Bio-based polyether from limonene oxide catalytic ROP as green polymeric plasticizer for PLA

Abstract

In this work, the polymerization of Limonene Oxide (LO) has been achieved using an Earth abundant metal-based catalyst developed in our group, that is very active in ring opening polymerization (ROP) processes. The bio-based polylimonene ether (PLO) obtained had low molecular weight and good thermal properties, thus being a potential green polymeric additive for other bio-based polymers such as PLA. Hence, we have explored its ability to influence PLA properties. The addition of only 10 wt %, led to the modification and improvement of PLA properties in terms of flexibility, thermal stability, and hydrophobicity. The results obtained are promising and open up the potential industrial application of polylimonene oxide (PLO) for the melt-processing of blends based on PLA/PLO. These new materials are totally based on renewable sources and may be interesting for many applications where biodegradability and reduced water adsorption is required, such as food packaging or agricultural mulch films.

Biodegradation of Poly(Lactic Acid) Biocomposites under Controlled Composting Conditions and Freshwater Biotope

“…A significant decrease in the thermal stability (initial decomposition temperature T 5 %) of PLA films was observed with the addition of the ATBC plasticiser. Similar results were observed by Maiza et al [ 3 ] and Sessini et al [ 35 ]. Nelson et al [ 46 ] reported that a higher degree of crystallinity is directly involved in the higher thermal stability of L-CNCs.…”

“…Furthermore, the C–O stretching bands of CH–O at 1180 cm −1 and O–C=O groups at 1127 cm −1 , 1080 cm −1 and 1043 cm −1 , respectively, were observed. The same absorption band characteristic was detected by Sessini et al [ 35 ], Lee et al [ 36 ], Weng et al [ 37 ] and Amorin et al [ 38 ]. Moreover, bending frequencies for CH 3 have bends identified at 1452 cm −1 , 1382 cm −1 and 1359 cm −1 , as well as bends related to the C=O double-bound around 700 cm −1 [ 39 ].…”

Improving the Mechanical Ductility and Toughness of Injection-molded Polylactide Pieces by the Dual Incorporation of Liquor Waste Derived Spent Coffee Grounds and Oligomers of Lactic Acid

“…Furthermore, green composite materials can strongly contribute to the development of the so-called Circular Bioeconomy as these are obtained from natural resources or, more sustainably, wastes and can be fully biodisintegrated under different composting conditions [5]. In the area of biodegradable polymers, polylactide (PLA) has made a large contribution since this biopolyester is both fully bio-based, obtained from starch-rich materials, and compostable in controlled industrial facilities [6,7]. PLA is a linear thermoplastic that shows high mechanical resistance and thermal stability, good transparency, and water-barrier performance, by which it can potentially substitute some polymer commodities, such as polypropylene (PP) or polystyrene (PS), in several applications, ranging from food packaging [8][9][10] to automotive [11], biomedicine [12], or electronics [13].…”

Terpenes and Terpenoids: Building Blocks to Produce Biopolymers

“…In 2012, Park described the photoinitiated cationic ring-opening polymerizations with diaryliodonium salts or triarylsufonium salts as photoinitiators with very poor control of the polymerization-the polymers generated had very low molecular weights and high disperties [130]. The only other example has been reported by us using a very active aluminum catalyst for ROP, [AlMeCl(OR)] (OR = 2,6-(CHPh 2 ) 2 -4-t Bu-C 6 H 2 O) (Scheme 8) [131,132]. This catalyst is able to efficiently polymerize (+)-limonene oxide in just 30 min, with a preference for cis-isomer polymerization.…”