Studies in reactive extrusion processing of biodegradable polymeric materials.

摘要

Various reaction chemistries such as Polymerization, Polymer cross-linking and Reactive grafting were investigated in twin-screw extruders. Poly (1,4-dioxan-2-one) (PPDX) was manufactured in melt by the continuous polymerization of 1,4-dioxan-2-one (PDX) monomer in a twin-screw extruder using Aluminum tri-sec butoxide (ATSB) initiator. Good and accurate control over molecular weight was obtained by controlling the ratio of monomer to initiator. A screw configuration consisting of only conveying elements was used for the polymerization. The polymerization reaction was characterized by a monomer-polymer dynamic equilibrium, above the melting temperature of the polymer, limiting the equilibrium conversion to 78-percent. Near complete (∼100-percent) conversion was obtained on co-polymerizing PDX monomer with a few mol-percent (around 8-percent) Caprolactone (CL) monomer in a twin-screw extruder using ATSB initiator. The co-polymers exhibited improved thermal stability with reduction in glass transition temperature. The extruder was modeled as an Axial Dispersed Plug Flow Reactor for the polymerization of CL monomer using Residence Time Distribution (RTD) Analysis. The model provided a good fit to the experimental RTD and conversion data.; Aliphatic and aliphatic-aromatic co-polyesters, namely Polycaprolactone (PCL) and Poly butylenes (adipate-co-terephthalate) (Ecoflex) were cross-linked in a twin-screw extruder using radical initiator to form micro-gel reinforced biodegradable polyesters. Cross-linked Ecoflex was further extrusion blended with talc to form blends suitable to be blown into films. A screw configuration consisting of conveying and kneading elements was found to be effective in dispersion of the talc particles (5--10 microns) in the polyester matrix. While the rates of crystallization increased for the talc filled polyester blends, overall crystallinity reduced. Mechanical, tear and puncture properties of films made using the talc filled polyester blends were comparable to linear low density Polyethylene (LDPE).; Ecoflex-Thermoplastic Starch (TPS) graft co-polymers were continuously manufactured in melt with maleic acid catalyst using a twin-screw co-rotating extruder. The graft co-polymer was completely extractable in Dichloromethane and formed transparent films on solvent casting. Regular corn-starch was maleated in a twin-screw extruder using maleic anhydride or maleic acid, glycerol plasticizer and optional radical initiator. Confirmation of reactivity of maleic acid onto the starch backbone was confirmed by Fourier Transformed Infra Red (FTIR) Spectroscopy. (Abstract shortened by UMI.)