Modified Forms of Natural Rubber

As natural rubber is a product of nature, its properties are determined by the biochemical pathway by which the polymer is synthesized in the plant. In the case of natural rubber the polymerization process cannot be tailored like that of synthetic rubbers. The only option to modify natural rubber is after it has been harvested from the tree. The important modified forms of natural rubber include hydrogenated natural rubber, chlorinated natural rubber, hydro-halogenated natural rubber, cyclized natural rubber, depolymerised liquid natural rubber, resin modified natural rubber, poly(methyl methacrylate) grafted natural rubber, poly(styrene) grafted natural rubber, and epoxidized natural rubber [33,34]. Thermoplastic natural rubber prepared by blending natural rubber and PP is considered as a physically modified form of natural rubber. 

A few of the modified forms of natural rubber which have assumed commercial and/or scientific importance are detailed below. 

Epoxidized natural rubber (ENR) is an important modified form of natural rubber whose properties are close to those of special purpose synthetic rubbers. ENR is prepared by reacting natural rubber in latex form with performic acid formed in situ by the reaction of formic acid and hydrogen peroxide under controlled conditions. [45,46]. The double bonds of natural rubber react readily with peracids to yield epoxide groups. Though any level of epoxidation can be achieved, only up to 50 mole percent is used in practice. 50, 25, and 10 mole% epoxidized products are termed ENR-50, ENR-25, and ENR-10. Studies using NMR have shown that the epoxide groups are randomly distributed along the natural rubber backbone [47]. 

B.George, R. Alex and N.M.Mathew, Modified forms of natural rubber, in P.J.George and C.K. Jacob eds. Natural Rubber Agromanagement and Crop Processing, Rubber Research Institute of India, Kottayam, India, p. 456, 2000. 

Epoxidized natural rubber is still a strain crystallizing mbber and therefore retains the high tensile strength of natural rubber. However, as can be seen from Table 5, in other respects they have very little in common. The epoxidation renders a much higher damping mbber, a much-improved resistance to oil swelling (insofar as a 50 mol % modified natural mbber has similar oil resistance to a 34% nitrile mbber), and much-reduced air permeability. This latest form of modified natural mbber therefore widens the applications base of the natural material and enables it to seek markets hitherto the sole province of some specialty synthetic mbbers. 

Membranes with extremely small pores ( < 2.5 nm diameter) can be made by pyrolysis of polymeric precursors or by modification methods listed above. Molecular sieve carbon or silica membranes with pore diameters of 1 nm have been made by controlled pyrolysis of certain thermoset polymers (e.g. Koresh, Jacob and Soffer 1983) or silicone rubbers (Lee and Khang 1986), respectively. There is, however, very little information in the published literature. Molecular sieve dimensions can also be obtained by modifying the pore system of an already formed membrane structure. It has been claimed that zeolitic membranes can be prepared by reaction of alumina membranes with silica and alkali followed by hydrothermal treatment (Suzuki 1987). Very small pores are also obtained by hydrolysis of organometallic silicium compounds in alumina membranes followed by heat treatment (Uhlhom, Keizer and Burggraaf 1989). Finally, oxides or metals can be precipitated or adsorbed from solutions or by gas phase deposition within the pores of an already formed membrane to modify the chemical nature of the membrane or to decrease the effective pore size. In the last case a high concentration of the precipitated material in the pore system is necessary. The above-mentioned methods have been reported very recently (1987-1989) and the results are not yet substantiated very well. 

Of the several types of the polymer-modified mortars and concretes used for various construction applications, latex-modified mortar and concrete are by far the most widely used materials. Latex-modified mortar and concrete are prepared by mixing a latex, either in a dispersed liquid or as a redispersible powder form with fresh cement mortar and concrete mixtures. The polymers are usually added to the mixing water just as other chemical admixtures, at a dosage of 5-20% by weight of cement. Polymer latexes are stable dispersions of very small (0.05-5 pm in diameter) polymer particles in water and are produced by emulsion polymerization. Natural rubber latex and epoxy latex are exceptions in that the former is tapped from rubber trees and the latter is produced by emulsifying an epoxy resin in water by the use of surfactants [87]. 

In rubber-modified polystyrenes, the rubber is dispersed in the polystyrene matrix in the form of discrete particles. The two-phase nature of rubber-modified polystyrene was first suggested by Buchdahl and Nielsen [47] based on data on dynamic mechanical properties obtained with a torsion pendulum. The existence of two prominent loss peaks led to this conclusion, one at low temperatures which is due to the a relaxation of the rubber (e.g. 193 K for polybutadiene) and one at high temperatures which is due to the a relaxation of the matrix (e.g. 373 K for polystyrene). Later, microscopy provided proof of the existence of the rubber phase as a discrete dispersed phase in polystyrene [48]. 

In addition to these forms of polymerization, naturally-occurring polymers may be modified to produce new polymers with desirable characteristics. The vulcanization of rubber is one example of a combination of natural and synthetic processes for creating a polymer. 

All the commercial PBT/PC and PET/PC blends also contain typically 10-20 wt% of an additional elastomeric impact modifier. The exact nature and the content of the impact modifier is kept proprietary and often forms the basis for a particular blend patent. Typically core-shell rubbers such as polymethylmethacrylate grafted butadiene-styrene rubber (MBS) or an all acrylic core-shell rubber such as poly (MMA-g-n-BuA) are used [Nakamura, 1975 Chung, 1985]. ABS (with high polybutadiene content S 50%) or ASA... 

Useful film-forming resin adhesives include polyvinyl esters and ethers and their copolymers and interpolymers with ethylene and vinyl monomers, acrylic resins and their copolymers, polyvinyl alcohol, water dispersion of polyolefin resins, polystyrene copolymers such as polystyrene butadiene, polyamide resins, natural rubber dispersions, and natural and modified carbohydrates (starch or carboxycellulose). Particularly preferred for use are aqueous dispersions of polyvinyl acetate and vinyl acetate-ethylene copolymers. 

Natural mbber crystallizes on elongation—a phenomenon called strain-induced crystallization—what enhances mechanical properties. However, a filler in the form of carbon black is typically added to natural rubber to additionally modify the mechanical properties. Elastomers which cannot undergo strain-induced crystallization contain even more fillers. Carbon black is used in such cases also, but silicone rubbers are filled with silica. 

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