PLA Chains Research Articles

Ageing of poly(lactic acid) films plasticized with commercial polyadipates

AbstractBACKGROUND: Amorphous poly(lactic acid) (PLA) was plasticized with two polyadipates with different molar masses. Some physical properties were studied over time to evaluate the stability of these blends. The aim of this study was to improve PLA ductility and consider the feasibility of its use in flexible films for food packaging.RESULTS: The addition of polyadipates caused a decrease of the glass transition temperature (Tg) and an increase of PLA chain mobility. Samples with Tg values above the storage temperature suffered physical ageing with a reduction in free volume. All the unaged blends were mainly amorphous, but samples with Tg below the storage temperature developed crystallinity during ageing leading to phase separation. Ductile properties of films improved with plasticizer content immediately after blending, but there was a deterioration in such properties upon ageing due to matrix densification and crystallization of PLA chains.CONCLUSION: PLA can be efficiently plasticized by polyadipates and the results have shown that some of the prepared films remain flexible with no phase separation after 150 days. Copyright © 2009 Society of Chemical Industry

Processing and characterization of poly(lactic acid) films plasticized with commercial adipates

AbstractThe high brittleness of Poly(lactic acid) is a major drawback for flexible food packaging applications. The aim of this work is to evaluate the potential use of commercial adipates as PLA plasticizers to obtain transparent films with enhanced mechanical properties. Processing conditions were optimized. The effect of plasticizers was characterized by a decrease on the glass transition temperature and an increase in PLA chains mobility, which induced crystallization on heating. Thermal stability was not significantly affected, and mechanical properties showed an increase in ductility with the plasticizer content. Oxygen transmission rate was also measured to evaluate the effect of the microstructures generated by the presence of these additives in PLA‐based films. The monomeric adipate presented lack of homogeneity that makes films plasticized with this additive not useful for the intended application. Good compatibility was observed between polyadipates (up to 20 wt %) and the matrix, making them promising materials for biodegradable films manufacturing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

A Study for Graft-reaction of PEG onto PLA Chains by Reactive Processing

A Study for Graft-reaction of PEG onto PLA Chains by Reactive Processing

Influences of poly(lactic acid)‐grafted carbon nanotube on thermal, mechanical, and electrical properties of poly(lactic acid)

AbstractPoly(lactic acid)‐grafted multiwalled carbon nanotubes (MWNT‐g‐PLA) were prepared by the direct melt‐polycondensation of L‐lactic acid with carboxylic acid‐functionalized MWNT (MWNT‐COOH) and then mixed with a commercially available neat PLA to prepare PLA/MWNT‐g‐PLA nanocomposites. Morphological, thermal, mechanical, and electrical characteristics of PLA/MWNT‐g‐PLA nanocomposites were investigated as a function of the MWNT content and compared with those of the neat PLA, PLA/MWNT, and PLA/MWNT‐COOH nanocomposites. It was identified from FE‐SEM images that PLA/MWNT‐g‐PLA nanocomposites exhibit good dispersion of MWNT‐g‐PLA in the PLA matrix, while PLA/MWNT and PLA/MWNT‐COOH nanocomposites display MWNT aggregates. As a result, initial moduli and tensile strengths of PLA/MWNT‐g‐PLA composites are much higher than those of neat PLA, PLA/MWNT, and PLA/MWNT‐COOH, which stems from the efficient reinforcing effect of MWNT‐g‐PLA in the PLA matrix. In addition, the crystallization rate of PLA/MWNT‐g‐PLA nanocomposites is faster than those of neat PLA, PLA/MWNT, and PLA/MWNT‐COOH, since MWNT‐g‐PLA dispersed in the PLA matrix serves efficiently as a nucleating agent. It is interesting that, unlike PLA/MWNT nanocomposites, surface resistivities of PLA/MWNT‐g‐PLA nanocomposites did not change noticeably depending on the MWNT content, demonstrating that MWNTs in PLA/MWNT‐g‐PLA are wrapped with the PLA chains of MWNT‐g‐PLA. Copyright © 2008 John Wiley & Sons, Ltd.

Rheo-optical FT-IR spectroscopy of poly(3-hydroxybutyrate)/poly(lactic acid) blend films

The orientation of poly(3-hydroxybutyrate) (PHB) and poly(lactic acid) (PLA) segments in PHB/PLA blend films cast from chloroform solutions with compositions PHB < PLA was studied during uniaxial elongation up to 250% strain at 50 °C by in-situ rheo-optical FT-IR spectroscopy. From the orientation functions of the ν(C O) bands of the blend components, it was derived that the PLA chains orient in the direction of elongation while the PHB chains orient perpendicular to the drawing direction. PHB homopolymer and PHB/PLA blend films with PHB > PLA compositions could only be oriented by cold drawing in ice water after quenching from the melt. The IR-dichroic effects of films drawn under these conditions indicate for both blend components a chain alignment parallel to the drawing direction.

Nanoporous Thin Films Based on Polylactide-Grafted Norbornene Copolymers

Thermally stable vinyl polymerized polynorbornene (PNB) is one of the challenging materials in porous low dielectric films for packaging applications. Nanoporous PNB thin films were obtained with poly(d,l-lactide) (PLA)-grafted norbornene copolymers. Thermally labile PLA chains act as pore generators in PNB films. Thermally stable PNB main chains were synthesized by Pd-catalyzed vinyl polymerization and PLA side chains were grafted onto the PNB main chains by ring opening polymerization. The brittle and poor processible properties of PNB could easily be controlled by the copolymerization with norbornene derivatives. In thin films, the PLA chains were found to thermally decompose at about 250 °C while the PNB matrix was stable during this pore generating process. The porosity of the porous PNB thin films could be controlled up to 18% with pore sizes below 5 nm range by varying the chain length of grafted PLA. Introduction of cross-linking epoxy groups onto the PNB main chains resulted in the formation of w...

Flexural, Morphological and Thermal Properties of Poly(Lactic Acid)/ Organo-Montmorillonite Nanocomposites

Poly(lactic acid) (PLA)/organo-montmorillonite (OMMT) nanocomposites were prepared by using solution intercalation and melt intercalation methods. For solution intercalation method, toluene was used as solvent. For melt intercalation method, PLA/OMMT composites were prepared by using single-screw extruder. The flexural properties of PLA/OMMT composites have been studied by using three point bending tests. Comparisons between the flexural properties of PLA/OMMT nanocomposites prepared by both methods have been carried out. The microstructures of the PLA/OMMT nanocomposites were assessed by Field Emission Scanning Electron Microscopy (FESEM) and X-ray Diffraction (XRD) analysis. The thermal properties of PLA/OMMT nanocomposites have been characterized by using Differential Scanning Calorimeter (DSC). The flexural modulus of PLA/OMMT nanocomposites prepared by both solution intercalation and melt intercalation methods increased significantly by the addition of OMMT. For both methods, it was found that the optimum flexural properties of the PLA nanocomposites was achieved at 1 wt.% OMMT loading. The dispersion of OMMT in the PLA prepared by solution intercalation is better than that of melt intercalation method. This is attributed to the ease of intercalation of PLA chain into the OMMT layered silicate during the solution intercalation process. XRD results revealed that intercalation of OMMT layered silicate occurred in the PLA matrix.

Preparation of orthogonally functionalized surface using micromolding in capillaries technique for the control of cellular adhesion

This study presents a simple method for the fabrication of an orthogonal surface that can be applied for cell patterning without the need to immobilize specific adhesive peptides, proteins, or extracellular matrix (ECM) for cell attachment. Micromolding in capillaries (MIMIC) produced two distinctive regions. One region contained poly(ethylene glycol)–poly( d, l-lactide) diblock copolymer (PEG–PLA) designed to provide a biological barrier to the nonspecific binding of proteins and fibroblast cells. The other region was coated with polyelectrolyte (PEL) to promote the adhesion of biomolecules including proteins and cells. Resistance to the adsorption of proteins increased with the length of PEG and PLA chains because the longer PEG chain increased the PEG layer thickness and the longer PLA chain induced stronger interaction with the PEL surface. The PEG5k–PLA2.5k (20 mg/ml) was the most efficient candidate for the prevention of protein adhesion among the PEG–PLA copolymers examined. The orthogonal functionality of prepared surfaces having PEL regions and background PEG–PLA regions resulted in rapid patterning of biomolecules. Fluorescein isothiocyanate-tagged bovine serum albumin (FITC-BSA) and fibroblast cells successfully adhered to the exposed PEL surfaces. Although methods for cell patterning generally require an adhesive protein layer on the desired area, these fabricated surfaces without adhesive proteins provide a gentle microenvironment for cells. In addition, our proposed approach could easily control patterns, sizes, and shapes at micron scale.

Effect of nucleation and plasticization on the crystallization of poly(lactic acid)

In this paper, different strategies to promote PLA crystallization were investigated with the objective of increasing the crystalline content under typical polymer processing conditions. The effect of heterogeneous nucleation was assessed by adding talc, sodium stearate and calcium lactate as potential nucleating agents. The PLA chain mobility was increased by adding up to 10wt% acetyl triethyl citrate and polyethylene glycol as plasticizers. The crystallization kinetics were studied using DSC analysis under both isothermal and non-isothermal conditions. The isothermal data showed that talc is highly effective in nucleating the PLA in the 80–120°C temperature range. In the non-isothermal DSC experiments, the crystallinity developed upon cooling was systematically studied at cooling rates of 10, 20, 40, and 80°C/min. The non-isothermal data showed that the combination of nucleant and plasticizer is necessary to develop significant crystallinity at high cooling rates. The nucleated and/or plasticized PLA samples were injection molded and the effect of mold temperature on crystallinity was determined. It was possible to mold the PLA formulations using mold temperatures either below 40°C or greater than 60°C. At low temperature, the molded parts were nearly amorphous while at high mold temperatures, the PLA formulation with proper nucleation and plasticization was shown to achieve crystallinity levels up to 40%, close to the maximum crystalline content of the material. Tensile mechanical properties and temperature resistance of these amorphous and semi-crystalline materials were examined.

Amphotericin B‐loaded poly(ethylene glycol)–poly(lactide) micelles: Preparation, freeze‐drying, and in vitro release

Polymeric micelles prepared from a series of poly(ethylene glycol)-poly(lactide) (PEG-PLA) diblock copolymers with various PLA chain lengths were designed as drug carriers for water insoluble drug amphotericin B (AmB). Physicochemical properties of AmB-loaded micelles were evaluated. Micelles were freeze-dried to obtain long-time stable formulations. The redispersibility of the freeze-dried samples was poor when the weight ratio of PLA block was bigger than the PEG block of the copolymer. Various types of lyoprotectants including saccharides and PEGs with different molecular weight were tested to improve the redispersion performance of the freeze-dried samples. PEG was proved to be more effective than saccharides on stabilizing the micelles during lyophilization when the weight ratio of PLA block was bigger than PEG block. The sustained release in vitro of AmB was evidenced. About 80% of AmB was released in 80 h. The in vitro release behavior could be best described by the first-order equation. The release rate was reduced as enhancing PLA chain length due to the stronger interaction between poorly water-soluble AmB and longer hydrophobic chain length of PLA.

Formation of poly(l,d-lactide) spheres with controlled size by direct dialysis

In this work, we show that simple dialysis of a poly(dl-lactic acid) (PLA) solution against water resulted in the spontaneous formation of PLA spheres. We observed initial formation of particles with irregular shape and large size, which then were disrupted into uniform and smooth nanospheres. Further, the formation process of PLA spheres was also investigated by dynamic light scattering technique (DLS) in situ. Based on these experimental results, it was proposed that the PLA spheres were formed in three steps: (1) aggregation – individual PLA chains got aggregated with each other in solution; (2) formation and disruption of PLA particles; (3) solidification of PLA spheres. In addition, the size of the spheres could be well controlled by the preparation conditions such as the speed of dialysis, initial solvent, initial water content and polymer concentration. The ease with which these spheres could be fabricated and the ability to control the size of spheres should facilitate investigations of their scope for drug delivery.

Rapidly in Situ Forming Biodegradable Robust Hydrogels by Combining Stereocomplexation and Photopolymerization

Our previous studies have shown that stereocomplexed hydrogels can be rapidly formed in vitro as well as in vivo upon mixing aqueous solutions of eight-arm poly(ethylene glycol)-poly(l-lactide) (PEG-PLLA) and poly(ethylene glycol)-poly(d-lactide) (PEG-PDLA) star block copolymers. In this study, stereocomplexation and photopolymerization are combined to yield rapidly in situ forming robust hydrogels. Two types of methacrylate-functionalized PEG-PLLA and PEG-PDLA star block copolymers, PEG-PLLA-MA and PEG-PDLA-MA, which have methacrylate groups at the PLA chain ends and PEG-MA/PLLA and PEG-MA/PDLA, which have methacrylate groups at the PEG chain ends, were designed and prepared. Results showed that stereocomplexed hydrogels could be rapidly formed (within 1-2 min) in a polymer concentration range of 12.5-17.5% (w/v), in which the methacrylate group hardly interfered with the stereocomplexation. When subsequently photopolymerized, these hydrogels showed largely increased storage moduli as compared to the corresponding hydrogels that were cross-linked by stereocomplexation or photopolymerization only. Interestingly, the storage modulus of stereocomplexed-photopolymerized PEG-PLA-MA hydrogels increased linearly with increasing stereocomplexation equilibration time prior to photopolymerization (from ca. 6 to 32 kPa), indicating that stereocomplexation aids in photopolymerization. Importantly, photopolymerization of stereocomplexed hydrogels could take place at very low initiator concentrations (0.003 wt %). Swelling/degradation studies showed that combining stereocomplexation and photopolymerization yielded hydrogels with prolonged degradation times as compared to corresponding hydrogels cross-linked by photopolymerization only (3 vs 1.5 weeks). Stereocomplexed-photopolymerized PEG-MA/PLA hydrogels degraded much slower than corresponding PEG-PLA-MA hydrogels, with degradation times ranging from 7 to more than 16 weeks. Therefore, combining stereocomplexation and photopolymerization is a novel approach to obtain rapidly in situ forming robust hydrogels.

Investigation of the degradation behaviour of poly(ethylene glycol- co- d, l-lactide) copolymer

The aim was to investigate the degradation behaviour of poly(ethylene glycol- co- d, l-lactide) (PEG- d, l-PLA) multiblock copolymer, in bulk and as microspheres, in aqueous medium. The degradation behaviour of PLA homopolymers in bulk and microspheres was evaluated as comparison. Microsphere preparation was performed by the double emulsion solvent evaporation method. Physical–chemical characterization of the raw polymers and the microspheres was performed by nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry (MDSC). Polymer molecular weight, before and after incubation in aqueous environment, was evaluated by GPC; water uptake and mass loss were determined gravimetrically. The presence of PEG segments inside PLA chains gave a characteristic spongy structure to the microspheres. A significant increase in polymer T g values was found for the microsphere formulations compared to polymer in bulk. After 63 days of incubation in the aqueous environment, the PEG- d, l-PLA microspheres achieved an average M w reduction of 47% compared to 20% for PLA microspheres. The corresponding M w decrease of the polymers in bulk was significantly higher: 72% and 41% for PEG- d, l-PLA and PLA, respectively. The data show how the degradation behaviour of polymer in bulk in an aqueous environment is significantly different from the behaviour of the corresponding microspheres. These results highlight the importance of performing a thorough physical–chemical characterization on microsphere formulations.

Novel synthesis of biodegradable star poly(ethylene glycol)‐block‐poly(lactide) copolymers

AbstractBiodegradable star‐shaped poly(ethylene glycol)‐block‐poly(lactide) copolymers were synthesized by ring‐opening polymerization of lactide, using star poly(ethylene glycol) as an initiator and potassium hexamethyldisilazide as a catalyst. Polymerizations were carried out in toluene at room temperature. Two series of three‐ and four‐armed PEG‐PLA copolymers were synthesized and characterized by gel permeation chromatography (GPC) as well as 1H and 13C NMR spectroscopy. The polymerization under the used conditions is very fast, yielding copolymers of controlled molecular weight and tailored molecular architecture. The chemical structure of the copolymers investigated by 1H and 13C NMR indicates the formation of block copolymers. The monomodal profile of molecular weight distribution by GPC provided further evidence of controlled and defined star‐shaped copolymers as well as the absence of cyclic oligomeric species. The effects of copolymer composition and lactide stereochemistry on the physical properties were investigated by GPC and differential scanning calorimetry. For the same PLA chain length, the materials obtained in the case of linear copolymers are more viscous, whereas in the case of star copolymer, solid materials are obtained with reduction in their Tg and Tm temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3966–3974, 2007

Novel polylactide/vermiculite nanocomposites by in situ intercalative polymerization. I. Preparation, characterization, and properties

AbstractPolylactide (PLA)/vermiculite nanocomposites were prepared by in situ intercalative polymerization of L,L‐lactide (LLA) in the presence of organomodified vermiculite (VMT). The d‐spacings of both the organomodified VMT and the exfoliated nanocomposites were investigated by X‐ray diffraction (XRD) analysis, and the morphology of exfoliated nanocomposites was examined by transmission electron microscopy (TEM). Thermogravimetric analysis (TGA) indicated that there is some enhancement in degradation behavior between the nanocomposites and the PLA matrix. Dynamic mechanical analysis (DMA) confirmed the constraint effect of exfoliated VMT layers on PLA chains, which is beneficial to the increased storage and loss modulus and increased glass transition temperature. The tensile strength showed that the exfoliated nanocomposites are reinforced and toughened by the addition of nanometer‐size vermiculite layers. POLYM. COMPOS., 28:545–550, 2007. © 2007 Society of Plastics Engineers

Properties of crosslinked polylactides (PLLA & PDLA) by radiation and its biodegradability

Crosslinked materials derived from poly(lactide) (PLA) have been produced by radiation modification in the presence of a suitable crosslinker (triallyl isocyanurate) (TAIC). The crosslinking structure introduced in PLA films has not only much improved the heat stability but also their mechanical properties. The properties of crosslinked samples are governed by crosslinking density and these improvement seemed to increase with radiation dose. This implied that the three dimensional networks have been introduced in material by radiation and the crosslinking density depended on the structure and length of PLA chains. Biodegradability of PLA was also determined by an enzymatic degradation test and burying in compost at 55 °C. Differing with PLLA, PDLA was insignificantly degraded by proteinase K. The degradation rate of PLA in compost was postponed with the introduction of crosslinks.

An AFM Study of Poly(L‐lactic acid) and Poly(D‐lactic acid) Macromolecules and Their Stereocomplexes at the Solid‐Air Interface

AbstractThe self assembly of PLA enantiomers have been studied at the nanometer scale using atomic force microscopy. At first, the conformation of D and L PLA macromolecules in dilute regime and the initial state of aggregation of both enantiomers were successively observed and compared with the aggregation of PLLA/PDLA blends. Our results points out differences in the aggregates structure between the homo‐aggregates of each enantiomers and the 3 Dimensional stereocomplexes formed with racemic mixture of D and L entities. On the one hand, D or L PLA chains, which adopt a rigid conformation in dilute regime, form gradually aggregates that tend to grow from a nucleation center. On the other hand, stereocomplexes have a non‐compact structure and are elongated with height variations within the fibrils that support the side by side aggregation of D and L helical structures to form thicker fibrils.

Thermo-mechanical characterization of plasticized PLA: Is the miscibility the only significant factor?

PLA is a widely used polymer which has received much attention in the last decade because of its originating from renewable resources and its potential biodegradability. PLA fulfils the packaging industry's requirements for most of the rigid objects but the polymer needs to be plasticized to be used as soft films. In this work, agreed plasticizers for food contact were melt mixed with L-PLA and then, the glass transition, melting, crystallization and mechanical properties of the blends were investigated. The experimental results were compared to the predicted results found through empirical interaction parameters and Fox equations. Molecular scale miscibility is assumed in the amorphous phase whatever the plasticizer. The mobility gained by the PLA chains in the plasticized blends yields crystallization, which is the driving force for various scale phase separations.

Novel polymeric micelles for hydrophobic drug delivery based on biodegradable poly(hexyl-substituted lactides)

Novel amphiphilic methoxy-poly(ethylene glycol)-poly(hexyl-substituted lactides) block copolymers were synthesized by ring-opening polymerization (ROP) of mono and dihexyl-substituted lactide (mHLA and diHLA) in bulk at 100 °C in the presence of tin(II) 2-ethylhexanoate (Sn(Oct) 2) as catalyst and methoxy-poly(ethylene glycol) (MPEG) as initiator. MPEG-PmHLA and MPEG-PdiHLA copolymers of predictable molecular weights and narrow polydispersities were obtained, as shown by 1H NMR and GPC. DSC experiments showed that the MPEG-PHLA block-copolymer presents a bulk microstructure containing MPEG domains segregated from the PHLA domains. Micelles were successfully prepared from these block copolymers, with sizes ranging from 30 to 80 nm. The critical micellar concentration (CMC) was found to decrease with the increasing number of hexyl groups on the polyester block (MPEG-PLA > MPEG-PmHLA > MPEG-PdiHLA) for copolymers of the same composition and molecular weight. The hydrophobicity of the micelle core in dependence of the number of hexyl groups along the PLA chain was evidenced by absorbance experiments with the incorporation of the dye Nile Red. These novel amphiphilic copolymers are interesting for micellar drug delivery and especially in regard to optimized hydrophobic drug loadings, as it was shown for griseofulvin as a model drug.

Synthesis of unimolecular reversed micelle consisting of a poly(L‐lactide) shell and hyperbranched D‐mannan core

AbstractA novel biodegradable unimolecular reversed micelle consisting of a poly(L‐lactide) (PLA) shell and a hyperbranched D‐mannan (HBM) core, that is, a chestnut‐shaped polymer (PLA–HBM), was synthesized by the polymerization of L‐lactide on HBM with 4‐(dimethylamino)pyridine (DMAP) as the catalyst. The obtained polymers were soluble in dimethyl sulfoxide, tetrahydrofuran, and chloroform but insoluble in H2O. The molecular weights of the PLA chain on PLA–HBM tended to increase with increasing polymerization time. The number of PLA chains on PLA–HBM could be controlled by the ratio of DMAP to the sugar unit in HBM. The obtained copolymer, PLA–HBM, acted as a unimolecular reversed micelle with an encapsulation ability toward the hydrophilic molecule. In addition, the entrapped hydrophilic molecules were slowly released from the core of PLA–HBM, and the release rate was accelerated by the breaking of the PLA chains of the shell when proteinase K as a hydrolase of PLA was used. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 406–413, 2006