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Plasma polymerization technique is used to apply thin, adherent, hydrophobic coatings from chlorotrifluoroethylene monomer. Apparently much of the chlorine contained in original monomer is lost during polymerization, and characteristic C-Cl absorption in infrared region is essentially absent.
Polyimides having high thermal and oxidative stability are prepared by the reaction of a mixture of monomers comprising (1) a dialkyl or tetraalkyl ester of an aromatic tetracarboxylic acid; (2) an aromatic diamine; and (3) a monoalkyl or dialkyl ester of a dicarboxylic acid where in the ratio of a:b:c is n:(n+1):2, wherein n has a value from 1 to 20. The mixture of monomers is prepared in a 30 to 70 percent by weight solution of an organic solvent, a substrate impregnated with the solution and heated at 50 to 205 C to remove said solvent and form a low molecular weight prepolymer, and thereafter heated at 275 to 350 C to cure to a high molecular weight polyimide.
Although the production of crystallinity in a polymeric system has historically led to commerically useful properties, the polyimides, prized for their high temperature characteristics, as customarily synthesized by melt or solution casting, are amorphous. It is shown that polymide containing residual crystallinity can be synthesized by isothermal annealing of crystals of the salt of the diisopropyl ester of pyromellitic acid and phenylene diamine. The reaction is topochemical in that the geometry of the polymer product is dependent upon that of the crystalline precursor. Infrared spectroscopy reveals the presence of imide absorption in the polymer, while powder diffractometry suggests residual crystallinity. Single crystal X-ray analysis of the monomer yields a structure of chains of alternating acid and base suggesting that the monomer is amenable to polymerization with a minimum of geometrical disruption.
A study has been made of the thermal behavior of polyimide precursors: an isomeric pair of crystals of the complex formed by p-phenylenediamine with the separated isomers of the di-isopropyl ester of pyromellitic acid. Specimens of this material were isothermally annealed in the temperature range 120 C to 170 C for periods of time up to 1 week. Although this temperature range is well below that customarily used for imidizations, the working hypothesis was that it would be more likely that a polymer embodying at least part of the precursor structure could be formed if the molecular motion was minimized to that actually required for the formation of the imide linkage. The progress of the annealing was followed by: infrared spectroscopy, differential thermal analysis, powder X-ray diffraction, and thermal gravimetric analysis. Single crystal X-ray analysis of the meta monomer yields a structure of chains of alternating acid and base and suggests that this monomer is amenable to polymerization with a minimum of geometrical disruption.
An ion exchange hollow fiber impregnated with a vinylpyridine base was developed. The basic exchange resin used to impart the necessary permselectivity to the hollow fiber is a copolymer of vinylpyridine and dibromoethane prepared according to Rembaum. A slight pressure was used to impregnate the exchange monomer mixture into the void structure of the fiber wall, and with maintenance of subambient temperatures, the rate of cross-linking is slow enough to allow the growing polymer to permeate the wall structure before significant increase in polymer molecular weight. These ion exchange fibers are produced from polyacrylonitrile hollow fibers with an appropriate wall structure that enables the impregnating vinylpyridine monomer mixture to form a truly semipermeable anion barrier after curing.
Polyimide polymers which are thermally stable and processable are developed. The addition of alkyl substituents to an aromatic ring in the polymer backbone is examined along with polyimide precursor amines containing functional groups that allow for post-cure crosslinking. The synthesis of key monomers is reported, including 2,4,6-tris (m-aminobenzyl) 1,3,5-trimethyl benzene and 2,4,6-tris (p-aminobenzyl) 1,3,5-trimethyl benzene. The preparation of a key monomer, 2,5,3-triamino benzophenone, is reported.
Spectral and chomatographic studies were conducted which established the presence of tri- and tetraester impurities in aged monomer solutions employed in fabrication of PMR-polyimide resin composites. The equilibrium constant and apparent rate of the esterification were determined. It was demonstrated, using differential scanning calorimetry, that the ortho-ester moiety of these impurities does not completely react at typical cure conditions. It is concluded that voids formed in composites fabricated with aged monomer solution are due to gaseous decomposition products evolved by ester impurities and/or unreacted amine during elevated temperature post-cure treatment.
Flame resistant fibrous materials for space shuttle application were developed through chemical modification of commercially available aromatic polyamide fibrous products. The new surface treatment was achieved in the laboratory by ultraviolet activation of the fabric in the presence of fluoroolefin monomers and a diluent gas. The monomers grafted under these conditions provide the improved properties of the fabric in flame resistance, chemical inertness, and nonwettability without the sacrifice of color or physical properties. The laboratory reaction vessel was scaled-up to a batch continuous process, which treats ten yards of the commercial width textiles. The treated commercial width Nomex (HT-10-41) from the scaled-up reactor is self-extinguishing in an oxygen-enriched environment, water-repellent, soft, silky, and improved in chemical resistance. Unlike most textile processes, the grafting unit operates under dry conditions and no chemical by-products have to be washed out of the finished product.
Co gamma irradiation of 2-hydroxyethyl methacrylate in the presence or in the absence of other acrylic monomers was found to constitute an effective technique for the synthesis of hydrophilic functional microspheres in the size range of approximately 0.3 to 3 microns in diameter. The effect of monomer concentration, steric stabilization, and electrostatic interaction on the particle size was investigated. Experimental conditions were determined to obtain desired particle sizes of relatively narrow distribution. It was shown that particles may be formed without intermediate micelles, i.e., by homogeneous nucleation, and the rate of particle formation is affected primarily by the rate of particle coalescence in the initial stages of the reaction. When covalently bound to antibodies these microspheres were successfully used to label murine and human lymphocytes.
The addition polyimide, LARC-160, which was originally synthesized from low cost liquid monomers as a laminating resin in ethanol, was prepared as a solventless, high viscosity, neat liquid resin. The resin was processed by hot-melt coating techniques into graphite prepreg with excellent tack and drape. Comparable data on graphite reinforced laminates made from solvent-coated and various hot-melt coated prepreg were generated. LARC-160, because of its liquid nature, can be easily autoclave processed to produce low void laminates. Liquid chromatographic fingerprints indicate good reaction control on resin scale ups. Minor changes in monomer ratios were also made to improve the thermal aging performance of graphite laminates.
A method is described for adhering bone to the surface of a rigid substrate such as a metal or resin prosthesis using an improved surgical bone cement. The bone cement has mechanical properties more nearly matched to those of animal bone and thermal curing characteristics which result in less traumatization of body tissues and comprises a dispersion of short high modulus graphite fibers within a bonder composition including polymer dissolved in reactive monomer such as polymethylmethacrylate dissolved in methylmethacrylate monomer.
Current PMR Polyimide prepreg technology utilizes methanol or ethanol solvents for preparation of the PMR prepreg solutions. The volatility of these solvents limits the tack and drape retention characteristics of unprotected prepreg exposed to ambient conditions. Studies conducted to achieve PMR 15 Polyimide prepreg with improved tack and drape characteristics were described. Improved tack and drape retention were obtained by incorporation of an additional monomer. The effects of various levels of the added monomer on the thermo-oxidative stability and mechanical properties of graphite fiber reinforced PMR 15 composites exposed and tested at 316 C (600 F) were discussed.
Thermally stable polyimide polymers were prepared. Parameters explored include asymmetry of substitution, addition of alkyl substituents to an aromatic ring, and an increase in the number of aromatic rings present in the diamine monomer. It is shown that the use of an asymmetrical diamine in the preparation of a polyimide produces a polymer with a markedly lowered glass transition temperature. This is achieved with little or no sacrifice of thermal stability. An alternate approach taken was to prepare imide monomers which are capable of addition-type polymerization.
Current PMR Polyimide prepreg technology utilizes methanol or ethanol solvents for preparation of the PMR prepreg solutions. The volatility of these solvents limits the tack and drape retention characteristics of unprotected prepreg exposed to ambient conditions. Studies conducted to achieve PMR 15 Polyimide prepreg with improved tack and drape characteristics are described. Improved tack and drape retention were obtained by incorporation of an additional monomer. The effects of various levels of the added monomer on the thermo-oxidative stability and mechanical properties of graphite fiber reinforced PMR 15 composites exposed and tested at 316 C (600 F) are discussed.
A plasma polymerization process for the deposition of a dielectric polymer coating on a substrate comprising disposing of the substrate in a closed reactor between two temperature controlled electrodes connected to a power supply is presented. A vacuum is maintained within the closed reactor, causing a monomer gas or gas mixture of a monomer and diluent to flow into the reactor, generating a plasma between the electrodes. The vacuum varies and controls the dielectric constant of the polymer coating being deposited by regulating the gas total and partial pressure, the electric field strength and frequency, and the current density.
A model is presented which enables the temperature at which olivine is in equilibrium with any alkali-depleted basaltic compound to be calculated to within + or - 30 C. It is noted that the error increases substantially when applied to terrestrial basalts which contain several weight percent alkalis. In addition the model predicts and quantifies the reduced activity of SiO4(4-) monomers due to increasing SiO2 concentrations in the melt. It is shown that the coordination of alumina in melts which precipitate olivine only appears to be dominantly octahedral, while titanium acts as a polmerizing agent by interconnecting previously isolated SiO4(4-) monomers. It is concluded that the model is sufficiently sensitive to show that there are small repulsive forces between Mg(2+) and calcium ions which are in association with normative diopside in the melt.
Eighteen aromatic unsaturated polyester prepolymers prepared by a modified interfacial condensation technique were investigated for their solubility in vinyl monomers and ability to provide high char yield forming unsaturated polyester resins. The best resin system contained a polyester prepolymer of phthalic, fumaric and diphenic acids reacted with 2,7-naphthalene diol and 9,9-bis(4-hydroxyphenyl)fluorene. This prepolymer is very soluble in styrene, divinyl benzene, triallyl cyanurate, diallyl isophthalate and methylvinylpyridine. It provided anaerobic char yields as high as 41 percent at 800 C. The combination of good solubility and char yield represents a significant improvement over state-of-the-art unsaturated polyester resins. The majority of the other prepolymers had only low or no solubility in vinyl monomers. Graphite composites from this prepolymer with styrene were investigated. The cause for the observed low shear strengths of the composites was not determined, however 12-week aging of the composites at 82 C showed that essentially no changes in the composites had occurred.
Polymeric membranes suitable for use in reverse osmosis water purification because of their high urea and salt rejection properties are prepared by generating a plasma of an unsaturated hydrocarbon monomer and nitrogen gas from an electrical source. A polymeric membrane is formed by depositing a polymer of the unsaturated monomer from the plasma onto a substrate, so that nitrogen from the nitrogen gas is incorporated within the polymer in a chemically combined form.