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Enhancing Materials Through Controlled Architectures With Ring Opening Metathesis Polymerization
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Book Synopsis Enhancing Materials Through Controlled Architectures with Ring-opening Metathesis Polymerization by : Oren Alexander Scherman
Download or read book Enhancing Materials Through Controlled Architectures with Ring-opening Metathesis Polymerization written by Oren Alexander Scherman and published by . This book was released on 2004 with total page 278 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Ring-opening Metathesis Polymerization of Cyclopropenes and Ladderenes by : Jessica Kalay Su
Download or read book Ring-opening Metathesis Polymerization of Cyclopropenes and Ladderenes written by Jessica Kalay Su and published by . This book was released on 2020 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The importance of polymer microstructure is manifested in nature, where the precisely regulated monomer sequence in biomacromolecules enables their controlled folding and assembly to afford vital biological functions. In the pursuit of man-made materials with sophisticated properties, the field of polymer chemistry has developed rapidly to enable the synthesis of polymers with controlled microstructures. Specifically, living polymerization techniques, such as ring-opening metathesis polymerization (ROMP), enable excellent control over polymer molecular weight, composition, and architecture. ROMP is driven primarily by the release of ring strain in cyclic olefin monomers, but surprisingly few studies have been performed on the ROMP of cyclopropenes (CPEs), the most strained monocyclic olefins. In 2015, our group discovered that a class of 1,1-disubstituted CPE undergoes selective single addition to Grubbs third generation catalyst. Monomers which undergo single addition are extremely rare for chain-growth polymerizations and are particularly useful for manipulating the monomer sequence in a polymer. As such, we focused our research efforts on discovering other CPEs that can undergo single addition and uncovering the mechanism and role of their substituents. We have synthesized a library of CPEs with various disubstitution patterns and substituents and systematically investigated their reactivity with Grubbs catalyst. We have found that 1,1-disubstitution of CPE is crucial for both preserving the stability of the propagating chain end and tuning the metathesis reactivity from living polymerization to single addition. The distinct reactivities stemmed from differences in sterics and/or chelation at the Ru alkylidene from C1 substituents after a single CPE ring-opening event, affecting the barrier to propagation. We have utilized the single addition reactivity of CPEs to synthesize alternating copolymers with diverse side chain and backbone functionalities from alternating ROMP of CPE with low-strain cyclic olefins. Recently, we have developed a strategy to precisely place discrete functionalities and side chains via ring-opened CPEs at pre-determined locations along a living ROMP polymer chain, with control over the location and number incorporated. This advance in polymer chemistry opens many exciting opportunities to manipulate the functionalities along well-controlled polymer chains for understanding the effects of their placement and sequence on polymer behaviors, controlling polymer folding/assembly, as well as synthesizing polymers with more complex nonlinear architectures with precision. Our group also recently reported a unique polymechanophore system, polyladderene, that undergoes force-triggered rearrangement into semi-conducting, insoluble polyacetylene. A notable feature in the design was the terminal strained cyclobutene on ladderene that allowed rapid ROMP. We have developed synthetic procedures to prepare triblock copolymers containing mechanically active polyladderene, since block copolymers can self-assemble in solution and bulk and facilitate incorporation of polyladderene with common polymers to impart the dramatic stress-response of polyladderene to diverse materials.
Book Synopsis Complex Macromolecular Architectures by : Nikos Hadjichristidis
Download or read book Complex Macromolecular Architectures written by Nikos Hadjichristidis and published by John Wiley & Sons. This book was released on 2011-04-20 with total page 840 pages. Available in PDF, EPUB and Kindle. Book excerpt: The field of CMA (complex macromolecular architecture) stands at the cutting edge of materials science, and has been a locus of intense research activity in recent years. This book gives an extensive description of the synthesis, characterization, and self-assembly of recently-developed advanced architectural materials with a number of potential applications. The architectural polymers, including bio-conjugated hybrid polymers with poly(amino acid)s and gluco-polymers, star-branched and dendrimer-like hyperbranched polymers, cyclic polymers, dendrigraft polymers, rod-coil and helix-coil block copolymers, are introduced chapter by chapter in the book. In particular, the book also emphasizes the topic of synthetic breakthroughs by living/controlled polymerization since 2000. Furthermore, renowned authors contribute on special topics such as helical polyisocyanates, metallopolymers, stereospecific polymers, hydrogen-bonded supramolecular polymers, conjugated polymers, and polyrotaxanes, which have attracted considerable interest as novel polymer materials with potential future applications. In addition, recent advances in reactive blending achieved with well-defined end-functionalized polymers are discussed from an industrial point of view. Topics on polymer-based nanotechnologies, including self-assembled architectures and suprastructures, nano-structured materials and devices, nanofabrication, surface nanostructures, and their AFM imaging analysis of hetero-phased polymers are also included. Provides comprehensive coverage of recently developed advanced architectural materials Covers hot new areas such as: click chemistry; chain walking; polyhomologation; ADMET Edited by highly regarded scientists in the field Contains contributions from 26 leading experts from Europe, North America, and Asia Researchers in academia and industry specializing in polymer chemistry will find this book to be an ideal survey of the most recent advances in the area. The book is also suitable as supplementary reading for students enrolled in Polymer Synthetic Chemistry, Polymer Synthesis, Polymer Design, Advanced Polymer Chemistry, Soft Matter Science, and Materials Science courses. Color versions of selected figures can be found at www.wiley.com/go/hadjichristidis
Book Synopsis Controlled and Living Polymerizations by : Krzysztof Matyjaszewski
Download or read book Controlled and Living Polymerizations written by Krzysztof Matyjaszewski and published by John Wiley & Sons. This book was released on 2009-09-28 with total page 640 pages. Available in PDF, EPUB and Kindle. Book excerpt: Written by a highly prestigious and knowledgeable team of top scientists in the field, this book provides an overview of the current status of controlled/living polymerization, combining the synthetic, mechanistic and application-oriented aspects. From the contents: * Anionic Vinyl Polymerization * Carbocationic Polymerization * Radical Polymerization * Coordinative Polymerization of Olefins * Ring-Opening Polymerization of Heterocycles * Ring-Opening Metathesis Polymerization * Macromolecular Architectures * Complex Functional Macromolecules * Synthesis of Block and Graft Copolymers * Bulk and Solution Structures of Block Copolymers * Industrial Applications While some of the material is based on chapters taken from the four-volume work "Macromolecular Engineering", it is completely updated and rewritten to reflect the focus of this monograph. Must-have knowledge for polymer and organic chemists, plastics technologists, materials scientists and chemical engineers.
Book Synopsis Controlled Macromolecular Architectures Via A) Ring-opening Olefin Metathesis Polymerization and B) Polymer Functionalization Methodologies by : Reeta Joshi
Download or read book Controlled Macromolecular Architectures Via A) Ring-opening Olefin Metathesis Polymerization and B) Polymer Functionalization Methodologies written by Reeta Joshi and published by . This book was released on 2006 with total page 211 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Advances in Ring Opening (Metathesis) Polymerization by :
Download or read book Advances in Ring Opening (Metathesis) Polymerization written by and published by Wiley-VCH. This book was released on 2000-09-12 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This volume of Macromolecular Symposia contains contributions presented at the RO(M)P'99 International Symposium in Mons, Belgium. At this meeting, over one hundred chemists, physico-chemists, chemical engineers from the world of academia and industry, as well as students, discussed recent developments in mechanisms and kinetics in RO(M)P, synthesis and characterization of new macromolecular architectures, and new materials and applications via RO(M)P.
Book Synopsis Controlled Molecular Architectures Via Ring Opening Metathesis Polymerisation by : Panagiotis Dounis
Download or read book Controlled Molecular Architectures Via Ring Opening Metathesis Polymerisation written by Panagiotis Dounis and published by . This book was released on 1994 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis and Applications of Ring Opening Metathesis Polymerization Based Functional Block Copolymers by : Sanchita Biswas
Download or read book Synthesis and Applications of Ring Opening Metathesis Polymerization Based Functional Block Copolymers written by Sanchita Biswas and published by . This book was released on 2010 with total page 172 pages. Available in PDF, EPUB and Kindle. Book excerpt: Ring opening metathesis polymerization (ROMP) is established as one of the efficient controlled living polymerization methods which have various applications in polymer science and technology fields. The research presented in this dissertation addresses several applications of multifunctional well-defined norbornene-based block copolymers synthesized by ROMP using ruthenium-based Grubbs catalysts. These novel block copolymers were applied to stabilize maghemite nanoparticles, creating the superparamagnetic polymeric nanocomposites. The J-aggregation properties of the porphyrin dyes were improved via self-assembly with a customized norbornene polymer. Novel multimodal copolymer probes were synthesized for two-photon fluorescence integrin-targeted bioimaging. In Chapter 1 a brief overview of ROMP along with ruthenium metal catalysts and selected applications of the polymers related to this research is presented. Superparamagnetic maghemite nanoparticles are important in biotechnology fields, such as enhanced magnetic resonance imaging (MRI), magnetically controlled drug delivery, and biomimetics. However, cluster formation and eventual loss of nano-dimensions is a major obstacle for these materials. Chapter 2 presents a solution to this problem through nanoparticles stabiulized in a polymer matrix. The synthesis and chracterization of novel diblock copolymers, consisting of epoxy pendant anchoring groups to chelate maghemite nanoparticles and steric stabilizing groups, as well as generation of nanocomposites and their characterization, including surface morphologies and magnetic properties, is discussed in Chapter 2. In Chapter 3, further improvement of the nanocomposites by ligand modification and the synthesis of pyrazole-templated diblock copolymers and their impact to stabilize the maghemite nanocomposite are presented. Additionally, the organic soluble magnetic nanocomposites with high magnetizations were encapsulated in an amphiphilic copolymer and dispersed in water to assess their water stability by TEM. To gain a preliminary measure of biocopatibility of the micelle-encapsulated polymeric magnetic nanocomposites, cell-viability was determined. In Chapter 4, aggregation behaviors of two porphyrin-based dyes were investigated. A new amphiphilic homopolymer containing secondary amine moieties was synthesized and characterized. In low pH, the polymer became water soluble and initiated the stable J-aggregation of the porphyrin. Spectroscopic data supported the aggregation behavior. Two photon fluorescence microscopy (2PFM) has become a powerful technique in bioimaging for non-invasive imaging and potential diagnosis and treatment of a number of diseases via excitation in the near-infrared (NIR) region. The fluorescence emission upon two-photon absorption (2PA) is quadratically dependent with the intensity of excitation light (compared to the linear dependence in the case of one-photon absoprtion), offering several advantages for biological applications over the conventional one-photon absorption (1PA) due to the high 3D spatial resolution that is confined near the focal point along with less photodamage and interference from the biological tissues at longer wavelength (~700-900 nm). Hence, efficient 2PA absorbing fluorophores conjugated with specific targeting moieties provides an even better bioimaging probe to diagnose desired cellular processes or areas of interest The [alpha subscript v beta subscript 3] integrin adhesive protein plays a significant role in regulating angiogenesis and is over-expressed in uncontrolled neovascularization during tumor growth, invasion, and metastasis. Cyclic-RGD peptides are well-known antagonists of [alpha subscript v beta subscript 3] integrin which suppress the angiogenesis process, thus preventing tumor growth. In Chapter 5 the synthesis, photophysical studies and bioimaging is reported for a versatile norbornene-based block copolymer multifunctional scaffold containing biocompatible (PEG), two-photon fluorescent (fluorenyl), and targeting (cyclic RGD peptide) moieties. This water-soluble polymeric multi scaffold probe with negligible cytotoxicity exhibited much stronger fluorescence and high localization in U87MG cells (that overexpress integrin) compared to control MCF7 cells. The norbornene-based polymers and copolymers have quite remarkable versatility for the creation of advanced functional magnetic, photonic, and biophotonic materials.
Book Synopsis Living and Controlled Polymerization by : Joseph Jagur-Grodzinski
Download or read book Living and Controlled Polymerization written by Joseph Jagur-Grodzinski and published by Nova Publishers. This book was released on 2006 with total page 398 pages. Available in PDF, EPUB and Kindle. Book excerpt: The living/controlled polymerisation techniques opened new vistas in polymer chemistry. The leading authorities in this field and its pioneers contributed chapters to this collective volume. The controlled polymerisation techniques have enabled preparation of polymers, copolymers, and block copolymers with predetermined molecular weights and narrow polydispersity, in which functional groups or biologically active molecules could be placed at well defined locations. They have also enabled preparation of advanced polymeric structures with precisely determined architectures and improved properties. Moreover, they have provided opportunities for preparation of novel polymeric materials from monomers, which before have not been suitable or accessible for such purposes. Properties of some of these polymeric materials may be significantly different from those of the existing ones. They provide opportunities for new applications. Several patents have already been approved for such speciality applications as, drug delivery, biocompatible surfaces, thermoplastic elastomers, moisture curable sealants, and so on. Many more products, based on polymers fabricated by the living/ controlled polymerisation techniques, will certainly emerge in such specialised areas as, nanotechnology, medical devices, "smart polymers", sensors , smart separation technologies, optical fibres and other optical applications, various biomaterials, etc.
Book Synopsis Ring Opening Metathesis Polymerisation and Related Chemistry by : Ezat Khosravi
Download or read book Ring Opening Metathesis Polymerisation and Related Chemistry written by Ezat Khosravi and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 489 pages. Available in PDF, EPUB and Kindle. Book excerpt: Since the last ASI in Turkey in Sept. 1995, the olefin metathesis has made remarkable strong developments with an incredible speed in various directions. New catalyst systems have been developed which have resulted in the synthesis of novel materials. Other fascinating developments have been the new catalysts for stereoselective metathesis and catalysts with considerable functional group tolerance. These new catalysts in addition to Ring Opening Metathesis Polymerisation (ROMP) and Acyclic Diene Metathesis (ADMET) are now powerful tools for Ring Closing Metathesis (RCM) and have found many applications in the synthesis of natural products. A lot of information has been established about all aspects of the olefin metathesis and there is a vast literature concerning the process, covering the initiators, mechanistic features and applications of this reaction in organic and polymer synthesis. The NATO ASI on rd th ROMP and Related Chemistry took place in Polanica-Zdroj, Poland during 3 to 15 Sept. 2000, to highlight the developments in this area and to discuss the prospects and visions for the year 2000 and beyond. The aims of the ASI were: to provide a platform for dissemination of knowledge; to promote communication between people who have a serious interest in this field of chemistry; to help establishing international scientific contacts and to provide an opportunity for the scientists with an appropriate scientific background to learn of recent developments in this field of science. There were 15 lecturers and 67 participants in this NATO ASI.
Book Synopsis Polymer Design Enabled by Catalysis by : Sean Gitter
Download or read book Polymer Design Enabled by Catalysis written by Sean Gitter and published by . This book was released on 2024 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Modern synthetic polymer chemistry is defined by control over macromolecular architecture. Among controlled polymerization schemes, ring-opening metathesis polymerization (ROMP) represents one of the most widely adopted strategies for precision polymer synthesis. Advances in metal-alkylidene initiator technologies have enabled access to polymers with unrivalled degrees of microstructural control via ROMP. Unfortunately, relying on stoichiometric amounts of organometallic initiators can be cost prohibitive and limit the utility of ROMP materials in metal-sensitive applications like biomedicine or electronics. Therefore, recent effort has been devoted to developing metal-free approaches to ROMP (MF-ROMP). The Boydston group has developed a strategy which relies on organic initiators and photoredox catalysts to achieve MF-ROMP. Despite precluding the deleterious metallic byproducts inherent to metal-mediated ROMP, MF-ROMP remains limited in comparison to metal-mediated approaches to ROMP. Outstanding challenges in MF-ROMP include achieving a high degree of control over polymer microstructure, the incorporation of functional (co)monomers in MF-ROMP materials, and conducting polymerizations in nonpolar media. My doctoral research has begun to address these challenges. First, I was part of a collaborative team that discovered an ion-pairing approach to stereoselectivity during MF-ROMP that affords materials with tunable alkene stereochemistry using simple to change reaction parameters. During a further investigation we discovered that ion-pairing can also be used to improve the molecular weight control of MF-ROMP. These findings directly led to the discovery that active esters are readily polymerizable under MF-ROMP conditions. Post-polymerization modification of these materials provided access to a diverse array of functionalized MF-ROMP polymers for the first time. Separately, I was also on a team that developed a method for the C-H functionalization and allylic amination of ROMP polynorbornenes (poly(NBEs)). Notably, our approach to C-H functionalization yielded materials with high and tunable degrees of amination without consuming or transposing the alkenes in the polymers' backbones. In combination these discoveries highlight the utility of catalysis to access polymeric architectures that are otherwise inaccessible.
Book Synopsis Development of Organic Photoredox-mediated Ring-opening Metathesis Polymerization Through Expanded Functionalities of Initiators and Monomers by : Pengtao Lu
Download or read book Development of Organic Photoredox-mediated Ring-opening Metathesis Polymerization Through Expanded Functionalities of Initiators and Monomers written by Pengtao Lu and published by . This book was released on 2019 with total page 110 pages. Available in PDF, EPUB and Kindle. Book excerpt: Ring-opening metathesis polymerization (ROMP), which is derived from transition-metal-based olefin metathesis, has evolved into one of the most prevalent technologies for making functional polymeric materials. Due to the nature of this polymerization method, the metal alkylidene remains covalently bound to the polymer chain end until the introduction of various quenchers to terminate the polymerization. However, the removal of resultant metal by-products requires multiple purification steps. Recently, our group pioneered establishment of organic photoredox-mediated ROMP (o-ROMP), which is driven by the motivation of developing a metal-free alternative to traditional ROMP. This thesis aims to contribute to the study of o-ROMP by describing our investigations in the field, with a particular emphasis on expanding scopes of functional initiators and monomers. Chapter 1 is an introduction to o-ROMP, which start with explanation of community interests on developing organic photoredox-mediated controlled polymerization (OPCP). The general mechanisms of these novel polymerizations, including the properties of various organic photoredox catalysts, will be reviewed first. The flowing discussion will focus on different kinds of established OPCPs, which emphasizes on unique scopes for each specific methods. We will end up the introduction part with our previous efforts on developing o-ROMP. Chapter 2 begins with our initial attempts on testing the feasibility of grafting o-ROMP from small-molecular multitopic initiators. The successful combination of this multidirectional growth mode with the design of macroinitiators facilitate preparation of polyether-based triblock copolymer and polystyrene-based graft copolymer, which are both acid cleavable. Chapter 3 describes our recent efforts on expanding the scope of macroinitiator towards polyesters and polycarbonates, which are derived from organocatalyzed ring-opening polymerization (o-ROP). Grafting from bifunctional initiators in one pot, stepwise o-ROP and o-ROMP succeed in making biocompatible block copolymers via a completely metal-free pathway. Finally, Chapter 4 discusses our ongoing efforts in the expansion of monomer scopes, aiming to make functional polymers solely through o-ROMP strategy. The successful adoption of those deprotection-free functional monomers not only make it possible to enable post-polymerization modification, but also provide opportunity to control chain architectures of resulted polymer.
Book Synopsis Improving Control and Functionality of Photoredox-mediated Metal-free Ring-opening Metathesis Polymerization by : Rachel Louise Tritt
Download or read book Improving Control and Functionality of Photoredox-mediated Metal-free Ring-opening Metathesis Polymerization written by Rachel Louise Tritt and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Ring-opening metathesis polymerization (ROMP) involves the reaction of strained cyclic olefins to create polymers that retain the unsaturation of the initial monomer. Traditionally, this transformation has been achieved using metal alkylidene initiators, typically centered around one of three transition metals (Ru, Mo, W). While this strategy has many advantages, such as well-defined initiators, functional group stability, and microstructural control, an alternate, fully organic mechanistic strategy is possible (MF-ROMP). This method is distinct from its metal-based predecessor as it is enabled by photoredox-generated radical cationic species. As a result, it is subject to different considerations, specifically surrounding the behavior of the active chain-end. MF-ROMP also has different capabilities and possible applications due to this change in reactivity, which makes the development of this technology of great interest to us.This dissertation will first contextualize MF-ROMP, providing background on traditional ROMP, as well as on the electrochemical and photochemical cyclobutanations that inspired the development of the metal-free, photoredox-mediated method on which this document is centered. The initial development of MF-ROMP will also be covered in this section (Chapter 1). Next, the proposal for and discovery of the cross-metathesis method for chain transfer in MF-ROMP will be discussed, leading into preliminary work to leverage this mechanism for a fully organic system for small molecule cross-metathesis (Chapter 2). The use of chain transfer will then continue into the development of silane-functionalized polymers and oligomers for use in fiber-reinforced composites. Future directions for these materials and methods are also included, as well as preliminary results for extending this work into surface-initiated MF-ROMP (Chapter 3). The modulation of molar mass dispersity (♯0) is introduced next, illustrating the effect that simple changes to reaction conditions have on the progression of the polymerization. Suggestions for additional investigations based on this discovery are also included (Chapter 4). Finally, a cursory study on the ability to use aromatic alkenes as initiators in MF-ROMP is summarized. This work is also accompanied by a reflection on current limitations and future development of the technology (Chapter 5).
Book Synopsis Single-Chain Polymer Nanoparticles by : José A. Pomposo
Download or read book Single-Chain Polymer Nanoparticles written by José A. Pomposo and published by John Wiley & Sons. This book was released on 2017-08-18 with total page 504 pages. Available in PDF, EPUB and Kindle. Book excerpt: This first book on this important and emerging topic presents an overview of the very latest results obtained in single-chain polymer nanoparticles obtained by folding synthetic single polymer chains, painting a complete picture from synthesis via characterization to everyday applications. The initial chapters describe the synthetics methods as well as the molecular simulation of these nanoparticles, while subsequent chapters discuss the analytical techniques that are applied to characterize them, including size and structural characterization as well as scattering techniques. The final chapters are then devoted to the practical applications in nanomedicine, sensing, catalysis and several other uses, concluding with a look at the future for such nanoparticles. Essential reading for polymer and materials scientists, materials engineers, biochemists as well as environmental chemists.
Book Synopsis Handbook of Ring-Opening Polymerization by : Philippe Dubois
Download or read book Handbook of Ring-Opening Polymerization written by Philippe Dubois and published by John Wiley & Sons. This book was released on 2009-03-02 with total page 427 pages. Available in PDF, EPUB and Kindle. Book excerpt: This comprehensive, truly one-stop reference discusses monomers, methods, stereochemistry, industrial applications and more. Chapters written by internationally acclaimed experts in their respective fields cover both basic principles and up-to-date information, ranging from the controlled ring-opening polymerization methods to polymer materials of industrial interest. All main classes of monomers including heterocyclics, cyclic olefins and alkynes, and cycloalkanes, are discussed separately as well as their specificities regarding the ring-opening polymerization techniques, the mechanisms, the degree of control, the properties of the related polymers and their applications. The two last chapters are devoted to the implementation of green chemistry in ring-opening polymerization processes. Of much interest to chemists in academia and industry.
Book Synopsis Dissertation Abstracts International by :
Download or read book Dissertation Abstracts International written by and published by . This book was released on 2008 with total page 868 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis New Avenues to Hybrid Polymer/Inorganic Nanoparticle Materials Using Surface-Initiated Ring-Opening Metathesis Polymerization and Reaction-Induced Phase Transitions by : Jacob LaNasa
Download or read book New Avenues to Hybrid Polymer/Inorganic Nanoparticle Materials Using Surface-Initiated Ring-Opening Metathesis Polymerization and Reaction-Induced Phase Transitions written by Jacob LaNasa and published by . This book was released on 2021 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Hybrid materials made from polymer and inorganic nanoparticles offer functionality that assists in creating advanced materials by either reinforcing existing polymer properties, or by introducing inorganic material properties. As a result, these hybrids can be tailored for use in a number of exciting areas including biomedical tissue engineering, energy storage, and high temperature applications where specific properties are desired. The material processing and resulting dispersion state of the inorganic nanoparticles within the polymer phase are critical and non-trivial considerations that influence the expression of enhanced properties, and need to be carefully addressed for desirable performance. An effective strategy for controlling dispersion in hybrid materials is to modify the nanoparticle surface with ligands or polymer chains. However, many established surface-initiated polymerization techniques yield a subset of graft chemistries that do not favorably interact with polyolefins used widely across consumer and industrial materials. To expand the versatility of polymer-grafted nanoparticles, a surface-initiated ring-open- ing metathesis polymerization (SI-ROMP) technique was developed to graft unsaturated backbones from particle surfaces. Strategies to quantify and mitigate unfavorable chain transfer during polymerization were utilized, as chain transfer is a key obstacle to SI- ROMP implementation. In addition, the unsaturated polymer backbones obtained with SI-ROMP were hydrogenated to drive crystallization from the particle surface or functionalized with macromolecules to access non-linear bottlebrush graft architectures. The versatility of these new capabilities enhance polymer-grafted nanoparticle functionality, structural conformation, and thermal response and can be used to influence properties in new and advanced materials. In addition, a new processing method termed a reaction-induced phase transition (RIPT) was developed to stabilize polymer-functionalized nanoparticles in polymer matrices and dictate dispersion state. Surface-functionalized nanoparticles can be easily dispersed within a polymer matrix though an in situ polymerization where nanoparticles are initially well-solubilized in a monomer solution prior to polymerization. The in situ polymerization arrests particle mobility as the matrix increases in chain length. During this process, particles are stabilized or driven to phase separate based on thermodynamic interactions between the matrix and the functional surface ligand. This method incorporates scalable polymerization processes to develop well-dispersed hybrid polymer/inorganic nanoparticle materials at a bulk scale. The development of these methods create new avenues to improved particle dispersion needed for advance material design.
