Reactions scission

Alkoxy radicals can abstract hydrogen (eq. 12), but they may undergo a -scission reaction (eq. 16). 

At the higher temperatures a decomposition of alkyl radicals, which is an olefin-producing variation of the -scission reaction, becomes competitive with reaction 23 (or sequence 2, 24) ... 

At combustion temperatures, the oxidation of butane [106-97-8] is similar to that of propane (153). This is because most butyl radicals are consumed by carbon—carbon bond scission (reaction 28). 

The proposed mechanism for producing ethanol [64-17-5] from butane involves -scission of a j -butoxy radical (eq. 38). The j -butoxy radicals are derived from j -butylperoxy radicals (reaction 14 (213)) and/or through some sequence involving reaction 33. If 25% of the carbon forms ethanol, over 50% must pass through the j -butoxy radical. Furthermore, the principal fate of j -butoxy radicals must be the P-scission reaction the ethoxy radical, on the other hand, must be converted to ethanol efficiently. 

Two secondary propagating reactions often accompany the initial peroxide decomposition radical-induced decompositions and -scission reactions. Both reactions affect the reactivity and efficiency of the initiation process. Peroxydicarbonates and hydroperoxides are particularly susceptible to radical-induced decompositions. In radical-induced decomposition, a radical in the system reacts with undecomposed peroxide, eg ... 

Although primary and secondary alkyl hydroperoxides are attacked by free radicals, as in equations 8 and 9, such reactions are not chain scission reactions since the alkylperoxy radicals terminate by disproportionation without forming the new radicals needed to continue the chain (53). Overall decomposition rates are faster than the tme first-order rates if radical-induced decompositions are not suppressed. 

Alkoxy radicals from hydroperoxides can undergo a -scission reaction (eq. 2) to yield an alkyl radical and a ketone. The higher stabiUty of the generated alkyl radical compared to that of the parent alkoxy radical provides the driving force for this reaction, and the R group involved is the one that forms the most stable alkyl radical. 

M. Cates. Reptation of living polymers Dynamics of entangled polymers in the presence of reversible chain-scission reactions. Macromolecules 20 2289-2296, 1987. 

It was observed that beyond optimum total dose the percentage of grafting decreased. This may be due to the fact that at higher total doses beyond optimum, chain degradation by /3-scission (reaction 35, 37, 38) occurs. Further at higher doses, hydroxyl radicals arising from... 

RAFT end groups are known to be unstable at very high temperatures (>200 °C). Thermal elimination has been used as a means of trithiocarbonate end group removal. For ps430,4W direct elimination is observed (Scheme 9.54). For poly(butyl acrylate)464 the major product suggests a hoinolysis/backbiting/ i-scission reaction is involved (Scheme 9.55). 

An alternative explanation suggested by the authors for the non-linearity of R° with dose is the formation of reactive solvent species capable of intercepting the scission reaction, with a yield which becomes greater the higher the absorbed dose per pulse. However, this mechanism does not explain the effect of oxygen. 

HEATRO = heat of reaction for the polymerization, cal/mole TF = reactor inlet temperature, °C DM0 = reactor fluid density, mole/l BETA = 3-scission reaction rate constant... 

The effect of oxidative irradiation on mechanical properties on the foams of E-plastomers has been investigated. In this study, stress relaxation and dynamic rheological experiments are used to probe the effects of oxidative irradiation on the stmcture and final properties of these polymeric foams. Experiments conducted on irradiated E-plastomer (octene comonomer) foams of two different densities reveal significantly different behavior. Gamma irradiation of the lighter foam causes stmctural degradation due to chain scission reactions. This is manifested in faster stress-relaxation rates and lower values of elastic modulus and gel fraction in the irradiated samples. The incorporation of O2 into the polymer backbone, verified by IR analysis, conftrms the hypothesis of... 

SCHEME 31. S (a) Oxidation, dehydrofluorination and crosslinking reactions as a result of EB irradiation of poly (vinylidenefluoride-co-hexafluoropropylene-co-tetrafluoroethylene). (b) Chain scission reactions as a result of EB irradiation of poly (vinylidenefluoride-co-hexafluoropropylene-co-tetrafluoroethylene). 

Displacement (a-scission) and Free Radical Arbuzov (P-scission) Reactions. 58... 

The term charring refers to the complete degradation of a polymer after which there is no longer any polymeric character to observe. Charring results from chain scission reactions that are left unchecked and is the typical process by which thermosets degrade. The resulting material is typically black and brittle. 

Formation of a trinuclear ruthenium carbene complex via the olefin scission reaction has also been noted (68) ... 

L. Lewis, General Electric Following you isolobal argument, would you expect or do you observe any metal carbon bond scission reactions Vollhardt et al. ( 1) observe C=C bond... 

P-parinaric acid, physical properties, 5 33t P-pentenoic acid, physical properties, 5 3 It P-peroxylactones, 18 484 Beta phase titanium, 24 838 in alloys, 24 854-856 properties of, 24 840, 941 P-phellandrene, 24 493 P-picoline, 21 110 from acrolein, 1 276 uses for, 21 120 P-pinene, 3 230 24 496-497 major products from, 24 478 /-menthol from, 24 522 as natural precursor for aroma chemicals, 3 232 terpenoids from, 24 478-479 P-propiolactone, polymerization of, 14 259 P-quartz solid solution, 12 637—638 Beta ratio, in filtration, 11 329—330 Beta (P) rays, 21 285 P-scission reactions, 14 280-281 P-skytanthine, 2 101 P-spodumene solid solution, 12 638-639 P-sulfur trioxide, 23 756 P-sultones, 23 527 P-tocopherol, 25 793 P-tocotrienol, 25 793 P-vinylacrylic acid, physical properties, 5 33t... 

Scintillation detector, 26 420, 433-434 SCISS P-Scission reactions, 24 280-281 SCK micelles, 20 489, 490 Sclareol, 24 573 Sclareolide, 24 573 Sclerenchyma cells, 22 18 Scleroglucan, 20 578, 4 724t... 

---