Polymer Chemistry Commons^™

Preparation And Evaluation Techniques Of Porous Materials And Mixed Matrix Membranes For Targeted Co2 Separation Applications, Tsemre Tessema

Theses and Dissertations

The use of porous sorbents for physisorptive capture of CO₂ from gas mixtures has been deemed attractive due to the low energy penalty associated with recycling of such materials. Porous organic polymers (POPs) have emerged as promising candidates with potential in the treatment of pre- and post- fuel combustion processes to separate CO₂ from gas mixtures. Concurrently, significant advances have been made in establishing calculation methods that evaluate the practicality of porous sorbents for targeted gas separation applications. However, these methods rely on single gas adsorption isotherms without accounting for the dynamic gas mixtures encountered in real-life applications. …

Design And Synthesis Of Dynamic Covalent Polymer Scaffolds With Controlled Architectures, Emily Annette Hoff

Dissertations

The design and synthesis of functional, controlled polymer architectures is essential to the development of new materials with precise and tailorable properties or applications. The work described in this dissertation focuses on the development of controlled polymer architectures with dynamic linkages for the design of multifunctional materials and surfaces via robust, efficient, and stimuli-responsive strategies.

In Chapter III, a post-polymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethyl pyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds …

Diazonium 4-(Trifluorovinyloxy) Perfluorobutanesulfonyl Benzenesulfonimide Zwitterionic Monomer Synthesis, Isaac D. Addo

Electronic Theses and Dissertations

3-Diazonium- 4-(trifluorovinyloxy) - perfluorobutanesulfonyl benzenesulfonimide zwitterionic monomer (see figure 1) is proposed to be polymerized and further act as a new electrolyte for Polymer exchange membrane fuel cells (PEMFCs). One reason is that, the aromatic trifluorovinyl aryl ether (TFVE) group can easily be homopolymerized to aromatic perfluorocyclobutane (PFCB) polymer. Furthermore, the diazonium moiety in the monomer is expected to covalently attach the electrolyte to the carbon electrodes support. The perfluoroalkyl(aryl) sulfonimide (PFSI) pendant provides good chemical and mechanical stability as well as better proton conductivity. Several multi-step synthetic schemes are designed to obtain such monomer from perfluoroalkyl(aryl) sulfonimide (PFSI). Among …

Direct Attachment Of 4-Hydroxybenzoic Acid Polymers And Capture Agents To Flat Sheet And Microdialysis Membranes For Improved Mass Transport, Sarah Jane Phillips

Graduate Theses and Dissertations

Microdialysis (MD) sampling is a diffusion-based separation method which has the ability to sample any analyte that can diffuse across the semi-permeable membrane. However one challenge for MD is that for soluble proteins greater than 10 kDa, the relative recovery (RR) using a 100 kDa MD probe is between 1-5%.1 There are two major barriers that lead to these low recovery values - nonspecific adsorption (NSA) and poor solute mass transport. To overcome these two barriers, the modification of PES-based MD membranes has been initiated by laccase. Previous researchers have used laccase to modify PES flat sheet and hollow fiber …

Synthesis, Self-Assembly, And Immunological Activity Of Α-Galactose-Functionalized Dendron–Lipid Amphiphiles, John Trant, Namrata Jain, D. M. Mazzuca, J Trevor Mcintosh, Bo Fan, S M Mansour Haeryfar, Sebastien Lecommandoux, Elizabeth Gillies

Chemistry Publications

Nanoassemblies presenting multivalent displays of biologically active carbohydrates are of significant interest for a wide array of biomedical applications ranging from drug delivery to immunotherapy. In this study, glycodendron–lipid hybrids were developed as a new and tunable class of dendritic amphiphiles. A modular synthesis was used to prepare dendron–lipid hybrids comprising distearylglycerol and 0 through 4th generation polyester dendrons with peripheral protected amines. Following deprotection of the amines, an isothiocyanate derivative of C-linked α-galactose (α-Gal) was conjugated to the dendron peripheries, affording amphiphiles with 1 to 16 α-Gal moieties. Self-assembly in …

A Comparison Of Solvent And Water-Borne Alkyd Coatings And The History Of Voc Regulations In The United States, Molly Elise Burns

Master's Theses

A Comparison of Solvent and Water-Borne Alkyd Coatings Abstract

Conventional solvent based alkyd coatings have gone out of favor due to concerns over volatile organic compound (VOC) content. However, due to recent focus on renewable raw materials, alkyds are making a comeback in waterborne form. Water based alkyd coatings are known to have poor shelf stability and corrosion resistance, as well as other problems during the formulation process. This project focused on comparing solvent borne to two types of water-borne alkyds, water reducible alkyds and alkyds emulsions. The purpose was to understand the differences between the three types of alkyds …

Calculating The Energy Barriers Required To Join Metal-Organic Framework Synthesis Intermediates With Non-Equilibrium Molecular Simulation, Marcus A. Tubbs, David Cantu, Roger Rousseau, Vassiliki-Alexandra Glezakou

STAR Program Research Presentations

Metal organic frameworks are synthetic porous materials with great capacity for adsorption of carbon dioxide and methane. They chemically appear as a chain-link fence with nodes of metal connected by organic linkers. The pores between the nodes define the characteristics of the material, allowing gas particles of specific size to pass through while blocking larger particulates. While there has been success in synthesizing small amounts of metal organic frameworks, the mechanistic details behind their assembly remain unknown. Understanding the synthesis mechanism is necessary to understand the kinetics involved and be able to produce this useful material on an industrial scale. …

Correlation Of Polymer Performance And Hansen Solubility Parameters, Daniel Jobse Mania

Master's Theses

Ready-to-use (RTU) grout is becoming more important to the finish and remodeling construction industry. Market research shows it is a fast-growing product that not only is creating its own space, but is beginning to supplant existing technology.

The original intent of this research was to investigate formulation parameters and how they affect grout performance. It was learned that particle size and oil absorption (OA) value are important filler properties that affect performance as much as adequate packing density and optimal pigment volume concentration (PVC) without going beyond critical PVC (CPVC).

Polymer architecture was also determined to be extremely important, but …

Synthesis Of Microgel Polymers As Catalysts, Hannah N. Miller

Chemistry & Biochemistry Undergraduate Honors Theses

New developments in organic synthesis show promise in achieving the best catalytic properties for the hydrolysis of glycosidic bonds through microgel polymers and transition metal complexes. A monomer mix of ethylene glycol dimethacrylate, butyl acrylate, and styrene form miniemulsion polymers after sonication and exposure to UV light. Gravimetrical analysis is used to determine the most suitable polymerization conditions by performing experiments at varying pH values, temperatures, monomer amounts, initiator amounts, and lamp heights. The final data show that the best polymerization conditions are a pH of 10.50 at 0°C with a high monomer ratio, 20% initiator amount, and a lamp …

Curing Of Polymer Thermosets Via Click Reactions, Mark Richard Brei

Dissertations

In the first project, an azide functional resin and tetra propargyl aromatic diamines were fabricated for use as a composite matrix. These systems take already established epoxy/amine matrices and functionalize them with click moieties. This allows lower temperatures to be used in the production of a thermoset part. These new systems yield many better mechanical properties than their epoxy/amine derivatives, but their T_gs are low in comparison.

The second project investigates the characterization of a linear system based off of the above azide functional resin and a difunctional alkyne. Through selectively choosing catalyst the linear system can show …

Synthesis Of Two Monomers For Proton Exchange Membrane Fuel Cells (Pemfcs), Abdulmajeed A. Alayyaf

Electronic Theses and Dissertations

The overall goal of this research is to synthesize two different monomers for proton exchange membrane (PEM) Fuel Cells. Such monomers are proposed to be polymerized to improve the efficiency and compatibility of electrodes and electrolytes in PEM fuel cells.

The first target is to synthesize 4-diazonium-3-fluoro PFSI zwitterionic monomer. Three steps were carried out in the lab. First one was the ammonolysis of 3-fluoro-4-nitrobenzenesulfonyl chloride. Second reaction was the bromination of Nafion monomer. The next coupling reaction, between brominated Nafion monomer and the 3-fluoro-4-nitrobenzenesulfonamide, was failed. The obstacles involve the harsh reaction condition and troublesome purification procedure.

The second …

To Bend Or Not To Bend – Are Heteroatom Interactions Within Conjugated Molecules Effective In Dictating Conformation And Planarity?, Gary Conboy, Howard J. Spencer, Enrico Angioni, Alexander L. Kanibolotsky, Neil J. Findlay, Simon J. Coles, Claire Wilson, Mateusz B. Pitak, Chad Risko, Veaceslav Coropceanu, Jean-Luc Brédas, Peter J. Skabara

Chemistry Faculty Publications

We consider the roles of heteroatoms (mainly nitrogen, the halogens and the chalcogens) in dictating the conformation of linear conjugated molecules and polymers through non-covalent intramolecular interactions. Whilst hydrogen bonding is a competitive and sometimes more influential interaction, we provide unambiguous evidence that heteroatoms are able to determine the conformation of such materials with reasonable predictability.

Synthesis And Properties Of Bisimidazolium And Poly(Ethylene Glycol)-Containing Michael Addition Polyester Networks, Joshua Allan Dippie

Murray State Theses and Dissertations

Poly(ionic liquid)s (PILs) have been examined in recent years for applications in various technologies, including solid-state lithium ion batteries and gas separation membranes. In this work, a series of bisimidazolium-containing, Michael addition donors were synthesized and used to produce a series of covalently crosslinked PIL polyester networks containing bis(trifluoromethylsulfonyl)imide as the counteranion. Within the series, the length of alkyl spacer between the two imidazolium cations and the diacrylate to acetoacetate monomer ratio were varied in an attempt to correlate structural variations with the thermal, mechanical, and conductive properties of the PILs. Keeping the diacrylate to acetoacetate ratio constant, increasing the …

Organometallic Materials: Ferroceno[C]Thiophenes And 1,2-Bisthienylmetallocenes, Surya R. Banks

Theses and Dissertations--Chemistry

Development of synthetic routes toward two general organometallic frameworks was undertaken. The first project involved synthetic attempts of substituted and unsubstituted ferroceno[c]thiophene while the second one was the synthesis of 1,2-dithienylmetallocenes. The long-term goal of this work is to lay the foundations for study of electronic, electrochromic, redox, and optical properties of thiophene-based materials integrated with organometallic systems such as ferrocene, ruthenocene and cymantrene. The synthetic pathway for the target molecule in the first project involved converting 1,2-bis(hydroxymethyl)ferrocene to 1,2-bis(thiouroniummethyl)ferrocene with thiourea under acidic conditions. Refluxing the salt in base followed by acidification resulted in 1,2-bis(mercaptomethyl)ferrocene, which is …

Analysis Of The Fabrication Conditions In Organic Field-Effect Transistors, Rachel M. Rahn, Yan Zhao, Jianguo Mei

The Summer Undergraduate Research Fellowship (SURF) Symposium

Polymer-based organic field-effect transistors have raised substantial awareness because they enable low-cost, solution processing techniques, and have the potential to be implemented in flexible, disposable organic electronic devices. The performance of these devices is highly dependent on the processing conditions, as well as the intrinsic properties of the polymer. Processing conditions play an important role in semiconductor film formation and device performance. These factors may provide an important link between structure and performance. In this study, an empirical analysis tool, Process Scout, was applied to assess processing factors such as polymer concentration and silicon modification. This sanctioned the creation of …

Development Of A Scalable Synthesis Of Hp-Β-Cd Pluronic Polyrotaxanes, Joseph L. Skulsky, Elizabeth A. Slepko, Bradley P. Loren, David H. Thompson

The Summer Undergraduate Research Fellowship (SURF) Symposium

Polyrotaxanes are polymers that have macrocycles threaded onto them, analogous to beads threaded onto a string. These materials are used for a variety of different biomedical applications.^1-3 The Thompson group has been developing 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) polyrotaxanes as therapeutics for the treatment of Niemann-Pick Type C (NPC) disease. NPC is a debilitating genetic disorder where cholesterol accumulates in the lysosomes of cells.⁴ Developing a scalable process is crucial for the advancement of these materials as NPC therapeutics. The goal of this project is to optimize the only protocol for the synthesis of HP-β-CD/Pluronic polyrotaxanes in order to develop a …

Tempo-Containing Romp Polymers As A Component For Treatment Of Traumatic Brain Injuries, Cameron H. Feriante

Honors College Theses

During a traumatic brain injury (TBI) sustained in combination with hemorrhagic shock the brain undergoes anoxic conditions resulting from swelling and blood loss. Traditional intravenous solutions are used to replace blood volume, but are unable to replace the blood’s oxygen carrying capacity. A proposed treatment based on isotonic solutions containing hemoglobin-based oxygen carriers (HBOC’s) which were intended to provide readily available oxygen was developed. However, cell-free hemoglobin was shown to have excessive oxidative potential. Polynitroxylated Pegylated Hemoglobin (PNPH) was developed to address this shortcoming. During PNPH synthesis a combination of polyethylene glycol (PEG) and (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), is bound to the …

Green Chemistry As A Tool For Understanding The Toxic Substances Control Act: A Lecture Module For Undergraduate Students, Molly R. Blessing

Honors Scholar Theses

The Toxic Substances Control Act (TSCA) is the central form of chemical regulation existent in the United States today, yet scientists are often unaware or uncertain of its provisions. Violations of TSCA by unknowing chemists set industry and government unnecessarily at odds. A lecture on TSCA was developed for undergraduate students that uses the concept of green chemistry to promote interest and incentivize learning. Green chemistry methods are cleaner and less wasteful than traditional chemical ones, and many companies using them are at the forefront of technological innovation. The lecture explains both green chemistry and TSCA, includes company case studies, …

Inhalable Nanocomposites And Anticancer Agents For Cancer Therapy, Nathanael A. Stocke

Theses and Dissertations--Chemical and Materials Engineering

Cancer is designated as the leading cause of mortality worldwide and lung cancer is responsible for nearly 30% of all cancer related deaths. Over the last few decades mortality rates have only marginally increased and rates of recurrence remain high. These factors, among others, suggest the need for more innovative treatment modalities in lung cancer therapy. Targeted pulmonary delivery is well established for treating pulmonary diseases such as asthma and provides a promising platform for lung cancer therapy. Increasing local deposition of anticancer agents (ACAs) and reducing systemic exposure of these toxic moieties could lead to better therapeutic outcomes and …

Diazaborole Linked Porous Polymers: Design, Synthesis, And Application To Gas Storage And Separation, Zafer Kahveci

Theses and Dissertations

The synthesis of highly porous organic polymers with predefined porosity has attracted considerable attention due to their potential in a wide range of applications. Porous organic polymers (POPs) offer novel properties such as permanent porosity, adjustable chemical nature, and noteworthy thermal and chemical stability. These remarkable properties of the POPs make them promising candidates for use in gas separation and storage. The emission of carbon dioxide (CO₂) from fossil fuel combustion is a major cause of global warming. Finding an efficient separation and/or storage material is essential for creating a cleaner environment. Therefore, the importance of the POPs …

Correlating Molecular Architecture Of A Radical Polymer Based Copolymer With Its Electrical Transport Properties, Holly Chan

Open Access Theses

The design and synthesis of electrically-conductive macromolecules can lead to significant improvements in the performance of polymer-based energy conversion devices (e.g., thermoelectric devices). For these organic electronic devices, conjugated polymers have dominated the area of conductive polymers; however, these materials are usually synthesized using conditions that lead to poorly-defined polymers. Furthermore, in these increasingly-standard polymers, the charge transport ability of the polymer thin films is largely affected by the degree of crystallinity, which is a difficult property to control in a reproducible fashion. Therefore, we seek to explore a new class of amorphous, non-conjugated polymers containing a stable radical …

Porphyrin Cross-Linkers For Generating Soluble Molecularly Imprinted Polymers From Polyethyleneimine, Mohammed R. Elshaer

Seton Hall University Dissertations and Theses (ETDs)

Molecular recognition is vital to many biochemical processes and is at the heart of promising bio-medically related technologies. Molecular imprinting has a long-standing history as a successful method for mimicking the molecular recognition phenomena exhibited by nature, whereby artificial receptors are prepared for a given target molecule based on synthetic polymers. The molecularly imprinted polymer (MIP) contains a three dimensional network with a memorized cavity specific to the shape and functionality of the templated target molecule. The utility of traditional MIPs has been limited due to an inherent lack of solubility. We have worked toward developing a system that allows …

Latent Cysteine Residues From Polymers Prepared Via Free And Controlled Radical Polymerizations, Douglas Vincent Amato

Master's Theses

One less commonly used “click” reaction is thiazolidine chemistry. Thiazolidine chemistry is a commonly used reaction used in biological systems because the reaction requires the presence of both cysteine (a common amino acid) and an aldehyde or ketone. If cysteine residues could be incorporated into a polymer then a variety of applications could be developed. Polymers containing free thiols (aka thiomers) have developed in the last decade to become great mucoadhesives. If there was a facile route to control the amount of free thiols along the polymer then more fine-tuned and potentially stronger adhesives could be made. For these reasons …

Fused Arenes-Based Molecular And Polymeric Materials For Organic Field Effect Transistors, Harista Irugulapati

Masters Theses & Specialist Projects

In the past decade, tremendous progress has been made in organic field effect
transistors. Fused oligothiophenes and anthracene molecules are fascinating
macromolecules having unique optoelectronic properties. These compounds are successfully employed as active components in optoelectronic devices including field effect transistors. Our goal is to design and synthesize conjugated molecular materials, which are highly functionalized through structural modifications in order to enhance their electronic, photonic, and morphological properties. The main desire is to synthesize novel organic fused-arenes having efficient charge carrier mobilities, as well as to optimize optical properties for organic field effect transistors (OFETs). Novel series of fused arene …

Experimenting With Polymer Blend Solar Cells And Active Layer Thickness, Ryan Blumenthal

Physics

Bulk heterojunction organic photovoltaics utilize the electrical characteristics of semi-conductive polymers. These solution processable materials are beneficial because of their low material cost, light weight, and simple fabrication requirements. Our devices employ multiple photoactive polymers, P3HT and PCPDTBT, to absorb photons over a wide spectral range. We optimized various device characteristics including thickness and thermal anneal usage to reach a power conversion efficiency of 3.0% in AM1.5 sunlight. Device performance degrades over time due to atmospheric water and oxygen, prompting us to investigate device packaging to extend cell lifetime for additional testing.

Molecularly Woven Materials From Metal-Organic Precursors, Gellert Mezei, Jaafar Hachem, Isurika R. Fernando, Natasha R. Wadhwa, Neil C. Hughes

Faculty Research and Creative Activities Award (FRACAA)

No abstract provided.

Fluorinated Arene, Imide And Unsaturated Pyrrolidinone Based Donor Acceptor Conjugated Polymers: Synthesis, Structure-Property And Device Studies, Arawwawala Don T. Liyanage

Theses and Dissertations--Chemistry

FLUORINATED ARENE, IMIDE AND LACTAM-FUNCTIONALIZED DONOR ACCEPTOR CONJUGATED POLYMERS: SYNTHESIS, STRUCTURE-PROPERTY AND DEVICE STUDIES

After the discovery of doped polyacetylene, organic semiconductor materials are widely studied as high impending active components in consumer electronics. They have received substantial consideration due to their potential for structural tailoring, low cost, large area and mechanically flexible alternatives to common inorganic semiconductors. To acquire maximum use of these materials, it is essential to get a strong idea about their chemical and physical nature. Material chemist has an enormous role to play in this novel area, including development of efficient synthetic methodologies and control the …

The Development Of Transparent, Processable, Thermally-Responsive Coatings, Christopher David Roland

Master's Theses

Polymer matrices are commonly used as guest-host systems for organic chromophores for use in non-linear optical materials. The chromophores must be aligned or poled in an electric field in order to impart anisotropy and non-linear activity to the material. This poling process raises several issues, the two largest being the eventual relaxation of the chromophores back into random orientations due to brownian motion, and high molecular weight polymer matrices limiting chromophore mobility during poling. The prevention of this relaxation process is an area of significant interest, especially in applications that require long term coating stability and activity. In this study, …

Polymers Used In Medicine: Common Types And Benefits Of Drug Delivery Systems, Camille Andrews

Natural Sciences Student Research Presentations

This poster describes the common types and benefits of drug delivery systems.

Synthesis And Structure Of A Substituted Pyridazine, Kiranmai Byrichetti

Masters Theses & Specialist Projects

Pyridazines are heterocyclic compounds with an N-N bond in their ring structure. Heterocyclic aromatic compounds are of great interest as a result of their novel properties and commercial applications. Our current research is focused on the potential role of pyridazines in next generation electronic devices that utilize organics as the semiconducting material. The synthesis of 5, 6-fused ring pyridazines beginning from fulvenes (Scheme 1) is described herein. These fused heterocycles will serve as synthetic models and building blocks for potential organic or organometallic conducting polymers.

Our goal was to modify the route of Snyder et al. previously reported for the …