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1.
The synthesis and characterization of poly(lactic acid)-co-aspartic acid copolymers (PLA-co-Asp) were presented. Subsequently, the synthesized PLA-co-Asp copolymers were tested as biodegradable carriers in drug delivery systems. PLA-co-Asp copolymers were synthesized by solution polycondensation procedure, using different molar ratios PLA/l-aspartic acid (2.33/1, 1/1, 1/2.33), manganese acetate and phosphoric acid as catalysts and N,N′-dimethyl formamide (DMF)/toluene as solvent mixture. The copolymers were characterized by FT-IR and 1H-NMR spectroscopy, gel permeation chromatography (GPC), DSC and TG-DTG analyses. Diclofenac sodium, a non steroidal anti-inflammatory drug was subsequently loaded into PLA-co-Asp copolymers. The in vitro drug release experiments were done by dialysis of the copolymer/drug systems, in phosphate buffer solution (pH = 7.4, at 37 °C) and monitored by UV spectroscopy.  相似文献   

2.
The development of synthetic biodegradable polymers using solvent free polymerization has a unique potential to be used as sustainable polymers in biomedical applications. The aim of this work was to synthesize and characterize a sustainable class of poly(lactic acid) (PLA) under different operating conditions via direct polycondensation of lactic acid (LA). Several parameters were tested including the absence of solvents and catalysts on the polymerization, in addition to polymerization temperature and time. Polymerization conditions were evaluated using response surface method (RSM) to optimize the impact of temperature, time, and catalyst. Results showed that molecular weight (Mw) of PLA increased with increasing polymerization time. Highest Mw of 28.4 kD with relatively a broad polydispersity 1.9 was achieved at polymerization temperature 170?°C at 24 h in the free solvent polymerization. This led to a relevant inherent viscosity of 0.37 dl/g. FTIR spectra exhibited a disappearance of the characteristic peak of the hydroxyl group in LA at 3482 cm?1 by increasing the intensity of carbonyl group. The 1H nuclear magnetic resonance (NMR) exhibited the main chain at 5.22 ppm and the signal of methyl proton at 1.61 ppm as well as a signal at 4.33 and 1.5 assigned to the methane proton next to the terminal hydroxyl group and carboxyl group respectively. Meanwhile, the PLA synthesized with a catalyst [Sn(Oct)2] in a free solvent demonstrated comparatively high thermal transition properties of glass transition, melting, and crystallinity temperatures of 48, 106, and 158?°C, respectively. These results are of significant interest to further expand the use of PLA in biomedical applications.  相似文献   

3.
There is a wide range of applications where calcium phosphate and hydroxyapatite (HA) are used as biomaterials, e.g. as synthetic bone grafts, coating on metal prostheses (like hip endoprostheses or dental implants) and drug carriers. In the study, the design and synthesis of composites based on poly(vinyl alcohol-co-lactic acid)/hydroxyapatite (PVA-co-LA/HA) with potential for biomedical applications, they are presented. The hydroxyapatite particles were surface-grafted with l(+)-lactic acid in the presence of manganese acetate as catalyst, resulting in modified hydroxyapatite (HAm) with improved capacity of bonding, respectively for the preparation of the composite based on PVA-co-LA/HAm. FT-IR spectra further confirmed the existence of PLA polymer on the surface of HA particles. In synthesis of PVA-co-LA copolymer the different molar ratios PVA/LA (2/1, 1/1, 1/2), toluene/water: 1/2 (as azeotrope solvent mixture) and manganese acetate as catalyst, were used. The composite materials were synthesized in situ with 10 wt% HA, and respectively HAm (reported to PVA and lactic acid components). The composite materials were characterized by FTIR spectroscopy, thermal analyses (DSC, DTG), 1H-NMR spectroscopy, particle size distribution and zeta potential.  相似文献   

4.
A poly(lactic acid) (PLA)/polyamide 11 (PA11)/SiO2 composite was mixed from PLA, PA11, and nanosilica particles through twin-screw extrusion. The PLA/PA11/SiO2 composite was evaluated with tensile and Izod impact tests, light transmission and haze measurement, and isothermal and nonisothermal crystallization behavior determinations. The PLA/PA11/SiO2 (97.0/3.0) composite had approximately 10.8% less ultimate tensile strength than neat PLA, but it had greater ductility and approximately ninefold greater elongation at break. A dimple morphology was observed on the fractural surface of the PLA/PA11/SiO2 composite, indicating that the incorporation of PA11 and nanosilica particles increased the ductility of the PLA matrix. PLA with less than 3 wt% of PA11 and 0.5 phr of nanosilica particles had an Izod impact strength of 8.72 kJ/m2. PA11 and nanosilica particles effectively toughened this PLA polymer; they accelerated both isothermal and nonisothermal crystallization rates and increased the crystallinities of the resulting composites under isothermal and nonisothermal crystallization processes.  相似文献   

5.
Poly(lactic acid) (PLA) presents high strength and modulus, but very low toughness as well as slow crystallization. Natural rubber (NR) was blended to enhance the toughness and nucleating agent was added to improve the crystallization. Cyclodextrin (CD), considered as a green compound, as well as calcium carbonate (CaCO3) and talc were used as nucleating agents. Effects of these nucleating agents on crystallization, mechanical properties and morphology of neat PLA and PLA/NR blend were investigated. It was found that the addition of talc and CD decreased cold crystallization temperature (Tcc) of the PLA. Same result was obtained in PLA/NR blend containing talc. All nucleating agents increased the degree of crystallinity (ΧC) of PLA, whereas only talc and CaCO3 increased ΧC of PLA in PLA/NR blends. The enhanced toughness of PLA by the addition of nucleating agent was attributed to its increased crystallinity, as well as decreased spherulite size. For PLA/NR blends, the increase in toughness was mainly contributed by the presence of the rubber.  相似文献   

6.
This work prepared poly (lactic acid) (PLA)/single-walled carbon nanotubes (SWCNTs) composites using a solution blend method, and investigated the influence of the physical properties of PLA/SWCNTs composites. In order to enhanced interfacial interactions between PLA and SWCNTs, the purified SWCNTs were given functionalisation treatments with a nitric acid/sulfuric acid mixture. These acid-treated SWCNTs (A-SWCNTs) were then grafted with 3-isocyanatopropyl triethoxysilane (A-SWCNTs-Si). When these functionalized SWCNTs were used to fill the PLA matrix, the fractured surface of composite does not present the pullout phenomenon. The dimensional stability obviously increased by a factor of approximately 72. The storage modulus was also significantly improved. The surface resistivity of the PLA/SWCNTs composites decreased from 1 × 1016 to 2.22 × 104 Ω/cm2.  相似文献   

7.
In attempt to enhance the compatibility of NR in PLA matrix, and furthermore to enhance mechanical properties of PLA, PLA/NR blends with strong interaction were prepared in Haake internal mixer, using dicumyl peroxide (DCP) as cross-linker. The effects of dicumyl peroxide on morphology, thermal properties, mechanical properties and rheological properties of PLA and PLA/NR blends were studied. The results indicated that dicumyl peroxide could increase the compatibility of poly(lactic acid) and natural rubber. With small amount of dicumyl peroxide, the effect on NR toughening PLA was enhanced and the tensile toughness of PLA/NR blends was improved. When the DCP content was up to 0.2 wt%, the PLA/NR blend reached the maximum elongation at break (26.21 %) which was 2.5 times of that of neat PLA (the elongation at break of neat PLA was 10.7 %). Meanwhile, with introducing 2 wt% DCP into PLA/NR blend, the maximum Charpy impact strength (7.36 kJ/m2) could be achieved which was 1.8 times of that of neat PLA (4.18 kJ/m2). Moreover, adding adequate amount of DCP could improve the processing properties of blends: the viscosity of PLA/NR blend decreased significantly and the lowest viscosity of the blends could be achieved when the DCP content was 0.5 wt%.  相似文献   

8.
Low-density polyethylene (LDPE) was employed to improve the thermal and rheological properties as well as the supercritical CO2 foaming behavior of poly(lactic acid) (PLA) through melt mixing and batch foaming method, due to its long branched chain structure, moderate crystallization capacity and good foamability. The differential scanning calorimetry and polarized optical microscope results showed that the introduction of LDPE had a slight effect for promoting the crystallization of PLA. An important synergistic effect on the rheological properties of PLA/LDPE blends was found through rotational rheometer. With the content of LDPE, the size of spherical LDPE dispersion phase became bigger gradually, which was observed by scanning electron microscope (SEM). A very interesting cellular morphology evolution from flower-like cellular structure to complex cellular structure and then to mono-porous cell structure was found in the SEM images of the PLA/LDPE blending foams with the foaming temperature at 95 °C. The effect of blending ratio and foaming temperature on the cellular morphology and foaming parameters was investigated.  相似文献   

9.
Poly(lactic acid) (PLA) has gained considerable attention nowadays as a biocompatible polymer owing to its advantage of being prepared from renewable resources. PLA exhibits excellent tensile strength, fabricability, thermal plasticity and biocompatibility properties comparable to many petroleum based plastics. However, low heat distortion temperature, brittleness and slow crystallization rate limit the practical applications of PLA. In order to address these limitations, an attempt has been made in the current work to prepare binary blends of PLA with ethylene vinyl acetate (EVA) at different compositions via melt mixing technique. Systematic investigation on the mechanical properties, thermal degradation and crystallization behavior for PLA-EVA blends was carried out. The impact strength of binary blends of PLA–EVA was found to increase significantly by 176% for 15 wt% of EVA compared to virgin PLA. This is due to the strong interfacial adhesion among PLA and EVA resulting in brittle to ductile transition. Scanning electron microscopy analysis for impact fractured surfaces of binary blends of PLA implied the toughening effect of PLA by EVA. Thermogravimetry analysis results revealed that the activation energy of PLA–EVA blends decreased with increase in EVA content in the PLA matrix. While, differential scanning calorimetry results obtained for PLA–EVA blends revealed the improvement in crystallinity when compared with neat PLA. The effect of EVA on non-isothermal melt crystallization kinetics of PLA was also examined via DSC at various heating rates. Decreasing trend in the t1/2 values indicated the faster rate of crystallization mechanism after addition of EVA in the PLA matrix.  相似文献   

10.
The evaluation method of biomass carbon ratio of polymer composite samples including organic and inorganic carbons individually was investigated. Biodegradable plastics and biobased plastics can have their mechanical properties improved by combining with inorganic fillers. Polymer composites consisting of biodegradable plastics and carbonate were prepared by two different methods. Poly(lactic acid) (PLA) composite was prepared by synthesis from l-lactide with catalyst and calcium carbonate (CaCO3) powders from lime. Poly(butylene succinate) (PBS) composite was prepared by hot-pressing the mixture of PBS powder and CaCO3 powders from oyster shells. The mechanical properties of composite samples were investigated by a tensile test and a compression test using an Instron type mechanical tester. Tensile test with a dumbbell shape specimen was performed for PBS composite samples and compression test with a column shape specimen for PLA composite samples. Strength, elastic modulus and fracture strain were obtained from the above tests. Biomass carbon ratio is regulated in the American Standards for Testing and Materials (ASTM). In ASTM standards on biomass carbon ratio, it is required that carbon atoms from carbonates, such as CaCO3, are omitted. Biomass carbon ratio was evaluated by ratio of 14C to 12C in the samples using Accelerator Mass Spectrometry (AMS). The effect of pretreatment, such as oxidation temperature and reaction by acid, on results of biomass carbon ratio was investigated. Mechanical properties decrease with increasing CaCO3 content. The possibility of an evaluation method of biomass carbon ratio of materials including organic and inorganic carbons was shown.  相似文献   

11.
The synthesis of polylactide (PLA)-b-poly (dimethyl siloxane) (PDMS) linear block copolymers and their use in blends with pure-PLA are described. PLA-b-PDMS linear block copolymers were obtained by the transesterification reaction in chloroform solution between poly(dimethyl siloxane) bis (2-aminopropyl ether) (molecular weight 2,000?Da) with PLA in the presence of stannous octoate. Molecular weights (Mw) of the block copolymers were varied from 53,800 to 63,600?Da while that of pristine PLA was 73,600?Da. The copolymers obtained were purified by fractional precipitation and then characterized by 1H NMR, FTIR, GPC, viscometry and DSC techniques. Blends of pure PLA with PLA-b-PDMS block copolymers displayed improved elastic properties (elongation up to 140%) compared to pure PLA (elongation ~9%). Thermal, mechanical and morphological characterization of the blends were also conducted.  相似文献   

12.
We herein report the effects of the component ratio and method of blending on the synthesis of stereocomplex poly(lactic acid) (SC-PLA) based on poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) prepolymers. PLLA and PDLA were prepared by direct melt polycondensation of lactic acid (DMP). Combined with the dual catalyst system, PLA prepolymers with Mw more than 20,000 were prepared by DMP. PLLA was mixed by powder blending or melt blended with PDLA. It is revealed that melt-point and spherulite growth rate of SC-PLA is strongly dependent on the perfection of SC structure. The melt point of PLA can be increased by nearly 50 °C because of the particular strong intermolecular interaction between PLLA and PDLA chains. Solid-state polycondensation (SSP) is an efficient method to increase the molecular weight of SC-PLA, but it can have a negative effect on the regularity of linear chains of SC-PLA. Thermogravimetry analyzer (TGA) results show that SC structure cannot cause the delay reaction on the thermal degradation of PLA.  相似文献   

13.
Two different polymerization routes, one-step and two-step bulk ring-opening polymerizations of d,l-lactide (LA) and p-dioxanone (PDO) monermers using stannous octoate [Sn(Oct)2]/n-dodecanol as the initiating system, were employed to synthesize poly(d,l-lactide-co-p-dioxanone) P(LA-co-PDO) random and segmented copolymers with different compositions and chain microstructure. For the two-step copolymers, the average sequence lengths of the lactidyl (LLA) and dioxanyl (LPDO) units calculated from the 1H-NMR spectra were much longer than those values for the one-step copolymers with the same LA/PDO feed ratio. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline even when the PDO content was as low as 14.5 mol%, while the one-step copolymers were completely amorphous with PDO content below 60.6 mol%. However, irrespective of polymerization route, both types of copolymers displayed a single glass transition temperature that was in a linear relation with composition. The decrease of maximum decomposition temperature of the copolymers was in accordance with the decrease of LPDO value. The mechanical and degradation properties of the copolymers were significantly affected by both the polymerization route and the chemical composition as well. In conclusion, the properties of P(LA-co-PDO) copolymers could be adjusted conveniently to meet specific applications by changing the composition and microstructure of the copolymers via different polymerization routes.  相似文献   

14.
A hydrophilic copolymer, ethylene–vinyl alcohol (EVOH), was incorporated into the poly(lactic acid) (PLA) matrix to improve the barrier property of PLA through twin-screw extrusion rather than the typical coextrusion process. A chain extender, poly[(ethylene)-co-(methyl acrylate)-co-(glycidyl methacrylate)] (PEMG), was used to reduce the probability of the thermal degradation of PLA during melt compounding. Biaxial stretching was used to enhance the microstructure and barrier property of PLA-PEMG/EVOH films. Experimentally, PEMG considerably reduced the probability of the thermal degradation of the PLA-PEMG sample. Biaxial stretching increased the tensile strength and decreased the value of elongation at break of the PLA-PEMG/EVOH80 (PLA/EVOH 100/80) film. Because of the efficient blending of PLA/EVOH in the twin-screw extruder, the dispersion of EVOH in the PLA matrix revealed homogeneous dispersion with a domain size of 1–5 μm. EVOH effectively improved the water vapour transmission rate (WVTR) of PLA through melt blending. Blending PLA-PEMG with EVOH substantially decreased the WVTR from 250 cc—20 μm/m2-day-atm for neat PLA to approximately 65 cc—20 μm/m2-day-atm for the PLA-PEMG/EVOH80 film, a decrease of approximately 74 % compared with neat PLA. Moreover, the WVTR decreased further from 65 cc—20 μm/m2-day-atm for the unstretched PLA-PEMG/EVOH80 film to 6.3 cc—20 μm/m2-day-atm for the film stretched at a stretch ratio of 3.5 × 3.5 and at 100 %/s, a decrease of approximately 90 % compared with neat PLA.  相似文献   

15.
In this study, the influence of alkali (NaOH) treatment on the mechanical, thermal and morphological properties of eco-composites of short flax fiber/poly(lactic acid) (PLA) was investigated. SEM analysis conducted on alkali treated flax fibers showed that the packed structure of the fibrils was deformed by the removal non-cellulosic materials. The fibrils were separated from each other and the surface roughness of the alkali treated flax fibers was improved. The mechanical tests indicated that the modulus of the untreated fiber/PLA composites was higher than that of PLA; on the other hand the modulus of alkali treated flax fiber/PLA was lower than PLA. Thermal properties of the PLA in the treated flax fiber composites were also affected. Tg values of treated flax fiber composites were lowered by nearly 10 °C for 10% NaOH treatment and 15 °C for 30% NaOH treatment. A bimodal melting behavior was observed for treated fiber composites different than both of neat PLA and untreated fiber composites. Furthermore, wide angle X-ray diffraction analysis showed that the crystalline structure of cellulose of flax fibers changed from cellulose-I structure to cellulose-II.  相似文献   

16.
Poly(lactic acid)/halloysite nanoclay composites (PLA/HNC) containing maleic anhydride grafted styrene-ethylene/butylene-styrene (SEBS-g-MAH) were produced using melt compounding followed by compression molding. The effects of hygrothermal aging on the thermal properties and functional groups changes of the HNC reinforced PLA (with and without SEBS-g-MAH) at three different temperatures (i.e., 30, 40 and 50 °C) were analyzed using differential scanning calorimetry and Fourier transform infrared spectroscopy techniques. The diffusion coefficient (D) of PLA was decreased by the incorporation of HNC and SEBS-g-MAH. The activation energy of water diffusion (E a ) of PLA/HNC/SEBS-g-MAH nanocomposites was higher than that of pure PLA. The glass transition temperature (T g ), cold-crystallization temperature (T cc ) and melting temperature (T m ) of the PLA sample were shifted to lower temperature and the effect was more pronounced at 50 °C. The carbonyl index values of all PLA samples increased after immersed in 40 and 50 °C, which is due to the formation of higher amount of carboxyl groups during the hydrolysis process.  相似文献   

17.
Bionanocomposites of poly(lactic acid) (PLA) and chemically modified, nanofibrillated cellulose (NFC) powders were prepared by extrusion, followed by injection molding. The chemically modified NFC powders were prepared by carboxymethylation and mechanical disintegration of refined, bleached beech pulp (c-NFC), and subsequent esterification with 1-hexanol (c-NFC-hex). A solvent mix was then prepared by precipitating a suspension of c-NFC-hex and acetone-dissolved PLA in ice-cold isopropanol (c-NFC-hexsm), extruded with PLA into pellets at different polymer/fiber ratios, and finally injection molded. Dynamic mechanical analysis and tensile tests were performed to study the reinforcing potential of dried and chemically modified NFC powders for PLA composite applications. The results showed a faint increase in modulus of elasticity of 10?% for composites with a loading of 7.5?% w/w of fibrils, irrespective of the type of chemically modified NFC powder. The increase in stiffness was accompanied by a slight decrease in tensile strength for all samples, as compared with neat PLA. The viscoelastic properties of the composites were essentially identical to neat PLA. The absence of a clear reinforcement of the polymer matrix was attributed to poor interactions with PLA and insufficient dispersion of the chemically modified NFC powders in the composite, as observed from scanning electron microscope images. Further explanation was found in the decrease of the thermal stability and crystallinity of the cellulose upon carboxymethylation.  相似文献   

18.
The main purpose of this study is challenging to dramatically improve the toughness of poly(lactic acid) (PLA)/starch by adding poly (ethylene glycol) (PEG) into the composites and grafting PEG molecules onto the surface of starch particles. It was found that the surface grafting of PEG onto starch induced the presence of PEG-rich regions located around the starch particles, caused by migration and aggregation of free PEG molecules. A novel interphase transition layer between PLA and starch was formed, which showed great ability for cavitation and vested large-scaled plastic deformation to PLA matrix. Further mechanical properties tests indicated the formation of interphase layer significantly increase the elongation at break from 10.2 to 254.5%, and notched impact strength from 1.56 to 2.37?kJ/m2 for PLA/PEG/starch ternary composites. The influence of PEG component, ethanol extraction and annealing was also investigated.  相似文献   

19.
Three high molecular weight (120,000 to 200,000 g mol–1) polylactic acid (PLA) plastic films from Chronopol (Ch-I) and Cargill Dow Polymers (GII and Ca-I) were analyzed for their degradation under various temperature and relative humidity (RH) conditions. Two sets of plastic films, each containing 11 samples, were randomly hung in a temperature/humidity-controlled chamber by means of plastic-coated paper clips. The tested conditions were 28, 40, and 55°C at 50 and 100% RH, respectively, and 55°C at 10% RH. The three tested PLA films started to lose their tensile properties when their weight-average molecular weight (M w) was in the range of 50,000 to 75,000 g mol–1. The average degradation rate of Ch-I, GII, and Ca-I was 28,931, 27,361, and 63,025 M w/week, respectively. Hence, GII had a faster degradation rate than Ch-I and Ca-I under all tested conditions. The degradation rate of PLA plastics was enhanced by the increase in temperature and relative humidity. This trend was observed in all three PLA plastics (Ca-I, GII, and Ch-I). Of the three tested films, Ch-I was the first to lose its mechanical properties, whereas Ca-I demonstrated the slowest loss, with mechanical properties under all tested conditions.  相似文献   

20.
Melt-pressed films of polycaprolactone (PCL) and poly(lactic acid) (PLA) with processing additives, CaCO3, SiO2, and erucamide, were subjected to pure fungal cultures Aspergillus fumigatus and Penicillium simplicissimum and to composting. The PCL films showed a rapid weight loss with a minor reduction in the molecular weight after 45 days in A. fumigatus. The addition of SiO2 to PCL increased the rate of (bio)erosion in A. fumigatus and in compost. The use of a slip additive, erucamide, was shown to modify the properties of the film surface without decreasing the rate of bio(erosion). Both the rate of weight loss and the rate of molecular weight reduction of PCL increased with decreasing film thickness. The addition of CaCO3 to PLA significantly reduced the thermal degradation during processing, but it also reduced the rate of the subsequent (bio)degradation in the pure fungal cultures. PLA without additives and PLA containing SiO2 exhibited the fastest (bio)degradation, followed by PLA with CaCO3. The degradation of the PLA films was initially governed by chemical hydrolysis, followed by an acceleration of the weight change and of the molecular weight reduction. PLA film subjected to composting exhibits a rapid decrease in molecular weight, which then remains unchanged during the measurement period, probably because of crystallization.  相似文献   

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