Organocatalytic Stereoselective Cyclic Polylactide Synthesis in Supercritical Carbon Dioxide under Plasticizing Conditions.
ABSTRACT: Cyclic polylactide (cPLA) is a structural isomer of linear polylactide (PLA) although it possesses unique functionalities in comparison to its linear counterpart. Hitherto, the control of stereochemical purity in conventional cPLA synthesis has not been achieved. In this study, highly stereochemically pure cPLA was synthesized in the absence of a metal catalyst and organic solvent, which required high consumption of the residual monomer. The synthesis was conducted in supercritical carbon dioxide under CO? plasticizing polymerization conditions in the presence of an organocatalyst and thiourea additives. In comparison with the stereocomplexes synthesized through conventional methods, cPLA from l-lactide (cPLLA) and cPLA from d-lactide (cPDLA) were synthesized with higher stereochemical purity and improved thermal stability. Moreover, the method presented herein is environmentally friendly and thus, applicable on an industrial level.
Project description:Stereocomplexation between enantiomeric poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) provides an avenue to greatly enhance performance of eco-friendly polylactide (PLA). Unfortunately, although the manufacturing of semicrystalline polymers generally involves melt processing, it is still hugely challenging to create high-performance stereocomplexed polylactide (sc-PLA) products from melt-processed high-molecular-weight PLLA/PDLA blends due to the weak crystallization memory effect of stereocomplex (sc) crystallites after complete melting as well as the substantial degradation of PLA chains at elevated melt-processing temperatures of ca. 240-260?°C. Inspired by the concept of powder metallurgy, here we report a new facile route to address these obstacles by sintering of sc-PLA powder at temperatures as low as 180-210?°C, which is distinctly different from traditional sintering of polymer powders performed at temperatures far exceeding their melting temperatures. The enantiomeric PLA chain segments from adjacent powder particles can interdiffuse across particle interfaces and co-crystallize into new sc crystallites capable of tightly welding the interfaces during the low-temperature sintering process, and thus highly transparent sc-PLA products with outstanding heat resistance, mechanical strength, and hydrolytic stability have been successfully fabricated for the first time.
Project description:A direct, efficient, and scalable method to prepare stereocomplexed polylactide (PLA)-based nanoparticles (NPs) is achieved. By an appropriate combination of fabrication parameters, NPs with controlled shape and crystalline morphology are obtained and even pure PLA stereocomplexes (PLASC) are successfully prepared using the spray-drying technology. The formed particles of varying D- and L-LA content have an average size of ?400 nm, where the smallest size is obtained for PLA50, which has an equimolar composition of PLLA and PDLA in solution. Raman spectra of the particles show the typical shifts for PLASC in PLA50, and thermal analysis indicates the presence of pure stereocomplexation, with only one melting peak at 226 °C. Topographic images of the particles exhibit a single phase with different surface roughness in correlation with the thermal analysis. A high yield of spherically shaped particles is obtained. The results clearly provide a proficient method for achieving PLASC NPs that are expected to function as renewable materials in PLA-based nanocomposites and potentially as more stable drug delivery carriers.
Project description:In this study, polylactide/urea complexes were successfully prepared by the electrospinning method, then the host urea component was removed to obtain a coalesced poly(L-lactide) (PLLA)/poly(D-lactide) (PDLA) blend. The crystallization behavior of the coalesced PLLA/PDLA blend (c-PLLA/PDLA) was studied by a differential scanning calorimeter (DSC) and Fourier transform infrared (FTIR) spectroscopy. The c-PLLA/PDLA was found to show better crystallization ability than normal PLLA/PDLA blend (r-PLLA/PDLA). More interestingly, the c-PLLA/PDLA effectively and solely crystallized into stereocomplex crystals during the non-isothermal melt-crystallization process, and the reason was attributed to the equally-distributing state of PLLA and PDLA chains in the PLLA/PDLA/urea complex, which led to good interconnection between PLLA and PDLA chains when the urea frameworks were instantly removed.
Project description:The demand for "green" degradable composite materials increases with growing environmental awareness. The key challenge is achieving the preferred physical properties and maintaining their eco-attributes in terms of the degradability of the matrix and the filler. Herein, we have designed a series of "green" homocomposites materials based purely on polylactide (PLA) polymers with different structures. Film-extruded homocomposites were prepared by melt-blending PLA matrixes (which had different degrees of crystallinity) with PLLA and PLA stereocomplex (SC) particles. The PLLA and SC particles were spherical and with 300-500 nm size. Interfacial crystalline structures in the form of stereocomplexes were obtained for certain particulate-homocomposite formulations. These SC crystallites were found at the particle/matrix interface when adding PLLA particles to a PLA matrix with d-lactide units, as confirmed by XRD and DSC data analyses. For all homocomposites, the PLLA and SC particles acted as nucleating agents and enhanced the crystallization of the PLA matrixes. The SC particles were more rigid and had a higher Young's modulus compared with the PLLA particles. The mechanical properties of the homocomposites varied with particle size, rigidity, and the interfacial adhesion between the particles and the matrix. An improved tensile strength in the homocomposites was achieved from the interfacial stereocomplex formation. Hereafter, homocomposites with tunable crystalline arrangements and subsequently physical properties, are promising alternatives in strive for eco-composites and by this, creating materials that are completely degradable and sustainable.
Project description:In this work, the preparation of nanocomposites based on poly(l-lactide) PLLA and graphite nanoplatelets (GNP) was assessed by applying, for the first time, the reactive extrusion (REX) polymerization approach, which is considered a low environmental impact method to prepare polymer systems and which allows an easy scalability. In particular, ad hoc synthesized molecules, constituted by a pyrene end group and a poly(d-lactide) (PDLA) chain (Pyr-d), capable of interacting with the surface of GNP layers as well as forming stereoblocks during the ring-opening polymerization (ROP) of l-lactide, were used. The nanocomposites were synthesized by adding to l-lactide the GNP/initiator system, prepared by dispersing the graphite in the acetone/Pyr-d solution, which was dried after the sonication process. DSC and X-ray diffraction measurements evidenced the stereocomplexation of the systems synthesized by using the pyrene-based initiators, whose extent turned out to depend on the PDLA chain length. All the prepared nanocomposites, including those synthesized starting from a classical initiator, that is, 1-dodecanol, retained similar electrical conductivity, whereas the thermal conductivity was found to increase in the stereocomplexed samples. Preferential localization of stereocomplexed PLA close to the interface with GNP was demonstrated by scanning probe microscopy (SPM) techniques, supporting an important role of local crystallinity in the thermal conductivity of the nanocomposites.
Project description:The rate of degradation of large-scale synthesized polylactide (PLA) of industrial origin was compared with that of laboratory-scale synthesized poly(L-lactide) (PLLA) of similar molar mass. The structural discrepancy between the two material types resulted in a significant difference in degradation rate. Although the hydrolysis of industrial PLA was substantially faster than that of PLLA, the PLA material became less brittle and fragmented to a lesser extent during degradation. In addition, a comprehensive picture of the degradation of industrial PLA was obtained by subjecting different PLA materials to hydrolytic degradation at various temperatures and pH's for up to 182 days. The surrounding environment had no effect on the degradation rate at physiological temperature, but the degradation was faster in water than in a phosphate buffer after prolonged degradation at temperatures above the T(g). The degree of crystallinity had a greater influence than the degradation environment on the rate of hydrolysis. For a future use of polylactide in applications where bulk plastics are generally used today, for example plastic packages, the appropriate PLA grade must be chosen based on the conditions prevailing in the degradation environment.
Project description:Cell functions can be mediated through their interactions with the microenvironments, which highly depend on the surface state of the substrate. However, how to finely adjust the surface of biomaterials is still very challenging. In this study, poly(d,l-lactide) (PDLLA) with high molecular weight was synthesized via ring opening polymerization, which was hot-pressed into PDLLA membrane. In order to modify the hydrophobicity of the membrane (a limiting factor for its biomedical application), an amphiphilic monomethoxyl poly(ethylene glycol)-b-poly(d,l-lactide) (PEG-PDLLA) was selected to improve its surface hydrophilicity through a simple self-assembly approach. It was found that the contact angles of the modified membrane can be well controlled by variation of PEG-PDLLA concentrations. In vitro cell biological study indicates that optimized cell adhesion can be achieved on the modified membrane with a contact angle of around 50° via its self-assembly with an ethanol/water solution of PEG-PDLA (35?mg?ml-1). The surface modification of the membrane also changed its biodegradation property in the process of its incubation period up to 240?days. The surface modification method may afford an effective way for adjustment of the surface (interface) of membrane (scaffolds) of different biomaterials, beyond polylactide.
Project description:All-biobased and biodegradable nanocomposites consisting of poly(l-lactide) (PLLA) and starch nanoplatelets (SNPs) were prepared via a new strategy involving supramolecular chemistry, i.e., stereocomplexation and hydrogen-bonding interactions. For this purpose, a poly(d-lactide)-b-poly(glycidyl methacrylate) block copolymer (PDLA-b-PGMA) was first synthesized via the combination of ring-opening polymerization and atom-transfer radical polymerization. NMR spectroscopy and size-exclusion chromatography analysis confirmed a complete control over the copolymer synthesis. The SNPs were then mixed up with the copolymer for producing a PDLA-b-PGMA/SNPs masterbatch. The masterbatch was processed by solvent casting for which a particular attention was given to the solvent selection to preserve SNPs morphology as evidenced by transmission electron microscopy. Near-infrared spectroscopy was used to highlight the copolymer-SNPs supramolecular interactions mostly via hydrogen bonding. The prepared masterbatch was melt-blended with virgin PLLA and then thin films of PLLA/PDLA-b-PGMA/SNPs nanocomposites (ca. 600 ?m) were melt-processed by compression molding. The resulting nanocomposite films were deeply characterized by thermogravimetric analysis and differential scanning calorimetry. Our findings suggest that supramolecular interactions based on stereocomplexation between the PLLA matrix and the PDLA block of the copolymer had a synergetic effect allowing the preservation of SNPs nanoplatelets and their morphology during melt processing. Quartz crystal microbalance and dynamic mechanical thermal analysis suggested a promising potential of the stereocomplex supramolecular approach in tuning PLLA/SNPs water vapor uptake and mechanical properties together with avoiding PLLA/SNPs degradation during melt processing.
Project description:Dual-functioning additives with plasticizing and antibacterial functions were designed by exploiting the natural aromatic compound eugenol and green platform chemical levulinic acid or valeric acid that can be produced from biobased resources. One-pot synthesis methodology was utilized to create three ester-rich plasticizers. The plasticizers were thoroughly characterized by several nuclear magnetic resonance techniques (1H NMR, 13C NMR, 31P NMR, HSQC, COSY, HMBC) and by electrospray ionization-mass spectrometry (ESI-MS) and their performances, as plasticizers for polylactide (PLA), were evaluated. The eugenyl valerate was equipped with a strong capability to depress the glass transition temperature (Tg) of PLA. Incorporating 30 wt% plasticizer led to a reduction of the Tg by 43 °C. This was also reflected by a remarkable change in mechanical properties, illustrated by a strain at break of 560%, almost 110 times the strain for the breaking of neat PLA. The two eugenyl levulinates also led to PLA with significantly increased strain at breaking. The eugenyl levulinates portrayed higher thermal stabilities than eugenyl valerate, both neat and in PLA blends. The different concentrations of phenol, carboxyl and alcohol functional groups in the three plasticizers caused different bactericidal activities. The eugenyl levulinate with the highest phenol-, carboxyl- and alcohol group content significantly inhibited the growth of Staphylococcus aureus and Escherichia coli, while the other two plasticizers could only inhibit the growth of Staphylococcus aureus. Thus, the utilization of eugenol as a building block in plasticizer design for PLA illustrated an interesting potential for production of additives with dual functions, being both plasticizers and antibacterial agents.
Project description:Camptothecin-polylactide conjugates (CMPT-PLA) were synthesized by covalent incorporation of CMPT into PLA of different microstructure, i.e., atactic PLA and atactic-block-isotactically enriched PLA (Pm = 0.79) via urethane bonds. The kinetic release of CPMT from CMPT-PLA conjugates, tested in vitro under different conditions, is possible in both cases and notably, strongly dependent on PLA microstructure. It shows that release properties of drug-PLA conjugates can be tailored by controlled design of the PLA microstructure, and allow in the case of CMPT-PLA conjugates for the development of highly controlled biodegradable CMPT systems-important delivery systems for anti-cancer agents.