Polyisoprene derivatives

From Table III, one can see that a common feature in both sets of shift parameters (that for 1,4-polyisoprene derivatives and that for 2-methylbutane derivatives) is a higher g effect for a methyl carbon (denoted g in Table III) than for a methylene carbon (denoted g in Table III). The difference between g and g effects is close to 4 ppm for the polymers whereas it is close to 3 ppm for the model compounds. On the other hand, one can see that there is no significant difference in the y effects whether the carbon under consideration is a methyl or methylene carbon. 

The empirical shift parameters calculated from the NMR data of the 1,4-polyisoprene derivatives will provide, hereafter, a basis for assigning the carbon resonances observed in the spectrum of hydrochlorinated 1,4-polydimethyl butadiene, which like hydro-chlorinated 1,4-polyisoprene has quaternary carbons substituted by one chlorine atom. 

Figure26-2. Biosynthesis of squalene, ubiquinone, dolichol, and other polyisoprene derivatives. (HMG, 3-hydroxy-3-methylglutaryl x, cytokinin.) A farnesyl residue is present in heme a of cytochrome oxidase. The carbon marked with asterisk becomes C or C,2 in squalene. Squalene synthetase is a microsomal enzyme all other enzymes indicated are soluble cytosolic proteins, and some are found in peroxisomes.

Once again one finds the striking stereospecificity withlithium dependent initiators and a rather conglomerate microstructure when the other alkali metals are involved as shown in Fig. 3. However, the use of nonhydrocarbon solvents drastically affects the structure of the polyisoprene derived from lithium-dependent initiators. This effect is lessened in the case of sodium and potassium as can be seen from the data in Table 2 (81). 

Gebelein and coworkers have prepared monomers and polymers based on the antineoplastic agents 5-fluorouracil and 6-mercapto-purine (26). These polymers would be potentially useful in treating various types of cancer or leukemia and some derivatives have shown biological activity. Previous work by this group has Included the synthesis of polyisoprene derivatives containing sulfa drug, carbamate, urea, oxazolldone and oxazole units (27.28). 

Terpenes such as limonene (in peel oil of citrus fruits and aromatic oils of caraway, dill, etc.), myrecene (in nutmeg) and zingiberine (in ginger) are polyisoprene derivatives (see Figure 7.23). They inhibit isoprenylation of the V2 -ras oncogene product isoprenylation is essential for action of the ras protein, which is known to be associated with pancreatic cancer. 

The principal steps in the mechanism of polyisoprene formation in plants are known and should help to improve the natural production of hydrocarbons. Mevalonic acid, a key intermediate derived from plant carbohydrate via acetylcoen2yme A, is transformed into isopentenyl pyrophosphate (IPP) via phosphorylation, dehydration, and decarboxylation (see Alkaloids). IPP then rearranges to dimethylaHyl pyrophosphate (DMAPP). DMAPP and... 

Al—Ti Catalyst for cis-l,4-PoIyisoprene. Of the many catalysts that polymerize isoprene, four have attained commercial importance. One is a coordination catalyst based on an aluminum alkyl and a vanadium salt which produces /n j -l,4-polyisoprene. A second is a lithium alkyl which produces 90% i7j -l,4-polyisoprene. Very high (99%) i7j -l,4-polyisoprene is produced with coordination catalysts consisting of a combination of titanium tetrachloride, TiCl, plus a trialkyl aluminum, R Al, or a combination of TiCl with an alane (aluminum hydride derivative) (86—88). 

Amorphous (most likely atactic) 3,4-polyisoprene of 94—100% 3,4-microstmcture was prepared with a (C2H 3A1—Ti(0—/ -C Hy) catalyst (11). Crystalline 3,4-polyisoprene containing about 70% 3,4-units and about 30% i7j -l,4-microstmcture was prepared using a catalyst derived from iron acetyl acetonate, trialkyl aluminum, and an amine in benzene (37). However, this polyisoprene contained gel and was obtained in poor yield. Essentially gel-free crystallizable 3,4-polyisoprene of 70—85% 3,4-microstmcture with the remainder being cis-1,4 microstmcture was prepared in conversions of greater than 95% with a water-modified tri alkyl aluminum, ferric acetyl acetonate, and 1,10-phenanthroline catalyst (38). The 3,4-polyisoprene is stereoregular and beheved to be syndiotactic or isotactic. 

An example of a nonlinear polymer derived by cross-linking an initially linear polymer is afforded by vulcanized natural rubber. In the usual vulcanization procedure involving the use of sulfur and accelerators, various types of cross-linkages may be introduced between occasional units (about one in a hundred) of the polyisoprene chains. Some of these bonds are indicated to be of the following type ... 

Aryl naphthylamine derivatives are good general antioxidants with moderate volatility and negligible effect on cure. These give a small degree of fatigue protection in natural and polyisoprene rubbers, but little in styrene-butadiene and butadiene vulcanisates. 

As we close this section, we would also like to point out that the purposeful preparation of organosoluble copolymers exhibiting protein-like solution behaviour in organic media, has not, to the best of our knowledge, so far been reported, although attempts have been undertaken (e.g., the preparation of the partially fluorosiloxylated derivative of polyisoprene [25]). One may hope that the results of such studies will be published soon. 

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. 

As with many polymers, polyisoprene exhibits non-Newtonian flow behavior at shear rates normally used for processing. The double bond can undergo most of the typical reactions such as carbene additions, hydrogenation, epoxidation, ozonolysis, hydrohalogena-tion, and halogenation. As with the case of the other 1,4-diene monomers, many copolymers are derived from polyisoprene or isoprene itself. 

While polymers that contain sites of unsaturation, such as polyisoprene and the polybutadienes, are most susceptible to oxygen and ozone oxidation, most other polymers also show some susceptibility to such degradation including NR, PS, PP, nylons, PEs, and most natural and naturally derived polymers. 

The search for a lightweight, nonbreakable, moldable material began with the invention of vulcanized rubber. This material is derived from natural rubber, which is a semisolid, elastic, natural polymer. The fundamental chemical unit of natural rubber is polyisoprene, which plants produce from isoprene molecules, as shown in Figure 18.5. In the 1700s, natural rubber was noted for its ability to rub off pencil marks, which is the origin of the term rubber. Natural rubber has few other uses, however, because it turns gooey at warm temperatures and brittle at cold temperatures. 

POLYOLEFIN. A class or group name for thermoplastic polymers derived from simple olefins among the more important are polyethylene, polyproplene, polybutenes, polyisoprene, and their copolymers. Many are produced in the form of fibers. This group comprises the largest tonnage of all thermoplastics produced. 

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