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Condensation Polymerization: History
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Contributor: Helena Kang

Step-growth union of bifunctional or multifunctional monomers with extrusion of a small molecule (water, alcohol, hydrogen halide, or the like) is condensation polymerization. Each linking step is a condensation reaction, and molecular weight rises only at high conversion according to Flory’s statistical relation between extent of reaction and degree of polymerization [1]. Typical products are polyesters, polyamides, polyimides, and related heteroatom-rich backbones. Chain-growth condensation polymerization is a controlled variant in which substituent or catalyst effects suppress random step-growth and confine propagation to the polymer end, yielding well-defined condensation polymers and block copolymers [2]. The same principle enables precision synthesis of aromatic polyamides and π-conjugated polymers when catalyst-transfer or substituent-transfer activation keeps the chain end uniquely reactive [3]. The conceptual boundary versus addition polymerization is the stoichiometric byproduct and the step-growth (or chain-growth-condensation) kinetics. Not every step-growth polymerization is a condensation: polyurethane formation by isocyanate–alcohol addition is step-growth addition, not condensation, because no small molecule is eliminated.

  • condensation polymerization
  • step-growth polymerization
  • Flory statistics
  • chain-growth condensation

References

  1. Paul J. Flory; Fundamental Principles of Condensation Polymerization. Chem. Rev. 1946, 39, 137-197, 10.1021/cr60122a003.
  2. Tsutomu Yokozawa; Akihiro Yokoyama; Chain-Growth Condensation Polymerization for the Synthesis of Well-Defined Condensation Polymers and π-Conjugated Polymers. Chem. Rev. 2009, 109, 5595-5619, 10.1021/cr900041c.
  3. Tsutomu Yokozawa; Yoshihiro Ohta; Scope of controlled synthesis via chain-growth condensation polymerization: from aromatic polyamides to π-conjugated polymers. Chem. Commun. 2013, 49, 8281-8310, 10.1039/c3cc43603a.
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