The free radical addition of saturated polymers and small molecules to unsaturated monomers is used to prepare functional derivatives under solvent-free, reactive extrusion conditions. Of particular interest are the dynamics and yields of conventional peroxide-initiated grafting of vinyltrialkoxysilanes to polyethylene, as well as the mechanisms through which bicumene initiates the process at high temperatures. Knowledge of these commercial processes is applied toward the development of new graft modification technology, including radical initiated polymer addition to alkynes, and a new variation of precipitation polymerization chemistry. The thermolysis of bicumene at temperatures ranging from 220°C to 270°C was used to initiate C-H bond addition from alkanes to vinylsilanes in a high-temperature analogue of conventional grafting practice. The initiation mechanism is shown to involve direct hydrogen atom abstraction by intermediate cumyl radicals, as well as autooxidation processes involving cumyl radicals and available oxygen. Conventional peroxide initiated graft modifications of polyethylene with vinylsilanes are examined from the standpoint of reaction dynamics and yields. The influence of peroxide loading and monomer concentration on these reaction variables can be described using a simple quasi-steady state kinetic analysis, while the unusual insensitivity of reaction yields to temperature requires further investigation. A new chemical modification of saturated polymers involving free radical addition to mono-substituted alkynes is presented and examined in terms of reaction yield, graft structure, and changes to molecular weight. Model compounds are used to characterize alkyne grafting products, and to probe the relationship between reagent properties, reaction yields, and product structures. The discovery of cross-linked particles in the products of polypropylene graft modifications with triallyltrimesate has led to a variation of precipitation polymerization wherein C-H bond addition to an allyl monomer contributes to molecular weight growth, thereby incorporating a significant amount of saturated hydrocarbon into the solid phase. The relationships between reaction conditions and solid-phase composition and morphology are discussed. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2008-12-18 14:35:52.483

Currently, extensive research in using bio‐derived polymers is being done, highlighting the importance of sustainable, green polymeric materials. Some sustainable alternatives to synthetic polymers include lignin, starch, cellulose or blends of these with petroleum‐based polymers. In New Zealand, large quantities of animal derived proteins are available at very low cost, making it ideal as a sustainable alternative to petroleum‐derived polymers. However, the processability of most proteins is very difficult, but can be improved by blending with synthetic polymers, such as polyolefins. To improve, the compatibility between these substances, a functional monomer could be grafted onto the polyolefin chain. Using an appropriate functional group, the polyolefin could then react with certain amino acids residues in the protein. Lysine and cystein are the two most appropriate amino acid residues because of their reactivity and stability at a wide pH range. In this study, free radical grafting of itaconic anhydride (IA) onto polyethylene was investigated. IA was selected because it is capable of reacting with polyethylene and amino acid residues, such as lysine. The objective of the research was to identify and investigate the effect of reaction parameters on grafting. These were: residence time, temperature, initial monomer concentration as well as peroxide concentration and type. Grafting was characterized in terms of the degree of grafting (DOG), percentage reacted and the extent of side reactions. The reaction temperature was taken above the melting point of the polyethylene, monomer and decomposition temperature of the initiator. It was found that above 160 C polymer degradation occurred, evident from sample discolouration. A higher degree of grafting can be achieved by increasing the initial monomer concentration up to a limiting concentration. The highest DOG achieved was about 1.2 mol IA per mol PE, using 2 wt% DCP. When using 2 wt % peroxide, the limiting concentration was found to be 6 wt% IA, above which no improvement in DOG was achieved. It was found that DCP is much more effective at grafting, compared to DTBP because DTBP is more prone to lead to side reactions than DCP. iv It was found that a residence time of 168 seconds resulted in the highest DOG, corresponding to 4 extrusions in series. However, it was also found that an increase in residence time resulted in an increase in polymer degradation. The tensile strength of PE decreased after two extrusions when using DTBP, and three extrusions, when using DCP. Young's modulus decreased only slightly, while all samples showed a dramatic decrease in ductility, even after one extrusion. It was concluded that degradation had a more pronounced effect on mechanical properties than cross‐linking, and residence time should therefore not exceed three extrusions in series, which corresponded to about 126 seconds. It can be concluded that a high reaction temperature and high initiator concentration lead to a low degree of grafting, accompanied by high cross‐linking and increased degradation. On the other hand, high monomer concentration and high residence time lead to a high degree of grafting. Optimising grafting is therefore a trade off between maximal DOG and minimising side reactions such as cross‐linking and degradation and optimal conditions do not necessarily correspond to a maximum DOG. Other factors, such as the use of additives to prevent degradation should also be investigated and may lead to different optimum conditions.

Orientador: André Luiz Barboza Formiga / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T00:53:19Z (GMT). No. of bitstreams: 1 Rollo_PedroMartinsdeAlmeida_M.pdf: 27184092 bytes, checksum: f3fc542db91febabadab91c184ba101d (MD5) Previous issue date: 2012 / Resumo: Este trabalho apresenta o estudo da funcionalizacão do polímero poliacrilonitrila a partir da hidrólise alcalina do material em meio homogêneo e os fatores que controlam essa reação. Uma investigação sistematica foi realizada para compreender o mecanismo reacional e a dependência da concentracão de base e de H2O com a composição final do polímero modificado. Estudos espectroscópicos assistidos por cálculos teóricos permitiram concluir que ambos os fatores possuem influência na reacão e que o produto formado depende do procedimento de modificacão empregado. Aborda-se também como a funcionalizacão das cadeias poliméricas altera as propriedades físico-químicas e mecânicas do material. É evidenciado que há uma mudança na cristalinidade do material, que por sua vez altera propriedades mecânicas do mesmo. O comportamento das cadeias poliméricas em solução também sofre modificações relevantes, sendo evidenciadas por viscosimetria de soluções diluídas. Por último, utiliza-se a poliacrilonitrila hidrolisada na preparação de membranas assimétricas por inversão de fase, com o intuito de comparar as propriedades das membranas de materiais modificados com membranas de material não modificado / Abstract: The work here reported deals with the alkaline hydrolysis of polyacrylonitrile in homogeneous medium and the experimental conditions that influence the reaction. A systematic investigation of the reaction mechanism was conducted, allowing to understand the influence of the concentration of base and H2O on the hydrolyzed product composition. Spectroscopic studies combined with theoretical calculations led to conclude that both factors have a noteworthy influence on the modified product. It is also reported an investigation on how the chemical functionalization alters the physico-chemical and mechanical properties of the material. It is noticed a significant change in the crystallinity of the material, that leads to changes on the mechanical properties for itself. The hydrodynamic properties of the polymer in solution also underwent significant changes with hydrolysis, this being evidenced by a rheological study. Lastly, hydrolyzed polyacrylonitrile was applied to membrane preparation by the method of non-solvent induced phase separation, with the intention to compare membranes of hydrolyzed materials with non-hydrolyzed ones / Mestrado / Quimica Inorganica / Mestre em Química

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Globalization and centralization have resulted in prolonged transportation time between producer and consumer, and thus put more demand on the perseveration of a product for longer duration and protect it from oxidation. The presence of oxygen in packages severely foreshortens the storage life as it yield losses of nutrients and allow microbial growth, which can cause changes in smell, taste as well as discoloration. Earlier food and beverage containers were made in inorganic materials e.g. metal and glass, however lately more and more focus have been on synthetic organic materials as these show several advantages, e.g. weight. However, still today most of the commercial packaging materials, organic or inorganic, are not considered to be environmental friendly. Thus, efforts have to be made today in order to invent alternative materials that can make the society of tomorrow more sustainable. Cellulose is the most abundant biopolymer in the world, hence making it desirable to use in “green” packaging applications. Furthermore, cellulose has proven being able to form films with great gas barrier potential under specific conditions. However, cellulose based materials are sensitive to moisture with severely increased oxygen transmission with increased relative humidity as a result; hence it is desired to make cellulose less hygroscopic by chemical modification. First, nanofibrillated cellulose (NFC) with 720 mmol carboxylic groups/g fiber was produced by oxidation of dissolving pulp before homogenization. Thereafter a polymer was synthesized utilizing Initiator A as an initiator at T1 and T2. The polymer synthesized at T1 yielded a polymer with a viscosity average molecular weight of 5770 g/mol.  The polymer was then grafted on the oxidized NFC through a coupling reaction performed in Buffer C using Coupling agent A. The grafting procedure was performed in Buffer C at ambient conditions giving rise to a material composed of 33 wt% synthetic polymer and 67 wt% NFC. The coupling was conducted several times in order to investigate how the final product can be affected by varying reactant feed and dispersion method. Finally, films of NFC and NFC-g-Polymer were manufactured by vacuum filtration from a 0.05 wt% Solvent A dispersion and were evaluated with field emission scanning electron microscopy.

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The stable free radical polymerization methodology for production of controlled macromolecules was investigated using a novel monomer, 2-vinylnaphthalene. Initial polymerizations resulted in molecular weight distributions typical of conventional free radical polymerization techniques (>2.0). Manipulation of the initiator concentration and the molar ratio of initiator to nitroxide demonstrated no significant control over the resulting polymer products. Analysis of the polymerization kinetics for a 2-vinylnaphthalene polymerization performed in the presence and absence of the free radical initiator revealed identical monomer consumption profiles as well as pseudo first order kinetics indicating a significant degree of the thermal polymerization was occurring at the polymerization temperature (130°C). Comparison of the thermal polymerization propensity of 2-vinylnaphthalene and styrene revealed an increased tendency for 2-vinylnapthahlene to undergo thermal polymerization. Styrene is considered highly active in its propensity to thermally polymerize. However, an Arhenius analysis using in situ FTIR was employed to determine the activation energy for the thermal polymerization of styrene and 2-vinylnaphthalene. The 2-vinylnaphthalene activation energy for thermal polymerization was determined for the first time to be almost 30 kJ/mol less than styrene. A novel modified Mayo mechanism was proposed for the 2-vinylnaphthalene thermal initiation mechanism. Moreover, this thermal initiation was employed to initiate nitroxide mediated polymerizations of styrene. This first use of a 2-vinylnaphthalene initiating system resulted in polystyrene with a large macrocyclic initiating fragment. The presence of the initiating moiety was studied using both UV-Vis spectroscopy and 1H NMR spectroscopy. The extension of stable free radical polymerization to the acrylate monomer family was examined using a novel nitroxide mediator, N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide (DEPN). The synthesis of DEPN was monitored using in situ FTIR spectroscopy to determine optimum reaction conditions. The purified nitroxide was subsequently employed in the synthesis of various block and random acrylate copolymers. The production of a unique amphiphilic block copolymer consisting of acrylic sequences was achieved. Poly(t-butyl acrylate-b-2ethylhexyl acrylate-b-t-butyl acrylate) was synthesized using the SFRP process. The t-butyl functionalities were subsequently removed in a post-polymerization acid catalyzed hydrolysis. The effect of steric bulk and electronic factors on the resulting SFRP process was also investigated and revealed similar polymerization kinetics for various alkyl acrylates. However, addition of a hydroxyl containing monomer, 2-hydroxyethyl acrylate, resulted in an increase in the polymerization rate up to 2 times. The rate enhancement was attributed to hydrogen bonding effects and this was confirmed using the unprecedented addition of dodecanol, which also demonstrated a significant rate enhancement. Block copolymers were also achieved using a novel difunctional nitroxide synthesized from 4-hydroxy TEMPO and 1,6-hexamethylene diisocyanate. The identity of the nitroxide was confirmed using mass spectrometry and 1H NMR. The dinitroxide was used in the polymerization of styrene and subsequently used to produce symmetric ABA triblock copolymers with t-butyl styrene using a unique two-step polymerization route. In addition, the dinitroxide demonstrated an increased tendency for decomposition due to the complex mediation equilibrium. The decomposition was studied using GPC to evaluate the decomposition effects on the polymerization. Results of the research efforts presented herein are written as individual research reports with contributing authors and pertinent literature reviews presented at the beginning of each chapter. / Ph. D.

Taking advantage of ATRP and using functionalized initiators, different functionalities were introduced in both α and ω chain-ends of synthetic polymers. These functionalized polymers could then go through modular synthetic pathways such as click cycloaddition (copper-catalyzed or copper-free) or amidation to couple synthetic polymers to other synthetic polymers, biomolecules or silica monoliths. Using this general strategy and designing these co/polymers so that they are thermoresponsive, yet bioinert and biocompatible with adjustable cloud point values (as it is the case in the present thesis), the whole generated system becomes "smart" and potentially applicable in different branches. The applications which were considered in the present thesis were in polymer post-functionalization (in situ functionalization of micellar aggregates with low and high molecular weight molecules), hydrophilic/hydrophobic tuning, chromatography and bioconjugation (enzyme thermoprecipitation and recovery, improvement of enzyme activity). Different α-functionalized co/polymers containing cholesterol moiety, aldehyde, t-Boc protected amine, TMS-protected alkyne and NHS-activated ester were designed and synthesized in this work. / In dieser Arbeit wurden mittels der ATRP Methode sowie durch Benutzung funktioneller Initiatoren verschiedene Funktionalitäten an der α- und ω-Position der synthetischen Polymere (Kettenenden) eingeführt. Diese funktionalisierten Polymere können durch modulare synthetische Methoden wie z.B. die “Klick-Zykloaddition” (kupferkatalysiert oder auch kupferfreie Methoden möglich), Amidierung mit anderen synthetischen Polymeren oder Biomolekülen, oder auch mit Silikatmonolithen gekuppelt werden. Den beschriebenen Strategien folgend und unter Benutzung von thermoresponsiven, bioinerten und biokompartiblen (Co-) Polymeren mit einstellbaren Trübungspunkten können mittels Temperaturänderungen leicht steuerbare, „smarte“ Polymersysteme für verschiedene Anwendungen hergestellt werden. Im Rahmen dieser Arbeit wurden speziell Anwendungen wie die Postfunktionalisierung (in situ Funktionalisierung mizellarer Aggregate mit Molekülen, die sowohl niedrige als auch höhere Molekulargewichte aufweisen), hydrophiles/hydrophobes Tuning von Polymeren, Chromatographie an Polymeren sowie Biokonjugation von Polymeren (Enzymthermoprezipitation und -Gewinnung, Enzymaktivitätsmodifizierung) genauer untersucht. Es wurden verschiedene α-funktionalisierte (Co-)Polymere, die Cholesterol, Aldehyde, t-Boc geschützte Amine, TMS-geschützte Alkine und NHS-aktivierte Ester entwickelt und hergestellt und mittels passender ATRP Initiatoren eingeführt.

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