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A general method for the synthesis of hyperbranched functional polymers in monoterpenes is described. During the polymerization of dicyclopentadiene, metathesis reactions between the growing polymer chain and monoterpenes produced soluble well-defined polymers. The molecular weight, intrinsic viscosity [η], and glass transition temperature ( T g ) values resulting from chain transfer to monoterpenes depended on the mode of monomer addition but generally decreased as follows: d -limonene > limonene oxide > β-pinene. Calculation of the Mark−Houwink−Sakarada values by gel permeation chromatography suggested that, in solution, the branched poly(dicyclopentadiene) had a smaller hydrodynamic volume than polynorbornene. Characterization by NMR spectroscopy indicated the hyperbranched polymer had a complex structure composed of linear, terminal, semidendritic, and dendritic units.
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Mathers et al. (2009) studied this question.
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