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Bulk polymerization of ε-caprolactone has been carried out both in a laboratory internal mixer (Brabender Plasticorder) and in a modular intermeshing co-rotating twin screw extruder. Various initiators, such as titanium n-butoxide, aluminum triisopropoxide, and sodium hydride were used to polymerize ε-caprolactone in an internal mixer. The continuous polymerization of ε-caprolactone was performed using aluminum triisopropoxide under a range of processing conditions, including barrel temperature profiles, throughput, and screw speed. This polymerization was investigated for various ratios of monomer to initiator. GPC analysis demonstrated that significant quantities of oligomers were produced together with high molecular weight polymer at different reaction temperatures. H NMR detected the hydroxylation of growing chain end group for bulk polymerization at high barrel temperature. The molecular weight was reduced along the screw axis once the maximum molecular weight was obtained after the first kneading disk block. Increasing screw speed caused further reductions in molecular weight.

Bulk Polymerization of ε-Caprolactone in an Internal Mixer and in a Twin Screw Extruder