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The distinction between "step-growth polymerization" and "chain-growth polymerization" was introduced by Paul Flory in 1953, and refers to the reaction mechanisms, respectively: [4] by functional groups (step-growth polymerization) by free-radical or ion (chain-growth polymerization)
This is true for step-growth polymerization of linear polymers. For chain-growth polymerization or for branched polymers, the Đ can be much higher. In practice the average length of the polymer chain is limited by such things as the purity of the reactants, the absence of any side reactions (i.e. high yield), and the viscosity of the medium.
The Flory–Stockmayer Theory allows for the prediction of when gelation occurs using percent conversion of initial monomer and is not confined to cases of stoichiometric balance. Additionally, the Flory–Stockmayer Theory can be used to predict whether gelation is possible through analyzing the limiting reagent of the step-growth polymerization.
Step-growth polymers increase in molecular weight at a very slow rate at lower conversions and reach moderately high molecular weights only at very high conversion (i.e., >95%). Solid state polymerization to afford polyamides (e.g., nylons) is an example of step-growth polymerization. [8]
ADMET is a type of step-growth, condensation polymerization. It should be distinguished from ring-opening metathesis polymerization (ROMP), which is a chain-growth, addition polymerization. [1] Whereas ADMET is driven by the release of volatile ethylene gas, ROMP is driven by the relief of ring-strain.
In conventional covalent polymerization, two models based on step-growth and chain-growth mechanisms are operative. Nowadays, a similar subdivision is acceptable for supramolecular polymerization; isodesmic also known as equal-K model (step-growth mechanism) and cooperative or nucleation-elongation model (chain-growth mechanism).
Ideal step-growth polymerization gives a polymer with dispersity of 2. Ideal living polymerization results in a dispersity of 1. By dissolving a polymer an insoluble high molar mass fraction may be filtered off resulting in a large reduction in M w and a small reduction in M n, thus reducing dispersity.
Acid Chloride Preparative Route for Nylon-6,10, which is often used in the nylon rope trick. The nylon rope trick is a scientific demonstration that illustrates some of the fundamental chemical principles of step-growth polymerization and provides students and other observers with a hands-on demonstration of the preparation of a synthetic polymer.