Thermodynamics of addition polymerization

✍ Scribed by K. J. Ivin

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 186 KB
• Volume: 38
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(20000615)38:12<2137::aid-pola20>3.0.co;2-d

✦ Synopsis

Addition polymerizations of both acyclic and cyclic monomers show the characteristic features of any aggregation process, in particular, a ceiling temperature above which the formation of the aggregate (long-chain polymer), under given conditions of monomer concentration, solvent, and pressure, would involve a positive change of free energy and is therefore impossible. Conversely, for a given temperature, pressure, and solvent, there is an equilibrium monomer concentration below which long-chain polymer cannot be formed. Monomers must therefore have a negative free energy of polymerization, under given conditions, if they are to be capable of undergoing a significant extent of polymerization. The effect of monomer structure, including ring size, on thermodynamic polymerizability is discussed, as well as the possibility of copoly-merizing monomers that cannot themselves give homopolymers. Examples are given for various possible mechanisms of polymerization.