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Polylactide chemical recycling to Lactide
Kučerová, Eliška ; Pospíšilová, Aneta (referee) ; Figalla, Silvestr (advisor)
This diploma thesis deals with chemical recyclation polylactide to lactide. In the theory is summarized actual state of knowledge about chemical recyclation of polylactides, their properties, preparations a possibilities of characterization. Experimental part of work verify ethanolysis of PLA withthe samples of granulate, waste filaments and textiles. In the experimental work is suggested an optimalization of alcoholysis to direct yield of oligomer suitable for depolymerization to lactide. This method was verified for 5 different samples of PLA, which 4 of them was made of waste PLA. The time needed for depolymerization was evaluated and the effect of catalysis. Lactide and PLA recyclates was further analyzed by NMR, FTIR, DSC and GPC.
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Preparation of Poly(3-hydroxybutyrate) based acrylic monomer
Liška, Marek ; Přikryl, Radek (referee) ; Figalla, Silvestr (advisor)
The main aim of this thesis is to research and prepare acrylic (methacrylic) monomers derived from poly(3-hydroxybutyrate). The monomers were prepared in two-step syntheses. In the first step P3HB was depolymerised with selected alcohols and afterwards, products of those syntheses were used as substrate and mixed with polymethylmethacrylate to produce their methacrylic derivates. The selected alcohols for the alcoholysis were ethanol and ethylene glycol. In total, four substances were prepared. Products of alcoholysis were ethyl-3- hydroxybutyrate, 2-hydroxyethyl-3-hydroxybutyrate and their methacrylic derivates. Significant part of this thesis is aimed towards the analysis of prepared substances and the analysis of reactions. In the process, titrations and instrumental methods, such as gel permeation chromatography (GPC), infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), thermogravimetry (TGA) and differential scanning calorimetry (DSC) were used. This work describes preparation and analysis of polymers prepared from methacrylates from the mentioned syntheses. Cross-linked polymers, because of their low glass-transition temperature are elastomers.
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Extraction of Poly(3-hydroxybutyrate) from Biomas
Jašek, Vojtěch ; Ing. Jiří Švrček, Ph.D (referee) ; Figalla, Silvestr (advisor)
Polyhydroxyalkanoates are a group of biopolymers which occur in cells of microorganisms. These biopolymers can be considered as alternatives to commonly used petrochemical materials such as polypropylene and polyethylene due to their physical and chemical properties. This bachelor thesis focuses on isolation of particular kind of PHA from biomass and contains both experimental and theoretical part. It consists of information about the origin and usage of PHA, challenges and problems of their biotechnological production and mainly various ways of downstream. Experimental part includes comparison of PHA extraction from biomass done by two ester solvents. Studied parameters were molecular weight of the polymer, solvent extraction ability and their resistance against hydrolysis. The main goal of this thesis was to verify the best process conditions of isolation done by nonhalogenated bio-solvent.
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Preparation and characterization of unsaturated bio-polyester resins
Žůrek, Michal ; Petrůj, Jaroslav (referee) ; Figalla, Silvestr (advisor)
The theoretical part of this work is devoted to the selection of suitable components for synthesis of a branched oligoester and their structural arrangement. Further, oligomers of lactic acid esterified with crotonic acid branched by erythritol or pentaerythritol are discussed. Crosslinking of prepared oligoesters is accomplished by free radical mechanism using vinyl acetate as reactive diluent and 2,2'-azo-bis-isobutyronitrile as initiator. Resin was cured by vinyl acetate in different mass ratios. Results show that there in an optimal ratio for curing between oligoester and reactive diluent. Using less vinyl acetate results in insufficient crosslink density or, on the contrary, using considerable excess of vinyl acetate causes rapid polymerization, that also results in lower density of crosslinking. The crosslink density was determined indirectly by extraction of the soluble part to acetone after curing and drying of the product.
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Functional foams with densit ygradient
Svatík, Juraj ; Figalla, Silvestr (referee) ; Jančář, Josef (advisor)
Vycházíme-li z lehčených přírodních materiálů, lze od porézních materiálů s gradientem porozity očekávat mechanické vlastnosti nadřazené konvenčím polymerním pěnám, a to díky jejich specifické architektuře. Tyto vlastnosti umožňují použití lehčených materiálů jako strukturních prvků. V této práci je popsaná příprava gradientních porézních materiálů pomocí laminování a/nebo 3D tisku. Provedeny byly statické a dynamické mechanické testy na obou kvazi homogenních a gradientně porézních pěnách poskytující experimentální podklad pro hypotézu deformační odezvy plynoucí ze strukturní architektury. Data se interpretovala užitím zavedených teoretických modelů. Naše výsledky vedly k závěru, že tyto teoretické modely odvozené od pěn s pravidelnou strukturou není vhodné aplikovat pro pěny s gradientem porozity, protože prokazují podstatně lepší mechanické vlastnosti než homogenně porézní pěny.
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Preparation of Ethyl 2-acetoxypropanoate
Kučerová, Eliška ; Pospíšilová, Aneta (referee) ; Figalla, Silvestr (advisor)
The bachelor thesis focuses on the preparation of ethyl 2-acetoxypropanoate as a potential nonpolar biosolvent. Selected preparation should provide the highest yield possible. For this purpose, a theoretical review of possible syntheses was developed, with emphasis on syntheses based on acetylation of ethyl lactate. The experimental part of the work then focuses in more detail on the possibility of isolating ethyl 2-acetoxypropanoate from the reaction mixture. Product isolation was verified by fractional distillation and extraction method. In the isolated product, the basic physical properties were determined and the spectrum measured by Fourier transformation infrared spectroscopy. Furthermore, the hydrolytic stability of ethyl 2-acetoxypropanoate was investigated and a series of calorimetric measurements were performed. From these measurements, the effect of reaction temperature on reaction rate and product conversion and the effect of catalyst presence was assessed.
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Effect of alternative agents on controlled degradation of polypropylene
Kadlecová, Zuzana ; Figalla, Silvestr (referee) ; Bílek, Vlastimil (advisor)
This bachelor’s thesis focuses on the effect of degradation agents in controlled rheology polypropylene and its efficiency. That was evaluated on several types of polypropylene with different molecular weight, the strength of stabilization and content of degradation reagents (organic peroxide and nitroxide Irgatec® CR 76). Melt flow rate, rheometry, and molecular weight distribution methods were applied. Results of each method for unstabilized, stabilized polypropylene and polypropylene containing degradation agent were compared. It was determined, that higher polymer chain degradation efficiency is provided by organic peroxide, lower by nitroxide. The molecular weight distribution of polypropylene was much narrower with peroxide than with nitroxide even though it should have been conversely according to published data. The molecular weight distribution of polypropylene (Mw/Mn) was much narrower with nitroxide than with peroxide at all process temperatures.
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New Processes of Lactid Acid Polymers Preparation
Figalla, Silvestr ; Svěrák, Tomáš (referee) ; Herink,, Tomáš (referee) ; Petrůj, Jaroslav (advisor)
The work focuses on new processes for the preparation of lactic acid derivatives. The main objective was to verify the feasibility of preparing high molecular weight polylactide using ethyl lactate as a precursor of lactide synthesis. Part of the work is devoted to the new ethyl lactate synthesis method. The experimental part of the thesis is divided into partial key steps on the way from the lactic acid to the high molecular polylactide. The preparation of anhydrous ethyl ester of lactic acid (EtLA) was solved in an innovative way using alcoholysis of the oligomeric lactic acid. A kinetic model for isothermal alcoholysis and equimolar reactants ratio was derived from this method. The ethyl lactate was oligomerized by transesterification into the low and high molecular weight oligomer with the help of newly found catalysts suitable for the reaction medium. Stannous lactate was used as catalyst for oligomerization of the low molecular weight polymer suitable for the preparation of lactide (Mn 1000 g.mol-1). Experimental polymerization of ethyl lactate into high molecular weight product in tens of kDa has been investigated with newly synthesized tetraethyllactoyl titanate, Ti(EtLA)4. The laboratory method was derived for the depolymerization of the oligomer into lactide. Optimal conditions found for lactidation are as follow: temperature 225 ° C, pressure 2 kPa, catalysis 0,05 mol% of stannous lactate (with respect to oligomer lactate units). The prepared lactide was refined to polymer grade purity by distillation and subsequent recrystallization from ethyl acetate and toluene. The method for the preparation of high molecular weight PLA through ROP polymerization of lactide has been optimized. By optimization, suitable catalyst concentration was found in combination with the polymerization temperature and the polymerization length. An equimolar mixture of Tin 2-ethylhexanoate and 1-decanol was used as the catalytic system. The optimal ROP conditions for achieving the maximum molecular weight and suppressed polymer coloration (yellowing) are: catalyst concentration 0,01 mol%, temperature 160 °C, and polymerization length 4 hours. PLA with molecular weight Mw= 447 ± 7,8 kg.mol-1 was prepared at these conditions and good repeatability of the result was achieved. The effect of naturally occurring lactide contaminants and their influence on the course and ROP result was experimentally verified on the optimized polymerization system. The purpose was to explore the effect of lactide contamination with water and ethanol as natural lactide contaminants. The results clearly confirm the orderly lower sensitivity of the polymerization system for the presence of ethanol as compared to water contamination. In the case of the presence of water, the course and the result of the polymerization in terms of both the conversion and achieved molecular weights are negatively affected, even when the water content is in the order of 0,001%. Conversely, the presence of ethanol has a positive effect on lactide conversion and polymer polydispersity. Lactides with an alcohol content of about one-tenth of a percent are suitable to reach molecular weights of PLA similar to commercially available products. This difference shoves a significant advantage in the proposed technology of preparing PLA from ethyl lactate, especially for easier purification of crude lactide into polymer grade purity.
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Functionalization of Polyethylene by Grafting
Hofmann, Jan ; Figalla, Silvestr (referee) ; Petrůj, Jaroslav (advisor)
The bachelor thesis deals with functionalization of polyethylene by grafting. The theoretical part summarizes informations about types of copolymers, free radical grafting techniques and the factors, that affect properties of modified polymers as well as their biodegradability. The experimental part deals with modification of polyethylene in kneader under various conditions. The blends are composed of polyethylene, polylactic acid and another aditives (initiator, stabilizers). The torque and the temperature were monitored during the kneading. Some mechanical properties of new materials were tested on Zwick Z010 apparatus. Rheological properties of samples were investigated with melt flow indexes.
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