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Author: Margaret Gerthoffer Publisher: ISBN: Category : Languages : en Pages : 0
Book Description
Strategies to synthesize sequence-defined polymers remain limited for industrial-scale applications, often due to time consuming iterative addition or polymerization methods possessing low functional group tolerances. Throughout my PhD, I have utilized both ring-opening metathesis polymerization (ROMP) and pressure-induced polymerization to form sequence-defined polymers from deliberately designed A-B monomers. ROMP of electronically-biased paracyclophanedienes (pCpd) can form donor-acceptor poly(arylenevinylene)s. In addition, the pressure-induced polymerization of engineered aryl/perfluoroaryl (Ar/ArF) co-crystals translates into sequence-specific sp3-saturated copolymers known as nanothreads. Both polymerization methods form sequence-specific copolymers as dictated by the supramolecular monomer design. The ROMP of ring-strained pCpds containing dialkyloxybenzene donor and benzothiadiazole acceptor obtains well-defined polymers with ruthenium-based initiators. This design promotes favors sequence specificity between the electronically-activated dialkyloxybenzene and electronically-deficient benzothiadiazole that can guide the initiator homogenously during ring opening and polymerization events. During my PhD, I have discovered that the presence of sterically asymmetric alkyloxy groups (methoxy and octyloxy) on the donor further guides the polymerization process. I have elucidated that the steric effects of the alkyloxy donor group can further control the rate of well-defined donor-acceptor copolymer synthesis due to supramolecular interactions with ruthenium-based initiators. To expand on this, I targeted the synthesis of various alkyloxybenzene donor groups in both linear and branched substitutions to compare ROMP rate and polymer sequence definition with benzothiadiazole acceptors. The investigated pCpds formed well-defined polymers that did not prohibit ruthenium-catalyst attachment as confirmed by GPC and NMR spectroscopy. I have moreover been able to synthesize ladderane-like polymers known as nanothreads by the pressure-induced polymerization (23+ GPa) of alternating eclipsed stacks of aromatic cores in solid-state Ar/ArF co-crystals. I have designed monomer pairs through preorganization of Ar/ArF synthons with varied quadrupole, hydrogen, and halogen bonding to understand the design elements necessary to form substituted nanothreads at reduced pressure thresholds. For all co-crystals, supramolecular engineering has reduced polymerization pressures compared to individual components as confirmed through in situ Raman, NMR, and XRD spectroscopies under pressure. Phenol:pentafluorophenol illustrates strong hydrogen bonding that stabilizes interstack interactions under pressure to form nanothreads. However, I discovered that hydrogen bonding amongst external functionalities can prohibit facile compressibility if the direction aligns to the putative Ar/ArF thread axis. Direct intrastack hydrogen bonding can in fact increase the required pressure of polymerization (30 GPa+). Designing appropriate hydrogen bonding scaffolds in Ar/ArF co-crystals thus offers the ability to target sequence-controlled nanothread production at a reduced pressure.
Author: Margaret Gerthoffer Publisher: ISBN: Category : Languages : en Pages : 0
Book Description
Strategies to synthesize sequence-defined polymers remain limited for industrial-scale applications, often due to time consuming iterative addition or polymerization methods possessing low functional group tolerances. Throughout my PhD, I have utilized both ring-opening metathesis polymerization (ROMP) and pressure-induced polymerization to form sequence-defined polymers from deliberately designed A-B monomers. ROMP of electronically-biased paracyclophanedienes (pCpd) can form donor-acceptor poly(arylenevinylene)s. In addition, the pressure-induced polymerization of engineered aryl/perfluoroaryl (Ar/ArF) co-crystals translates into sequence-specific sp3-saturated copolymers known as nanothreads. Both polymerization methods form sequence-specific copolymers as dictated by the supramolecular monomer design. The ROMP of ring-strained pCpds containing dialkyloxybenzene donor and benzothiadiazole acceptor obtains well-defined polymers with ruthenium-based initiators. This design promotes favors sequence specificity between the electronically-activated dialkyloxybenzene and electronically-deficient benzothiadiazole that can guide the initiator homogenously during ring opening and polymerization events. During my PhD, I have discovered that the presence of sterically asymmetric alkyloxy groups (methoxy and octyloxy) on the donor further guides the polymerization process. I have elucidated that the steric effects of the alkyloxy donor group can further control the rate of well-defined donor-acceptor copolymer synthesis due to supramolecular interactions with ruthenium-based initiators. To expand on this, I targeted the synthesis of various alkyloxybenzene donor groups in both linear and branched substitutions to compare ROMP rate and polymer sequence definition with benzothiadiazole acceptors. The investigated pCpds formed well-defined polymers that did not prohibit ruthenium-catalyst attachment as confirmed by GPC and NMR spectroscopy. I have moreover been able to synthesize ladderane-like polymers known as nanothreads by the pressure-induced polymerization (23+ GPa) of alternating eclipsed stacks of aromatic cores in solid-state Ar/ArF co-crystals. I have designed monomer pairs through preorganization of Ar/ArF synthons with varied quadrupole, hydrogen, and halogen bonding to understand the design elements necessary to form substituted nanothreads at reduced pressure thresholds. For all co-crystals, supramolecular engineering has reduced polymerization pressures compared to individual components as confirmed through in situ Raman, NMR, and XRD spectroscopies under pressure. Phenol:pentafluorophenol illustrates strong hydrogen bonding that stabilizes interstack interactions under pressure to form nanothreads. However, I discovered that hydrogen bonding amongst external functionalities can prohibit facile compressibility if the direction aligns to the putative Ar/ArF thread axis. Direct intrastack hydrogen bonding can in fact increase the required pressure of polymerization (30 GPa+). Designing appropriate hydrogen bonding scaffolds in Ar/ArF co-crystals thus offers the ability to target sequence-controlled nanothread production at a reduced pressure.
Author: Jean-François Lutz Publisher: John Wiley & Sons ISBN: 3527806105 Category : Technology & Engineering Languages : en Pages : 817
Book Description
Edited by a leading authority in the field, the first book on this important and emerging topic provides an overview of the latest trends in sequence-controlled polymers. Following a brief introduction, the book goes on to discuss various synthetic approaches to sequence-controlled polymers, including template polymerization, genetic engineering and solid-phase chemistry. Moreover, monomer sequence regulation in classical polymerization techniques such as step-growth polymerization, living ionic polymerizations and controlled radical polymerizations are explained, before concluding with a look at the future for sequence-controlled polymers. With its unique coverage of this interdisciplinary field, the text will prove invaluable to polymer and environmental chemists, as well as biochemists and bioengineers.
Author: Dieter A. Schlüter Publisher: John Wiley & Sons ISBN: 3527327576 Category : Science Languages : en Pages : 1229
Book Description
Polymers are huge macromolecules composed of repeating structural units. While polymer in popular usage suggests plastic, the term actually refers to a large class of natural and synthetic materials. Due to the extraordinary range of properties accessible, polymers have come to play an essential and ubiquitous role in everyday life - from plastics and elastomers on the one hand to natural biopolymers such as DNA and proteins on the other hand. The study of polymer science begins with understanding the methods in which these materials are synthesized. Polymer synthesis is a complex procedure and can take place in a variety of ways. This book brings together the "Who is who" of polymer science to give the readers an overview of the large field of polymer synthesis. It is a one-stop reference and a must-have for all Chemists, Polymer Chemists, Chemists in Industry, and Materials Scientists.
Author: Richard G Jones Publisher: Royal Society of Chemistry ISBN: 1847559425 Category : Science Languages : en Pages : 465
Book Description
The IUPAC system of polymer nomenclature has aided the generation of unambiguous names that re ect the historical development of chemistry. However, the explosion in the circulation of information and the globalization of human activities mean that it is now necessary to have a common language for use in legal situations, patents, export-import regulations, and environmental health and safety information. Rather than recommending a ‘unique name’ for each structure, rules have been developed for assigning ‘preferred IUPAC names’, while continuing to allow alternatives in order to preserve the diversity and adaptability of nomenclature. Compendium of Polymer Terminology and Nomenclature is the only publication to collect the most important work on this subject into a single volume. It serves as a handy compendium for scientists and removes the need for time consuming literature searches. One of a series issued by the International Union of Pure and Applied Chemistry (IUPAC), it covers the terminology used in many and varied aspects of polymer science as well as the nomenclature of several di erent types of polymer including regular and irregular single-strand organic polymers, copolymers and regular double-strand (ladder and spiro) organic polymers.
Author: Wei-Fang Su Publisher: Springer Science & Business Media ISBN: 3642387306 Category : Technology & Engineering Languages : en Pages : 314
Book Description
How can a scientist or engineer synthesize and utilize polymers to solve our daily problems? This introductory text, aimed at the advanced undergraduate or graduate student, provides future scientists and engineers with the fundamental knowledge of polymer design and synthesis to achieve specific properties required in everyday applications. In the first five chapters, this book discusses the properties and characterization of polymers, since designing a polymer initially requires us to understand the effects of chemical structure on physical and chemical characteristics. Six further chapters discuss the principles of polymerization reactions including step, radical chain, ionic chain, chain copolymerization, coordination and ring opening. Finally, material is also included on how commonly known polymers are synthesized in a laboratory and a factory. This book is suitable for a one semester course in polymer chemistry and does not demand prior knowledge of polymer science.
Author: Jean-François Lutz Publisher: John Wiley & Sons ISBN: 3527342370 Category : Technology & Engineering Languages : en Pages : 532
Book Description
Edited by a leading authority in the field, the first book on this important and emerging topic provides an overview of the latest trends in sequence-controlled polymers. Following a brief introduction, the book goes on to discuss various synthetic approaches to sequence-controlled polymers, including template polymerization, genetic engineering and solid-phase chemistry. Moreover, monomer sequence regulation in classical polymerization techniques such as step-growth polymerization, living ionic polymerizations and controlled radical polymerizations are explained, before concluding with a look at the future for sequence-controlled polymers. With its unique coverage of this interdisciplinary field, the text will prove invaluable to polymer and environmental chemists, as well as biochemists and bioengineers.
Author: Kathleen O. Havelka Publisher: ISBN: Category : Science Languages : en Pages : 262
Book Description
Unlike generic plastics, specialty polymers are custom tailored for specific applications and are typically used in higher value products requiring improved performance. Interest in the field is growing steadily, and this book examines the recent advances in the synthesis, fundamental understanding and applications of specialty polymers. It is comprehensive in scope, covering and providing current information on topics ranging from the fundamentals to polymer synthesis and applications. Emphasis is placed on a nummber of materials issues including: developing a fundamental understanding of structure-property relationship that will lead to the rational design of polymers from specialty monomores, the synthesis of specialty monomers, and the elegant chemistry performed with these monomers to obtain polymers with unique properties.
Author: Stephen Koehler Publisher: ISBN: Category : Languages : en Pages : 0
Book Description
Donor-Acceptor poly(p-arylenevinylenes) (DA PAVs) are an untapped class of materials owing largely to their challenging synthesis. The Elacqua group recently reported the synthesis of such polymers by Ring-Opening Metathesis Polymerization (ROMP). The newly synthesized monomer polymerized with good control over molecular weight and was able to form block copolymers with poly(norbornene). In Chapter 2, the inherent steric and electronic bias of ROMP is leveraged within the same monomer scaffold to study how to monitor and influence polymer sequence. A combination of monomer steric bulk, reaction solvent, and temperature are all variables that can influence the sequence. While further study is needed, non-symmetric substitution of alkyl chains appears to be important in achieving controlled polymerizations. This comes with many limitations, namely a challenging monomer synthesis, for which we provide some perspective and insight to overcome this deficit. Given the remaining synthetic challenges, computational chemistry will be a particularly powerful tool to deliberately identify synthetic targets. Simulating polymer properties is a difficult task in itself; in Chapter 3, a high throughput screening method which is both more accurate and an order of magnitude faster than leading quantum mechanical methods was developed. Preliminary data supports a size-parameter relationship between monomers, which could be leveraged to further enhance the accuracy, and potentially used in simulating higher-dimensional conjugated structures like covalent organic frameworks. Circling back to screening-driven polymer design, Chapter 4 presents time-dependent density functional theory calculations that identify DA PAVs as a promising class of materials for singlet fission. This is due, in part to the planarization afforded by the vinyl-spacer. This is observed both when replicating reported methods, as well as when applying the high throughput screening capabilities developed in Chapter 3. Chapter 5 looks toward multifunctional devices or stimuli responsive organic electronics, wherein the synthesis of thiophene-appended spiropyran oligomers which can reversibly change their band gap energy are presented. The observed band gap energies agree well with DFT calculations, suggesting more diverse spiropyran-oligomers could be explored. However, fast isomerization with oligomer-appended spiropyran was not observed, though it is hypothesized that spirothiopyran could be an effective tool to overcome this. Overall, this work demonstrates progress in both synthetic and computational methodology to advance the development and discovery of organic electronic materials.
Author: Mario Leclerc Publisher: John Wiley & Sons ISBN: 9783527629794 Category : Technology & Engineering Languages : en Pages : 379
Book Description
This first systematic compilation of synthesis methods for different classes of polymers describes well-tested and reproducible procedures, thus saving time, money and chemicals. Each chapter presents the latest method for a specific class of conjugated polymers with a particular emphasis on the design aspects for organo-electronic applications. In this concise and practically oriented manner, readers are introduced to the strategies of influencing and controlling the polymer properties with respect to their use in the desired device. This style of presentation quickly helps researchers in their daily lab work and prevents them from reinventing the wheel over and over again.
Author: Margaret Gerthoffer
Author: Margaret Gerthoffer
Author: Jean-François Lutz
Author: Dieter A. Schlüter
Author: American Chemical Society. Division of Polymer Chemistry
Author: Richard G Jones
Author: Wei-Fang Su
Author: Jean-François Lutz
Author: Kathleen O. Havelka
Author: Stephen Koehler
Author: Mario Leclerc