COCH3. What are the structures of these polymers ... 

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 ... 

There is another product called gutta-percha, which is a geometric isomer of rubber, but is useless as an elastomer. Draw its structure and identify which is cis and which is trans. 

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]. 

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. 

At the end of the 19th century, rubber, with gutta-percha, was used mainly as an electrical insulator on wires and cables. Demand was limited, and the supply of natural rubber at a reasonable price (about 1.00/lb in 1900) was ensured. Some work was done during these years on practical syntheses of isoprene and on the replacement of isoprene by its simpler homolog, butadiene, which had been known since 1863. However, advent of the automobile and accelerated use of electric power rapidly increased the demand for rubber, thus raising its price to about 3.00/lb in 1911. These circumstances focused new attention on the production of a synthetic rubber. S. B. Lebedev polymerized butadiene in 1910, and Carl Dietrich Harries, between 1900 and 1910 established qualitatively the structure of rubber as a 1,A-polyisoprene and synthesized larger quantities of rubberlike materials from isoprene and other dienes. 

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