The disposal of large amounts of waste from daily use polymers is among one of the foremost concerns in the current era. Effective utilization of bio-renewable materials procured from natural sources has been proposed as a potential solution to this problem. Among such different polymers, Poly lactic acid (PLA) which is a bio-degradable polymer, resembles quite promotable features, which can be polymerized from sustainable sources as chips sugarcane, starch and corn. Ring-opening polymerization (ROP) of Lactide (LA) monomer considering catalysts such as Al, Sn or Zn is one of the efficient methods for the PLA synthesis. However, the PLA polymerized through this type of catalysts may contain trace elements of the catalyst. Due to their carcinogenic nature, the traces of such catalysts should be (ideally) removed from the synthesis process. The use of alternative energy (AE-UV, Microwave) sources could be a potential route. Alternative development of non-metal catalysts is best alternatives for the processing of PLA through ROP. PLA layer based composite materials are gaining huge interest due to their multiple application (food, medical etc.) as eco-friendly material. In this article, we review on the implementation of AE sources for PLA processing and to populate the current state-of-the-art associated with the PLA research, especially application in nanocomposite materials field. A C C E P T E DACCEPTED MANUSCRIPT 2 ROP of Monomers through Metal/ ROP of Monomers through Metal/ ROP of Monomers through Metal/ ROP of Monomers through Metal/metal metal metal metal----free free free free Catalyst Catalyst Catalyst CatalystThe basis of the ROP process starts with opening the cyclic ring of monomers like amides (lactams), esters (lactones) and a cyclic ether. Then the opened ring acts as an active centre where other monomers join to create a longer polymer chain via ionic propagation consisting of initiation/ propagation as well as termination reactions [12]. In last two decades, several different classes of catalysts were implemented to synthesis PLA however, metal-based catalysts are the most common [7][8][9][10][11]. Apart from metal, organic and enzyme-based catalysts were also tried but with regards to the efficiency and reaction time, metal based catalysts show a more promising effect than non-metal based catalysts. Among many, Sn(Oct) 2 was a highly approved catalyst by United State food and drugs association (USFDA) for catalysis of LA. Once the monomer gets activated by the initiator (catalyst), the active site attracts other monomers to attach and increase the chain length. Thermodynamic and reaction kinetic are key factors for the suitability of polymerization of cyclic monomers [12], [13].
The reported research work was a multi-disciplinary, collaborative effort. Author SPD is the lead researcher and author of this manuscript. A detailed literature review and information regarding the ROP of lactide in the literature was conducted by author SPD as part of his doctoral thesis. Authors SPD, VM, HAA, JLB and KB contributed to the development of detailed study for the state-of-the art in the field of chronological development in the field of PLA processing. The author's contributed equally for making the manuscript more scientific and meaningful in terms of English language.
PLA is one of the most promising bio-compostable and bio-degradable thermoplastic polymers made from renewable sources. PLA is generally produced by ring opening polymerization (ROP) of lactide using the metallic/bimetallic catalyst (Sn, Zn, and Al) or other organic catalysts in a suitable solvent. In this work, reactive extrusion experiments using stannous octoate Sn(Oct) 2 and tri-phenyl phosphine (PPh) 3 were considered to perform ROP of lactide. Ultrasound energy source was used for activating and/or boosting the polymerization as an alternative energy (AE) source. Ludovic ® software, designed for simulation of the extrusion process, had to be modified in order to simulate the reactive extrusion of lactide and for the application of an AE source in an extruder. A mathematical model for the ROP of lactide reaction was developed to estimate the kinetics of the polymerization process. The isothermal curves generated through this model were then used by Ludovic software to simulate the "reactive" extrusion process of ROP of lactide. Results from the experiments and simulations were compared to validate the simulation methodology. It was observed that the application of an AE source boosts the polymerization of lactide monomers. However, it was also observed that the predicted residence time was shorter than the experimental one. There is potentially a case for reducing the residence time distribution (RTD) in Ludovic ® due to the 'liquid' monomer flow in the extruder. Although this change in parameters resulted in validation of the simulation, it was concluded that further research is needed to validate this assumption.
The most commonly used batch process to manufacture PLA is ring opening polymerization (ROP) of lactide monomer in a suitable solvent, in the presence of a metallic/bimetallic catalyst (Sn, Zn, and Al) or other organic catalysts. However, this process does not lend itself to safer/cleaner and high throughput (and high volume) manufacturing. Continuous reactive extrusion of lactide monomer using a suitable reaction input has the potential to increase the throughput, and this route has been explored in the literature. In this work, reactive extrusion experiments using stannous octoate Sn(Oct) 2 and tri-phenyl phosphine (PPh) 3 , were considered to perform ROP of lactide monomer using the microwave as an alternative energy (AE) source for activating and/or boosting the polymerization. Implementation of a microwave generator in a section of the extruder is one of the novelties of this research. A simulation model of ROP of PLA was formulated to estimate the impact of reaction kinetics and AE source on the polymerization process. Ludovic® software was used for the simulation of continuous reactive extrusion of the process. Experimental and simulated results were compared for the validation of the methodology. This work also highlights the advantages and drawbacks of most conventional metal catalysts, the effect of alternative energies on reaction mechanism, and safe and efficient production of PLA.
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