Design And Synthesis Of Monomers Toward Sequence Controlled Polymers
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Sequence-Controlled Polymers
Author: Jean-François Lutz
language: en
Publisher: John Wiley & Sons
Release Date: 2018-04-09
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.
Design and Synthesis of Monomers Toward Sequence-Controlled Polymers
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.
Compendium of Polymer Terminology and Nomenclature
Author: Richard G Jones
language: en
Publisher: Royal Society of Chemistry
Release Date: 2009-01-19
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.