Chemical modification of poly(lactic acid) and its use as matrix in poly(lactic acid) poly(butylene adipate-co-terephthalate) blends

Poly(lactic acid), PLA, was chemically modified with maleic anhydride (MA) by reactive extrusion. The effect of this modification on molar mass (MM) and acidity was assessed by means of size-exclusion chromatography (SEC) and titration, respectively. PLA MM decreased in the presence of MA solely and of MA and peroxide. Reduction in MM was monitored by the increase in acidity. PLA blends containing poly(butylene adipate-co-terephthalate) (PBAT) were prepared through different mixing protocols, PLA/PBAT, PLA-g-MA/PBAT and PLA/PBAT/MA/peroxide (PLA/PBAT in situ). SEC results and rheological properties revealed reduction in MM and viscosity of the modified blends. PLA/PBAT presented increase in MM and bimodal MM distribution. The calculated interfacial tension was significantly lower for the modified blends, despite the lower average particle area of PLA/PBAT. Surprisingly, the modified blends presented higher yield strength than that predicted by the rule of mixtures, which might indicate interfacial reactions.     

Biodegradation of poly(lactic acid) and its nanocomposites

PLA nanocomposites based on organically modified montmorillonites at 5% w/w loading were prepared by melt blending using an internal mixer and then degraded in a commercial compost. The addition of nanoclays was found to increase the PLA degradation rate, especially for the highest dispersed clay in the polymer matrix. Biodegradation by microorganisms isolated from the compost showed the bacterium Bacillus licheniformis as one of the responsible for PLA biodegradation in compost. It was also found that clays can influence the polymer bacterial degradation depending on their chemical structure and affinity of the bacterium towards the clay.     

XPS and wettability characterization of modified poly(lactic acid) and poly(lactic/glycolic acid) films

Poly(lactic acid) (PLA) and poly(lactic/glycolic acid) copolymers (PLGA) are biodegradable drug carriers of great importance, although successful pharmaceutical application requires adjustment of the surface properties of the polymeric drug delivery system to be compatible with the biological environment. For that reason, reduction of the original hydrophobicity of the PLA or PLGA surfaces was performed by applying a hydrophilic polymer poly(ethylene oxide) (PEO) with the aim to improve biocompatibility of the original polymer. PEO-containing surfaces were prepared by incorporation of block copolymeric surfactants, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (Pluronic), into the hydrophobic surface. Films of polymer blends from PLA or PLGA (with lactic/glycolic acid ratios of 75/25 and 50/50) and from Pluronics (PE6800, PE6400, and PE6100) were obtained by the solvent casting method, applying the Pluronics at different concentrations between 1 and 9.1% w/w. Wettability was measured to monitor the change in surface hydrophobicity, while X-ray photoelectron spectroscopy (XPS) was applied to determine the composition and chemical structure of the polymer surface and its change with surface modification. Substantial reduction of surface hydrophobicity was achieved on both the PLA homopolymer and the PLGA copolymers by applying the Pluronics at various concentrations. In accordance with the wettability changes the accumulation of Pluronics in the surface layer was greatly affected by the initial hydrophobicity of the polymer, namely, by the lactide content of the copolymer. The extent of surface modification was also found to be dependent on the type of blended Pluronics. Surface activity of the modifying Pluronic component was interpreted by using the solubility parameters.     

Biodegradability and biocompatibility study of poly(chitosan-g-lactic acid) scaffolds

A biodegradable, biocompatible poly(chitosan-g-lactic acid) (PCLA) scaffold was prepared and evaluated in vitro and in vivo. The PCLA scaffold was obtained by grafting lactic acid (LA) onto the amino groups on chitosan (CS) without a catalyst. The PCLA scaffolds were characterized by Fourier Transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The biodegradabilty was determined by mass loss in vitro, and degradation in vivo as a function of feed ratio of LA/CS. Bone marrow mesenchymal stem cell (BMSC) culture experiments and histological examination were performed to evaluate the PCLA scaffolds' biocompatibility. The results indicated that PCLA was promising for tissue engineering application.     

Conjugation of bioactive groups to poly(lactic acid) and poly[(lactic acid)-co-(glycolic acid)] films

A novel PLA-based polymer containing reactive pendent ketone or hydroxyl groups was synthesized by the copolymerization of L-lactide with epsilon-caprolactone-based monomers. The polymer was activated with NPC, resulting in an amine-reactive polymer which was then cast into thin polymeric films, either alone or as part of a blend with PLGA, before immersion into a solution of the cell adhesion peptide GRGDS in PBS buffer allowed for conjugation of GRGDS to the film surfaces. Subsequent 3T3 fibroblast cell adhesion studies demonstrated an increase in cellular adhesion and spreading over films cast from unmodified PLGA. Hence the new polymer can be used to obtain covalent linkage of amine-containing molecules to polymer surfaces.     

Biodegradation behaviour of poly(lactic acid) and (lactic acid-ethylene glycol-malonic or succinic acid) copolymers under controlled composting conditions in a laboratory test system

(Lactic acid, ethylene glycol, malonic or succinic acid) copolymers [(LA-EG-MA) and (LA-EG-SA) copolymers] were synthesized with different monomer feed ratios by direct polycondensation. The copolymers were characterized in terms of various properties such as acid value and number average molecular weight. The aerobic biodegradation under controlled composting conditions of commercially available and laboratory synthesized poly(l-lactic acid) (PLA) and synthesized copolymers was carried out according to ISO 14855-1:2005. The biodegradability of tested materials was found to be strongly dependent on the lactic acid content, ranging from 94% (method A) and 104% (method B) to 43% (method A) and 46% (method B) over the 110-days of the 50 °C composting.     

Electrospun fibers of poly(ethylene terephthalate) blended with poly(lactic acid)

Fibrous blends of polyethylene terephthalate (PET) and polylactic acid (PLA) were fabricated by electrospinning (ES) from a common solvent, at concentrations of PET/PLA = 100/0, 70/30, 50/50, 30/70, and 0/100. Oriented fiber mats were studied either as-spun, or after a cold-crystallization treatment. Scanning electron microscopy of as-spun amorphous fibers showed that addition of PLA into the ES solution prevents occurrence of beads. In some compositions, two glass transitions were observed by temperature-modulated differential scanning calorimetry indicating that the two components in the ES fibers were phase separated. Thermogravimetric analysis was used to study thermal degradation at high temperatures. PLA degrades at a temperature about 100 °C lower than that of PET, and holding or cycling the blends to high temperature can result in the degradation of PLA. Degree of crystallinity was determined using DSC for as-spun and cold-crystallized ES blend fibers. The degree of crystallinity of each blend component is reduced by the presence of the other blend component, and the overall crystallinity of the blend fibers is less than that of the homopolymer fibers. Wide-angle X-ray scattering results show that oriented crystals were formed in the blended electrospun fibers collected on a rotating collector. The cold-crystallization process leads to both PET and PLA crystallizations. Oriented crystallites form even when the fiber is crystallized with its ends free to shrink.     

Protein interaction with a Pluronic-modified poly(lactic acid) Langmuir monolayer

Interaction of bovine serum albumin (BSA) with poly(lactic acid) (PLA) layers mixed with poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers (Pluronic) at air/solution interfaces was studied by the Langmuir balance technique. Wettability of the mixed PLA-Pluronic system was characterized in the form of a transferred one-layer Langmuir-Blodgett film, and considerable hydrophilization was obtained for all of the Pluronics (6400, 6800, 10500, and 12700) applied here. The density of PEO chains in the monolayer and hence the coverage of PLA was controlled by the composition and the compression of the mixed monolayers. Tensiometric investigations revealed that a significant reduction of BSA adsorption/penetration was achieved by applying the Pluronic 6800 and 12700 with long PEO blocks for hydrophilization of PLA. Interaction of BSA with the modified PLA monolayer depended on the density and length of the PEO chains. The surface morphological characteristics of the films determined by atomic force microscopy were in good correlation with the results of BSA interaction. The average roughness of the polymer LB layer was high due to BSA penetration into the PLA film, while smooth surfaces with small roughness were obtained when the PLA layer was modified by Pluronic 6800.     

Poly(lactic acid) composites with poly(lactic acid)‐modified carbon nanotubes

This work reports the study of the effect of chemical functionalization of carbon nanotubes on their dispersion in poly(lactic acid). The nanotubes were functionalized by the 1,3‐dipolar cycloaddition reaction, generating pyrrolidine groups at the nanotube surface. Further reaction of the pyrrolidine groups with poly(lactic acid) was studied in solution and in the polymer melt. The former involved refluxing the nanotubes in a dimethylformamide/polymer solution; the latter was carried out by direct melt mixing in a microcompounder. The carbon nanotubes collected after each process were characterized by thermogravimetry and by X‐ray photoelectron spectroscopy, showing evidence of polymer bonded to the nanotube surface only when the reaction was carried out in the polymer melt. The composites with polymer modified nanotubes present smaller average agglomerate area and a narrower agglomerate area distribution. In addition, they show improved tensile properties at low CNT concentration and present lower electrical resistivity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3740–3750     

Poly(lactic acid)-coated mesoporous silica nanosphere for controlled release of venlafaxine

Two types of mesoporous silica nanospheres (MSNs) were synthesized for use as controlled-release agents. One was prepared by grafting with 5,6-dihydroxyhexylsilane (DH-MSN) and the other one by further coating with cholic acid-crosslinked poly(lactic acid) (CA-PLA-MSN). We studied the release of the antidepressant venlafaxine from each of the materials in simulated gastric fluid (SGF), in simulated gastric acid solution (SGA), and in simulated intestinal fluid without pancreatin (SIF). The CA-PLA-MSN material was able to significantly delay the release of the drug in intestinal condition compared with gastric acid surrounding due to the fast decomposition rate of PLA in gastric acid. Moreover, it successfully avoided the initial burst to a certain extent in SGF. The enzyme pepsin played a favorable obstruct role in both DH-MSN and CA-PLA-MSN systems to reduce release rate. A model based on Weibull model was built to fit the release results, and based on it, the mechanisms about release processes were brought out tentatively.     

Characterisation of multi-extruded poly(lactic acid)

The effect of multiple (up to 10 times) extrusion of polylactide on its mechanical properties (determined by a static tension test), Charpy impact strength, melt flow rate, phase transition temperatures, degradation temperature, and permeability of water vapour and oxygen is presented. It was found that, with raising the number of the extrusion cycles, the tensile strength at break slightly diminished and the impact strength clearly decreased, while the melt flow rate and water vapour and oxygen transmission rates steadily increased. Variation of the number of extrusion cycles did not affect the glass transition temperature, whereas it did cause a lowering of the cold crystallisation temperature and slight diminishing of the melting point. The presented results indicate that PLA technological waste is suitable to be reused as an additive to a neat polymer.     

Stereoblock poly(lactic acid): synthesis via solid-state polycondensation of a stereocomplexed mixture of poly(L-lactic acid) and poly(D-lactic acid)

Stereoblock poly(lactic acid) consisting of D- and L-lactate stereosequences can be successfully synthesized by solid-state polycondensation of a 1:1 mixture of poly(L-lactic acid) and poly(D-lactic acid). In the first step, melt-polycondensation of L- and D-lactic acids is conducted to synthesize poly(L-lactic acid) and poly(D-lactic acid) with a medium-molecular-weight, respectively. In the next step, these poly(L-lactic acid) and poly(D-lactic acid) are melt-blended in 1:1 ratio to allow formation of their stereocomplex. In the last step, this melt-blend is subjected to solid-state polycondensation at temperature where the dehydrative condensation is allowed to promote chain extension in the amorphous phase with the stereocomplex crystals preserved. Finally, stereoblock poly(lactic acid) having high-molecular-weight is obtained. The stereoblock poly(lactic acid) synthesized by this way shows a higher melting temperature in consequence of the controlled block lengths and the resulting higher-molecular-weight. The product characterization as well as the optimization of the polymerization conditions is described. Changes in M(w) of stereoblock poly(lactic acid) (sb-PLA) as a function of the reaction time.     

Effect of vermiculite dispersion in poly(lactic acid) preparation and its biodegradability

In the present work, the research on the preparation, crystallization behavior and biodegradability of poly(lactic acid)-vermiculite nano-composites was carried out. Surfactant modified vermiculite was used accompanied with the poly(lactic acid) to prepare the nano-composites via in situ intercalative polymerization. The purpose was to evaluate the impact of the vermiculite and its different content on the morphology and properties of nano-composites. The crystal structure and morphology of poly(lactic acid) before and after nano-composites preparation were examined by wide-angle X-ray diffraction, polar optical microscopy and differential scanning calorimetry. The as-prepared nano-composites exhibited remarkable improvement of multiple materials properties due to the decrease in crystallinity. The enhanced biodegradability of nanocomposites was also presented along with the increase of vermiculite content.     

Enhanced properties of poly(lactic acid) with silica nanoparticles

The objective of this article is to fabricate poly(lactic acid) (PLA) and nano silica (SiO₂) composites and investigate effect of SiO₂ on the properties of PLA composites. Surface‐grafting modification was used in this study by grafting 3‐Glycidoxypropyltrimethoxysilane (KH‐560) onto the surface of silica nanoparticles. The surface‐grafting reaction was confirmed by Fourier transform infrared spectroscopy and thermogravimetric analysis. Then the hydrophilic silica nanoparticles became hydrophobic and dispersed homogeneously in PLA matrix. Scanning electron microscope and Dynamic thermomechanical analysis (DMA) results revealed that the compatibility between PLA and SiO₂ was improved. Differential scanning calorimetry and polarized optical microscope tests showed that nano‐silica had a good effect on crystallization of PLA. The transparency analysis showed an increase in transparency of PLA, which had great benefit for the application of PLA. The thermal stability, fire resistance, and mechanical properties were also enhanced because of the addition of nano silica particles. Copyright © 2016 John Wiley & Sons, Ltd.     

Enhanced stereocomplex formation of poly(L-lactic acid) and poly(D-lactic acid) in the presence of stereoblock poly(lactic acid)

Stereoblock poly(lactic acid) (sb-PLA) is incorporated into a 1:1 polymer blend system of poly(L-lactic acid) (PLLA) and poly(D-lactic acid) (PDLA) that has a high molecular weight to study its addition effect on the stereocomplex (sc) formation of PLLA and PDLA. The ternary polymer blend films are first prepared by casting polymer solutions of sb-PLA, PLLA, and PDLA with different compositions. Upon increasing the content of sb-PLA in the blend films the sc crystallization is driven to a higher degree, while the formation of homo-chiral (hc) crystals is decreased. Lowering the molecular weight of the incorporated sb-PLA effectively increases the sc formation. Consequently, it is revealed that sb-PLA can work as a compatibilizer to improve the poor sc formation in the polymer blend of PLLA and PDLA.     

Increased covalent conjugation of a model antigen to poly(lactic acid)-g-maleic anhydride nanoparticles compared to bare poly(lactic acid) nanoparticles

Maleic anhydride (MA) grafted poly(lactic acid) (PLA) (PLA-g-MA) was synthesized from PLA. Proton nuclear magnetic resonance confirmed the grafting of the MA. PLA-g-MA and PLA were used to prepare polymeric nanoparticles. Particle size distributions were measured by dynamic light scattering, and colloidal stability was determined by (zeta) ζ-potential. The ζ-potential becomes more negative for PLA-g-MA than PLA nanoparticle dispersions, due to the presence of deprotonated carboxylic acid groups on the backbone of the PLA and confirms the MA grafting results. Maleic anhydride grafted on PLA backbone improves the covalent conjugation with ovalbumin (OVA) compared to OVA physically adsorbed on the particles. The chemical conjugation was carried out via amide linkages between the carboxylic groups of the nanoparticles, activated with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and the amino groups of the protein. The amount of protein conjugated was measured by using the bicinchoninic acid method and is threefold higher compared to the adsorbed OVA. Moreover, the PLA-g-MA nanoparticles increased the amount of conjugated OVA by 36 wt% compared to PLA nanoparticles. OVA adsorption and OVA conjugation provided colloidal dispersions with excellent stability.     

Stabilization of poly(lactic acid) by polycarbodiimide

Polycarbodiimide (CDI) was used to improve the thermal stability of poly(l-lactic acid) (PLA) during processing. The properties of PLA containing various amounts of CDI were characterized by GPC, DSC, rheology, and tensile tests. The results showed that an addition of CDI in an amount of 0.1-0.7 wt% with respect to PLA led to stabilization of PLA at even 210 °C for up to 30 min, as evidenced by much smaller changes in molecular weight, melt viscosity, and tensile strength and elongation compared to the blank PLA samples. In order to examine the possible stabilization mechanism, CDI was reacted with water, acetic acid, l-lactic acid, ethanol and low molecular weight PLA. The molecular structures of the reaction products were measured with FTIR. The results showed that CDI could react with the residual or newly formed moisture and lactic acid, or carboxyl and hydroxyl end groups in the PLA samples, and thus hamper the thermal degradation and hydrolysis of PLA.     

Gas permeation properties of poly(lactic acid)

The need for the development of polymeric materials based on renewable resources has led to the development of poly(lactic acid) (PLA) which is being produced from a feedstock of corn rather than petroleum. The present study examines the permeation of nitrogen, oxygen, carbon dioxide, and methane in amorphous films of PLA cast from solution. The properties of PLA are compared to other commodity plastics and it is shown that PLA permeation closely resembles that of polystyrene. At 30°C, N₂ permeation in PLA is 1.3 (10⁻¹⁰ cm³ (STP) cm/cm² s cmHg) and the activation energy is 11.2 kJ/mol. For oxygen the corresponding values are 3.3 (10⁻¹⁰ cm³(STP) cm/cm² s cm Hg) and 11.1 kJ/mol. The values for carbon dioxide permeation are 1.2 (10⁻¹⁰ cm³ (STP) cm/cm² s cmHg) and 6.1 kJ/mol. For methane values of 1.0 (10⁻¹⁰ cm³ (STP) cm/cm² s cmHg) and an activation energy of 13.0 kJ/mol are found. Studies with pure gases show that polymer chain branching and small changes in l:d stereochemical content have no effect on permeation properties. Crystallinity is found to dominate permeation properties in a biaxially oriented film. The separation factor for a CO₂/CH₄ mixed gas system is measured between 0 and 50°C and does not deviate significantly from the calculated ideal separation factor; at 0°C the separation factor is 16, a value that suggests continued studies of PLA as a separation medium are warranted.     

Design,synthesis and characterization of novel poly(urethane-urea) based on a macrodiol from poly(lactic acid) and poly(p-dioxanone)

A series of novel poly(urethane-urea)(PUU) was synthesized from poly(lactide-co-p-dioxanone) macrodiol(HO-P(LA-co-PDO)-OH), hexamethylene diisocyanate(HDI) and butanediamine(BDA).The obtained PUU,which is recorded as P(LA-co-PDO)-PUU here,may demonstrate enhanced phase separation and thus improved shape memory property.FTIR was employed to characterize the copolymers,and the effects of NCO/OH molar ratios on T_g of PUU was investigated by means of differential scanning calorimetry (DSC).The results revealed the successful synthesis of P(LA-co-PDO)-PUU.In addition,the T_g of P(LA-co-PDO)-PUU increased from 37.9℃to 44.2℃with the increase NCO/OH ratios from 1.1 to 1.2.The P(LA-co-PDO)-PUU with T_g close to body temperature will have potential applications as shape memory polymers in biomedical fields,especially in minimally invasive surgery.