Ring-opening Polymerization Process Research Articles

Application of ultrasound-assisted compression and 3D-printing semi-solid extrusion techniques to the development of sustained-release drug delivery systems based on a novel biodegradable aliphatic copolyester

The purpose of this study was to investigate the ability of two advanced hot-processing technologies, Ultrasound-Assisted Compression (USAC) and 3D-printing Semi-solid Extrusion (SSE), to manufacture sustained-release drug delivery systems based on a novel biodegradable aliphatic copolyester. The copolymer was synthesized from ω-pentadecalactone (PDL), 1,4-cyclohexanedimethanol (CHDM) and dimethyl succinate (DMS) (monomer ratio PDL/CHDM/DMS 70/30/30) by enzymatic ring opening polymerization and two-step melt polycondensation processes and has a random microstructure, a high molecular weight (107,100 g mol−1) and a relatively low melting point (∼65 °C). The antibacterial agent metronidazole (MTZ) was chosen as model drug and binary physical mixtures copolymer:drug were prepared at 90:10 and 70:30 w/w ratios. Thermal analysis studies evidenced that the formulations could be processed below their degradation temperatures. Drug delivery devices with dense and meshed structures were manufactured using USAC and SSE techniques, respectively, with USAC devices exhibiting more reproducible physical properties than the SSE systems. Powder X-ray diffraction and scanning electron microscopy studies showed a partial sintering of the copolyester during USAC processing while MTZ remained mostly crystalline. In contrast, the copolymer melted and the drug underwent some amorphization when processed using SSE. In vitro drug release studies in phosphate buffer (pH 6.8) showed that, after an initial burst release of metronidazole, USAC and SSE devices exhibited a prolonged and/or sustained drug release over 20 days. The initial burst release was dependent on the manufacturing technique and the drug/polymer ratio, being minimized for SSE devices containing 10 wt% MTZ. The whole drug release profiles fitted well to the Peppas-Sahlin model, being drug diffusion the predominant release mechanism. After the burst release, the sustained release period of USAC and SSE devices containing 10 wt% MTZ showed a good fit to the zero-order kinetic model, with faster drug release from the SSE devices due to the larger surface area of their meshed structure. In conclusion, this work demonstrates that processing the aliphatic copolyester by both USAC and SSE technologies provides an attractive strategy to manufacture biodegradable drug delivery systems for long-term release of metronidazole.

Quinolyl/pyridyl-amino Li complexes as dual catalysts for the ring-opening polymerization of cyclic esters and degradation toward a circular economy approach

Bi- and tetra-lithium quinolyl/pyridyl-amino complexes 1–4 were synthesized and characterized. These lithium complexes were capable of initiating the polymerization of rac-lactice (rac-LA) and ε-caprolactone (ε-CL) with high catalytic activity, respectively, whether in the presence or absence of BnOH. Both number of metal centers and ligand structures are identified as the crucial factors that determine the reactivity of a catalyst in the ROP. Their kinetic analyses indicated that tetrametallic complex 3 showed a more cooperativity comparable to that achieved with bimetallic analogues in the ring-opening polymerization (ROP) of ε-CL, however, number of metal centers has no obvious effect on catalytic activity for the ROP of rac-LA. Polymer end-group analysis by 1H NMR and MALDI-TOF MS support the reaction initiated by Li complexes without or with BnOH switching mechanism from a coordination-insertion to an active monomer in the ROP processes reasonably. The diblock copolymer PCL-b-PLA can be effectively prepared by polymerizing ε-CL firstly followed by addition of rac-LA. However, the formation of PLA-b-PCL or PLA-random-PCL is limited, and the resulting copolymers only contain a short sequence of PCL moieties which produced by the transesterification between PLA and ε-CL, whether the two monomers are added sequentially or simultaneously. Interestingly, these Li complexes not only exhibit a high activity for the polymerization of PLA, but also can fully degrade the resultant PLA into methyl lactate (Me-La) in the presence of MeOH, which is a rare example of making or breaking polymer for chemical recycling.

Poly lactic acid production using the ring opening polymerization (ROP) method using Lewis acid surfactant combined iron (Fe) catalyst (Fe(DS)3)

LASC catalyst synthesis process was carried out using iron metal (Fe) and its characterization properties were tested. There are five stages carried out, namely, the manufacture of the LASC Fe(DS)3 catalyst, lactic acid dehydration, polycondensation of lactic acid into l-lactic acid oligomers (OLLA), depolymerization of oligomers into l-lactide, and the ROP process to convert l-lactide into Polymers. l-lactic acid (PLLA). The analysis used is as follows, Karl-Fisher; Spectroscopy Fourier Transform Infrared (FTIR); and Nuclear Magnetic Resonance (HNMR); Gel Permeation Chromatography (GPC); Thermogravimetry Gravity Analysis (TGA) and X-Ray Diffraction (XRD). Based on the experimental results, the catalyst Fe(DS)3 has a crystallinity value of 24% which indicates an amorphous nature and is easy to react. The value of the thermal stability of the catalyst is at 180 °C where the catalyst is able to process up to a temperature of 180 °C. Each step of the ROP is validated by FTIR analysis which shows that the components of the group are in accordance with the expected product. The comparison of the crystallinity values of PLA produced with FeCl3 and Fe(DS)3 were 37.5 and 49%, respectively. Melting temperature (Tm) values are 111 and 107 °C, respectively, Td values are 327 and 352 °C, and the resulting molecular weights are 23,720 and 20,232 g/mol. Based on the results obtained, it can be seen that the use of a LASC catalyst in the form of Fe(DS)3 is more effective than without using a LASC catalyst.

Mono-material product design with bio-based, circular, and biodegradable polymers

Mono-material product design with bio-based, circular, and biodegradable polymers

Supercritical CO2 as an Efficient Medium for Macromolecular Carbonate Synthesis through Ring-Opening Co- and Teroligomerization

Ring-opening polymerization and teroligomerization processes that involve two different epoxides and carbon dioxide are significantly more efficiently executed in a supercritical CO2 medium. Here, we demonstrate that this generally considered green medium is advantageous for the catalytic formation of both conventional and biobased co- and teroligomers avoiding the occurrence of diffusion-limited catalysis while maximizing the polymer quality, yield, and carbonate content.

Poly(Lactic Acid) Composites with Lignin and Nanolignin Synthesized by In Situ Reactive Processing.

Poly(lactic acid) (PLA) composites with 0.5 wt% lignin or nanolignin were prepared with two different techniques: (a) conventional melt-mixing and (b) in situ Ring Opening Polymerization (ROP) by reactive processing. The ROP process was monitored by measuring the torque. The composites were synthesized rapidly using reactive processing that took under 20 min. When the catalyst amount was doubled, the reaction time was reduced to under 15 min. The dispersion, thermal transitions, mechanical properties, antioxidant activity, and optical properties of the resulting PLA-based composites were evaluated with SEM, DSC, nanoindentation, DPPH assay, and DRS spectroscopy. All reactive processing-prepared composites were characterized by means of SEM, GPC, and NMR to assess their morphology, molecular weight, and free lactide content. The benefits of the size reduction of lignin and the use of in situ ROP by reactive processing were demonstrated, as the reactive processing-produced nanolignin-containing composites had superior crystallization, mechanical, and antioxidant properties. These improvements were attributed to the participation of nanolignin in the ROP of lactide as a macroinitiator, resulting in PLA-grafted nanolignin particles that improved its dispersion.

Free-radical photoring-opening polymerization of cyclic allylic sulfide: From photocleavable photoinitiators to three components photoredox systems

Photopolymers form a family of materials that have been developed to meet specific demands in fields such as coatings, varnishes, semiconductors, optical fibers, printing plates, holographic recording, etc. However, the multifunctional acrylate monomers currently used present an important volume contraction. A drawback for applications where little shrinkage during polymerization is mandatory to keep shapes and properties of the material. To overcome this problem, monomers reacting by ring opening polymerization can be used. Among possible monomers, cyclic allylic sulfides are very interesting candidates: they are highly reactive and their polymerization mechanism is almost not affected by the presence of oxygen. In this work the effects of the photoinitiating systems on the free radical ring opening photopolymerization kinetics of an eight-member cyclic allylic sulfide is studied. It is shown that cleavable type I, bimolecular type II and three components redox photoinitiating systems allow the formation of linear photopolymers with high polymerization rates and final conversions. The photopolymerization kinetics obtained show that the photopolymerization is not sensitive to oxygen which leads to reduced exposure time and higher sensitivity. This remarkable property should also extend the usage of such monomers in the coating applications where oxygen inhibition is a drawback. Finally, the benefit of ring opening polymerization process is demonstrated trough the volume contraction measurement which was found to be lower than 1.5%.

Controlled Synthesis of Dendrite-like Polyglycerols Using Aluminum Complex for Biomedical Applications.

This work describes a one-pot synthesis of dendrite-like hyperbranched polyglycerols (HPGs) via a ring-opening multibranching polymerization (ROMBP) process using a bis(5,7-dichloro-2-methyl-8-quinolinolato)methyl aluminum complex (1) as a catalyst and 1,1,1-tris(hydroxymethyl)propane/trimethylol propane (TMP) as an initiator. Single-crystal X-ray diffraction (XRD) analysis was used to elucidate the molecular structure of complex 1. Inverse-gated (IG)13C NMR analysis of HPGs showed degree of branching between 0.50 and 0.57. Gel permeation chromatography (GPC) analysis of the HPG polymers provided low, medium, and high-molecular weight (M n) polymers ranging from 14 to 73 kDa and molecular weight distributions (M w/M n) between 1.16 and 1.35. The obtained HPGs exhibited high wettability with water contact angle between 18 and 21° and T g ranging between -39 and -55 °C. Notably, ancillary ligand-supported aluminum complexes as catalysts for HPG polymerization reactions have not been reported to date. The obtained HPG polymers in the presence of the aluminum complex (1) can be used for various biomedical applications. Here, nanocomposite electrospun fibers were fabricated with synthesized HPG polymer. The nanofibers were subjected to cell culture experiments to evaluate cytocompatibility behavior with L929 and MG63 cells. The cytocompatibility studies of HPG polymer and nanocomposite scaffold showed high cell viability and spreading. The study results concluded, synthesized HPG polymers and composite nanofibers can be used for various biomedical applications.

Diazoacetates as Terminating Agents in Living Ring-Opening Metathesis Polymerization: Synthesis of Chain-End-Functionalized Polymers

We report herein a simple, efficient strategy to access diverse end-functionalized polymers from a living ring-opening metathesis polymerization process using diazoacetates as a new terminating agent. Such a terminating process occurs via a C═C bond-forming reaction between the chain-end ruthenium carbenes and the diazoacetates, resulting in the rapid construction of a unique, α,β-unsaturated carbonyl motif at more than 95% of the chain end within 5 min. A variety of easily accessible and diversely substituted diazoacetates could be used, allowing for the facile introduction of an additional panel of useful functionalities at the polymer chain end. Diverse postpolymerization modifications, including Michael addition, “click” reaction, and chain extension, have been further demonstrated.

Ring-Opening Polymerization of L-Lactide Catalyzed by Potassium-Based Complexes: Mechanistic Studies.

Two non-toxic potassium compounds, 1 and 2, with a commercial oximate ligand have been prepared and fully spectroscopically characterized. Their activity as catalysts for the ring-opening polymerization (ROP) process of LLA has been studied, showing that they are extremely active and able to polymerize the monomer in a few minutes. For derivative 2, the presence of a crown ether in the potassium coordination sphere affects the nuclearity of the compound and consequently its solubility, with both aspects having an influence in the polymerization process. Detailed studies of the polymerization mechanism have been performed, and an unusual anionic mechanism was observed in absence of a co-initiator. Indeed, the monomer deprotonation generates a lactide enolate, which initiates the polymerization propagation. On the contrary, when a 1:1 ratio of cat:BnOH is used, a mixture of mechanisms is observed, the anionic mechanism and the activated monomer one, while from a cat:BnOH ratio of 1:2 and over, only the activated monomer mechanism is observed.

Tertiary-Butylbenzene Functionalization as a Strategy for β-Sheet Polypeptides.

β-Sheet forming polypeptides are one of the least explored synthetic systems due to their uncontrolled precipitation in the ring-opening polymerization (ROP) synthetic methodology. Here, a new t-butylbenzene functionalization approach is introduced to overcome this limitation by sterically controlling the propagating polymer chains, and homogeneous polymerization with good control over chain growth was accomplished. New bulky N-carboxyanhydride monomers were designed having t-butylbenzene pendant by multistep organic synthesis, and N-heterocyclic carbene was explored as a catalyst to make high-molecular-weight and narrow polydisperse soluble polypeptides. This ROP process was successfully demonstrated for two β-sheet forming polypeptides such as poly(l-serine) and poly(l-cysteine). These new t-butylbenzene-functionalized polypeptides were found to be readily soluble in tetrahydrofuran, chloroform, and so forth, and they were produced in high molecular weights having Mn = 32 kDa with dispersity D̵ ≤ 1.3. ROP kinetics were studied by real-time Fourier transform infrared and 1H NMR to determine the actual content of the secondary structures in the propagating chains. These studies established that the α-helical conformational front in the propagation chain was speeding up the polymerization kinetics with good degree of control in the ROP process. Reversible-conformational transitions in the post-polymerization deprotection were found to restore the β-sheet secondary structures in poly(l-serine)s. The newly developed t-butylbenzene-substituted steric-hindrance approach is valuable in yielding soluble polymers, and this approach could be useful for exploring new polypeptide architectures for long-term impact.

Evaluation of 20(S)-ginsenoside Rg3 loaded hydrogel for the treatment of perianal ulcer in a rat model

BackgroundAs a kind of common complication of the surgery of perianal diseases, perianal ulcer is known as a nuisance. This study aims to develop a kind of 20(S)-ginsenoside Rg3 (Rg3)-loaded hydrogel to treat perianal ulcers in a rat model. MethodsThe copolymers PLGA1600-PEG1000-PLGA1600 were synthesized by ring-opening polymerization process and Rg3-loaded hydrogel was then developed. The perianal ulcer rat model was established to analyze the treatment efficacy of Rg3-loaded hydrogel for ulceration healing for 15 days. The animals were divided into control group, hydrogel group, free Rg3 group, Rg3-loaded hydrogel group, and Lidocaine Gel® group. The residual wound area rate was calculated and the blood concentrations of interleukin-1 (IL-1), interleukin-6 (IL-6), and vascular endothelial growth factor (VEGF) were recorded. Hematoxylin and eosin (H&E) staining, Masson's Trichrome (MT) staining, and tumor necrosis factor α (TNF-α), Ki-67, CD31, ERK1/2, and NF-κB immunohistochemical staining were performed. ResultsThe biodegradable and biocompatible hydrogel carries a homogenous interactive porous structure with 10 μm pore size and five weeks in vivo degradation time. The loaded Rg3 can be released sustainably. The in vitro cytotoxicity study showed that the hydrogel had no effect on survival rate of murine skin fibroblasts L929. The Rg3-loaded hydrogel can facilitate perianal ulcer healing by inhibiting local and systematic inflammatory responses, swelling the proliferation of nuclear cells, collagen deposition, and vascularization, and activating ERK signal pathway. ConclusionThe Rg3-loaded hydrogel shows the best treatment efficacy of perianal ulcer and may be a candidate for perianal ulcer treatment.

Thionolactone as a Resin Additive to Prepare (Bio)degradable 3D Objects via VAT Photopolymerization.

Three-dimensional (3D) printing and especially VAT photopolymerization leads to cross-linked materials with high thermal, chemical, and mechanical stability. Nevertheless, these properties are incompatible with requirements of degradability and re/upcyclability. We show here that thionolactone and in particular dibenzo[c,e]-oxepane-5-thione (DOT) can be used as an additive (2 wt %) to acrylate-based resins to introduce weak bonds into the network via a radical ring-opening polymerization process. The low amount of additive makes it possible to modify the printability of the resin only slightly, keep its resolution intact, and maintain the mechanical properties of the 3D object. The resin with additive was used in UV microfabrication and two-photon stereolithography setups and commercial 3D printers. The fabricated objects were shown to degrade in basic solvent as well in a homemade compost. The rate of degradation is nonetheless dependent on the size of the object. This feature was used to prepare 3D objects with support structures that could be easily solubilized.

Model Predictive Control with Integrated Model Reduction for a Continuous Lactide Ring-Opening Polymerization Process.

Poly(lactic acid) production has received increasing attention, mainly due to its inherent biodegradable thermoplastic properties and to its renewable-resource-based composition. This process is affected by changes in the operating conditions and by raw material impurities which influence the reaction rate and degrade the polymer properties. As the system model is multivariable with coupled dynamics and constraints, linear model predictive control (LMPC) is employed here. A model reduction technique is proposed to obtain an approximate linear representation of the nonlinear system around the operating point to minimize the calculation cost of the controller. The proposed LMPC approach is validated by simulation and is compared to a proportional-integral controller and a nonlinear model predictive control. It is found that LMPC has a superior performance in terms of off-spec time when a disturbance occurs in the feed, and it can restore the target conditions better and faster.

On the identification and quantification of proton-initiated species in the synthesis of poly(2-alkyl-2-oxazoline)s by high resolution liquid chromatography

Hydrophilic poly(2-oxazoline)s represent a promising alternative to replace poly(ethylene glycol) in the biomedical field. For that purpose, reliable analytical protocols to confirm identity and quantity of impurities are required. In particular, side products deriving from chain transfer reactions occurring during the cationic ring-opening polymerization and incomplete end-capping processes may be present. The analytical approach must hence be capable of separating polymers according to minor changes regarding their end group. We demonstrate that liquid chromatography, relying on a monolithic C18-modified silica column and isocratic as well as gradient elution using water / acetonitrile mixtures and varying detectors, can accomplish such demanding high resolution separations. Poly(2-ethyl-2-oxazoline)s (PEtOx) with acetyl, hydroxyl, and phthalimide ω-end groups were investigated. Identification of side products was achieved through coupling with electrospray ionization mass spectrometry. UV / Vis detection was applied to quantify chain transfer products in PEtOx comprising biphenyl moieties. In addition, gradient elution enabled the separation of PEtOx into macromolecules according to their specific degrees of polymerization in molar mass ranges around 2,000 g mol-1.

Development of High-Molecular-Weight Fully Renewable Biopolyesters Based on Oxabicyclic Diacid and 2,5-Furandicarboxylic Acid: Promising as Packaging and Medical Materials

Renewable and biodegradable linear polyesters with oxabicyclic units based on the ring-opening polymerization (ROP) have attracted considerable interest as alternatives to petrochemical-based polyesters. However, incorporating bio-based aromatic building blocks into the linear polyesters with oxabicyclic units by the ROP process is limited. Herein, we report three series of oxabicyclic renewable polyesters based on oxabicyclic diacid (OBDA), monomethyl oxabicyclic diacid (MBDA), and oxabicyclic anhydride with dimethyl substituents (d-MBDA) derived from bio-based furanics and synthesized via melt polymerization (MP). The molecular weights of the polyesters obtained from OBDA were significantly higher than those of the reported polyesters based on OBDA anhydride derivatives, leading to significantly higher glass-transition temperature (Tg) values and tensile strength. Furthermore, a series of fully bio-based copolyesters (PBOBmFn) was first obtained via the MP strategy by the incremental replacement of OBDA with bio-based 2,5-furandicarboxylic acid (FDCA). The incorporation of FDCA units significantly improved the thermal stabilities and mechanical properties of the linear polyesters with oxabicyclic units and endowed them with gas barrier properties that were better than those of commercial poly(ethylene terephthalate) (PET). The Tg values of PBOBmFn ranged from 38.8 to 40.8 °C and were comparable with that of the commercial biomedical material Vicryl. Additionally, the trade-off between OBDA and FDCA units can control the fast biodegradation and environmental durability of the PBOBmFn polyester series. PBOBmFn also showed excellent biocompatibility to and was safe for both RAW264.7 and PC12 cells. The strategy of the incorporation of FDCA building blocks via MP enhanced the comprehensive properties of the linear polyesters with oxabicyclic units; moreover, the adjustment between FDCA and OBDA units can be leveraged to control the polyester roles between packaging and biomedical fields while retaining the completely renewable nature of the parent of polyesters.

Prefunctionalised PLGA microparticles with dimethylaminoethyl moieties promote surface cell adhesion at physiological condition

Synthetic hydrolytically degradable polyesters have seen widespread translation into a variety of clinical and biomedical settings; finding use as cell culture systems, drug delivery systems, tissue repair scaffolds, and medical devices. This success is owed in part due to their biocompatible nature and tuneable degradation profile. However, the lack of adhesion moieties limits the capacity of the polyesters to interact with cellular material and as such hampers their effectiveness within these applications. Several physical and chemical post-modification techniques have been developed to insert adhesion moieties; however, the nature of these methods remains complex and troublesome for translational medicine. To combat this flaw, we present a novel prefunctionalization method for the generation of poly (lactic-co-glycolic acid) PLGA microparticles with integrated adhesion moieties as a proof-of-principle. This strategy promotes surface cell adhesion at physiological conditions without the requirement for further post-modification. The basis of the prefunctionalization method was to utilise the 2-2-dimethylaminoethanol as an initiator in a standard bulk Ring Opening Polymerization process to obtain PLGADMAE polymers. The resultant polymers were subsequently used in the fabrication of the microparticles, via membrane emulsion. This process allowed control over the morphology and size distribution of the microparticles. The surface cell adhesive properties of the new PLGADMAE microparticles were investigated via co-culture with Adipose-Derived Stem Cells. Scanning Electron Microscopy showed that the new PLGADMAE microparticles readily promote adhesion of the ADSCs at physiological conditions. LDH and LIVE/DEAD assays demonstrated that the surface functionalised PLGADMAE microparticles maintained a low toxicity profile compared to the unmodified PLGA microparticles. Both thermogravimetric and differential scanning calorimetric analysis confirmed that the bulk properties of the polymer remained unchanged compared to the control PLGA. Gel Permeation Chromatography and Scanning Electron Microscopy imaging showed that the degradation profile of the new PLGADMAE was enhanced compared to that of standard PLGA polymers. This novel prefunctionalization strategy eliminates the need for post-modification and could evolve rapidly to develop biodegradable biomaterials with enhanced cell adhesion and tuneable surface chemistry to allow greater control and/or maintain interaction with living cells and tissues. The implication of this new approach would be far reaching in the field of cell delivery, cell expansion, tissue engineering and regenerative medicine.

Poly(chitosan-ester-ether-urethane) Hydrogels as Highly Controlled Genistein Release Systems.

Polymeric hydrogels play an increasingly important role in medicine, pharmacy and cosmetology. They appear to be one of the most promising groups of biomaterials due to their favorable physicochemical properties and biocompatibility. The objective of the presented study was to synthesize new poly(chitosan-ester-ether-urethane) hydrogels and to study the kinetic release of genistein (GEN) from these biomaterials. In view of the above, six non-toxic hydrogels were synthesized via the Ring-Opening Polymerization (ROP) and polyaddition processes. The poly(ester-ether) components of the hydrogels have been produced in the presence of the enzyme as a biocatalyst. In some cases, the in vitro release rate of GEN from the obtained hydrogels was characterized by near-zero-order kinetics, without “burst release” and with non-Fickian transport. It is important to note that developed hydrogels have been shown to possess the desired safety profile due to lack of cytotoxicity to skin cells (keratinocytes and fibroblasts). Taking into account the non-toxicity of hydrogels and the relatively highly controlled release profile of GEN, these results may provide fresh insight into polymeric hydrogels as an effective dermatological and/or cosmetological tool.

Hydrogels Based on Poly(Ether-Ester)s as Highly Controlled 5-Fluorouracil Delivery Systems-Synthesis and Characterization.

A novel and promising hydrogel drug delivery system (DDS) capable of releasing 5‑fluorouracil (5-FU) in a prolonged and controlled manner was obtained using ε‑caprolactone‑poly(ethylene glycol) (CL-PEG) or rac‑lactide-poly(ethylene glycol) (rac‑LA-PEG) copolymers. Copolymers were synthesized via the ring-opening polymerization (ROP) process of cyclic monomers, ε‑caprolactone (CL) or rac-lactide (rac-LA), in the presence of zirconium(IV) octoate (Zr(Oct)4) and poly(ethylene glycol) 200 (PEG 200) as catalyst and initiator, respectively. Obtained triblock copolymers were characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) techniques; the structure and tacticity of the macromolecules were determined. The relationship between the copolymer structure and the reaction conditions was evaluated. The optimal conditions were specified as 140 °C and 24 h. In the next step, CL-PEG and rac-LA-PEG copolymers were chemically crosslinked using hexamethylene diisocyanate (HDI). Selected hydrogels were subjected to in vitro antitumor drug release studies, and the release data were analyzed using zero-order, first-order, and Korsmeyer-Peppas mathematical models. Controlled and prolonged (up to 432 h) 5-FU release profiles were observed for all examined hydrogels with first-order or zero-order kinetics. The drug release mechanism was generally denoted as non-Fickian transport.

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

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 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.