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:High crystallization rate and thermomechanical stability make polylactide stereocomplexes effective nanosized physical netpoints. Here, we address the need for soft, form-stable degradable elastomers for medical applications by designing such blends from (co)polyesters, whose mechanical properties are ruled by their nanodimensional architecture and which are applied as single components in implants. By careful controlling of the copolymer composition and sequence structure of poly[(<i>L</i>-lactide)-<i>co</i>-(<i>ε</i>-caprolactone)], it is possible to prepare hyperelastic polymer blends formed through stereocomplexation by adding poly(<i>D</i>-lactide) (PDLA). Low glass transition temperature <i>T</i><sub>g</sub> ≤ 0 °C of the mixed amorphous phase contributes to the low Young's modulus <i>E</i>. The formation of stereocomplexes is shown in DSC by melting transitions <i>T</i><sub>m</sub> > 190 °C and in WAXS by distinct scattering maxima at 2<i>θ</i> = 12° and 21°. Tensile testing demonstrated that the blends are soft (<i>E</i> = 12-80 MPa) and show an excellent hyperelastic recovery R<sub>rec</sub> = 66-85% while having high elongation at break <i>ε</i><sub>b</sub> up to >1000%. These properties of the blends are attained only when the copolymer has 56-62 wt% lactide content, a weight average molar mass >140 kg·mol<sup>-1</sup>, and number average lactide sequence length ≥4.8, while the blend is formed with a content of 5-10 wt% of PDLA. The devised strategy to identify a suitable copolymer for stereocomplexation and blend formation is transferable to further polymer systems and will support the development of thermoplastic elastomers suitable for medical applications.
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: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:Polylactide (PLA)-based polymers, functionalized with biobased antioxidants, were synthesized, to develop an intrinsically active, biobased and potentially biodegradable material for food packaging applications. To achieve this result, phenolic antioxidants were exploited as initiators in the ring opening polymerization of l-lactide. The molecular weight, thermal properties and in vitro radical scavenging activity of the polymers obtained were compared with the ones of a PLA Natureworks 4043D, commonly used for flexible food packaging applications. The most promising synthesized polymer, bearing vanillyl alcohol as initiator (PLA-VA), was evaluated for active food packaging applications. Packaging with PLA-VA films reduced color and fat oxidation of salami during its shelf life.
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: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:The control of nanostructuration of graphene and graphene related materials (GRM) into self-assembled structures is strictly related to the nanoflakes chemical functionalization, which may be obtained via covalent grafting of non-covalent interactions, mostly exploiting ?-stacking. As the non-covalent functionalization does not affect the sp2 carbon structure, this is often exploited to preserve the thermal and electrical properties of the GRM and it is a well-known route to tailor the interaction between GRM and organic media. In this work, non-covalent functionalization of graphite nanoplatelets (GnP) was carried out with ad-hoc synthesized pyrene-terminated oligomers of polylactic acid (PLA), aiming at the modification of GnP nanopapers thermal properties. PLA was selected based on the possibility to self-assemble in crystalline domains via stereocomplexation of complementary poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) enantiomers. Pyrene-initiated PLLA and PDLA were indeed demonstrated to anchor to the GnP surface. Calorimetric and X-ray diffraction investigations highlighted the enantiomeric PLAs adsorbed on the surface of the nanoplatelets self-organize to produce highly crystalline stereocomplex domains. Most importantly, PLLA/PDLA stereocomplexation delivered a significantly higher efficiency in nanopapers heat transfer, in particular through the thickness of the nanopaper. This is explained by a thermal bridging effect of crystalline domains between overlapped GnP, promoting heat transfer across the nanoparticles contacts. This work demonstrates the possibility to enhance the physical properties of contacts within a percolating network of GRM via the self-assembly of macromolecules and opens a new way for the engineering of GRM-based nanostructures.
Project description:The crystallization and morphology of PLA-mb-PBS copolymers and their corresponding stereocomplexes were studied. The effect of flexible blocks (i.e., polybutylene succinate, PBS) on the crystallization of the copolymers and stereocomplex formation were investigated using polarized light optical microscopy (PLOM), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), and carbon-13 nuclear magnetic resonance spectroscopy (13C-NMR). The PLA and PBS multiple blocks were miscible in the melt and in the glassy state. When the PLA-mb-PBS copolymers are cooled from the melt, the PLA component crystallizes first creating superstructures, such as spherulites or axialites, which constitute a template within which the PBS component has to crystallize when the sample is further cooled down. The Avrami theory was able to fit the overall crystallization kinetics of both semi-crystalline components, and the n values for both blocks in all the samples had a correspondence with the superstructural morphology observed by PLOM. Solution mixtures of PLLA-mb-PBS and PLDA-mb-PBS copolymers were prepared, as well as copolymer/homopolymer blends with the aim to study the stereocomplexation of PLLA and PDLA chain segments. A lower amount of stereocomplex formation was observed in copolymer mixtures as compared to neat L100/D100 stereocomplexes. The results show that PBS chain segments perturb the formation of stereocomplexes and this perturbation increases with the amount of PBS in the samples. However, when relatively low amounts of PBS in the copolymer blends are present, the rate of stereocomplex formation is enhanced. This effect dissappears when higher amounts of PBS are present. The stereocomplexation was confirmed by FTIR and solid state 13C-NMR analyses.