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RESEARCH PRODUCT

Size, Form and Flexibility of the Rubber Molecule

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Abstract Natural rubber can be brominated in dilute cyclohexane solution, whereby the molecular weight, corresponding to the bromine content, increases. For brominated rubber, increasing bromine content makes cyclohexane an increasingly poorer solvent, which is shown by a contraction of the molecule coils and a decrease in the second virial coefficient. Quantitative results were obtained through viscosity and light scattering measurements. Cyclohexane solutions of brominated rubber containing about 43% bromine have a θ point at room temperature. Here the second virial coefficient is zero and the coil has an ideal Gaussian density distribution. In this state the coil diameter is about 1.6 times bigger than for completely free rotation. A comparison of these data with X-ray low angle scattering could yield a quantitative measure of possible molecular branching. Brominated rubber with about one bromine per isoprene residue is a good starting material for the preparation of electron-microscope samples which can be used for the determination of the molecular weight distribution in rubber. The value of the weight average degree of polymerization determined by an electron microscope is in agreement with that determined through (1) light scattering and (2) ultracentrifuge and diffusion measurements. The molecular inhomogeneity of our sample is of the order of 0.5.