The Reaction of Benzoyloxy Radicals with Styrene—Implications Concerning the Structure of Polystyrene

Abstract The selectivity of the reaction of benzoyloxy radicals with styrene has been examined. Analysis of the products formed when benzoyl peroxide is decomposed in styrene at 60°C in the presence of a radical trapping agent (2,2,6,6-tetramethylpiperidine-1-oxyl) shows that the reaction of benzoyloxy radicals with styrene proceeds with 80% “tail” addition, 5% “head” addition, and 15% aromatic substitution. Phenyl radicals (formed by decarboxylation of benzoyloxy radicals) also may add to either the double bond or the aromatic ring of styrene. The importance of the above-mentioned processes to the structure and properties of benzoyl-peroxide-initiated polystyrene is discussed.

[1]  D. Carlsson,et al.  The thermal decomposition of 1-(2′-cyano-2′-propoxy)-4-oxo-2,2,6,6-tetramethylpiperidine , 1979 .

[2]  O. Vogl,et al.  Head-to-head polymers, 14. Thermal degradation of head-to-head and head-to-tail polystyrenes and poly(vinylcyclohexane)s† , 1979 .

[3]  A. Arnoldi,et al.  Nucleophilic character of alkyl radicals. 18. Absolute rate constants for the addition of primary alkyl radicals to conjugated olefins and 1,4-benzoquinone , 1979 .

[4]  E. Rizzardo,et al.  A new method for investigating the mechanism of initiation of radical polymerization , 1979 .

[5]  T. Sloane,et al.  COMPETITION BETWEEN REACTIVE SITES IN THE REACTIONS OF OXYGEN ATOMS AND HYDROXYL RADICALS WITH PHENYLACETYLENE AND STYRENE , 1979 .

[6]  J. Tait,et al.  2,2,6,6-Tetramethyl-4-oxo-1-(1,1-diphenylethoxy)piperidine: synthesis and thermal stability , 1978 .

[7]  G. G. Cameron,et al.  Thermal Degradation of Polystyrene. 3. A Reappraisal , 1978 .

[8]  K. Ingold,et al.  KINETIC APPLICATIONS OF ELECTRON PARAMAGNETIC RESONANCE SPECTROSCOPY. 34. RATE CONSTANTS FOR SPIN TRAPPING. 2. SECONDARY ALKYL RADICALS , 1978 .

[9]  P. C. Deb,et al.  Radical Vinyl Polymerization. Reactions of Benzoyl Peroxide during Bulk Polymerization of Styrene with Labeled Initiator , 1977 .

[10]  Tsuneyuki Sato,et al.  Application of spin trapping technique to radical polymerization, 14. Initiation reaction of vinyl monomers with the tert-butoxyl radical and evaluation of monomer reactivities† , 1977 .

[11]  M. Hocking.  Isomeric Mixture Analysis of Some Ring-opening Reactions of Styrene Oxide , 1974 .

[12]  Jacqueline I. Kroschwitz,et al.  Encyclopedia of Polymer Science and Technology , 1970 .

[13]  D. DeTar.  Theoretical study of the elementary steps involved in the reaction of benzoyl peroxide with benzene , 1967 .

[14]  R. A. Long,et al.  Quantitative product study and a critical evaluation of the thermal decomposition of benzoyl peroxide in benzene , 1967 .

[15]  K. Ingold,et al.  Absolute rate constants for hydrocarbon autoxidation. VI. Alkyl aromatic and olefinic hydrocarbons , 1967 .

[16]  W. J. Dale,et al.  Substituted Styrenes. III. The Syntheses and Some Chemical Properties of the Vinylphenols1,2 , 1958 .

[17]  J. C. Bevington,et al.  Nature of the end groups in polystyrene prepared using benzoyl peroxide as sensitizer , 1956 .

[18]  E. Rizzardo,et al.  Initiation Pathways in the Polymerization of Alkyl Methacrylates with tert-Butoxy Radicals , 1982 .

[19]  G. Moad,et al.  The reaction of acyl peroxides with 2,2,6,6-tetramethylpiperidinyl-1-oxy , 1981 .

[20]  K. Asmus,et al.  Kinetics of nitroxyl radical reactions. A pulse-radiolysis conductivity study. , 1976, International journal of radiation biology and related studies in physics, chemistry, and medicine.

[21]  A. Davison,et al.  Pulse radiolysis of styrene and acrylate monomers , 1975 .

[22]  T. Kunitake,et al.  An application of spin trapping to radical polymerizations , 1974 .

[23]  W. R. Foster,et al.  560. Aroyl peroxides. Part I. The decomposition of benzoyl peroxide in alkylbenzenes , 1962 .

[24]  W. Cooper.  687. The effect of structure of diacyl peroxides on the rates of initiation of the polymerisation of styrene , 1951 .