Journal of Polymer Science Part A-1 Polymer Chemistry · 1967 · 24 citations · 3 references
Macromolecular ChemistryEngineeringPart IiiOrganic ChemistryChemistryCopolymer CompositionAnionic PolymerizationPolymersChemical EngineeringMacromolecular EngineeringAddition ReactionPolymer ChemistryBiopolymersPolymer SynthesisBiomolecular EngineeringPolymer SciencePolymer CharacterizationPolymerization KineticsPolymer ReactionSynthetic ChemistryRate Constants
Abstract On reacting acetylcaprolactam (AcCL) and pyrrolidonate MgBr (Py − ) in tetrahydrofuran solution, transacetylation takes place, giving acetylpyrrolidone (AcPy) and caprolactamate MgBr (CL − ). The rate constants for the transacetylation reactions were measured at 25°C. Their values in units of liters/mole‐second were: The rate constants for the addition reactions measured were: As the transacetylation is much faster than the addition reaction the copolymer composition should be given by the equation: where K trans , the transacetylation equilibrium constant, equals 0.3 while K acidity reflects the relative acidities of the monomers and its value (from the literature) is about 0.4. Pyrrolidone is, therefore, more reactive than caprolactam in anionic copolymerization by a factor of about 8.
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