Natural rubber structural changes

TPEs from blends of rubber and plastics constitute an important category of TPEs. These can be prepared either by the melt mixing of plastics and rubbers in an internal mixer or by solvent casting from a suitable solvent. The commonly used plastics and rubbers include polypropylene (PP), polyethylene (PE), polystyrene (PS), nylon, ethylene propylene diene monomer rubber (EPDM), natural rubber (NR), butyl rubber, nitrile rubber, etc. TPEs from blends of rubbers and plastics have certain typical advantages over the other TPEs. In this case, the required properties can easily be achieved by the proper selection of rubbers and plastics and by the proper change in their ratios. The overall performance of the resultant TPEs can be improved by changing the phase structure and crystallinity of plastics and also by the proper incorporation of suitable fillers, crosslinkers, and interfacial agents. 

Natural rubber (NR) and guttapercha consist essentially of polyisoprene in cis-l, 4 and trans-1,4 isomers, respectively. Commercially produced synthetic polyisoprenes have more or less identical structure but reduced chain regularity, although some may contain certain proportions of 1,2- and 3,4-isomers. Microstructure differences not only cause the polymers to have different physical properties but also affect their response to radiation. The most apparent change in microstructure on irradiation is the decrease in unsaturation. It is further promoted by the addition of thiols and other compounds.130 On the other hand, antioxidants and sulfur were found to reduce the rate of decay of unsaturation.131 A significant loss in unsaturation was found, particularly in polyisoprenes composed primarily of 1,2- and 3,4-isomers.132,133... 

Fig. 1 indicates that no drastic structuralmodifications of polyisoprene are effected by changing alkali metals with the glaring exception of lithium. Sodium, potassium, rubidium and cesium produce a polyisoprene containing between 43% (sodium) and 55% (cesium) 1,4 structure, 90—100% trans. The point for the emulsion polymerization has been included in order to give an example of the structure of a free radical produced polymer. Lithium of course stands far away by itself giving a polymer almost identical in structure with natural rubber (hevea). 

A critical requirement for obtaining engineering properties from a rubbery material is its existence in a network structure. Charles Goodyear s discovery of vulcanization changed natural rubber from a material that became sticky when hot and brittle when cold into a material that could be used over a wide range of conditions. Basically, he had found a way to chemically connect the individual polymer chains into a three-dimensional network. Chains that previously could flow past one another under stress now had only limited extensibility, which allowed for the support of considerable stress and retraction upon release of the stress. The terms vulcanization, rubber cure, and cross-linking all refer to the same general phenomenon. 

Some polymorphic modifications can be converted from one to another by a change in temperature. Phase transitions can be also induced by an external stress field. Phase transitions under tensile stress can be observed in natural rubber when it orients and crystallizes under tension and reverts to its original amorphous state by relaxation (Mandelkem, 1964). Stress-induced transitions are also observed in some crystalline polymers, e.g. PBT (Jakeways etal., 1975 Yokouchi etal., 1976) and its block copolymers with polyftetramethylene oxide) (PTMO) (Tashiro et al, 1986), PEO (Takahashi et al., 1973 Tashiro Tadokoro, 1978), polyoxacyclobutane (Takahashi et al., 1980), PA6 (Miyasaka Ishikawa, 1968), PVF2 (Lando et al, 1966 Hasegawa et al, 1972), polypivalolactone (Prud homme Marchessault, 1974), keratin (Astbury Woods, 1933 Hearle et al, 1971), and others. These stress-induced phase transitions are either reversible, i.e. the crystal structure reverts to the original structure on relaxation, or irreversible, i.e. the newly formed structure does not revert after relaxation. Examples of the former include PBT, PEO and keratin. 

In some colloidal dispersions, the shear rate (flow) remains at zero until a threshold shear stress is reached, termed the yield stress (ry), and then Newtonian or pseudoplastic flow begins. A common cause of such behaviour is the existence of an inter-particle or inter-molecular network, which initially acts like a solid and offers resistance to any positional changes of the volume elements. In this case, flow only occurs when the applied stress exceeds the strength of the network and what was a solid becomes a fluid. Examples include oil well drilling muds, greases, lipstick, toothpaste and natural rubber polymers. An illustration is provided in Figure 6.13. Here, the flocculated structures are responsible for the existence of a yield stress. Once disrupted, the nature of the floe break-up process determines the extent of shear-thinning behaviour as shear rate increases. 

For natural rubber the summary change in the density of the space lattice occurs at the lowest rate, which indicates a small difference in the rates of destruction-and structuring. The rapid decrease in the strength indices during irradiation of natural rubber vulcanizates is due to the influence of the lattice formed on the ability to crystallize during stretching. 

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