Effect of the annealing procedure and the molecular weight on the crystalline phase morphology and thermal properties of polylactide

The thermomechanical properties of poly(lactide) (PLA) are strongly related to its semicrystalline microstructure and morphology. Thermal annealing is a strategy to improve the crystallinity of PLA. However, the different techniques and specimen types needed for each kind of characterization could lead to misleading conclusions. In this work, annealed samples of three PLA grades with different molecular weights were studied by DSC, wide angle X‐ray scattering and polarized optical microscopy (POM) and the results are related to their thermomechanical and impact properties. Special focus is put on the POM results obtained by different approaches and the suitability of each of them to be related to the thermomechanical properties. By annealing medium molecular weight PLA specimens at 140 °C an important increase of the heat distortion temperature was obtained, which was not related to the spherulite size but to the combination of high crystallinity degree together with high α/α′ crystal type ratio. However, the impact properties of annealed PLA decreased with increase in the annealing temperature according to an increment in crystallinity and in the α/α′ crystal ratio. © 2019 Society of Chemical Industry     

The Effect of Antibacterial Particle Incorporation on the Mechanical Properties,Biodegradability, and Biocompatibility of PLA and PHBV Composites

The composites based on polylactide (PLA) and poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) with the addition of antibacterial particles: silver (Ag) and copper oxide (CuO) are characterized. Basic mechanical properties and biodegradation processes, as well as biocompatibility of materials with human cells are determined. The addition of Ag or CuO to the polymers do not significantly affect their mechanical properties, flammability, or biodegradation rate. However, several differences between the base materials are observed. PLA‐based composites have higher tensile and impact strength values, while PHBV‐based ones have a higher modulus of elasticity, as well as better mechanical properties at elevated temperatures. Concerning biocompatibility, each of the tested materials support the growth of fibroblasts over time, although large differences are observed in the initial cell attachment. The analysis of hydrolytic degradation effects on the structure of materials shows that PHBV degrades much faster than PLA. The results of this study confirm the good potential of the investigated biodegradable polymer composites with antibacterial particles for future biomedical applications.     

Enzymatic ring‐opening polymerization (ROP) of polylactones: roles of non‐aqueous solvents

Aliphatic polyesters such as polylactides (PLAs) and other polylactones are thermoplastic, biodegradable and biocompatible polymers with the potential to replace petro‐chemical‐based synthetic polymers. A benign route for synthesizing these polyesters is through the enzyme‐catalyzed ring‐opening polymerization (ROP) reaction; this type of enzymatic process is very sensitive to reaction conditions such as solvents, water content and temperature. This review systematically evaluates the crucial roles of different solvents (such as solvent‐free/in bulk, organic solvents, supercritical fluids, ionic liquids, and aqueous biphasic systems) on the degree of polymerization and polydispersity. In general, many studies suggest that hydrophobic organic solvents with minimum water contents lead to efficient enzymatic polymerization and subsequently high molecular weights of polyesters; the selection of solvents is also limited by the reaction temperature, e.g. the ROP of lactide is often conducted at above 100 °C, therefore, the solvent typically needs to have its boiling point above this temperature. The use of supercritical fluids could be limited by its scaling‐up potential, while ionic liquids have exhibited many advantages including their low‐volatility, high thermal stability, controllable enzyme‐compatibility, and a wide range of choices. However, the fundamental and mechanistic understanding of the specific roles of ionic liquids in enzymatic ROP reactions is still lacking. Furthermore, the lipase specificity towards l ‐ and d ‐lactide is also surveyed, followed by the discussion of engineered lipases with improved enantioselectivity and thermal stability. In addition, the preparation of polyester‐derived materials such as polyester‐grafted cellulose by the enzymatic ROP method is briefly reviewed. © 2017 Society of Chemical Industry     

Thermal degradation behavior and gas phase flame‐retardant mechanism of polylactide/PCPP blends

The thermal degradation behavior of the blend based on polylactide (PLA) and poly(1,2‐propanediol 2‐carboxyethyl phenyl phosphinate) (PCPP) was investigated by the thermogravimetric analysis (TGA). Thermal degradation activation energies (E_a) of neat PLA and PLA/15% PCPP blend were calculated via the Flynn–Wall–Ozawa method. The E_a of the blends increased with the addition of PCPP increasing when the conversion was higher than 10%. In addition, the appropriate conversion models for the thermal degradation process of PLA and PLA/15% PCPP were studied via the Criado method. At the same time, the main gaseous decomposition products of PLA and its blend were identified by TGA/infrared spectrometry (TGA–FTIR) analysis. And it revealed that the PCPP improved the flame‐retardant property of PLA via altering the release of the flammable gas and nonflammable gas. Moreover, the PCPP improved the flame‐retardant property of PLA by inhibiting exothermic oxidation reactions in the combustion, which was further proved by pyrolysis–gas chromatography–mass spectrometry analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40480.     

Strain‐induced deformation mechanisms of polylactide plasticized with acrylated poly(ethylene glycol) obtained by reactive extrusion

This work aimed at identifying the tensile deformation mechanisms of an original grade of plasticized polylactide (pPLA) obtained by reactive extrusion. This material had a glass transition temperature of 32.6 °C and consisted of a polylactide (PLA) matrix grafted with poly(acryl‐poly(ethylene glycol)) (poly(Acryl‐PEG)) inclusions. pPLA behaved like a rubber‐toughened amorphous polymer at 20 °C, and its tensile behavior evolved toward a rubbery semicrystalline polymer with increasing temperature. The drawing of pPLA involved orientation of amorphous and crystalline chains, crystallization, and destruction of crystals. It was found that crystal formation and crystal destruction were in competition below 50 °C, resulting in a constant or slightly decreasing crystallinity with strain. Increasing temperature enhanced crystal formation and limited crystal destruction, resulting in an increased crystallinity with the strain level. Drawing yielded a transformation of the initial spherical poly(Acryl‐PEG) inclusions into ellipsoids oriented in the tensile direction. This mechanism may engender the formation of nanovoids within the inclusions due to a decreased density, assumed to be responsible for the whitening of the specimen. © 2015 Society of Chemical Industry     

Spontaneous formation of polylactide stereocomplex microspheres containing metal ions

Linear poly(l ‐lactides) (PLLAs ) and poly(d ‐lactides) (PDLAs ) with M _n in the range 2000 ? 4300 containing a different number and placement of carboxyl groups were obtained via cationic ring‐opening polymerization and post‐polymerization functionalization. PLA stereoisomers (PLLA ‐(COOH )_x and PDLA ‐(COOH )_x , where x = 1 ? 3) were used for the investigation of stereocomplexation in solution performed in the presence of metal cations such as Ca²⁺, Mg²⁺, Zn²⁺, Fe³⁺. Spherical microparticles with a diameter in the range 0.7 ? 3.0 µm were obtained in all cases which was confirmed on the basis of scanning electron microscopy (SEM ) analysis. The microsphere size and homogeneity were analyzed depending on the stereocomplexation conditions and the molecular weight as well as the number of carboxyl end groups in the PLLA and PDLA used for stereocomplexation. The PLA microspheres obtained were analyzed by Fourier transform IR spectroscopy, wide angle X‐ray spectroscopy and energy‐dispersive X‐ray spectroscopy methods which confirmed the presence of metal cations inside. The application of regular microspheres with metal ions as drug delivery systems is considered. © 2016 Society of Chemical Industry     

A Study on the FTIR Spectroscopy of Polylactide Doped with Nano-Aluminium Oxide and Nano-Cupric Oxide

Elucidation of the structure of naturally existing or synthesized substances is an important criterion in the study of materials to predict the application of the substance. In this study, polylactide was doped with nano-aluminium oxide and nano-cupric oxide with 1 and 3 mg of concentration variants. The interaction between the polymer matrix and the nanoparticles has been studied using Fourier transform infrared. Successful doping of the polymer has been observed. Attention has been drawn to check the intermolecular bonding in films having varying thicknesses, films prepared at higher sonication temperatures, and chemical homogeneity of the doped polymer films.