Chemistry Commons^™

Tetrabutylammonium Benzoate‐Initiated Polymerization Of Propylene Oxide, Xuemin Chen, Michael R. Van De Mark

Chemistry Faculty Research & Creative Works

The polymerization of propylene oxide by the benzoate anion was aided through the use of the tetrabutylammonium counterion. The effect of the tetrabutylammonium ion was to increase the solubility of the salt and to increase the ion separation. The polymerization was carried out in a pressure reactor at temperatures from 40 to 108°C, producing polymer yields of 2–78%. The study addressed the general effects of solvent, temperature, and ratio of initiator to monomer. © 1993 John Wiley & Sons, Inc. Copyright © 1993 John Wiley & Sons, Inc.

Synthesis Of Organometallic Polymers, Po-Chang Chiang

Masters Theses

By the middle of the nineteenth century, organic chemists found high molecular weight compounds as by-products of some of their experiments. These compounds were thought of as products of a failed reaction. It was not until sixty years ago that the first polymers were deliberately synthesized. Today polymers are used in almost every facet of life and they are becoming more important with each passing day.

This research project focused on synthesizing conducting organometallic polymers. By linking aromatic rings with transition metals, the resultant polymers should have good electrical conductivity because of the interaction of (a) the p electrons on …

Reductive Chemistry Of Dicyanoalkane Reactive Intermediates, Beshakeh Fonkeng

Masters Theses & Specialist Projects

Radical ions are reactive intermediates that are both radicals and ions (either a radical cation or a radical anion). The intrinsic properties of radical ions are not yet well -characterized. Such knowledge is mechanistically important to the organic chemist.

The specific question that motivates this research is as follows: is it possible to controllably express free radical processes in a radical ion independent of ionic chemistry (and vice versa) and, if so, what factors dictate which type of chemistry is expressed?

Our investigation focused on the chemistry of radical anions of dicyanoalkanes that are formed upon metal reduction. Factors influencing …

The Role Of The Voltage Gradient In The Agarose Gel Electrophoresis Of Dna, David Wheeler

Theses and Dissertations in Biomedical Sciences

In Part I of this dissertation, empirical equations for predicting DNA mobility during agarose gel electrophoresis (AGE) from voltage gradient are developed from the data of McDonnel (36) for electrophoresis in a 1.6% agarose gel. These equations represented the data well for DNA between 2 and 10 kilobase pairs (KBp) in length. A computer program, called GELSIM, which incorporates these equations is described in Part II. GELSIM was designed to allow researchers to analyze electrophoresis data by predicting the effect on DNA migration of altering the voltage of electrophoresis. In this way, electrophoretic banding patterns produced using different voltages could …

Study Of Deposition Methods For Silicon Powder, Kamesh V. Gadepally, Kevin B. Tennal, Roger M. Hawk, Al Robles, James A. Gribel

Journal of the Arkansas Academy of Science

Silicon powder tends to agglomerate at normal atmospheric conditions and is, hence, difficult to aerosolize. Several methods of aerosolizing silicon powder and finally depositing it on various substrates were investigated. This paper presents the investigated methods of aerosolization. The electrostatic spray coating used in dry paint application was found to be the most suitable. The general merits of this method and its use for silicon powder deposition to form films are discussed.

Stress-Induced Infrared Frequency Shifts In Polyethylene, George A. Pfeffer, Donald W. Noid

Chemistry Faculty Publications

The molecular dynamics technique is used to study the spectral response of a polyethylene chain in a crystal environment under a mechanical deformation. The MUSIC method, which was previously shown to accurately compute dispersion curves from the time-dependent structure factor, is used. A complete characterization of frequency shifts is presented for various lamellar thickness, temperatures, stress (or pressure), and mass defects.

Computer Simulation Of The Melting Process In Linear Macromolecules, Donald W. Noid, George A. Pfeffer, Stephen Z.D. Cheng, Bernhard Wunderlich

Chemistry Faculty Publications

Polymer crystal melting kinetics is simulated by using molecular dynamics. A simplified molecular model of polyethylene crystal melting consisting of one extended chain on a polyethylene-like crystal surface is presented. The simulation data indicate that the end-to-end distance (eed) of radius of gyration (rg) has a simple exponential dependence on time. The rate constants for eed and rg are found to be temperature and molecular length dependent. A more detailed analysis of polymer crystal melting will be described.

Investigation Of The Synthesis And Polymerization Behavior Of Vinyl Benzoate, Selim Mehmet Erhan

Dissertations

The goal of this study is to present a method that gives higher conversions and molecular weights for the polymerization of vinyl benzoate than obtained in previous investigations.

Polyvinyl benzoate has benzene rings attached to the backbone chain, therefore is hard and rigid. This is a characteristic which has a large application area. However previous studies in polymerizing vinyl benzoate with bulk and solution polymerizations reported low yields and troublesome crosslinking, which has limited its application. Emulsion polymerization method has the advantage of giving high polymerization rates together with high molecular weights, and therefore was chosen as the method for …

Gas Permeation Measurements On Small Polymer Specimens, Karen S. Burns

Chemistry & Biochemistry Theses & Dissertations

Mass spectrometry was used to measure oxygen and nitrogen permeabilities while polarography was used to measure oxygen permeabilities for several contact lens materials. Applicable sample holders were designed and fabricated to accommodate curved and flat specimens with surface areas of 0.5 cm² and 1.0 cm² and thicknesses between 0.025 mm and 0.500 mm. A prepared standard was used to calibrate the mass spectrometric analyses.

The oxygen permeability values determined by mass spectrometry were significantly greater than those determined by polarography. This was attributed to the phase boundary phenomena and the limiting oxygen permeance of water inherent in the …

Investigation Of Complex Formation By Oligomers Of Cytosine And Guanosine, Steven Roberts Davis

Chemistry & Biochemistry Theses & Dissertations

Duplex formation between oligo(C:G) _n where n=3 to 4 was shown not to occur under conditions favorable for duplex formation between poly G and poly C. Instead, a stable guano sine self-structure was found to form which a T_m of 50°C for (Gp)₃ and 80°C for (Gp)₄ at strand concentrations of 10^-5M in 1M NaCl. Neither a duplex nor a self-structure formed in the absence of salt.

Oligomers of guanosine and cytosine were obtained by basic hydrolysis and separated according to chain length using DEAE Sephadex column chromatography. Separation of cytosine oligomers with chain lengths …

Studies Of Radiation Effects In Three High Polymers, Heidi Rene-Mitchell Ries

Physics Theses & Dissertations

Three high polymers, Mylar®, Ultem®, and Kapton®, were irradiated to total doses of 1, 5, and 9.5 gigarad using 1-MeV electrons. The glass transition temperatures (T_g) of the materials before and after irradiation were measured using an AC electrical dissipation factor technique. From the T_g data, it was found that the electron radiation at these total doses results in net chain scissioning in Mylar and net crosslinking in Ultem, while self-mending is predominant in Kapton. The dielectric constant was measured before and after irradiation, but no significant changes due to irradiation were observed. Electron paramagnetic resonance (EPR) …

Interaction Of Calcium With Hema/Maa Copolymers., Michael R. Van De Mark, N. D. Lian, M. Brandon, E. C. Eckstein

Chemistry Faculty Research & Creative Works

Polymeric materials based upon 2-hydroxyethyl methacrylate (HEMA) have been extensively used, especially in biomedical applications. Several reports have appeared in the literature during the past 20 years regarding the behavior of these materials upon exposure to body fluids. The results of these studies have ranged from good biocompatibility to calcification. The presence of methacrylic acid (MAA), in HEMA-based copolymers gives rise to a swelling transition at pH 7. The present study relates the swollen volume of HEMA/MAA gels to the concentrations of calcium salts at a pH where the MAA is ionized, as would occur for implanted gels. This swollen …

Excluded-Volume Effect On Quasi-Elastic Light Scattering By Flexible Macromolecules, Genzo Tanaka, Walter H. Stockmayer

Dartmouth Scholarship

First-order perturbation expressions are developed for the first cumulant (initial time derivative) of the dynamic structure factor observable by photon-correlation measurements of the light scattered by flexible chain molecules in solution. A dimensionless coefficient C, which measures the initial departure of the first cumulant from proportionality to the square of the scattering vector, is found to be only slightly altered by excluded-volume effects.

Chemistry Of Chromium Oxyfluorides And Group Vib Perfluoroglutarates, Bruce Michael Johnson

Dissertations and Theses

Pure chromium oxide trifluoride was prepared for the first time by reaction of CrO₃ and ClF with subsequent multiple fluorine treatments at 120°C. On the basis of its infrared spectrum, the purple CrOF₃ was assigned as a fluorine-bridged polymer with terminal oxygen groups. Chromium oxide trifluoride was found to be stable to 300°C, where it decomposes with the loss of oxygen to CrF₃.

High Performance Liquid Chromatographic Analysis Of Biogenic Amines, Thais Edwina Ahrendt Keegan

Chemistry & Biochemistry Theses & Dissertations

The objectives of this research were to develop a sensitive method for separation and quantitation of biogenic amines and to apply that procedure by monitoring neurochemical changes resulting from stimuli to the test system.

Primary aromatic amines were derivatized with o-phthalaldehyde-mercaptoethanol prior to chromatography, Separation of the fluorescent adduct was achieved using a μBondapak/ phenyl reversed-phase column and a two-step gradient of methanol:0.08 M acetic acid, pH J.O. Fluorescence was monitored using a J40 nm excitation energy and an emission filter which transmits radiation greater than 400 nm (50% T at 418 nanometers).

Following optimization of the chromatographic conditions, studies …

Kinetic Studies Of Polymer-Bound Rhodium (I) Hydrogenation Catalyst, Nee-Yin Chou

Masters Theses & Specialist Projects

For many years, it has been customary to classify catalysts as homogeneous or heterogeneous. Generally, the former are more active and more selective. But the major disadvantage of the homogeneous catalysts is the need to separate the reaction products and to recover the catalyst, which is often somewhat more expensive than a "classical" heterogeneous catalyst. It has been considered, especially in the last ten years, that there might be advantages in chemically binding a homogeneous catalyst to a solid support.

Polymer-bound, anthranilic acid anchored rhodium (I) catalysts have been prepared. The rate of hydrogenation of cyclohexene has been studied quantitatively, …

The Synthesis Of New Maleimide Addition Polymer Precursors, Richard B. Brown

Chemistry & Biochemistry Theses & Dissertations

1H-2,3-dimethylpyrrolo(1,2-a) benzimidazol-l-one (27) and 1H,9H- 2,3,7,8-tetramethyl-bispyrrolo(1,2-a:6,7-a')benzodiimidazo1-1,9-dione (32) have been synthesized from dimethylmaleic anhydride and o-phenylenediamine and 1,2,4,5-tetraaminobenzene, respectively. The presence of reactive olefinic double bonds in the synthesized compounds was of interest as a site for possible addition polymerization.

The synthetic route involved, in both cases, a simple nucleophilic substitution reaction between the diamine(or tetraamine) and the anhydride to form an intermediate amide-acid-amine which rapidly cyclized to the imide amine. The final ring closure required more rigorous conditions and occurred at melt reaction temperatures.