Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Krzysztof Szalewicz, Dept. of Physics and Astronomy. Includes bibliographical references.

Th. doct.-ing.--Toulouse, I.N.P., 1979. N°: 39.

This study has focussed on the application of synthetic, kinetic and exploratory theoretical methods in elucidating the reaction mechanisms of four Morita-Baylis-Hillman (MBH) type reactions, viz, i) the reactions of the disulfide 2,2'-dithiodibenzaldehyde with various activated alkenes in the presence of DBU and Ph₃P, ii) the reactions of chromone-3-carbaldehydes with MVK, iii) the reactions of chromone-2-carbaldehydes with acrylonitrile and iv) with methyl acrylate. Attention has also been given to the origin of the observed regioselectivity in Michaelis-Arbuzov reactions of 3-(halomethyl)coumarins. Cleavage of the sulfur-sulfur bond of aryl and heteroaryl disulfides by the nitrogen nucleophile DBU has been demonstrated, and a dramatic increase in the rate of tandem MBH and disulfide cleavage reactions of 2,2'-dithiodibenzaldehyde with the activated alkenes, MVK, EVK, acrylonitrile, methyl acrylate and tert-butyl acrylate has been achieved through the use of the dual organo-catalyst system, DBU-Ph₃P – an improvement accompanied by an increase in the yields of the isolated products. Detailed NMR-based kinetic studies have been conducted on the DBU-catalysed reactions of 2,2'-dithiodibenzaldehyde with MVK and methyl acrylate, and a theoretical kinetic model has been developed and complementary computational studies using Gaussian 03, at the DFT-B3LYP/6-31G(d) level of theory have provided valuable insights into the mechanism of these complex transformations. Reactions of chromone-3-carbaldehydes with MVK to afford chromone dimers and tricyclic products have been repeated, and a novel, intermediate MBH adduct has been isolated. The mechanisms of the competing pathways have been elucidated by DFT calculations and the development of a detailed theoretical kinetic model has ensued. Unusual transformations in MBH-type reactions of chromone-2-carbaldehydes with acrylonitrile and methyl acrylate have been explored and the structures of the unexpected products have been established using 1- and 2-D NMR, HRMS and X-ray crystallographic techniques. Attention has also been given to the synthesis of 3-(halomethyl)coumarins via the MBH reaction, and their subsequent Michaelis-Arbuzov reactions with triethyl phosphite. An exploratory study of the kinetics of the phosphonation reaction has been undertaken and the regio-selectivity of nucleophilic attack at the 4- and 1'-positions in the 3-chloro- and 3-(iodomethyl)coumarins has been investigated by calculating Mulliken charges, LUMO surfaces and Fukui condensed local softness functions.

Orientadores: Antonio Carlos Luz Lisboa, Aparecido dos Reis Coutinho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-16T04:55:51Z (GMT). No. of bitstreams: 1 Kumakawa_MarcosMassami_M.pdf: 1227960 bytes, checksum: c51bd4943e441f3b0bc7ab68955d8d8f (MD5) Previous issue date: 2010 / Resumo: A preocupação com a segurança e a redução de prejuízos diante de um acidente envolvendo fogo tem gerado a busca por materiais que possam ser utilizados nestas situações. Para locais que envolvem altas temperaturas, existem os materiais que não propagam chama. Os materiais que não propagam chama e que atuam como isolantes térmicos possuem inúmeras aplicações. São utilizados para isolar tanques, motores, caldeiras; são aplicados também no setor aeronáutico, automobilístico, em residências e indústrias. Os materiais mais conhecidos são a lã de rocha, lã de vidro e fibra cerâmica. As fibras de poliacrilonitrila (PAN) são utilizadas industrialmente na produção de tecidos, de materiais isolantes térmicos, como precursores na fabricação de fibras de carbono e outros. Quando submetidas a tratamentos térmicos em atmosfera oxidante (estabilização térmica ou termo-oxidativa) sofrem alterações em sua cadeia polimérica e consequentemente as propriedades físicas e químicas são modificadas tornando as fibras de poliacrilonitrila resistentes ao fogo e atuando como isolante térmico. O presente projeto visa estabelecer as condições de tratamento térmico de fibras PAN, controlando a taxa de aquecimento e a temperatura, com o objetivo de produzir materiais com alto desempenho (elevada resistividade térmica e tempo de degradação) quando exposto a altas temperaturas. As fibras estabilizadas com elevadas taxas de aquecimento apresentaram resultados insatisfatórios. Contudo, ao diminuir a taxa de aquecimento, os tecidos de fibras PAN estabilizados termicamente apresentaram resistividade térmica em torno de 35 m2.K.W-1, valor próximo ao da lã de vidro que é um material muito utilizado como isolante térmico e um tempo de resistência ao contato direto com a chama superior a 20 minutos visto que a matéria prima em contato direto com a chama degrada-se em poucos segundos / Abstract: Concern for safety and reduction of losses before a crash involving fire, has generated a search for materials that can be used on these situations. For problems that involve high temperatures, there are materials that do not propagate flame. Materials that do not propagate flame and which act as insulators have many applications. They are used to isolate tanks, engines, boilers, are also applied in the aviation industry, automobile, in homes and industries. The materials are the most popular rock wool, glass wool and ceramic fiber. The polyacrylonitrile (PAN) are used industrially in the production of fabrics, thermal insulation materials, as precursors for the manufacture of carbon fiber and others. When subjected to heat treatment in oxidizing atmosphere (thermal stabilization or thermal-oxidative) unchanged in its polymer chain, therefore, the physical and chemical properties are also modified by making polyacrylonitrile fire resistant and acts as a thermal insulator. This project aims to establish the conditions for heat treatment of PAN fibers by controlling the heating rate and temperature, with the goal of producing materials with high performance (high resistivity and thermal degradation time) when exposed to high temperatures. Fibers stabilized with high heating rates showed unsatisfactory results. However, by reducing the heating rate, the tissues of PAN fibers showed thermal resistivity around 35 m2.KW-1, similar value of glass wool which is a material widely used as insulation and a time of resistance to direct contact with the flame of more than 20 minutes as the raw material in direct contact with the flame deteriorates in a few seconds / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

The products and mechanisms of some photo-reactions of indenes and naphthalene with acrylonitrile have been studied. Indene reacts with acrylonitrile with the hydrocarbon absorbs light, or when a triplet sensitizer is absorbing. Photolysis under the former condition yields 2-(1-indenyl)- and 2-(3-indenyl)propionitrile, and 6-cyano-2,3-benzobicyclo[3,2,0]hep-2-ene. Base-catalyzed isomerizations of the substituted indenes are reported. On sensitization, cis- and trans-isomers of 7-cyano-2,3-benzobicyclo[3,2,0]hep-2-ene are formed; the known indene dimer is a minor product. Adducts 1,1-dimethyl- and 1,1-diphenylidene with acrylonitrile are also described. Naphthalene adds to acrylonitrile on photolysis to afford trans-8-cyano-2,3-benzobicyclo[4.2.0] octa-2,4-diene and 1- and 2-naphthyl-2-propionitriles. Sensitization gives no detectable products. Studies on fluorescence quenching, solvent effect and deuterium-labelling indicates that exciplexes are formed between acrylonitrile and the excited hydrocarbons. Inter- or intra-molecular protonation of the exciplexes with subsequent reaction of the carbonium ion formed, is suggested to produce indenes or naphthalenes. Possible mechanisms for the formation of other products are proposed. / Thesis / Doctor of Philosophy (PhD)

This thesis is concerned with the development of engineering technologies that facilitate melt spinning of carbon fiber precursors in both an environmentally sound and cost effective manner. More specifically, methods were developed to avoid a degradative process in acrylonitrile copolymers (typically used in textiles and as carbon fiber precursors) that occurs as melt spinning temperatures are approached. The following set of analyses was developed to define the rheological properties required for a melt processable acrylic copolymer suitable for use as a carbon fiber precursor, and accordingly facilitated development of a processing window: measurement of steady shear viscosity as a function of both temperature and time, measurement of the magnitude of the complex viscosity (|η*|) as a function of temperature using a temperature sweep, and measurement of the angular frequency dependence of |η*|. Through a systematic screening process, the following properties were identified to afford melt spinnable acrylic precursors suitable for conversion to carbon fibers: emulsion polymerization, 85-88 mole % acrylonitrile, 11-14 mole % methyl acrylate, 1 mole % acryloyl benzophenone, intrinsic viscosity < 0.6 dL/g, steady shear viscosity ≤ 1000-2000 Pa*s at a shear rate (γ) of 0.1 s⁻¹, viscosity increases ≤ 45% over a period of 1800 seconds at 200-220°C and γ=0.1 s⁻¹. Use of the rheological analyses assisted in development of a melt spinnable carbon fiber precursor, which resulted in carbon fibers possessing a tensile strength and modulus of approximately 1.0 and 120 GPa, respectively. A second approach was evaluated using carbon dioxide (CO₂) to plasticize AN copolymers to an extent that facilitates processing at reduced temperatures, below where thermal degradation is significant. A batch saturation method to absorb CO₂ in AN copolymers was developed. Differential scanning calorimetry and thermogravimetric analyses were used to measure the glass transition temperature (T_g) reduction and amount of absorbed CO₂ (respectively). A pressurized rheometer and measurement procedure was designed to obtain viscosity measurements of saturated AN copolymers. Up to 6.7 wt. % CO₂ was found to absorb into a 65 mole % AN copolymer with the saturation method used, resulting in a 31°C glass transition temperature (T_g) reduction, 60% viscosity reduction, and 30°C potential processing temperature reduction. It was found that CO₂ can absorb into copolymers containing up to 90 mole % AN (with the absorption methods used) with the following results (for a 90/10 mole % AN/MA copolymer): 3.0 wt. % uptake, 27°C T_g reduction, 56% viscosity reduction, and potential processing temperature reduction of 9°C. Via estimates of the required pressure, sealing fluid flow rate, and length of a pressure chamber to prevent foaming of the saturated polymer melt during extrusion, melt spinning of saturated AN copolymers appears feasible. / Ph. D.

Statistical copolymers of acrylonitrile (AN) and methyl acrylate (MA) were successfully prepared and characterized using reversible addition-fragmentation chain transfer (RAFT) copolymerization. A typical copolymer was charged with 15 wt. % MA content. This thesis describes a systematic variation of the RAFT copolymerization variables to optimize this system. In particular, the effects of chain transfer agent, initiator, temperature, and solvent on the copolymer properties were studied. / Master of Science

Treatment of industrial wastewaters contaminated with toxic and hazardous organics can be a costly process. In the case of acrylonitrile production, due to highly volatile and toxic nature of the contaminant organics, production wastewaters are currently disposed by deepwell injection without treatment. Under the terms granting deepwell injection of the waste, alternative treatments must be investigated, and an effective treatment identified. Cells of two Gram-positive bacteria, Rhodococcus sp. DAP 96253 and R. rhodochrous DAP 96622 were evaluated for their potential as biocatalysts for detoxification of acrylonitrile production wastewaters. Rhodococcus sp. DAP 96253 and R. rhodochrous DAP 96622 when multiply induced, are capable of utilizing the hazardous nitrile and amide components present in the wastewater as sole carbon and/or nitrogen sources, employing a 2-step enzymatic system involving nitrile hydratase (NHase) and amidase enzymes. There is a significant potential for overproduction of NHase upon multiple induction. However, high-level multiple induction required the presence of highly toxic nitriles and/or amides in the growth medium. Asparagine and glutamine were identified as potent inducers with overexpression at 40% of total soluble cellular protein as NHase. In native form (either cell free enzymes or whole cells) the desired NHase is very labile. In order to develop a practical catalyst to detoxify acrylonitrile production wastewaters, it is necessary to significantly improve and enhance the stability of NHase. Stabilization of desired NHase activity was achieved over a broad range of thermal and pH conditions using simultaneous immobilization and chemical stabilization. Previously where 100% of NHase activity was lost in 24 hours in the non-stabilized cells, retention of 20% of initial activity was retained over 260 days when maintained at 50-55 C, and for over 570 days for selected catalyst formulations maintained at proposed temperature of the biodetoxification process. In addition, NHase and amidase enzymes from Rhodococcus sp. DAP 96253 were purified. Cell free NHase was characterized for its substrate range and effect of common enzyme inhibitors and was compared to available information for NHase from other organisms. As a result of this research a practical alternative to the deepwell injection of acrylonitrile production wastewaters is closer to reality.

Acrylonitrile (AN) is a major volatile waste generated in the production of acrylamide and often associated with aromatic contaminants (toluene and styrene) in plant effluents. We examined Rhodococcus rhodochrous DAP 96622 to determine if it could be adapted to efficient biodegradation of acrylonitrile (AN) in a bioreactor. A model bioreactor with granular activated carbon (GAC) as a substratum for Rhodococcus with AN as sole carbon or in combination with toluene was established. The kinetics of AN biodegradation by immobilized and planktonic cells were evaluated and compared. Inlet load and empty retention time were varied to test the removal efficiency in fed-batch and single-pass mode reactor. In addition, the three dimensional structure and characteristics of the biofilm were followed using confocal scanning laser microscopy (CSLM) and relative software. Immobilized cells in the bioreactor, at starting concentrations of AN up to 1150 mg l-1 in the presence of Tol, had at least 13 fold higher AN degradation rates than that seen of planktonic cells. A near steady state of AN degradation was maintained at 75-85% for AN and 80%-90% for Tol within the parameter of EBRT=8 min and AN and Tol inlet loads between 50-200 mg l-1 h-1 and 200-500 mg l-1h-1, respectively. However, when the inlet load of AN was increased to more than 200mg l-1 h-1 and 500 mg l-1 h-1 for Tol, a reduction in efficiency of AN degradation was observed. Biofilms with discrete microcolonies interspersed with voids and channels were observed. Precise measurement of biofilm characteristics agreed with the assumption that the biomass and thickness of the biofilm increased along the carbon column depth. With a porous attachment material like GAC, substrate diffusion is most likely not a limiting factor for AN degradation. Rhodococcus rhodochrous DAP 96622 in a non-sterile activated charcoal column showed efficient degradation of AN in the presence of Tol. The Rhodococcus bioreactor may provide a potential practical waste gas and water treatment system.

The polymer materials industry is heavily dependent on the use of petroleum based plastics. This poses a problem, as the world is facing ongoing petroleum supply problems. A need exists for a bio-carbon based polymer material that has the performance and cost of currently used petroleum plastics. However, the overall performance of current bio-based plastics indicate that they must be somehow supplemented to achieve the properties of that of petroleum-based polymers. The low impact strength and thermal stability of poly(lactic acid), PLA are targets for improvement. One option is for development is through blending with acrylonitrile butadiene styrene (ABS). The viability and efficacy of using these two polymers as blending partners is investigated. The PLA used in these studies has unique and interesting crystallization properties. These have been examined and detailed in part 1. The second part of study includes neat polymer properties, miscibility analysis, and large scale process results. This results in an optimized blending ratio on which to go forward with development. The mechanical, thermal, and morphological properties are investigated in these studies. Significance of this research and development is widespread, as the material developed has the potential to reduce the use of petroleum-based carbon in plastics. / The financial support from the 2010 Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA)/University of Guelph -Bioeconomy for Industrial Uses Research Program, Natural Sciences and Engineering Research Council (NSERC) AUTO21 NCE project and Grain Farmers of Ontario (GFO), to carry out this research is gratefully acknowledged.