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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 805-829 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: During the past decade the aerospace industry has sought materials for bonding stainless-steel and titanium alloys that have a high degree of thermal and oxidative stability. The Air Force Materials Laboratory has anticipated these requirements and sponsored many development programs aimed at achieving these goals. This paper describes the results of one such program devoted to development of high-temperature adhesives from aromatic imide polymers. The family of polymeric materials known as aromatic polyimides possess excellent thermal and oxidative resistance at temperatures up to 650°F. Mechanical and electrical properties of glass-fiber-reinforced laminates prepared with these polymers have been reported. This work has been extended to the development of structural adhesives that will withstand long-time exposure in air at 600°F. Stainless steel and titanium have been successfully bonded with adhesives made from aromatic imide and benzimidazole imide polymers. Bonds made with stainless steel have retained approximately 80% of their original strength at 600°F. after 1000 hr. of aging at 600°F. Adhesives made with benzimidazole imide polymers are the prepared materials for bonding titanium. Initial bond strengths of 1300 psi have been measured at 600°F. After 1000 hr. at 600°F. the bond strengths drop to 800 psi. The processing conditions for making a bond are quite moderate, except that a high temperature is required. The preparation and processing conditions associated with these adhesives are described. A large number of aromatic imide and amide-imide polymers have been prepared and adhesives formulated. By comparing the bond strengths obtained with these adhesives it is possible to deduce the effect of molecular weight and various molecular components on bond strength.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2063-2075 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Divalent organochromium compounds, Cr(Lig)2, often become active catalysts for the polymerization of ethylene when deposited onto an oxide carrier such as silica or aluminophosphate. Hydroxyl groups are thought to react, releasing one ligand and binding the chromium to the surface. The behavior of the catalyst is then governed by the remaining ligand and the type of carrier. In this study two types of ligands were investigated: cyclopentadienyl and its open ring analog dimethylpentadienyl. This small difference in the type of ligand produces a fundamental difference in the polymerization mechanism. For comparison the mixed ligand chromocene, with one open and one closed ligand, was also synthesized and tested for polymerization.
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  • 3
    ISSN: 0006-3525
    Keywords: antifungal therapy ; Candida albicans ; peptidic inhibitors ; peptidomimetic inhibitors ; myristoylCoA ; protein N-myristoyltransferase ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: MyristoylCoA: protein N-myristoyltransferase (NMT) catalyzes the cotranslational covalent attachment of a rare cellular fatty acid, myristate, to the N-terminal Gly residue of a variety of eukaryotic proteins. The myristoyl moiety is often essential for expression of the biological functions for these proteins. Attachment of C14:0 alone provides barely enough hydrophobicity to allow stable association with membranes. The partitioning of N-myrisotyl-proteins is therefore often modulated by “switches” that function through additional covalent or noncovalent modifications.Candida albicans, the principal cause of systemic fungal infection in immunocompromised humans, contains a single NMT gene that is essential for its viability. The functional properties of the acylCoA binding site of human and C. albicans NMT are very similar. However, there are distinct differences in their peptide binding sites. An ADP ribosylation factor (Arf) is included among the few cellular protein substrates of the fungal enzyme. Alanine scanning mutagenesis of an octapeptide derived from an N-terminal Arf sequence (GLYASKLS-NH2) disclosed that Gly1, Ser5, and Lys6 play predominant roles in binding. ALYASKLS-NH2 is an inhibitor competitive for peptide [Ki(app) = 15.3±6.4 μM] and noncompetitive for myristoylCoA. Remarkably, replacement of the N-terminal tetrapeptide with an 11-aminoundecanoyl group results in a competitive inhibitor (11-aminoundecanoyl-SKLS-NH2) that is ∼ 40-fold more potent [Ki(app) = 0.40 ± 0.03 μM] than the starting octapeptide. Removal of Leu-Ser from the C-terminus generates a competitive dipeptide inhibitor (11-aminoundecanoyl-SK-NH2) with a Ki(app) of 11.7 ± 0.4 μM, equivalent to that of the starting octapeptide. A derivative dipeptide inhibitor containing a C-terminal N-cyclohexylethyl lysinamide moiety has the advantage of being more potent (IC50 = 0.11 ± 0.03 μM) and resistant to digestion by cellular carboxypeptidases. Rigidifying the flexible aminoundecanoyl chain results in very potent general NMT inhibitors (IC50 = 40-50 nM). Substituting a 2-methylimidazole for the N-terminal amine and adding a benzylic α-methyl group with R streochemistry to the rigidifying element produces even more potent inhibitors (IC50 = 20-50 nM) that are up to 500-fold selective for the fungal compared to human enzyme. A related less potent member of this series of compounds in fungistatic. Its growth inhibitory effects are associated with a reduction in cellular protein N-myristoylation, judged using cellular Arf as a reporter. These studies establish that NMT is a new antifungal target. © 1997 John Wiley & Sons, Inc. Biopoly 43: 43-71, 1997
    Additional Material: 75 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2613-2621 
    ISSN: 0887-6266
    Keywords: poly(1-trimethylsilyl-1-propyne) ; poly(1-phenyl-1-propyne) ; blends ; hydrocarbons ; hydrogen ; mixed gas transport ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The gas permeation properties of poly(1-trimethylsilyl-1-propyne) (PTMSP), poly(1-phenyl-1-propyne) (PPP), and blends of PTMSP and PPP have been determined with hydrocarbon/hydrogen mixtures. For a glassy polymer, PTMSP has unusual gas permeation properties which result from its very high free volume. Transport in PPP is similar to that observed in conventional, low-free-volume glassy polymers. In experiments with n-butane/hydrogen gas mixtures, PTMSP and PTMSP/PPP blend membranes were more permeable to n-butane than to hydrogen. PPP, on the other hand, was more permeable to hydrogen than to n-butane. As the PTMSP composition in the blend increased from 0 to 100%, n-butane permeability increased by a factor of 2600, and n-butane/hydrogen selectivity increased from 0.4 to 24. Thus, both hydrocarbon permeability and hydrocarbon/hydrogen selectivity increase with the PTMSP content in the blend. The selectivities measured with gas mixtures were markedly higher than selectivities calculated from the corresponding ratio of pure gas permeabilities. The difference between mixed gas and pure gas selectivity becomes more pronounced as the PTMSP content in the blend increases. The mixed gas selectivities are higher than pure gas selectivities because the hydrogen permeability in the mixture is much lower than the pure hydrogen permeability. For example, the hydrogen permeability in PTMSP decreased by a factor of 20 as the relative propane pressure (p/psat) in propane/hydrogen mixtures increased from 0 to 0.8. This marked reduction in permanent gas permeability in the presence of a more condensable hydrocarbon component is reminiscent of blocking of permanent gas transport in microporous materials by preferential sorption of the condensable component in the pores. The permeability of PTMSP to a five-component hydrocarbon/hydrogen mixture, similar to that found in refinery waste gas, was determined and compared with published permeation results for a 6-Å microporous carbon membrane. PTMSP exhibited lower selectivities than those of the carbon membrane, but permeability coefficients in PTMSP were nearly three orders of magnitude higher. © 1996 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2981-3000 
    ISSN: 0887-6266
    Keywords: sorption ; diffusion ; acetone ; poly(ethylene terephthalate) ; poly(ethylene 2,6-naphthalate) ; copolymers ; positron annihilation lifetime spectroscopy ; infrared spectroscopy ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Random copolymers of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalate) (PEN) were synthesized by melt condensation. In a series of thin, solvent cast films of varying PEN content, acetone diffusivity and solubility were determined at 35°C and an acetone pressure of 5.4 cm Hg. The kinetics of acetone sorption in the copolymer films are well described by a Fickian model. Both solubility and diffusivity decrease with increasing PEN content. The acetone diffusion coefficient decreases 93% from PET to PET/85PEN, a copolymer in which 85 weight percent of the dimethyl terephthalate in PET has been replace by dimethyl naphthalate 2,6-dicarboxylate. The acetone solubility coefficient in the amorphous regions of the polymer decreases by approximately a factor of two over the same composition range. The glass/rubber transition temperatures of these materials rise monotonically with increasing PEN content. Copolymers containing 20 to 80 wt % PEN are amorphous. Samples with 〈20% or 〉80% PEN contain measurable levels of crystallinity. Estimated fractional free volume in the amorphous regions of these samples is lower in the copolymers than in either of the homopolymers. Relative free volume as probed by positron annihilation lifetime spectroscopy (PALS) decreases systematically with increasing PEN content. Acetone diffusion coefficients correlate well with PALS results. Infrared spectroscopy suggests an increase in the fraction of ethylene glycol units in the trans conformation in the amorphous phase as the concentration of PEN in the copolymer increases. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2981-3000, 1998
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  • 6
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The kinetics of the thermal decomposition of the polyester, Laminac 4116, were investigated in air and argon at atmospheric pressure by means of a continuous recording thermobalance and by differential thermal analysis. Samples were heated from ambient temperature to 600°C. at rates of 5°/min. and 15°/min. In air and argon, decompostion commences at 200°C. and is complete at 550 and 450°C., respectively. Four modes of degradation in oxygen and two in argon are indicated from derivative plots of the thermogravimetric curves. The kinetics of reaction were evaluated by the method of Freeman and Carroll. In the presence of air, the initial stage of reaction appears to involve formation of an unstable hydroperoxide intermediate which undergoes rearrangement and degradation. The energy of activation was calculated to be 19 kcal./mole. An exotherm corresponding to this first stage of degradation is observed by differential thermal analysis. The second and third stages of reaction in air correspond approximately to the two stages in argon with respect to their endothermal nature and to the temperature regions over which they occur. Mass spectrometric and infrared analysis were employed for identification of gaseous and volatile products. The fourth stage of reaction in air appears to involve the oxidation of carbon to carbon dioxide. Mechanisms of reaction are proposed and discussed.
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  • 7
    ISSN: 0887-6266
    Keywords: liquid crystalline polymer ; nematic ; isotropic/nematic transition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An aromatic copolyester composed of 25 mol % phenyl hydroquinone, 10 mol % isophthalic acid, 40 mol % chloroterephthalic acid, and 25 mol % t-butyl hydroquinone (PICT) has been synthesized. This amorphous, glassy polymer is soluble in common organic solvents such as methylene chloride. Thin, solution-cast films may be prepared which are in a metastable, vitrified, optically isotropic state. On first heating of an isotropic film at 20°C/min in a calorimeter, one glass transition is observed at low temperature (approximately 49°C) and is ascribed to the glass/rubber transition of the metastable, isotropic polymer. This thermal event is followed by a small exotherm due to the development of order during the scan, which results in a second Tg at approximately 125°C. This Tg is associated with the glass/rubber transition of the ordered polymer. Nematic order can be developed by thermal annealing. The lower Tg increases toward the upper Tg as annealing time is increased. For an initially isotropic film annealed at 90°C, the increase of the lower Tg with annealing time and the increase in birefringence observed by optical microscopy are governed by similar kinetics. Isotropization occurs in the temperature range of 250-300°C. The nematic polymer is slightly more dense than its isotropic analog. No detectable differences between isotropic and nematic samples were observed in rotating frame proton spin lattice relaxation times. © 1996 John Wiley & Sons, Inc.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 1925-1934 
    ISSN: 0887-6266
    Keywords: poly(1-trimethylsilyl-1-propyne) ; poly(1-phenyl-1-propyne) ; blends ; sorption ; hydrocarbons ; sorption models ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Propane and n-butane sorption in blends of poly(1-trimethylsilyl-1-propyne) (PTMSP) and poly(1-phenyl-1-propyne) (PPP) have been determined. Solubilities of propane and n-butane increased as the PTMSP content in the blends increased. This result is consistent with the higher free volume of PTMSP-rich blends and the better thermodynamic compatibility between PTMSP and these hydrocarbons. Propane and n-butane sorption isotherms were well described by the dual-mode model for sorption in glassy polymers. PTMSP/PPP blends are strongly phase-separated, heterogeneous materials. A noninteracting domain model developed for sorption in phase-separated glassy polymer blends suggests that sorption in the Henry's law regions (i.e., the equilibrium, dense phase of the blends) is consistent with the model. However, Langmuir capacity parameters in the blends are lower than predicted from the domain model, suggesting that the amount of nonequilibrium excess free volume associated with the Langmuir sites depends on blend composition. © 1996 John Wiley & Sons, Inc.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2209-2222 
    ISSN: 0887-6266
    Keywords: poly(1-trimethylsilyl-1-propyne) ; poly(1-phenyl-1-propyne) ; blends ; gas and vapor transport ; NMR ; Maxwell model ; Bruggeman model ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Pure gas and hydrocarbon vapor transport properties of blends of two glassy, polyacetylene-based polymers, poly(1-trimethylsilyl-1-propyne) [PTMSP] and poly(1-phenyl-1-propyne) [PPP], have been determined. Solid-state CP/MAS NMR proton rotating frame relaxation times were determined in the pure polymers and the blends. NMR studies show that PTMSP and PPP form strongly phase-separated blends. The permeabilities of the pure polymers and each blend were determined with hydrogen, nitrogen, oxygen, carbon dioxide, and n-butane. PTMSP exhibits unusual gas and vapor transport properties which result from its extremely high free volume. PTMSP is more permeable to large organic vapors, such as n-butane, than to small, permanent gases, such as hydrogen. PPP exhibits gas permeation characteristics of conventional low free volume glassy polymers; PPP is more permeable to hydrogen than to n-butane. In PTMSP/PPP blends, both n-butane permeability and n-butane/hydrogen selectivity increase as the PTMSP content of the blends increases. © 1996 John Wiley & Sons, Inc.
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1483-1490 
    ISSN: 0887-6266
    Keywords: poly(1-trimethylsilyl-1-propyne) ; physical aging ; hydrocarbon vapors ; mixed gas permeation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(1-trimethylsilyl-1-propyne) (PTMSP), a high free-volume glassy di-substituted polyacetylene, has the highest gas permeabilities of all known polymers. The high gas permeabilities in PTMSP result from its very high excess free volume and connectivity of free volume elements. Permeability coefficients of permanent gases in PTMSP decrease dramatically over time due to loss of excess free volume. The effects of aging on gas permeability and selectivity of PTMSP membranes continuously exposed to a 2 mol % n-butane/98 mol % hydrogen mixture over a period of 47 days are reported. The permeation properties of PTMSP membranes are quite stable when the polymer is continuously exposed to a gas mixture containing a highly sorbing organic vapor such af n-butane. The n-butane/hydrogen selectivity was essentially constant for the 47-day test period at a value of 29, or 88% of the initial value of the as-cast film of 33. Condensable gases such as n-butane may serve as a “filler” in the nonequilibrium free volume of the polymer, thereby preserving the high level of excess free volume. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1483-1490, 1997
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