Termination mechanism of polymethyl methacrylate and polystyrene studied by ultrasonic degradation technique


Catalgil-Giz H., Giz A. T. , ONCUL-KOC A.

POLYMER BULLETIN, vol.43, pp.215-222, 1999 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 43
  • Publication Date: 1999
  • Doi Number: 10.1007/s002890050555
  • Title of Journal : POLYMER BULLETIN
  • Page Numbers: pp.215-222

Abstract

A new method for determining the dominant termination mechanism in radical polymerization based on ultrasonic scission of long chains is used to study the termination of polystyrene and polymethyl methacrylate. The method is extended to obtain the disproportionation/combination ratio. Long dead polymer chains in solution were broken by ultrasound. The chain radicals thus formed were then allowed to terminate in the presence and absence of a chain terminating agent (radical trap). The resulting molecular weights are compared to find the dominant termination mechanism. It is found that the dominant mechanism in polystyrene is combination and that in polymethyl methacrylate is disproportionation. These results are in accordance with those quoted in the literature and obtained by other methods. The effectiveness of the radical trap used (2-chloroethyl benzene) was tested by NMR and it was found that when the trapping agent is present it terminates 100% of the polymethyl methacrylate chains. The time evolution of the degree of polymerization was compared to simulations based on Schmid's model. The disproportionation/combination ratios were found for polymethyl methacrylate as 2 and for polystyrene as 1/7 respectively through simulation studies.