Acrylic acid polymerization kinetics

✍ Scribed by S. S. Cutié; P. B. Smith; D. E. Henton; T. L. Staples; C. Powell

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 311 KB
• Volume: 35
• Category: Article
• ISSN: 0887-6266
• DOI: 10.1002/(sici)1099-0488(19970930)35:13<2029::aid-polb4>3.0.co;2-r

✦ Synopsis

The kinetics of the isothermal polymerization of acrylic acid were determined utilizing 1 H-NMR spectroscopy. The polymerization rate was observed to depend approximately on the 3 2 power of monomer and the 1 2 power of sodium persulfate concentration. This is consistent with a model in which the rate of initiation is itself dependent on the monomer concentration. The polymerization rate was also observed to have a strong dependence on percent neutralization, decreasing with increasing level of neutralization up to 75 to 100% neutralization, and then increasing again. The activation energy for the rate of polymerization was between 9 and 13 kcal/mol except for 100% neutralized acrylic acid, which had an activation energy of 18 kcal/mol. These data suggest that a transition in mechanism occurred at 100% neutralization. Increasing the ionic strength by the addition of sodium chloride also increased the rate. The dependence of the molecular weight on the above variables was also quantified for use in the model. It decreased with increasing conversion, decreasing ionic strength and increasing initiator.