Methyl carbon polyisoprenes

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. 

ABA copolymers poly(methyl methacrylate)-polyisoprene-poly(methyl methacrylate) having polyisoprene with a high vinyl content as central block have been synthetized by Cole et al. 2I°. Dynamic mechanical properties of films of these ABA copolymers have been studied as a function of the copolymer composition, the temperature and the nature of the solvent (carbon tetrachloride, toluene, ethyl acetate, methylethyl ketone, dioxane) used for film preparation210. ... 

The chemical shifts of the characteristic carbon signals in acyclic terpenes, polyprenols, and cis-trans isomerized poly-isoprenes are plotted in Fig. 3. Here, the chemical shifts are correlated using the w C-5 methyl carbon signal at 17.66 ppm as an internal standard (except for isomerized polyisoprenes) in order to compensate for the effect of solution concentration. It is clear that these chemical shifts are independent of the chain length of the compounds and can be used for the determination of the arrangement of isoprene units as well as the terminal units in various isoprenoid compounds (8). 

In the NMR spectrum, the tetra-substituted olefinic carbon gives rise to the peaks from 130 to 140 ppm. The tri-substituted olefinic carbon accounts for the peaks from 118 to 128 ppm, and the aliphatic methyl carbon results in peaks from 20 to 25 ppm. This latter set of peaks can be used to distinguish c/s-l,4-polyisoprene from trans-, 4- and... 

A number of plants and some trees contain a white, milky liquid that is released when the stem or bark is cut. The liquid is called a latex from the Latin meaning liquid. Common sources include dandelions, milkweed, goldenrod, and potted rubber plants. Rubber trees, from which substantial quantities of latex can be harvested, grow in some tropical areas of the world. A major constituent of this latex is a homopolymer of isoprene (2-methyl-1,3-butadiene), called polyisoprene. Polyisoprene, as well as a number of other elastomers, has a carbon-carbon double bond in every repeat unit. The properties of polyisoprene are the result of the presence of these double bonds. Just as stereochemistry plays a critical role in both proteins and polysaccharides, we will see its importance here. 

The best-known elastomer is natural rubber, poly-isoprene (Scheme 6.10). Isoprene (Scheme 6.10a) is a liquid at room temperature, which polymerises readily to give the elastomer polyisoprene (Scheme 6.10b). The polymerisation produces two main geometrical isomers (see Section S2.1.) Natural rubber is the aU-c form of polyisoprene (Scheme 6.10c), in which the methyl (—CH3) groups and hydrogen (H) atoms are on the same side of the carbon-carbon double bond. Rubber latex, a milky liquid, is a suspension of rubber in water. It is found in many plants (e.g. in dandelions) as well as mbber... 

To synthesize polyethylene a double carbon bond in the starting material ethylene (CH2=CH2) breaks to allow attachment to other ethylene molecules resulting in a high molecular weight material or macromolecule. Other polymers which are formed by a similar process include polystyrene (repeat unit or monomer is styrene), polypropylene (monomer propene), poly (methyl methacrylate) where the monomer is methyl methacryalate, 1,4-polybutadiene (monomer is buta-1,3-diene) and 1,4-polyisoprene (monomer is isoprene) which has the same formula as natural rubber. Detaik of how polymers are prepared and processed are presented in Chapter 3. 

Figure 5.27 illustrates the crystal structure of P-tra i -l,4-poly(2-methyl butadiene), also known as traw -polyisoprene or gutta-percha. The a-crystal is more stable, but not fully identified. The -CHj-group is attached to position 2 in the helix 4 1/1, drawn in the sketch of Fig. 5.27. The methyl group is in this case on the carbon atom that has undergone a right-handed rotation out of the planar zig-zag by about...

A typical entropy-elastic material is cross-linked natural rubber, ds-poly(l-methyl-1-butenylene) or cts-l,4-polyisoprene, as summarized in Fig. 5.166 (see also Fig. 1.15). Its extensibility is 500 to 1,000%, in contrast to the 1% of typical energy-elastic sohds. Natural rubber has a molar mass of perhaps 350,000 Da (about 5,000 isoprene monomers or 20,000 carbon backbone bonds) and is then vulcanized to have about 1% cross-links (see Fig. 3.50). A rubber with a Young s modulus of 10 Pa (depending on cross-link density) must be compared to its bulk modulus (= 1/p,... 

The polymerization of butadiene monomer proceeds with chain propagation via 1,2-,, A-trans- or 1,4-cw-additions. If the polymerization is controlled to form mostly the 1,2-addition product, the polymer has a — CH2— chain with a terminal vinyl, — CH=CH2, substituent, at alternating carbon atoms. However, if 1,4-addition dominates the polymerization proceeds to form a polymer chain with a molecular structure of — (CH2 —CH=CH—CH2) —, normally with a trans configuration at the double bond. 2-Chloro-1,3-butadiene (CH2=CC1—CH=CH2 chloroprene) and 2-methyl-1,3-butadiene (isoprene) are polymerized in a similar manner. With these compounds, the asymmetry of the carbon atoms at positions 1 and 4 produces a variety of addition products with 1,2-, 1,4-cw,, A-trans, and 3,4-configurations. In the case of polyisoprene, which in nature occurs as natural rubber, the 1,4-cis configuration is the dominant structure. A summary of the polymerization products of butadiene, isoprene, and chloroprene is provided in Fig. 31. 

Polyisoprene has also been pyrolysed in an inert atmosphere and here the main products are isoprene and l-methyl-4-isoprenylcyclohexene. The latter compound can disproportionate to l-methyl-4-isopropyIbenzene and methyl-l-iso-propylcyclohexenes and this reaction is catalysed by Ziegler-Natta catalyst residues or by carbon black. The dominant initiation process is j9-chain scission with the formation of two allylic radicals. The kinetics of thermal decomposition have been studied for cis- and rraiw-1,4-polyisoprene and the copolymer of isoprene with 4-isopropyl-methyl styrene and also for isoprene polymers containing 4-CjH4—Z—4-C(H4— and —CjH4—Z—C5H4N=N— units, where Z may be O, CHj, SOj or a single bond. ... 

Tg measurements have been performed on many other polymers and copolymers including phenol bark resins [71], PS [72-74], p-nitrobenzene substituted polymethacrylates [75], PC [76], polyimines [77], polyurethanes (PU) [78], Novolac resins [71], polyisoprene, polybutadiene, polychloroprene, nitrile rubber, ethylene-propylene-diene terpolymer and butyl rubber [79], bisphenol-A epoxy diacrylate-trimethylolpropane triacrylate [80], mono and dipolyphosphazenes [81], polyethylene glycol-polylactic acid entrapment polymers [82], polyether nitrile copolymers [83], polyacrylate-polyoxyethylene grafts [84], Novolak type thermosets [71], polyester carbonates [85], polyethylene naphthalene, 2,6, dicarboxylate [86], PET-polyethylene 2,6-naphthalone carboxylate blends [87], a-phenyl substituted aromatic-aliphatic polyamides [88], sodium acrylate-methyl methacrylate multiblock copolymers [89], telechelic sulfonate polyester ionomers [90], aromatic polyamides [91], polyimides [91], 4,4"-bis(4-oxyphenoxy)benzophenone diglycidyl ether - 3,4 epoxycyclohexyl methyl 3,4 epoxy cyclohexane carboxylate blends [92], PET [93], polyhydroxybutyrate [94], polyetherimides [95], macrocyclic aromatic disulfide oligomers [96], acrylics [97], PU urea elastomers [97], glass reinforced epoxy resin composites [98], PVOH [99], polymethyl methacrylate-N-phenyl maleimide, styrene copolymers [100], chiral... 

The concentration of zinc accelerator-thiolate complexes in the rubber is not the only factor determining the balance of the two reactions in NR. Both the rate of desulfuration of polysulfide crosslinks and the rate of their thermal decomposition depend upon the positions of attachment of the sulfur chains to the backbone rubber chains and the detailed structure of the hydrocarbon at the ends of the crosslinks. In the course of normal accelerated vulcanization there are three different positions of attack on the polyisoprene backbone two of these are methylene groups in the main chain (labelled d and a in 3), and the third is the side chain methyl group (labelled b in 3). Direct analysis of the distribution of the sites of attack cannot yet be made on actual rubber vulcanizates, and information has had to be obtained solely by sulfuration of the model alkene 2-methyl-2-pentene and, more recently, 2,6-dimethyl-2,6-octadiene. The former (4) models the a-methylic site but only one of the two a-methylenic sites of polyisoprene the latter (5) models all three sites, but at the present time these are not all supported by the synthesis of relevant sulfides. Because allylic rearrangements are common in subsequent reactions of the sulfurated rubber, sulfur substituents appear not only on allylic carbon atoms but on isoallylic carbon atoms. Thus, from 2-methyl-2-pentene, the groups shown in Scheme 2 are formed. 

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