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The last equation shows that the maximum value of the Đ is 2, which occurs at a monomer conversion of 100% (or p = 1). This is true for step-growth polymerization of linear polymers. For chain-growth polymerization or for branched polymers, the Đ can be much higher.
A generic representation of a step-growth polymerization. (Single white dots represent monomers and black chains represent oligomers and polymers) [1] Comparison of molecular weight vs conversion plot between step-growth and living chain-growth polymerization
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In 1995, a key step in the "degenerate" reversible chain transfer step for chain equilibration was brought to attention. The essential feature is that the product of chain transfer is also a chain transfer agent with similar activity to the precursor transfer agent. [5]
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That is, r −1 ≪ r 2, so that r 1 − r 2 ≈ 0. But the overall rate of reaction is the rate of formation of final product (here CO 2), so that r = r 2 ≈ r 1. That is, the overall rate is determined by the rate of the first step, and (almost) all molecules that react at the first step continue to the fast second step.
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