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SYNTHESIS AND CHARACTERIZATION OF NEW TETRAALKYLBORATE INITIATORS FOR NOVEL POLYMERIZATION APPLICATIONSNikolaeva, Ekaterina S. 29 June 2006 (has links)
No description available.
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Living Polymerization for the Introduction of Tailored Hydrogen BondingElkins, Casey Lynn 15 August 2005 (has links)
In an effort to synthesize macromolecules comprising both covalent and non-covalent bonding to tune ultimate physical properties, a variety of methodologies and functionalization strategies were employed. First, protected functional initiation, namely 3-[(N-benzyl-N-methyl)amino]-1-propyllithium and 3-(t-butyldimethylsilyloxy)-1-propyllithium, in living anionic polymerization of isoprene was used to yield well-defined chain end functional macromolecules. Using both initiating systems, polymers with good molar mass control and narrow molar mass distributions were obtained and well-defined chain end functionality was observed. There was no observed effect on the polymer microstructure from the polar functionality in the initiator, with ~92% 1,4- and 8% 3,4-enchainment observed in each case. Further investigation of the 3-[(N-benzyl-N-methyl)amino]-1-propyllithium initiated polyisoprenes proved that facile deprotection was not possible and residual catalyst was not removable from the polymer. However, polymers initiated with 3-(t-butyldimethylsilyloxy)-1-propyllithium were quantitatively hydrogenated and deprotected under relatively mild conditions to yield hydroxyl functional macromolecules in several architectures, including linear and star-shaped. Excellent conversion from arm polymer to star polymer was observed and well-defined macromolecules were obtained. Subsequently, a series of non-functional, hydroxyl functional, and 2-ureido-4[1H]-pyrimidone (UPy) chain end functional linear and star-shaped poly(ethylene-co-propylene)s were synthesized and characterized. The melt phase properties were investigated using melt rheology and the effect of macromolecular topology and multiple hydrogen bond functionality was investigated. Linear UPy functional poly(ethylene-co-propylene)s exhibited increased viscosity and shear thinning onset at lower frequencies than non-functional polymers of similar molar mass due to interaction of the multiple hydrogen bonding groups. Star-shaped UPy functional poly(ethylene-co-propylene)s showed inhibition to terminal flow and the absence of a zero shear viscosity in melt rheological characterization, indicative of a network like structure imparted from the multiple hydrogen bonding interactions.
In addition, the living anionic polymerization of D3 was controlled using the functionalized initiators3-[(N-benzyl-N-methyl)amino]-1-propyllithium and 3-(t-butyldimethylsilyloxy)-1-propyllithium. Good molar mass control and narrow molar mass distributions were observed. In contrast to the polyisoprene homopolymers, facile deprotection of the 3-(t-butyldimethylsilyloxy)-1-propyllithium was not possible due to the acid sensitivity of the poly(dimethylsiloxane) backbone. However, facile deprotection of the protected secondary amine was achieved through hydrogenolysis and well-defined terminal amine functionalized poly(dimethylsiloxane) was synthesized, which are then amenable to further functionalization reactions.
In contrast to the well-defined polymers synthesized using living anionic polymerization, free radical polymerizations was used to synthesize free radical copolymers with broader polydispersities and pendant UPy groups. These copolymers were compared with a simple dimeric hydrogen bonding carboxylic acid containing copolymer. Melt rheological characterization revealed that, at similar concentrations, the effect of the UPy group was much greater than the carboxylic acid, and broadened plateau moduli and increased viscosity for the UPy containing polymers were observed, while the acid containing polymer exhibited similar results to a non-functional control. The dynamic viscosity was observed to increase systematically with increasing UPyMA incorporation and the quadruple hydrogen bonding interactions were observed to dissociate between ~80-150 °C. / Ph. D.
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Imidazole-Containing Polymerized Ionic Liquids for Emerging Applications: From Gene Delivery to Thermoplastic ElastomersAllen, Michael H. Jr. 07 January 2013 (has links)
Novel imidazole-containing polyelectrolytes based on poly(1-vinylimidazole) (poly(1VIM)) were functionalized with various hydroxyalkyl-substituents to investigate the influence of charge density and hydrogen bonding on nonviral DNA delivery. Copolymers with higher charge densities exhibited increased cytotoxicity, whereas increased hydroxyl concentrations remained nontoxic. DNA binding affinity increased with increased charge densities and increased hydroxyl content. Dynamic light scattering determined the copolymers which delivered DNA most effectively maintained an intermediate binding affinity between copolymer and DNA. Copolymers containing higher charge densities or hydroxyl concentrations bound DNA too tightly, preventing its release inside the cell. Copolymers with lower charge densities failed to protect the DNA from enzymatic degradation. Tuning hydrogen bonding concentration allowed for a less toxic and more effective alternative to conventional, highly charged polymers for the development of nonviral DNA delivery vehicles. The synthesis of amine-containing imidazolium copolymers functionalized with low concentrations of folic acid enabled the investigation of additional polymer modifications on nonviral gene delivery.
Functionalization of 1VIM with various hydroxyalkyl and alkyl groups and subsequent conventional free radical polymerization afforded a series of imidazolium-containing polyelectrolytes. Hydroxyl-containing homopolymers exhibited higher thermal stabilities and lower T<sub>g</sub>'s compared to the respective alkyl-analog. X-ray scattering demonstrated the polarity of the hydroxyl group facilitated solvation of the electrostatic interactions disrupting the nanophase-separated morphology observed in the alkylated systems. Impedance spectroscopy determined hydroxyl-containing imidazolium homopolymers displayed higher ionic conductivities compared to the alkyl-containing analogs which was attributed to increased solvation of electrostatic interactions in the hydroxyl analogs.
Beyond functionalizing 1VIM monomers and homopolymers to tailor various properties, the synthesis of novel architectures in a controlled fashion remains difficult due to the radically unstable N-vinyl propagating radical. The regioisomer 4-vinylimidazole (4VIM) contains two resonance structures affording increased radical stability of the propagating radical. Nitroxide-mediated polymerization (NMP) and atom transfer radical polymerization (ATRP) failed to control 4VIM homopolymerizations; however, reversible addition-fragmentation chain transfer (RAFT) demonstrated unprecedented control. Linear pseudo-first order kinetics were observed and successful chain extension with additional 4VIM suggested preservation of the trithiocarbonate functionality.
Effectively controlling the polymerization of 4VIM enabled the design of amphoteric block copolymers for emerging applications. The design of ABA triblock copolymers with 4VIM as a high T<sub>g</sub> supporting outer block and di(ethylene glycol) methyl ether methacrylate (DEGMEMA) as a low T<sub>g</sub>, inner block, required the development of a new difunctional RAFT chain transfer agent (CTA). The difunctional CTA successfully mediated the synthesis of the ABA triblock copolymer, poly(4VIM-b-DEGMEMA-b-4VIM), which exhibited microphase separated morphologies. The amphoteric nature of the imidazole ring required substantially lower concentrations of outer block incorporation compared to traditional triblock copolymers to achieve similar mechanical properties and microphase separated morphologies. / Ph. D.
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Cooperative Electrostatic Polymer-Antibiotic NanoplexesVadala, Timothy Patrick 24 June 2010 (has links)
Many pathogenic bacteria can enter phagocytic cells and replicate in them, and these intracellular bacteria are difficult to treat because the recommended antibiotics do not transport into the cells efficiently. Examples include food-borne bacteria such as Salmonella and Listeria as well as more toxic bacteria such as Brucella and the Mycobacteria that lead to tuberculosis. Current treatments utilize aminoglycoside antibiotics that are polar and positively charged and such drugs do not enter the cells in sufficient concentrations to eradicate the intracellular infections. We have developed core-shell polymeric drug delivery vehicles containing gentamicin to potentially overcome this challenge. Pentablock and diblock copolymers comprised of amphiphilic nonionic polyether blocks and anionic poly(sodium acrylate) blocks have been complexed with the cationic aminoglycoside gentamicin. The electrostatic interaction between the anionic polyacrylates and the cationic aminoglycosides form the cores of the nanoplexes, while the amphiphilic nature of the polyethers stabilize their dispersion in physiological media. The amphiphilic nature of the polyethers in the outer shell aid in interaction of the nanoplexes with extra- and intra-cellular components and help to protect the electrostatic core from any physiological media. This thesis investigates the electrostatic cooperativity between the anionic polyacrylates and cationic aminoglycosides and evaluated the release rates of gentamicin as a function of pH. / Master of Science
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Advanced Control of Polymer Structure Based on Multiple Control in Radical Polymerization / ラジカル重合の多元制御に基づく高度な高分子構造制御法の開発Imamura, Yuji 23 May 2023 (has links)
京都大学 / 新制・課程博士 / 博士(工学) / 甲第24813号 / 工博第5156号 / 新制||工||1985(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 山子 茂, 教授 辻井 敬亘, 教授 大内 誠 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM
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Supramolecular architectures: macrocycles, catenanes and polyrotaxanesLee, Sang-Hun 23 August 2007 (has links)
Polyrotaxanes are molecular composites consisting of three components: linear polymers, bulky stoppers at the ends of polymer chains and macrocycles threaded by the polymers.
A series of tetraarylmethyl derivatives as blocking groups were synthesized. Using tris(p-ten-butylphenyl)( 4-hydroxyphenyl)methane a new blocking groupfmitiator (BO(mit) was synthesized. The BG(mit's ability of blockingfmitiation in free radical polymerizations was established by polymerization of styrene.
As cyclic components, aliphatic crown ethers (30-crown-lO, "42-crown-14" and "6O-crown-20") were synthesized by multi-piece combination methods. The purification of the crown ethers was achieved by treatment with poly(methacryloyl chloride), column chromatography and recrystallization; by NMR in DMSO-<i>d₆</i> the purity of the products was demonstrated. The 42-crown-based [2]catenane was isolated while synthesizing "42- crown-14" and characterized in terms of its physically interlocked structure. Two new hydrocarbon-based macrocycles were prepared by two-piece combination method. / Ph. D.
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Polymerization And Characterization Of Poly(ethyl Methacrylate)Bakioglu, Levent 01 January 2004 (has links) (PDF)
In this study, ethyl methacrylate was polymerized by free radical polymerization at 600C, 700C, 800C at open atmosphere / atom transfer radical polymerization, (ATRP), at 800C in vacuum and in gamma irradiation in vacuum. The polymer obtained was white, hard material. The kinetic curves for free radical polymerization and ATRP by gamma radiation were S-type. However, the curve for polymerization by gamma irradiation raises more smoothly. For ATRP by thermal initiation gives a lineer change of conversion with time. It was observed that the molecular weight can be controlled and low molecular weight polymer could be obtained by ATRP method. The characterization of polymers were made by FTIR, DSC, 1H and 13C NMR techniques.
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Metal-Catalyzed Radical Polymerization up to High PressureSchröder, Hendrik 02 September 2015 (has links)
No description available.
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Design and Utilization of New Organotellurium Chain Transfer Agents for Advanced Polymer Synthesis / 先進高分子合成のための新規有機テルル連鎖移動剤の設計と利用Fan, Weijia 23 May 2019 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21963号 / 工博第4618号 / 新制||工||1720(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 山子 茂, 教授 辻井 敬亘, 教授 大内 誠 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM
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NMR studies on the mechanism of iodine mediated polymerisationWright, Trevor 12 1900 (has links)
Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: In reverse iodine transfer polymerisation (RITP), chain transfer agents (CTAs) are
generated in situ from the reaction between 2,2’-azobis(isobutyronitrile) (AIBN) and
molecular iodine. This stage of RITP is the inhibition period, which ends when all
iodine has been consumed. The evolution of CTAs was studied for the
polymerisation reactions of n-butyl acrylate and styrene respectively. RITP of n-butyl
acrylate was performed at 70 °C. In situ 1H nuclear magnetic resonance (NMR)
experiments were carried out to study the evolution of CTAs during the inhibition
period of n-butyl acrylate polymerisation and the structures A-I and A-Mn-I (where A
represents the moiety originating from AIBN, M represents the monomer unit and n is
the mean number degree of polymerisation) were observed. A polymer with the
general structure A-Mm-I is formed. The molecular weight of poly(n-butyl acrylate)
(PnBA) was evaluated with size exclusion chromatography (SEC) and NMR.
Structural analysis of PnBA was done using NMR spectroscopy and matrix-assisted
laser desorption/ionisation time-of-flight (MALDI-ToF) mass spectrometry. Similar
conditions to those used for n-butyl acrylate polymerisation were used for RITP of
styrene. The evolution of CTAs during the inhibition period of styrene polymerisation
was studied using in situ 1H NMR. The inhibition period of styrene polymerised by
RITP was much shorter than expected. This is due the consumption of iodine in the
reaction between styrene and iodine which reversibly forms 1,2-diiodo-ethyl benzene.
The CTAs A-I and A-Mn-I are formed, as well as 1-phenylethyl iodide (1-PEI). The
molecular weight of polystyrene (PS) was determined using SEC and NMR and the
functionality was evaluated using 1H NMR. The structure of PS was confirmed with
1H NMR and MALDI-ToF mass spectrometry. By increasing the temperature of the
reaction, the inhibition period can be shortened. Both polymerisation systems retain
control over molecular weight with an increase in temperature, however, n-butyl
acrylate is limited due to the possible formation of mid-chain radicals. The formation
of an A–Mm–A population (direct combination of the initiator and styrene) in RITP of
styrene results in more initiator being consumed than for n-butyl acrylate, despite
limited conversion of styrene to polymer. / AFRIKAANSE OPSOMMING: In omgekeerde-jodium-oordrag polimerisasie, is die kettingoordragagente
gegenereer in situ van die reaksie tussen 2,2’-azobis(isobutironitriel) (AIBN) en
molekulêre jodium. Hierdie fase van RITP is die inhibisie tydperk wat eindig wanneer
alle jodium verbruik is. Die evolusie van kettingoordragagente is vir die
polimerisasiereaksies van butielakrilaat en stireen onderskeidelik bestudeer.
Omgekeerde-jodium-oordrag polimerisasie van butielakrilaat was uitgevoer by 70 °C.
In situ 1H kernmagnetieseresonans (KMR) eksperimente is uitgevoer om die evolusie
van die kettingoordragagente te bestudeer tydens die inhibisie van butielakrilaat
polymerisasie en die strukture A-I en A-Mn-I (waar A die gedeelte voorstel wat
afkomstig is van AIBN, M die monomeer-eenheid en n die gemiddelde aantal
polymerisasiegraad verteenwoordig) is ge-identifiseer. 'n Polimeer met die algemene
struktuur A-Mm-I is gevorm. Die molekulêre gewig van poli(butielakrilaat) (PnBA) was
geëvalueer deur grootte-uitsluitings chromatografie en KMR spektroskopie.
Strukturele ontleding van PnBA is gedoen deur die KMR spektroskopie en matriks
ge-assisteerde laser desorpsie/ionisasie tyd-van-vlug massaspektroskopie.
Soortgelyke kondisies as dié wat gebruik word vir butielakrilaat polymerisasie, is
gebruik vir omgekeerde-jodium-oordrag polimerisasie van stireen. Die evolusie van
die ketting oordrag agente gedurende die inhibisie periode van stireen polymerisasie
is deur in situ 1H KMR bestudeer en die inhibisie periode is baie korter as verwag. Dit
is as gevolg van die opname van jodium in die reaksie tussen stireen en jodium wat
omkeerbare stireen-di-jodied tot gevolg hê. Die ketting oordrag agente A-I en A-Mn-I
is gevorm, sowel as 1-feniel-etiel jodied. Die molekulêre massa van polistireen (PS)
is bepaal met behulp van grootte-uitsluitings chromatografie en KMR spektroskopie
en die funksioneering is geëvalueer met behulp van 1H KMR. Die struktuur van PS is
bevestig deur 1H KMR en matriks ge-assisteerde laser desorpsie/ionisasie tyd-vanvlug
massaspektroskopie. Deur die verhoging van die temperatuur van die reaksie,
kan die inhibisie periode verkort word. Beide polimerisasie sisteme behou beheer oor
die molekulêre massa met 'n toename in temperatuur, alhoewel butielakrilaat beperk
word as gevolg van die moontlike vorming van middel kettingradikale. Die vorming
van die A-Mm-A spesie (direkte kombinering van AIBN en stireen) in omgekeerdejodium-
oordrag polimerisasie van stireen veroorsaak dat meer AIBN verbruik word as
butielakrilaat, ten spyte van die beperkte omskakeling van stireen tot polimeer.
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