Relevant bibliographies by topics / Nitroxide-Mediated Radical Polymerization

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  1. Journal articles
  2. Dissertations / Theses
  3. Book chapters
  4. Conference papers

Academic literature on the topic 'Nitroxide-Mediated Radical Polymerization'

Author: Grafiati
Published: 4 June 2021
Last updated: 2 February 2022

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Journal articles on the topic "Nitroxide-Mediated Radical Polymerization"

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Chen, Mao, Honghong Gong, and Yu Gu. "Controlled/Living Radical Polymerization of Semifluorinated (Meth)acrylates." Synlett 29, no. 12 (April 18, 2018): 1543–51. http://dx.doi.org/10.1055/s-0036-1591974.

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Fluorinated polymers are important materials for applications in many areas. This article summarizes the development of controlled/living radical polymerization (CRP) of semifluorinated (meth)acrylates, and briefly introduces their reaction mechanisms. While the classical CRP such as atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization and nitroxide-mediated radical polymerization (NMP) have promoted the preparation of semifluorinated polymers with tailor-designed architectures, recent development of photo-CRP has led to unprecedented accuracy and monomer scope. We expect that synthetic advances will facilitate the engineering of advanced fluorinated materials with unique properties.1 Introduction2 Atom Transfer Radical Polymerization3 Reversible Addition-Fragmentation Chain Transfer Polymerization4 Nitroxide-Mediated Radical Polymerization5 Photo-CRP Mediated with Metal Complexes6 Metal-free Photo-CRP7 Conclusion
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Wakamatsu, Junpei, Masahiro Kawasaki, Per B. Zetterlund, and Masayoshi Okubo. "Nitroxide-Mediated Radical Polymerization in Microemulsion." Macromolecular Rapid Communications 28, no. 24 (December 14, 2007): 2346–53. http://dx.doi.org/10.1002/marc.200700576.

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Sill, Kevin, and Todd Emrick. "Nitroxide-Mediated Radical Polymerization from CdSe Nanoparticles." Chemistry of Materials 16, no. 7 (April 2004): 1240–43. http://dx.doi.org/10.1021/cm035077b.

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Li, Jieai, Xiulin Zhu, Jian Zhu, and Zhenping Cheng. "Imidazoline Nitroxide‐Mediated Radical Polymerization of Styrene." Journal of Macromolecular Science, Part A 44, no. 1 (January 2007): 41–46. http://dx.doi.org/10.1080/10601320601044401.

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Cano-Valdez, Andrés, Enrique Saldívar-Guerra, Roberto González-Blanco, Michael F. Cunningham, and Jorge Herrera-Ordóñez. "Nitroxide Mediated Radical Emulsion Polymerization: Mathematical Modeling." Macromolecular Symposia 374, no. 1 (August 2017): 1600150. http://dx.doi.org/10.1002/masy.201600150.

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Cunningham, M. F., K. Tortosa, J. W. Ma, K. B. McAuley, B. Keoshkerian, and M. K. Georges. "Nitroxide mediated living radical polymerization in miniemulsion." Macromolecular Symposia 182, no. 1 (June 2002): 273–82. http://dx.doi.org/10.1002/1521-3900(200206)182:1<273::aid-masy273>3.0.co;2-l.

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Ruehl, Jean, Niwat Ningnuek, Thanchanok Thongpaisanwong, and Rebecca Braslau. "Cyclic alkoxyamines for nitroxide-mediated radical polymerization." Journal of Polymer Science Part A: Polymer Chemistry 46, no. 24 (December 15, 2008): 8049–69. http://dx.doi.org/10.1002/pola.23103.

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Fu, Yao, Michael F. Cunningham, and Robin A. Hutchinson. "Modeling of Nitroxide-Mediated Semibatch Radical Polymerization." Macromolecular Reaction Engineering 1, no. 2 (February 7, 2007): 243–52. http://dx.doi.org/10.1002/mren.200600024.

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Georges, Michael K., R. Andrew Kee, Richard P. N. Veregin, Gordon K. Hamer, and Peter M. Kazmaier. "Nitroxide mediated free radical polymerization process - autopolymerization." Journal of Physical Organic Chemistry 8, no. 4 (April 1995): 301–5. http://dx.doi.org/10.1002/poc.610080413.

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Grubbs, Robert B. "Nitroxide-Mediated Radical Polymerization: Limitations and Versatility." Polymer Reviews 51, no. 2 (April 22, 2011): 104–37. http://dx.doi.org/10.1080/15583724.2011.566405.

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Dissertations / Theses on the topic "Nitroxide-Mediated Radical Polymerization"

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Lin, Anna. "Nitroxide-mediated photo-polymerization." Electronic Thesis or Diss., Aix-Marseille, 2019. http://www.theses.fr/2019AIXM0264.

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De nos jours, la photopolymérisation est devenue un procédé important dans le domaine de la science des polymères. Cette méthode présente de nombreux avantages : la rapidité de la réaction, l‘aspect environnemental (formation limitée de composés organiques volatils et possibilité de réaction à température ambiante) ou encore un contrôle spatial et temporel. Ce mode d‘activation photochimique appliqué pendant les dernières décennies aux techniques de polymérisation radicalaire contrôlée telles que l‘ATRP, la RAFT ou la NMP permet de contrôler les propriétés des polymères mais aussi la préparation de polymères à blocs. Parmi ces techniques, la photopolymérisation contrôlée par les nitroxydes (NMP²) nécessite l‘utilisation d‘une alcoxyamine photosensible dont un groupement chromophore est porté par un nitroxyde. Dans ce manuscrit, nous présentons aussi bien la préparation d‘alcoxyamines photosensibles que les études de leurs propriétés photochimiques analysées par spectroscopie d‘absorption et par expériences de résonance paramagnétique électronique. Nous avons évalué les capacités de polymérisation des meilleurs candidats obtenus dans des conditions de NMP². Enfin, une autre méthode a été testée en effectuant une réaction de NMP² à partir d‘alcoxyamines produites par ESCP (Enhanced Spin Capturing Polymerization) ou par NMRC (Nitrone-Mediated Radical Coupling)
Nowadays, photopolymerization has become an important process in the field of polymer science. This method presents several advantages such as the speed of the reaction, the environmental-friendly side (limited formation of released volatile organic compound and possibility of a reaction at room temperature) but also a spatial and temporal control. This photochemical approach applied in the past decades to controlled radical polymerization techniques such as ATRP, RAFT or NMP enable the control of polymer properties but also the preparation of block polymers. Among these techniques, the Nitroxide-Mediated Photopolymerization (NMP²) requires the use of a photosensitive alkoxyamine which has a chromophore group on the nitroxide moiety. In this manuscript, we present both the synthesis of photosensitive alkoxyamines and the studies of their photochemical properties investigated by absorption spectroscopy and by electron spin resonance experiments. We evaluated the polymerization abilities of the best obtained candidates. Finally, another approach has been tested to perform a reaction of NMP² from alkoxyamines made by ESCP (Enhanced Spin Capturing Polymerization) or via NMRC (Nitrone-Mediated Radical Coupling)
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Xie, Min. "Nitroxide-mediated living radical styrene polymerization in miniemulsion." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape3/PQDD_0020/MQ54494.pdf.

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Ruehl, Jean K. "Alkoxyamine initiators for nitroxide mediated radical polymerization : synthesis, characterization, and applications /." Diss., Digital Dissertations Database. Restricted to UC campuses, 2008. http://uclibs.org/PID/11984.

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Hlalele, Lebohang. "Kinetic and mechanistic features of nitroxide mediated (co)polymerization." Thesis, Stellenbosch : University of Stellenbosch, 2011. http://hdl.handle.net/10019.1/6515.

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Skene, William G. "Investigation of nitroxide-mediated thermal and photochemical reactions of living free radical polymerization." Thesis, University of Ottawa (Canada), 2002. http://hdl.handle.net/10393/6351.

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The work presented in this thesis deals primarily with living free radical polymerization (LFRP). Two main specific areas of this process have been studied; thermal and photochemical reaction sequences. Stoichiometric unimolecular initiators were found to be ideal probes for studying the reactions involved in the LFRP process. The bond dissociation energy (BDE) of the labile C-O bond of the alkoxyamine initiators was found to be ca. 28 kcal/mol and is dependent on the resulting carbon centered radical produced upon thermal decomposition. Lower activation energies were measured for more stable carbon centered radicals. Complementary to the thermal studies, photoacoustic studies (PAC) involving photochemical decomposition of the initiators led to the homolytic N-O and C-O bond cleavages in addition to disproportionation product formation. The BDE for the N-O bond of these initiators is ca. 43 kcal/mol. These studies also provided insight into volume effects, where a strict homologous solvent series is not required for extrapolating true enthalpies of reactions and volume correction factors for PAC. The decomposition quantum yields of a series of ketone based actinometers used for PAC BDE studies were re-evaluated and found to be solvent independent. The specific kinetics of thermal LFRP were equally investigated through the use of probes which are normally used for thermal initiation. Fast time resolved techniques of laser flash photolysis (LFP) were used to measure the bi-molecular rate constant for the coupling reaction between a carbon centered radical and a nitroxide radical involved in LFRP. Typical values lay in the area of 108 M-1 s-1 and are influenced by the structure of the carbon centered radical and not that of the nitroxide. The rate constants were observed to be slower with more stable carbon centered radicals, similar to the BDE results where weaker dissociation energies were observed. The formation of minor disproportionation products upon thermal decomposition of the unimolecular initiators was assigned to a concerted four center elimination ultimately responsible for the lack of controlled polymerization with acrylates. The incorporation of steric effects into the monomer or the nitroxide suppressed the formation of these products by increasing the energy barrier necessary for correct orbital alignment required for the elimination reaction. Living polymerization of acrylate monomers was achieved with a nitroxide containing bulky substituents in its 2 and 6 positions. Moderate success of living polymerization was also achieved with acrylate type monomers through the use of an additional phase not miscible with the bulk phase. Chromophores producing triplet states upon excitation were found to undergo fast and efficient energy transfer to a covalently linked alkoxyamine subsequently promoting C-O bond homolysis. The orientation of the C-O bond relative to the chromophore in addition to the distance separating the two influences the efficiency of energy transfer and bond cleavage. Using a benzophenone type chromophore with a covalently linked alkoxyamine initiator promoted photoinduced living type polymerization of acrylate.
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Lessard, Benoît. "Advances in Nitroxide-mediated controlled radical polymerization from Poly(Methacrylate)s to perfectly alternating copolymers." Thesis, McGill University, 2012. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=110396.

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Nitroxide mediated controlled radical polymerization (NMP) has been utilized since the early 1990s, as a simple and robust technique for the synthesis of various new polymeric architectures. Since the development of second generation initiators based on SG1 and TIPNO stable radicals, NMP is no longer restricted to the polymerization of just styrenics as it was initially and can now homopolymerize a plethoraof monomers such as acrylates and acrylamides. In this thesis, several advances in NMP due to these second generation initiators, were explored. The homopolymerization of methacrylates, by NMP, results inexcessive irreversible termination due to the elevated concentration of free radicals generated in the initial stages of the polymerization. However, the use of a small amount of a "controlling" comonomer can be used to control the copolymerization, as characterized by a linear increase in number average molecular weight (Mn), versus conversion (X) and a narrow molecular weight distribution (Mw/Mn < 1.5). The use of styrene ( 10 mol%) as a "controlling" comonomer for ethyl methacrylate, n-butyl methacrylate and tert-butyl methacrylate resulted in a controlled copolymerization of pseudo-"living" random copolymers characterized by a narrow molecular weight distributions (Mw/Mn = 1.2-1.5). In addition to styrene, 9-(4-vinylbenzyl)-9H-carbazole) (VBK) was used as a "controlling" comonomer for methyl methacrylate and 2-(dimethylamino)ethyl methacrylate, requiring as little as 1-2 mol% VBK relative to methacrylate, resulting in a controlled pseudo-"living" polymerization. In the second part of the thesis, NMP was utilized to control the copolymer microstructure. When using a non-equimolar feed of maleic anhydride (MA) and styrene (S), the synthesis of poly(MA-alt-S)-b-poly(S) block copolymers characterized by narrow molecular weight distributions (Mw/Mn = 1.3) where one block consisted of alternating MA and S monomers, was possible when the polymerization temperature was kept below 90 C. Finally a poly(ethylene-co-butylene)-SG12 initiator was synthesized and was used to successfully polymerize S and S/MA mixtures. The final poly(ethylene-co-butylene)-poly(MA-alt-S)2 block copolymers were tested as compatibilizers in blends with nylon-6.
L'utilisation de la polymèrisation radicale contrôlée en présence de radicaux nitroxyde (NMP) a débuté vers les annèes 1990s. Cette technique est simple et robuste, portant facilement à la synthèse de diverses nouvelles architectures de polymères. Grâce au développement d'initiateurs de deuxième génération basés sur radicaux stables de SG1 et de TIPNO, l'NMP n'est plus limité à la polymérisation des styrènes et peut maintenant homopolymériser une varietée de monoméres tels que des acrylates et des acrylamides. Dans cette thèse, plusieurs développements de l'NMP dus à ces initiateurs de deuxième génération, ont été explorés. L'homopolymérisation des methacrylates, par NMP, a pour consèquence un excés de terminaisons irréversibles en raison de à la concentration élevée de radicaux libres produits au début de la polymérisation. Cependant, une petite quantité de comonomère "contrôlant" peut être utilisée pour contrôler la copolymèrisation, donnant comme résultat une augmentation linéaire de la masse molaire moyenne en nombre (Mn) avec la conversion (X) ainsi que des copolymères qui possèdent une distribution moléculaire étroite (Mw/Mn < 1.5). Le styrène ( 10 mol%) a été utilisé comme comonomère "contrôlant" pour la synthèse du méthacrylate éthylique, le méthacrylate n-butylique et le méthacrylate de tert- butyl. Dans tous les cas la copolymèrisation était contrôlée, donnant comme résultat un copolymère qui est "vivant" et qui possède une distribution moléculaire étroite (Mw/Mn = 1.2-1.5). En ajout du styrène, 9-(4-vinylbenzyl)-9H-carbazole) (VBK) a été employé comme comonomère "contr^olant" pour le méthacrylate méthylique et le méthacrylate de 2-diméthylaminoéthyle, mais cette fois exigeant que 1-2 mol% de VBK par rapport aux méthacrylates, ayant comme résultat une copolymèrisationcontr^olée et des copolymères _naux qui sont "vivants". Dans la deuxième partie de la thèse, NMP a été utilisé pour contrôler la microstructure de divers copolymères. En employant une formulation non-équimolaire d'anhydride maléique (MA) et de styrène (s), la synthèse de blocs copolymères poly(MA-alt-S)-b-poly(S) ayant une distribution moléculaire étroite (Mw/Mn = 1.3) a été réalisée lorsque la température de polymérisation était maintenue en dessous de 90C. Finalement l'initiateur poly(éthyléne-co-butyléne)-SG12 a été synthètisé et employé pour la polymèrisation de S et de mélanges de S/MA. Finalement, des copolymères en bloc poly(éthyléne-co-butyléne)-poly(MA-alt-S)2 ont été examinés comme compatibilisateur de mélanges avec le nylon-6.
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Klumperman, Bert. "NMR studies of radical polymerization processes." Thesis, Stellenbosch : Stellenbosch University, 2012. http://hdl.handle.net/10019.1/71596.

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Thesis (DSc)--Stellenbosch University, 2012.
ENGLISH ABSTRACT: Examples of the use of NMR spectroscopy in the study of radical polymerization processes have been described. The studies presented have made a significant contribution to the understanding of the fundamental mechanistic processes in these polymerization systems. It is pointed out that NMR in conventional radical polymerization is of limited use due to the concurrent occurrence of all elementary reactions (initiation, propagation and termination). Conversely, for living radical polymerization, NMR has great value. In that case, the elementary reactions are somewhat more restricted to specific times of the polymerization process. This allows for example the detailed study of the early stages of chain growth in Reversible Addition-­‐Fragmentation Chain Transfer (RAFT) mediated polymerization. Two different studies are described. The first is related to the early stages of RAFT-­‐mediated polymerization. A process for which we coined the name initialization was studied via in situ 1H NMR spectroscopy. It is shown that in many cases, there is a selective reaction that converts the original RAFT agent into its single monomer adduct. A few different examples and their mechanistic interpretation are discussed. It is also shown that NMR spectroscopy can be a valuable tool for the assessment of a RAFT agent in conjunction with a specific monomer and polymerization conditions. In the second study, 15N NMR, 31P NMR and 1H NMR are used for two different types of experiments. The first is a conventional radical copolymerization in which the growing chains are trapped by a 15N labeled nitroxide to yield a stable product. In the second experiment, a similar copolymerization is conducted under nitroxide-­‐mediated conditions. The nitroxide of choice contains phosphorous, which enables the quantification of the terminal monomer in the dormant chains. Each of the experiments individually provides interesting information on conventional radical copolymerization and nitroxide-­‐mediated copolymerization, respectively. Combination of the experimental data reveals an interesting discrepancy in the ratio of terminal monomer units in active chains and dormant chains. Although not unexpected, this result is interesting and useful from a mechanistic as well as a synthetic point of view. In terms of future perspectives, it is expected that the advanced analytical techniques as described here will remain crucial in polymer science. Present developments in radical polymerization, such as investigations into monomer sequence control, rely on accurate knowledge of kinetic and mechanistic details of elementary reactions. It is expected that such detailed studies will be a main challenge for the next decade of polymer research.
AFRIKAANSE OPSOMMING: Voorbeelde van die gebruik van KMR-­‐spektroskopie in die studie van radikaalpolimerisasies word beskryf. Hierdie studies het ʼn beduidende bydrae gelewer tot die verstaan van die fundamentele meganistiese prosesse in hierdie polimerisasiesisteme. Dit het daarop gewys dat KMR beperkte gebruike het in konvensionele radikaalpolimerisasies as gevolg van die gelyktydige voorkoms van alle basiese reaksies (afsetting, voortsetting en beëindiging). Aan die anderkant het KMR groot waarde vir lewende radikaalpolimerisasie. In hierdie geval is die elementêre reaksies ietwat meer beperk tot spesifieke tye van die polimerisasieproses. Gedetailleerde studies kan byvoorbeeld van die vroeë stadiums van die kettinggroei in Omkeerbare Addisie-­‐Fragmentasie-­‐ KettingOordrag (OAFO)-­‐bemiddelde polimerisasie gedoen word. Twee verskillende studies is beskryf. Die eerste het betrekking op die vroeë stadiums van die OAFO-­‐bemiddelde polimerisasie. 'n Proses wat “inisialisering” genoem is, is bestudeer deur middel van in situ 1H KMR-­‐spektroskopie. Dit is bewys dat daar in baie gevalle 'n selektiewe reaksie is wat die oorspronklike OAFO-­‐agent in sy enkelmonomeeradduk verander voor polimerisasie. 'n Paar ander voorbeelde en hul meganistiese interpretasie is bespreek. Dit is ook bewys dat KMR-­‐spektroskopie 'n waardevolle hulpmiddel kan wees vir die assessering van 'n OAFO-­‐agent in samewerking met 'n spesifieke monomeer en polimerisasie toestande. In die tweede studie is 15N KMR, 31P KMR en 1H KMR gebruik vir twee verskillende tipes van die eksperiment. Die eerste is 'n konvensionele radikaalkopolimerisasie waarin die groeiende kettings vasgevang word deur 'n 15N-­‐gemerkte nitroksied om 'n stabiele produk te lewer. In die tweede eksperiment is 'n soortgelyke kopolimerisasie gedoen onder nitroksied-­‐ bemiddelde toestande. Die gekose nitroksied bevat fosfor wat die kwantifisering van die terminale monomeer in die dormante kettings moontlik maak. Elkeen van die individuele eksperimente lewer interessante inligting oor konvensionele radikale kopolimerisasie en nitroksied-­‐bemiddelde kopolimerisasie, onderskeidelik. ʼn Kombinasie van die eksperimentele data toon 'n interessante verskil aan in die verhouding van die terminale monomeereenhede in die aktiewe en sluimerende kettings. Alhoewel dit nie onverwags is nie, is die resultate interessant en van waarde vanuit 'n meganistiese-­‐ sowel as 'n sintetiese oogpunt. In terme van toekomstige perspektiewe word daar verwag dat gevorderde analitiese tegnieke soos hier beskryf, belangrik sal bly in polimeerwetenskap. Huidige ontwikkelinge in radikaalpolimerisasie, soos ondersoeke na die beheer van monomeervolgorde, maak staat op akkurate kennis van kinetiese en meganistiese besonderhede van die basiese reaksies. Daar word verwag dat sulke gedetailleerde studies ʼn uitdaging sal bied vir die volgende dekade van polimeernavorsing.
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Nilsen, Aaron. "The design, synthesis and testing of n-alkoxy amine initiators for nitroxide-mediated 'living' free radical polymerization /." Diss., Digital Dissertations Database. Restricted to UC campuses, 2005. http://uclibs.org/PID/11984.

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Pasquale, Anthony J. "Synthesis and Characterization of Multi-Component Polymeric Materials Prepared via Free Radical Polymerization." Diss., Virginia Tech, 2002. http://hdl.handle.net/10919/27251.

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High molecular weight star-shaped polystyrenes were prepared via the coupling of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) terminated polystyrene oligomers with divinylbenzene (DVB) in m-xylene at 138 °C. Linear polystyrene oligomers (Mn = 19,300 g/mol, Mw/Mn = 1.10) were synthesized in bulk styrene using benzoyl peroxide in the presence of TEMPO at approximately 130 °C. In situ mid-infrared spectroscopy was successfully utilized to follow initiation, monomer conversion, and polymer formation. Real-time data allowed for the determination of apparent rate constants of 2.1E-5 s-1 at 132 °C and 1.2E-5 s-1 at 126 °C from the profile of the decaying styrene vinyl carbon-hydrogen (=CH2) absorbance at 907 cm-1. Coupling of the TEMPO terminated oligomers under optimum conditions resulted in a compact and dense product with a number average molecular weight exceeding 300,000 g/mol (Mw/Mn = 3.03) after 24 h, suggesting the formation of relatively well-defined star-shaped polymers. Synthetic factors that affected the molecular weight, yield, and composition of maleic anhydride (MAH), norbornene (Nb), and tert-butyl 5-norbornene-2-carboxylate (NbTBE) terpolymers were investigated. Pseudo first order kinetic analysis using in situ FTIR indicated that the observed rate of reaction was a strong function of the Nb/NbTBE ratio with a maximum of 6.7E-5 s-1 for a 50/0/50 Nb/NbTBE/MAH monomer ratio and a minimum of 1.1E-5 s-1 for a 0/50/50 Nb/NbTBE/MAH ratio. Polymer yields were also observed to be a function of the Nb/NbTBE ratio and also decreased with increasing NbTBE. Calculated work of adhesion values (Wadh) values were observed to increase as the content of NbTBE was increased. 193 nm photoresist formulations incorporating polymers with high NbTBE content showed increased imaging performance using 193 nm light and successfully produced sharp and defined features as small as 110 nm, which was demonstrated via scanning electron microscopy (SEM). Additional functionality was introduced via the copolymerization of MAH with several norbornene (Nb) derivatives that were synthesized from facile Diels-Alder cycloaddition reactions of cyclopentadiene with a-olefins containing electron withdrawing groups. Subsequent hydrolysis of the anhydride offered further versatility and provided an avenue to introduce aqueous base solubility into Nb/MAH copolymers.
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Hamelinck, Paul Johan. "Functional surface-initiated polymers : device applications and polymerization techniques." Thesis, University of Cambridge, 2008. https://www.repository.cam.ac.uk/handle/1810/270327.

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Self-assembled monolayers and surface-initiated polymer, or polymer brushes, have attracted attention as they form dense layers with much higher structural order than bulk or solution polymers. Another field of research which has emerged over the last two decades is the field of organic and polymer electronics. In this field molecular order and surface modification are of major influence on the device performance, hence that both self-assembled monolayers as polymer brushes have been investigated to find applications in organic electronic devices. After an introduction into the field self-assembled monolayers, polymer brushes and organic electronics, the first part of this thesis focusses on three applications of surface modification techniques for applications in devices. Alignment of the active material is crucial for high mobilities in organic electronics. Chapter 2 discusses the synthesis of a liquid crystalline surface-initiated polymer and its application to induce strong homeotropic alignment. The alignment is homogeneous over large areas and can be patterned by combining the polymerization with soft lithographic techniques. Mobilities of organic electronic materials can also be strongly influenced by dopants in the material. In field-effect transistors the positioning of the dopant is thought to be crucial, as the conductance predominantly takes place in only a small channel near the dielectric interface. In chapter 3 dopant functionalized monolayers and polymer brushes are presented which enable the localized deposition of dopants in the channel of organic transistors. It is shown that the mobility of charges and hence the device performance is affected by the introduction of this dopant layer. Polymer brushes have been suggested for the fabrication of highly ordered semiconducting polymers. In chapter 4 the use of a thiophene functionalized polymer brush is shown, that can be used as a template for the subsequent growth of highly conjugated surface grafted polythiophene layers. Thick polythiophene layers are obtained, that are low in roughness and show photoluminescence and polychromism upon doping. The second part (chapter 5 and 6) of this thesis presents new techniques for surface polymerizations. It is attractive to investigate reduction of reactor volume for polymer brush growth. Chapter 5 discusses a method to achieve volume reduction by back-filling the superfluous volume with beads. It is found that this influences the polymerization kinetics significantly. The combined advantages of less volume and enhanced reaction speeds enable reduction of the total amount of monomer needed by up to 90%. Chapter 6 presents a controlled way to convert initiators for atom transfer radical polymerization into initiators for nitroxide mediated polymerization. In this way mixed polymer brushes and block co-polymer brushes become accessible. This combination makes it an attractive tool to fabricate complex polymer architectures. The technologies used in this thesis show that the synthesis of polymer brushes enable the fabrication of complex architectures without the wastes normally associated with surface-initiated polymers. Combined with several functionalized polymer brushes with properties that enhance order, influence mobility or serve as template for the growth of surface attached conjugated polymers this shows the high potential for the application of surface-initiated polymers in organic electronics.
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Book chapters on the topic "Nitroxide-Mediated Radical Polymerization"

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Nicolas, Julien, and Yohann Guillaneuf. "Living Radical Polymerization: Nitroxide-Mediated Polymerization." In Encyclopedia of Polymeric Nanomaterials, 1133–48. Berlin, Heidelberg: Springer Berlin Heidelberg, 2015. http://dx.doi.org/10.1007/978-3-642-29648-2_191.

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Nicolas, Julien, and Yohann Guillaneuf. "Living Radical Polymerization: Nitroxide-Mediated Polymerization." In Encyclopedia of Polymeric Nanomaterials, 1–16. Berlin, Heidelberg: Springer Berlin Heidelberg, 2014. http://dx.doi.org/10.1007/978-3-642-36199-9_191-1.

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Phan, Trang N. T., Jacques Jestin, and Didier Gigmes. "Nitroxide-Mediated Polymerization from Surfaces." In Controlled Radical Polymerization at and from Solid Surfaces, 1–27. Cham: Springer International Publishing, 2015. http://dx.doi.org/10.1007/12_2015_317.

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Zhu, Yucheng, I. Q. Li, B. A. Howell, and D. B. Priddy. "Nitroxide-Mediated Radical Polymerization: End-Group Analysis." In ACS Symposium Series, 214–24. Washington, DC: American Chemical Society, 1998. http://dx.doi.org/10.1021/bk-1998-0685.ch013.

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Cunningham, Michael, Marcus Lin, Jodi-Anne Smith, John Ma, Kim McAuley, Barkev Keoshkerian, and Michael Georges. "Nitroxide-mediated living radical polymerization in dispersed systems." In Aqueous Polymer Dispersions, 88–93. Berlin, Heidelberg: Springer Berlin Heidelberg, 2004. http://dx.doi.org/10.1007/b12144.

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Cunningham, Michael, Marcus Lin, Jodi-Anne Smith, John Ma, Kim McAuley, Barkev Keoshkerian, and Michael Georges. "Nitroxide-mediated living radical polymerization in dispersed systems." In Aqueous Polymer Dispersions, 88–93. Berlin, Heidelberg: Springer Berlin Heidelberg, 2004. http://dx.doi.org/10.1007/978-3-540-36474-0_18.

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Bon, Stefan A. F., Frank A. C. Bergman, J. J. G. Steven van Es, Bert Klumperman, and Anton L. German. "Nitroxide-Mediated Controlled Radical Polymerization: Toward Control of Molar Mass." In ACS Symposium Series, 236–55. Washington, DC: American Chemical Society, 1998. http://dx.doi.org/10.1021/bk-1998-0685.ch015.

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Robin, Sophie, and Yves Gnanou. "Synthesis of Polystyrene—Polyacrylate Block Copolymers by Nitroxide-Mediated Radical Polymerization." In ACS Symposium Series, 334–46. Washington, DC: American Chemical Society, 2000. http://dx.doi.org/10.1021/bk-2000-0768.ch023.

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Lansalot, M., C. Farcet, B. Charleux, J. P. Vairon, R. Pirri, and P. Tordo. "Nitroxide-Mediated Controlled Free-Radical Emulsion and Miniemulsion Polymerizations of Styrene." In ACS Symposium Series, 138–51. Washington, DC: American Chemical Society, 2000. http://dx.doi.org/10.1021/bk-2000-0768.ch010.

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Fischer, Hanns. "Criteria for Livingness and Control in Nitroxide-Mediated and Related Radical Polymerizations." In ACS Symposium Series, 10–23. Washington, DC: American Chemical Society, 2003. http://dx.doi.org/10.1021/bk-2003-0854.ch002.

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Conference papers on the topic "Nitroxide-Mediated Radical Polymerization"

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Kollár, Jozef, Štefan Chmela, Ľudmila Hrčková, and Pavol Hrdlovič. "Fluorescent dye-labelled polymer synthesis by nitroxide mediated radical polymerization." In 6TH INTERNATIONAL CONFERENCE ON TIMES OF POLYMERS (TOP) AND COMPOSITES. AIP, 2012. http://dx.doi.org/10.1063/1.4738438.

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