Mechanistic insights into ozone-initiated oxidative degradation of saturated hydrocarbons and polymers
Lee, R; Coote, ML
| HERO ID | 4248250 |
|---|---|
| In Press | No |
| Year | 2016 |
| Title | Mechanistic insights into ozone-initiated oxidative degradation of saturated hydrocarbons and polymers |
| Authors | Lee, R; Coote, ML |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 18 |
| Issue | 35 |
| Page Numbers | 24663-24671 |
| Abstract | Accurate quantum chemical calculations were employed to investigate the mechanism of ozone-initiated oxidation of C-H bonds of saturated hydrocarbons and polymers. Step wise hydrogen atom abstraction generates the first resting state the trihydroxide -COOOH, which undergoes decomposition to produce the free radical species alkoxyl -CO˙ and peroxyl ˙OOH thereby setting off a complex chain of radical processes. The H transfer from peroxyl radical to alkoxyl allows formation of inactive alcohol and the singlet excited dioxygen. Other competitive processes include the self fragmentation or β-scission of the alkoxyl -CO˙ to give rise to a carbonyl (ketone or aldehyde) and a C-centred free radical species. Tertiary C-H bonds are most susceptible to O3 oxidation followed by secondary and primary. Among the polymers studied, poly(styrene) is the least resistant to C-H bond ozonation, followed by poly(propylene), poly(methacrylate), poly(methyl methacrylate) and poly(vinyl chloride). Calculations also reveal catalytic effects of water in promoting the C-H bond oxidation process in polymer systems without competing H-bond donor groups. |
| Doi | 10.1039/c6cp05064f |
| Pmid | 27545312 |
| Wosid | WOS:000382766300056 |
| Url | <Go to ISI>://WOS:000382766300056 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |