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Biodegradable poly(lactic acid) nanocomposites: synthesis and characterizationLi, Yonghui January 1900 (has links)
Doctor of Philosophy / Department of Grain Science and Industry / X. Susan Sun / Biobased polymers derived from renewable resources are increasingly important due to acute concerns about the environmental issues and limited petroleum resources. Poly(lactic acid) (PLA) is such a polymer that has shown great potential to produce biodegradable plastics. However, low glass transition temperature (Tg), low thermal stability, slow biodegradation rate, and high cost limit its broad applications. This dissertation seeks to overcome these limitations by reinforcing PLA with inorganic nanoparticles and low-cost agricultural residues. We first synthesized PLA nanocomposites by in situ melt polycondensation of L-lactic acid and surface-hydroxylized nanoparticles (MgO nanocrystals and TiO2 nanowires) and investigated the structure-property relationships. PLA grafted nanoparticles (PLA-g-MgO, PLA-g-TiO2) were isolated from the bulk nanocomposites via repeated dispersion/centrifugation processes. The covalent grafting of PLA chains onto nanoparticle surface was confirmed by Fourier transform infrared spectroscopy and thermalgravimetric analysis (TGA). Transmission electron microscopy and differential scanning calorimetry (DSC) results also sustained the presence of the third phase. Morphological images showed uniform dispersion of nanoparticles in the PLA matrix and demonstrated a strong interfacial interaction between them. Calculation based on TGA revealed that more than 42.5% PLA was successfully grafted into PLA-g-MgO and more than 30% was grafted into PLA-g-TiO2. Those grafted PLA chains exhibited significantly increased thermal stability. The Tg of PLA-g-TiO2 was improved by 7 °C compared with that of pure PLA. We also reinforced PLA with low-value agricultural residues, including wood flour (WF), soy flour (SF), and distillers dried grains with solubles (DDGS) by thermal blending. Tensile measurements and morphological images indicated that methylene diphenyl diisocyanate (MDI) was an effective coupling agent for PLA/WF and PLA/DDGS systems. MDI compatibilized PLA/WF and PLA/DDGS composites showed comparable tensile strength and elongation at break as pure PLA, with obviously increased Young’s modulus. Increased crystallinity was observed for PLA composites with SF and DDGS. Such PLA composites have similar or superior properties compared with pure PLA, especially at a lower cost and higher biodegradation rate than pure PLA.
The results from this study are promising. These novel PLA thermoplastic composites with enhanced properties have potential for many applications, such as packaging materials, textiles, appliance components, autoparts, and medical implants.
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Water vapour permeability of bio-based polymersDuan, Zhouyang January 2013 (has links)
This project investigates the moisture barrier properties of bio-based polymers and ways of improving them. The first section addresses the effect of crystallinity on the water permeability of poly(lactic acid) (PLA). The second section investigates PLA/talc composites and PLA/ montmorillonite nanocomposites. The third section is focused on a new polymer, polybutylene succinate (PBS), and its nanocomposites with montmorillonite. In the first section, the water vapour transmission rates (WVTR) through samples of polylactic acid of different crystallinities have been measured. Three different grades of commercial PLA were used with different ratios of L-lactide and D-lactide to give a range of crystallinities from 0 to 50%. Sheets of PLA were prepared by melt compounding followed by compression moulding and annealing at different temperatures and for different times to give the range of crystallinities required. Crystallinity was measured by differential scanning calorimetry (DSC) and the morphology of the samples was observed under crossed polars in a transmitted light microscope. Water vapour transmission rates through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased linearly with increasing crystallinity of the PLA from 0 to 50%. The results are discussed in terms of the effect of crystallinity on solubility and shown to fit the tortuous path model. The model was also successfully used to explain published data on water permeability of polyethylene terephthalate. In the second section, a series of PLA/talc composites and PLA/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The morphologies of the composites were investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was found that the fillers were well dispersed in the polymer matrix. The average aspect ratio of the compounded talc was found to be 8, and that of the nanoclay was found to be 50. Water vapour transmission rates (WVTR) through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased with increasing filler content and the results gave good agreement with predictions from the Nielsen tortuous path model. In the third section, PBS/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The melting and crystallisation behaviour of the pure PBS samples were investigated using differential scanning calorimetry (DSC) and cross polarised optical microscopy. A slight decrease of the degree of crystallinity was found in PBS containing 5% nanoclay. The morphology of the composites was investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was confirmed that that composite structures were intercalated. Water vapour transmission rates (WVTR) through the PBS sheets were measured using a MOCON Permatran-W®398. The measured values of WVTR decreased with increasing nanoclay content. However, the experimental values were all higher than the values predicted by the Nielsen tortuosity model. This result shows that in the case of PBS, which is a highly crystalline polymer, the nanoclay is not as well dispersed and is not as effective in reducing water vapour permeability as in the case of PLA.
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Environmentally friendly packaging materials from renewable resources as alternatives for oil-based polymersSilva, Kodikara Manjula Dilkushi January 2011 (has links)
Nearly 60 m tonnes of waste is produced annually in Europe from “plastic packaging” engendering significant challenges for legislative controls and minimisation of environmental impact. There is an increasing demand for biodegradable packaging, which can be disposed of with minimum environmental impact, but the growing market is still in its infancy predominantly due to a lack of materials having environmental, practical and economic suitability. This research project dealt with some processing challenges of environmentally friendly packaging materials from renewable resources, as a long term solution to mitigate some issues associated with oil based plastic packaging. In this work, novel Polylactic acid (PLA) and starch based composites were developed with the requisite technical properties to fill the gap in the food packaging and cosmetic packaging industry. It was found that starch can be incorporated in a PLA matrix at the 10% level without difficulty in processing in the presence of 2% methyldiphenyl diisocyante. The blend shows properties similar to pure PLA. It was also found that the elongation at break and impact properties of PLA can be increased remarkably by the addition of a biostrength impact modifier. Furthermore, mixing of PLA and starch in the blend is efficient when the PLA particle size is reduced. It was also found that flexible and tougher PLA/starch blend pellets, that can be injection moulded, can be produced by an extrusion process with a range of additives. Each additive has a maximum level that exhibits optimum properties. The blends also established that 15% starch can be incorporated into the PLA matrix to reduce the cost without any processing difficulties. Encouragingly, the presence of an impact modifier in the PLA/starch blends has shown more desirable properties. Furthermore, the mechanical properties of the pellets exposed to increased residence time in the injection moulding barrel and of the test specimens stored for 9 months at 21ºC were also satisfactory for the new blend. The overall results exhibited some attractive properties in the tri blend system, which can be easily adopted by the plastics industry for development of an injection moulded product within the scope of applications such as dry food packaging or cosmetic packaging. A further finding of this project is that biodegradation under a home composting environment can be improved by incorporating starch and certain other modifiers into PLA.
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Solubility Ratios, Encapsulation Efficiency, and Size of Beta-sitosterol Loaded Poly(Lactide)-Block-Poly(Ethylene glycol) Polymeric MicellesAlqarni, Ali 31 July 2019 (has links)
β-sitosterol/poly(ethylene glycol)-block-poly(lactic acid) (PLA-b-PEG) complexes were prepared by solution blending in purified water and ethanol. The mixture of water and ethanol is a suitable solvent system for the two components. The complex was studied by using Nuclear Magnetic Resonance (NMR) spectroscopy and Differential Scanning Calorimetry (DSC). β-sitosterol is a drug that may reduce the swelling of benign prostatic hyperplasia (BPH) and diminishing inflammation. However, it is hydrophobic and difficult to deliver in aqueous solution. Since PLA-b-PEG has amphiphilic properties, the complex described here may enhance delivery of this drug for treatment of BPH.
Proton NMR (1HNMR) of the complexes shows that the methylene (CH2) protons of the PEG, the (-O-CH-) of PLA, and (CH3) of PLA are slightly shifted because of its non-covalent interaction with β-sitosterol. The complex formation was supported by 2-D NMR (NOESY) spectroscopy. NOESY spectra show cross peaks, indicating the interaction between the two components.
DSC of the complexes shows thermal characteristics that are different from the individual components. In particular, the PEG in the complex shows a lower melting point and decreased crystallinity compared to the pure PEG. The melting point is lowered from 57°C to 55.3 °C for the PEG-b-PLA/β-sitosterol (5%) complex. Under the same condition, the melting point of PLA dropped from 170 °C to 130 °C.
Atomic force microscopy shows changes in the surface morphology of the copolymer from crystalline to amorphous when incorporated with the drug. NMR, DSC, AFM, and MTT assay studies suggest the formation of a relatively stable β-sitosterol/poly(lactic acid)-block-poly(ethylene glycol) complex. The cell proliferation assay (MTT assay) suggests significant inhibition of the stimulation of growth of prostate cancer cells upon addition the complex.
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Eco Friendly Composites Prepared from Lactic Acid Based Resin and Natural FiberEsmaeili, Nima, Javanshir, Shahrzad January 2014 (has links)
Lactic acid based thermoset were synthesised by reacting lactic acid with glycerol andfunctionalizing lactic acid branches by methacrylic anhydride. Resins with different chainlength were prepared and their thermo mechanical properties were examined through DMAanalysis and their molecular structures were analyzed by NMR method and their viscositywere investigated through rheometry analysis and three monomers were selected as the bestchain length. Degree of reaction in different reaction times was evaluated by a modifiedtitration method and bulk preparation of resin was performed by optimal process condition.DSC analysis was conducted in order to evaluate curing behaviour of resin with benzoylperoxide as cross-linking initiator. TGA analysis was performed to check thermo stability ofthe resin. Bio composites by viscose unidirectional and bidirectional knitted fabrics and alsonon woven viscose fiber with different fiber loads were prepared by ordinary hand layupimpregnation followed by compress moulding and their mechanical and thermo mechanicalproperties were characterized by tensile, flexural, charpy and DMA analysis and optimumfiber loads were identified for each fiber type. Ageing properties of prepared composites wereexamined by placing samples in climate chamber to simulate long time ageing and ageingexperiment was followed by tensile and flexural test to evaluate mechanical properties afterageing simulation. Composite`s swelling properties for water and some other solvents wereinvestigated and also their chemical resistance were evaluated by immersing them in 1M HCland KOH. The resin was also compared with a commercial oil based thermoset by preparingglass fiber reinforced composites and also effect of adding styrene to the resin were evaluated.Results of this work demonstrated that the novel synthesised have very high mechanical andthermo mechanical properties surpassing commercial oil based poly esters but ageingbehaviour is not very good however adding styrene can improve ageing properties. Also theresin is compatible with cellulosic natural fibers and forms strong composites. / Program: Masterutbildning i energi- och material
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Indium complexes and their role in the ring-opening polymerization of lactideDouglas, Amy Frances 05 1900 (has links)
The synthesis and characterization of a series of chiral indium complexes bearing a tridentate NNO ligand are reported. The ligand 2-[[[(dimethylamino)cyclohexyl]amino]methyl]- 4,6-bis(tert-butyl) phenol (H₂NNO) was synthesized via a previously published procedure and bound to indium by both a protonolysis and salt metathesis route. A dimethylated indium complex (NNO)InMe₂ (1) was isolated by reaction of InMe₃ with H₂NNO. A one-pot saltmetathesis route was used to produce a unique mixed-bridge dinuclear indium complex [(NNO)InCl] ₂(μ-OEt)(μ-Cl) (3) from a mixture of indium trichloride, potassium ethoxide and the monopotassiated salt of the ligand, KH(NNO). Direct reaction of KH(NNO) and indium trichloride resulted in the formation of (NNO)InCl₂ (4) which was carried forward to 3 by reaction with sodium ethoxide.
The complex 3 is active for the ROP of β-butyrolactone ε-caprolactone and lactide and is the first reported indium-based catalyst for lactide or β-butyrolactone ROP. Kinetic studies of 3 for ROP of LA revealed that catalyst was well-behaved, and that the rate was first order with
regard to lactide and catalyst. The enthalpy and entropy of activation for the ROP were experimentally determined. Polymer produced by ROP by 3 has narrow molecular weight distribution and a good correlation is seen between the observed moleular weight and monomer loading. A mechanism was proposed for 3 acting as a catalyst for the ROP of lactide; however further experiments are required to confirm this mechanism. Polymer samples isolated from the
ROP of rac-lactide by rac-3 show isotactic enrichment. It is postulated that the chiral catalyst 3 is exerting stereocontrol via an enantiomorphic site control mechanism.
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Indium complexes and their role in the ring-opening polymerization of lactideDouglas, Amy Frances 05 1900 (has links)
The synthesis and characterization of a series of chiral indium complexes bearing a tridentate NNO ligand are reported. The ligand 2-[[[(dimethylamino)cyclohexyl]amino]methyl]- 4,6-bis(tert-butyl) phenol (H₂NNO) was synthesized via a previously published procedure and bound to indium by both a protonolysis and salt metathesis route. A dimethylated indium complex (NNO)InMe₂ (1) was isolated by reaction of InMe₃ with H₂NNO. A one-pot saltmetathesis route was used to produce a unique mixed-bridge dinuclear indium complex [(NNO)InCl] ₂(μ-OEt)(μ-Cl) (3) from a mixture of indium trichloride, potassium ethoxide and the monopotassiated salt of the ligand, KH(NNO). Direct reaction of KH(NNO) and indium trichloride resulted in the formation of (NNO)InCl₂ (4) which was carried forward to 3 by reaction with sodium ethoxide.
The complex 3 is active for the ROP of β-butyrolactone ε-caprolactone and lactide and is the first reported indium-based catalyst for lactide or β-butyrolactone ROP. Kinetic studies of 3 for ROP of LA revealed that catalyst was well-behaved, and that the rate was first order with
regard to lactide and catalyst. The enthalpy and entropy of activation for the ROP were experimentally determined. Polymer produced by ROP by 3 has narrow molecular weight distribution and a good correlation is seen between the observed moleular weight and monomer loading. A mechanism was proposed for 3 acting as a catalyst for the ROP of lactide; however further experiments are required to confirm this mechanism. Polymer samples isolated from the
ROP of rac-lactide by rac-3 show isotactic enrichment. It is postulated that the chiral catalyst 3 is exerting stereocontrol via an enantiomorphic site control mechanism.
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Bioparticle engineering using dense gas technologiesLam, Un Teng, Chemical Sciences & Engineering, Faculty of Engineering, UNSW January 2009 (has links)
The applications of dense gas technology (DGT) in modern particle engineering have shown promising results in producing submicron particles with uniform particle morphology. In this study, two configurations of dense gas antisolvent processes were employed for the micronization, encapsulation and co-precipitation of pharmaceutical compounds. The encapsulation of superparamagnetic iron oxide nanoparticles (SPIONs) by a pH-responsive polymer (Eudragit?? S100) was successfully performed using the supercritical antisolvent (SAS) process. Nanocomposites of less than 200nm in diameter with encapsulated SPIONs content as high as 16 wt% were achieved. Magnetic characterization of the product was also performed and the data were fitted by the Langevin equation. The superparamagnetic properties of the composites were preserved and the effective magnetic size was about 10 nm. The magnetically and pH-responsive nanocomposites can be potentially utilized as magnetic resonance imaging contrast agents and drug carriers. Screening experiments of 8 active pharmaceutical ingredients and 5 pharmaceutical excipients were performed using the recently patented atomized rapid injection solvent extraction (ARISE) process. Candidates with promising product morphology and recovery were selected for co-precipitation studies. The co-precipitation of the anti-cancer drug 5-fluorouracil (5FU) and poly l-lactic acid (PLLA) was conducted to develop a controlled release system. Experiments were designed based on a two-level, three-factor factorial design, in order to investigate the effects of processing parameters on product characteristics. Submicron PLLA-5FU composites (diameter<0.8 ??m) with a drug loading of 7.4 wt% were produced.
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Modification of poly(lactic acid) via olefin cross-metathesisSinclair, Fern January 2017 (has links)
Poly(lactic acid), PLA, is a viable replacement to petroleum derived polymers due to its renewable feedstock, biodegradability and bioassimilability, yet improvements in its physical, thermal and mechanical properties are required before it can fully enter all commodity markets. This thesis investigates olefin cross-metathesis (CM) as a synthetic strategy to modify the properties of PLA. The use of novel lanthanide and actinide catalysts on the microstructure control of PLA are also explored. The Tebbe reagent was used in a new synthetic strategy to produce a novel olefin derivative of lactide (MML). Olefin CM of MML with hex-1-ene was successful but polymerisation pre- and post-CM was unsuccessful due to monomer instability. CM of another olefin derivative of lactide, 3-methylenated lactide (3-ML) was successful with aliphatic alkenes; hex-1-ene to dodec-1-ene. To overcome competing alcoholysis of the functionalised monomers, which prevented polymerisation, hydrogenation was used to remove the olefin entity followed by successful ring-opening polymerisation (ROP) to produce polymers of low glass-transition temperatures (Tg). Post-polymerisation CM on an olefin containing polymer P(β-heptenolactone) P(β-HL), with methyl acrylate and an epoxide, generated functionalised homopolymers with increased Tg’s. Co-polymerisation of lactide with β-HL generated novel gradient-copolymers. Olefin CM with 15 different cross-partners produced functionalised copolymers with different thermal properties. Based on this route a new methodology was created to introduce two unique functionalities into the polymer backbone by manipulation of the olefin reactivities. Finally, in a collaborative project, uranium and cerium catalysts, Me3SiOU(OArP)3 and Me3SiOCe(OArP)3 - designed out-with the group- were tested and compared as ROP catalysts for lactide. Both catalysts were active in living polymerisations of L-lactide and under immortal conditions the activity and rates of the catalysts were switched, accounted for by a change in the coordination sphere due to ligand displacement. ROP of rac-lactide using the uranium analogue produced heterotactic-biased PLA with a Pr = 0.79.
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Efeito de modificadores poliméricos e argila organofílica nas propriedades do biopolímero poli (ácido lático) – PLA.CUNHA, Bartira Brandão da. 06 July 2018 (has links)
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Previous issue date: 2015-01-29 / Capes / A crescente busca por materiais alternativos que tragam menos dano ao meio ambiente resultou no desenvolvimento dos polímeros biodegradáveis. Estes materiais, do ponto de vista do processamento de obtenção, apresentam redução no consumo energético que aliada à ausência de inércia na sua degradação implicam na redução do acúmulo de lixo plástico no meio ambiente. Entretanto, alguns desses polímeros, como o poli (ácido lático) - PLA, por exemplo, apresentam algumas limitações quanto a sua aplicação, por ser um polímero de alta fragilidade e rigidez. A fim de ampliar o uso comercial do PLA, algumas pesquisas estão sendo desenvolvidas com o intuito de melhorar essas propriedades. Com base nisto, o atual trabalho de doutorado teve por objetivo estudar o efeito de modificadores poliméricos e argila organofílica nas propriedades do PLA a fim de se obter maior conhecimento sobre esse novo tipo de material. Para tanto o trabalho ocorreu em duas etapas: na primeira foram usados três modificadores poliméricos diferentes, cada um foi usado individualmente com o PLA, na proporção 90/10 (PLA/Modificador); na segunda, para cada sistema PLA/Modificador, foi acrescentado o teor de 3 pcr (partes por cem de resina) de argila organofílica. Os modificadores utilizados foram o Biostrength 150, o Paraloid e o EGMA, e a argila foi a Brasgel bentonítica. As misturas foram realizadas por meio de fusão. Para avaliar o efeito da modificação no PLA as amostras foram caracterizadas por meio das técnicas de Difração de Raios X (DRX), Espectroscopia na Região do Infravermelho por Transformada de Fourier (FTIR), Ensaios Mecânicos de Tração e Impacto, Microscopia Eletrônica de Varredura (MEV) Análises Térmicas por Calorimetria Exploratória Diferencial (DSC), Termogravimetria (TG) e DinâmicoMecânica (DMTA), Reologia e análise por temperatura de Distorção Térmica (HDT). Os resultados apontaram que as propriedades mecânicas de resistência ao impacto melhoraram significativamente, dependendo do modificador em uso, e também quando houve a combinação com a argila organofílica. No geral as propriedades mecânicas indicam que houve a tenacificação no PLA sem perda expressiva do módulo de elasticidade. As análises morfológicas apontaram uma boa dispersão do material. E as propriedades térmicas não sofreram grandes alterações. Os dados obtidos no ensaio reológico sugerem a formação de uma rede percolada na presença da argila. Concluindo-se por tanto que os modificadores poliméricos atuaram como dissipadores de energia e uso da argila inibiu a coalescência dos modificadores em meio a matriz polimérica, atuando de fato como uma barreira. / The increasing search for alternative materials that bring less damage to the environment resulted in the development of biodegradable polymers. These materials, from the viewpoint of obtaining processing, show a reduction in the energy consumption and the lack of inertia in its degradation imply the reduction of plastic waste accumulation in the environment. However, some of these polymers such as poly (lactic acid) - PLA, for example, have some limitations on their application, being a polymer of high rigidity and brittleness. In order to expand the commercial use of PLA, some research is being done with the aim of improving these properties. On this basis, the current doctoral work aimed to study the effect of polymeric modifiers and organoclay in PLA properties in order to obtain greater insight into this new type of material. For this work occurred in two stages: the first were used three different polymeric modifiers, each was used individually with the PLA in proportion 90/10 (PLA / Modifier); the second, for each PLA / modifier system was added 3 phr of the content (parts per hundred resin) of organophilic clay. The modifiers used were Biostrength 150, the Paraloid and E-GMA, and bentonite clay was the Brasgel. The mixtures were made by way of merger. To evaluate the effect of change in PLA samples were characterized by the techniques of X-ray Diffraction (XRD), Infrared Spectroscopy in the Region Fourier Transform (FTIR), Traction Mechanical Testing and Impact, Scanning Electron Microscopy (SEM) Thermal Analysis by Differential Scanning Calorimetry (DSC), thermogravimetry (TG) and Dynamic-Mechanical (DMTA), Rheology and analysis Temperature Heat Distortion (HDT). The results showed that the mechanical properties of impact resistance improved significantly with the use of polymeric modifiers and also when it was the combination with the organoclay. Overall mechanical properties indicate that there was no significant toughening the PLA loss modulus. Morphological analysis showed a good dispersion of the material. And the thermal properties did not change much. Rheological data obtained in testing suggest the formation of a percolating network in the presence of the clay. In conclusion therefore is that polymeric modifiers acted as energy sinks and use of the clay modifiers inhibit coalescence of the polymer matrix in the middle, in fact acting as a barrier.
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