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At least 289 records · Page 16

Perfluoroether triazine elastomers

The synthesis of high performance elastomers with the high thermal stability and chemical, inertness of perfluoroalkylene triazine and a low glass transition temperature is discussed. Perfluorether triazine elastomers were proposed as potentially superior. It is concluded that the difficulties experienced in fluoroalkytriazine elastomer synthesis can be overcome by a four-step reaction process involving chain extension, triazine ring closure, crosslinking, and elastomer curing. Molecular weight can be controlled in the initial polymer formation so that elastomer modulus can be determined. The final product elastomers exhibit a useful elastomeric range of approximately 45 to 325 C with an oxidative stability superior to other broad range elastomers.

Korus, R. A.↗

Template-directed oligonucleotide ligation on hydroxylapatite

It has been suggested that the prebiotic synthesis of the precursors of biopolymers could have occurred on a solid surface such as that provided by clay or some other mineral. One such scheme envisages that growing polymers were localized by adsorption to a mineral surface where an activating agent or activated monomers were supplied continuously or cyclically. Here, it is reported that a sequence of reactions in which initially formed oligo(G)s are reactivated by conversion to phosphorimidazolides in the presence of poly(C) and then allowed to ligate is ideal, in that repeated cycles can be carried out on the surface of hydroxylapatite, whereas in the liquid phase the cycle could be achieved only with considerable difficulty.

Acevedo, O. L.↗

Preparation of B-trichloroborazine

The present invention relates to a method of preparing B-trichloroborazine. Generally, the method includes the combination of gaseous boron trichloride in an anhydrous aprotic organic solvent followed by addition of excess gaseous ammonia at ambient temperature or below. The reaction mixture is heated to about 100 to 140 C followed by cooling, removal of the solid ammonium chloride at ambient temperature, distillation of the solvent under vacuum if necessary at a temperature of up to about 112 C, and recovery of the B-trichloroborazine. Solvents include toluene, benzene, xylene, chlorinated hydrocarbons, chlorinated aromatic compounds, or mixtures thereof. Toluene is a preferred solvent. The process provides a convenient synthesis of a material which often decomposes on standing. B-trichloroborazine is useful in a number of chemical reactions, and particularly in the formation of high temperature inorganic polymers and polymer precursors.

Riccitiello, Salvatore R.↗

Non-Genomic Origins of Proteins and Metabolism

It is proposed that evolution of inanimate matter to cells endowed with a nucleic acid- based coding of genetic information was preceded by an evolutionary phase, in which peptides not coded by nucleic acids were able to self-organize into networks capable of evolution towards increasing metabolic complexity. Recent findings that truly different, simple peptides (Keefe and Szostak, 2001) can perform the same function (such as ATP binding) provide experimental support for this mechanism of early protobiological evolution. The central concept underlying this mechanism is that the reproduction of cellular functions alone was sufficient for self-maintenance of protocells, and that self- replication of macromolecules was not required at this stage of evolution. The precise transfer of information between successive generations of the earliest protocells was unnecessary and, possibly, undesirable. The key requirement in the initial stage of protocellular evolution was an ability to rapidly explore a large number of protein sequences in order to discover a set of molecules capable of supporting self- maintenance and growth of protocells. Undoubtedly, the essential protocellular functions were carried out by molecules not nearly as efficient or as specific as contemporary proteins. Many, potentially unrelated sequences could have performed each of these functions at an evolutionarily acceptable level. As evolution progressed, however proteins must have performed their functions with increasing efficiency and specificity. This, in turn, put additional constraints on protein sequences and the fraction of proteins capable of performing their functions at the required level decreased. At some point, the likelihood of generating a sufficiently efficient set of proteins through a non-coded synthesis was so small that further evolution was not possible without storing information about the sequences of these proteins. Beyond this point, further evolution required coupling between proteins and informational polymers that is characteristic to all known forms of life. The emergence of such coupling must be postulated in any scenario of the origin of life, no matter whether it starts with RNA or proteins. To examine the evolutionary potential of non-genomic systems, a simple, computationally tractable model, which is still capable of capturing the essential features of the real system, has been studied computationally. Both constructive and destructive processes have been introduced into the model in a stochastic manner. Instead of assuming random reaction sets, only a suite of protobiologically plausible reactions has been considered. Peptides have been explicitly considered as protoenzymes and their catalytic efficiencies have been assigned on the basis of biochemical principles and experimental estimates. Simulations have been carried out using a novel approach (The Next Reaction Method) that is appropriate even for very low concentrations of reactants. Studies have focused on global autocatalytic processes and their diversity.

Pohorille, Andrew↗

Evaluating experimental artifacts in hydrothermal prebiotic synthesis experiments

Control experiments with ultra pure deionized water were conducted to evaluate the organic contamination in hydrothermal prebiotic experiments. Different combinations of reaction vessel material, sampling tubing and stirring were tested and the amounts of organic contaminants determined. All tested types of polymer tubing were proven to introduce organic contaminants (formate, acetate and propionate ions) into the reacting solution. Stainless steel has a catalytic effect on the decomposition of formate, consistent with earlier work at high temperatures and pressures.

Equipment and Supplies↗

Effects of multifunctional crosslinking agents on the thermomechanical properties of polyimide films

The potential of high temperature resistant polymers such as polyimides (PI) and polyphenylquinoxalines (PPQ) as matrix resins in fiber-reinforced composites has not been fully realized to date. One of the problems associated with these resins is that they exhibit creep, or thermoplastic yielding under load at temperatures approaching 316 C (600 F). The purpose of this investigation was to further reduce thermoplastic behavior of polyimide resins by substituting a controlled amount of the diamine monomer with crosslinking agents having a higher amine functionality. The knowledge gained from a study of the thermomechanical properties of the crosslinked resins would then be used in the fabrication of fiber-reinforced polyimide composites. This report describes the synthesis and characterization of three new polyfunctional amines. Polyimide films containing varying amounts of the cross-linking agents were prepared, and their properties compared with those of control samples prepared with difunctional amines. The effect of crosslink density on isothermal weight loss, polymer softening, and glass transition temperatures is discussed.

Delvigs, P.↗

Development of Highly-Conductive Polyelectrolytes for Lithium Batteries

Future NASA and Air Force missions require reliable and safe sources of energy with high specific energy and energy density that can provide thousands of charge-discharge cycles at more than 40% depth- of-discharge and that can operate at low temperatures. All solid-state batteries have substantial advantages with respect to stability, energy density, storage fife and cyclability. Among all solid-state batteries, those with flexible polymer electrolytes offer substantial advantages in cell dimensionality and commensurability, low temperature operation and thin film design. The above considerations suggest that lithium-polymer electrolyte systems are promising for high energy density batteries and should be the systems of choice for NASA and US Air Force applications. Polyelectrolytes (single ion conductors) are among most promising avenues for achieving a major breakthrough 'in the applicability of polymer- based electrolyte systems. Their major advantages include unit transference number for the cation, reduced cell polarization, minimal salt precipitation, and favorable electrolyte stability at interfaces. Our research is focused on synthesis, modeling and cell testing of single ion carriers, polyelectrolytes. During the first year of this project we attempted the synthesis of two polyelectrolytes. The synthesis of the first one, the poly(ethyleneoxide methoxy acrylateco-lithium 1,1,2-trifluorobutanesulfonate acrylate, was attempted few times and it was unsuccessful. We followed the synthetic route described by Cowie and Spence. The yield was extremely low and the final product could not be separated from the impurities. The synthesis of this polyelectrolyte is not described in this report. The second polyelectrolyte, comb polysiloxane polyelectrolyte containing oligoether and perfluoroether sidechains, was synthesized in sufficient quantity to study the range of properties such as thermal stability, Li- ion- conductivity and stability toward lithium metal. Also, the batteries containing this polyelectrolyte were assembled and tested. The results are detailed below. The synthesis of another polyelectrolyte similar to polysiloxane polyelectrolyte has been started, however, the synthesis was not completed due to termination of the project.

Shriver, D. F.↗

Ketimine modifications as a route to novel amorphous and derived semicrystalline poly(arylene ether ketone) homo- and copolymers

A series of amine terminal amorphous poly(arylene ether ketone) oligomers of controlled molecular weights (2-15 K) were synthesized. These oligomers have been found to undergo 'self-crosslinking' reactions upon heating above 220 C, via the reaction of the terminal amine groups with the in-chain keto carbonyl functionalities. The resulting networks are ductile, chemically resistant, and nonporous. The networks obtained via generated ketimine functionality were characterized by solid state NMR. They have also been found to be remarkably stable toward hydrolysis. Ketimine functional bishalide monomers have also been synthesized. Such monomers have been utilized to synthesize a wide variety of amorphous poly(arylene ether) ketimine polymers. A high molecular weight hydroquinone functional poly(arylene ether) ketimine has been acid treated to regenerate a poly(arylene ether ketone) backbone in solution. This novel procedure thus allows for the synthesis of important matrix resins under relatively mild conditions.

Mohanty, D. K.↗

Easily Processable High-Temperature Polyimide

Polymerization without volatile gases leads to high-quality resins. N-CYCAP (amiNe substituted CYClophane Addition Polyimide) is thermoset polyimide developed containing 4-amino{2.2}paracyclophane as end cap. Current improvements in synthesis of end cap include increasing yield to 60 percent overall and decreasing manufacturing time by simplifying synthetic procedure. Enables large-scale production and increases viability of cyclophane end caps for polymers for high-temperature applications. In comparison with neat resin moldings and composite matrix resins made of PMR-II-50, those made of N-CYCAP polymers found to be processable with lower void content and higher thermo-oxidative stability.

Sutter, James K.↗

On the Oxidative Degradation of Nadic End-Capped Polyimides: Synthesis and Characterization of Model Compounds for End-Cap Degradation Products - 3

The oxidative degradation of PMR (for polymerization of monomeric reactants) polyimides at elevated temperatures was followed by cross-polarized magic angle spinning (CP-MAS) NMR. Labeling of selected sites in the polymers with C-13 allowed for direct observation of the transformations arising from oxidation processes. The formation of several degradation products has been proposed to be occurring in the cross-links derived from the nadic end caps on oxidation. Model compounds have been synthesized and characterized by CPMAS NMR with both normal and delayed decoupling to distinguish between protonated and unprotonated carbons. Comparison of these spectra to predicted chemical shifts of proposed products for the aged polymer provides further insight to degradation occurring in the cross-linked moieties.

Meador, Mary Ann B.↗

Synthesis of Flexible Polyamide Aerogels Cross-Linked with a Tri-Isocyanate

A new series of flexible polyamide (PA) aerogels was synthesized using terephthaloyl chloride (TPC), 2,2′-dimethylbenzidine (DMBZ) and cross-linked with an inexpensive, commercially available tri-isocyanate (Desmodur N3300A) at polymer concentrations of 6–8 wt.% total solids and repeating units, n, from 30 to 60. The cross-linked DMBZ-based polyamide aerogels obtained, after supercritically drying using liquid CO 2 , had shrinkages of 19–27% with densities ranging from 0.12 g/cm 3 to 0.22 g/cm 3 , porosity and surface areas up to 91% and 309 m 2 /g, respectively, and modulus values ranging from 20.6 to 109 MPa. Evidence suggests that a higher flexibility could be achieved using DMBZ in the polyamide backbone with N3300A as a cross-linker, when compared to previously reported TPC-mPDA-BTC PA aerogels, N3300A-polyimide aerogels, and N3300-reinforced silica aerogels.

aerogels↗

Synthesis and Characterization of Modified Phenylethynyl Terminated Polyimides

As an ongoing effort to develop structural adhesives for high performance aerospace applications, recent work has focused on phenylethynyl terminated imide (PETI) oligomers. The work reported herein involves the synthesis and characterization of a series of phenylethynyl containing oligomers designated LARC (TM) MPEI (Modified Phenylethynyl Terminated Polyimide). These oligomers contain mixtures of linear, branched and star-shaped molecules. The fully imidized polymers exhibited minimum melt viscosity as low as 600 poise at 335 C. Ti/Ti lap shear specimens processed at 288 C under 15 psi showed tensile shear strength of approx. 6000 psi and 5200 psi at ambient and 350 F temperatures, respectively. The chemistry and properties of these new MPEIs are presented and compared to an optimized linear PETI, LaRC(Tm) -PETI-5.

Chang, Alice C.↗

Synthesis and Characterization of Modified Phenylethynyl Imides

As an ongoing effort to develop structural adhesives for high-performance aerospace applications, recent work has focused on phenylethynyl terminated imide (PETI) oligomers. The work reported herein involves the synthesis and characterization of a series of phenylethynyl containing oligomers designated LARC(TM) MPEI (modified phenylethynyl imide). These oligomers presumably contain mixtures of linear, branched and star-shaped molecules. The fully imidized polymers exhibited minimum melt viscosities as low as 600 poise at 335 C, significantly lower than equivalent molecular weight linear materials. Ti/Ti lap shear specimens processed at 288 C under 15 psi showed tensile shear strengths as high as approx. 6000 psi and 5200 psi at ambient temperature and 177 C respectively. The chemistry and properties of these new MPEIs are presented and compared with an optimized linear PETI, LARC(TM)PETI-5.

Jensen, B. J.↗

Flame Synthesis Used to Create Metal-Catalyzed Carbon Nanotubes

Metal-catalyzed carbon nanotubes are highly ordered carbon structures of nanoscale dimensions. They may be thought of as hollow cylinders whose walls are formed by single atomic layers of graphite. Such cylinders may be composed of many nested, concentric atomic layers of carbon or only a single layer, the latter forming a single-walled carbon nanotube. This article reports unique results using a flame for their synthesis. Only recently were carbon nanotubes discovered within an arc discharge and recognized as fullerene derivatives. Today metal-catalyzed carbon nanotubes are of great interest for many reasons. They can be used as supports for the metal catalysts like those found in catalytic converters. Open-ended nanotubes are highly desirable because they can be filled by other elements, metals or gases, for battery and fuel cell applications. Because of their highly crystalline structure, they are significantly stronger than the commercial carbon fibers that are currently available (10 times as strong as steel but possessing one-sixth of the weight). This property makes them highly desirable for strengthening polymer and ceramic composite materials. Current methods of synthesizing carbon nanotubes include thermal pyrolysis of organometallics, laser ablation of metal targets within hydrocarbon atmospheres at high temperatures, and arc discharges. Each of these methods is costly, and it is unclear if they can be scaled for the commercial synthesis of carbon nanotubes. In contrast, flame synthesis is an economical means of bulk synthesis of a variety of aerosol materials such as carbon black. Flame synthesis of carbon nanotubes could potentially realize an economy of scale that would enable their use in common structural materials such as car-body panels. The top figure is a transmission electron micrograph of a multiwalled carbon nanotube. The image shows a cross section of the atomic structure of the nanotube. The dark lines are individual atomic layer planes of carbon, seen here in cross section. They form a nested series of concentric cylinders, much like the growth rings on a tree. This sample was obtained by the supported catalyst method, whereby the nanoscale catalysts are dispersed on a substrate providing their support. The substrate with catalyst particles was immersed within an acetylene diffusion flame to which nitrogen had been added to eliminate soot formation. Upon removal from the flame, the nanotubes were dispersed on a holder suitable for electron microscopy. Although not seen in the figure, the tube diameter reflects that of the catalyst particle.

VanderWal, Randy L.↗

Development of modified poly(perfluoropropyleneoxide) urethane systems for use in liquid oxygen and in enriched 100 percent oxygen atmosphere

This program consisted of two separate though related phases. The initial phase was directed toward improving the mechanical and adhesive properties of the very highly fluorinated-polyurethane resin system derived from the hydroxyl-terminated polyperfluoropropylene oxide and 6-chloro-2,4,5-trifluoro-m-phenylene diisocyanate. Various new curing agents for this system were investigated, with the goal of providing a more thermally stable crosslink (cure) mechanism to provide wider applicability and fuller utilization of the outstanding oxygen resistance of the PFPO system. Complete resistance to liquid- and gaseous-oxygen impact at presures as high as 1035 N/sq cm were attained with the use of the PFPO resin castings. The second corollary phase was directed toward investigating the feasibility and optimization of the allophanate cured, urethane extended polymer derived from hydroxyl-terminated polyperfluoropropyleneoxide and 6-chloro-2,4,5-trifluoro-m-phenylene diisocyanate, as the adhesive system for use in a weld-bond configuration for liquid oxygen tankage. The synthesis and application procedures of the adhesive system to insure liquid oxygen compatibility (under 10 kg-m loading), and the development of procedures and techniques to provide high quality weld-bonded joint configurations were studied.

Harrison, E. S.↗

Di(hydroxyphenyl)- benzimidazole monomers

Di(hydroxyphenyl)benzimidazole monomers were prepared from phenyl-hydroxybenzoate and aromatic bis(o-diamine)s. These monomers were used in the synthesis of soluble polybenzimidazoles. The reaction involved the aromatic nucleophilic displacement of various di(hydroxyphenyl)benzimidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds in the presence of an alkali metal base. These polymers exhibited lower glass transition temperatures, improved solubility, and better compression moldability over their commercial counterparts.

Connell, John W.↗

Polybenzimidazole via aromatic nucleophilic displacement

Di(hydroxyphenyl)benzimidazole monomers were prepared from phenyl-4-hydroxybenzoate and aromatic bis(o-diamine)s. These monomers were used in the synthesis of soluble polybenzimidazoles. The reaction involved the aromatic nucleophilic displacement of various di(hydroxyphenyl)benzimidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds in the presence of an alkali metal base. These polymers exhibited lower glass transition temperatures, improved solubility, and better compression moldability over their commercial counterparts.

Connell, John W.↗