Unter Einhaltung standardisierter Reaktionsbedingungen wird die Empfindlichkeit der Monomerenreaktivitätsverhältnisse und der Durchschnittspolymerisationsgrade gegenüber Substituenteneinfluß bei der kationischen Copolymerisation nach folgenden beiden Beziehungen untersucht:
Die Durchschnittspolymerisationsgrade erfahren dabei eine geringere Beeinflussung als das Verhältnis der relativen Reaktivitäten. Copolymere, in denen p‐Fluorstyrol enthalten ist, haben von den obigen Beziehungen stark abweichende Durchschnittspolymerisationsgrade.
As a continuation of the thermochemical analysis of the cationic polymerization, the initiation as well as the transfer and termination reactions were thermodynamically treated as competing reactions to the cationic propagation using recent data for the formation enthalpies of the carbocations.
Latterly, the formation cnthalpies were determined for many carbocations by means of thermochemical methods. Therefore a thermodynamical view is possible for the propagation reactions of the cationic polymerization to a larger extent.
Zzir Therniodynanrik der kationischen Polymerisation. 1. Kalionisches WachstumIn letzter Zeit wurden fur viele Carbokationen die Bildungsenthalpien thermochemisch bestimmt. Damit wird in erweitertem Umfang die thermodynamische Betrachtung der Wachstumsreaktionen der kationischen Polymerisation moglich. 0 mepfiodunamae tcamuounoiL noawepuiayuu.
Model Calculations on the Counterion Effect in the Cationic Polymerization; Decay of the Mixed Halogenoantimonates SbCl5Br− and SbClBr 5−
The decay of the halogenoantimonates SbCl5Br− and SbClBr 5− according to SbCl5Br− → SbCl5 + Br− resp. SbCl4Br + Cl− and SbClBr 5− → SbBr5 + Cl− resp. SbClBr4 + Br− has been investigated by the quantum‐chemical CNDO/2 method including geometry optimization. The calculations show that the dissociation of the SbCl bond needs more energy (7,8 kcal/mol) than the dissociation of the SbBr bond.
Dissociation of the complex anions is facilitated with increasing Br content.
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