“Surface-photografting”: new applications to synthetic fibers

“Surface-photografting” with UV-irradiation of polypropylene (PP) fiber and film and high-strength polyethylene (HSPE) yarn has been made with acrylic acid (AA) and acrylamide (AM) as monomers and benzophenone (BP), 4-chlorobenzophenone (4-BCP) and hydroxylcyclohexylacetophenone (HHA) as photoinitiators using a new continuous method. The grafting reaction occurs in a thin liquid layer on the fiber or film substrate, which is presoaked in a solution containing initiator and monomer. After irradiation with a highpressure mercury lamp, HPM 15 (2 kW) from Philips, for 5–20 sec at about 50°C the fiber and film surface is completely covered with a 2–8 nm thick layer of grafted polymer, analyzed by electron spectroscopy for chemical analysis. The grafting efficiency is 70–80%, i.e. only 20–30% of the polymer is homopolymer which can be removed by extraction. The grafted layers are so thin that they cannot be analyzed as weight increase (<0.1% of fiber weight). Absolute values for the amount of grafted AA polymer is analyzed by microtitration of the COOH groups at the fiber surface. The results agree well with the relative ESCA values. Grafting of commercial PP yarn with AA increases the adsorption of Crystal Violet dye with a factor of about 6. Grafting the same yarn with AM increases the adhesion to epoxy resin by a factor of 3–4 without affecting the mechanical properties of the fiber more than a few percent. For comparison, strips of blown PP film (5 mm wide) are modified by “surface-photografting” with AM. With increasing grafting, the contact angle for drops of distilled water decreases from 90° to 20°, indicating extensive wetting. The adhesion to epoxy resin increases from about 0.35 to 1.7 N/mm², i.e. with a factor of about 5 when the film surface is completely covered. Other comparisons are made with grafting of commercial HSPE yarn. Grafting with AA increases the adsorption of Crystal Violet dye by a factor of about 6. Grafting with AM increases the adhesion to epoxy resin from 0.25 to 1.3 N/nm², i.e. with a factor of 5. The bulk mechanical properties of the HSPE filaments are not affected by the grafting measured as tensile strength 2.7±0.1 GPa, elongation at break 4.8±0.3%, and Young's modulus 55±3 GPa, both before and after “surface-photografting”.     

On the applicability of the “abt” concept

Kaiser's “abt” concept rests on the experimental establishment of a linear relation between band width at half height, b_0.5, and capacity ratio, k, according to His column specification quantity, h_real, is dependent on the square of the slope a, obtained from a linear regression analysis based on this relation. It is shown in the present paper that an improvement of the experimental conditions leading to a lower extra-column contribution to band broadening, b, introduces a tendency towards a negative curvature in the plot at low k values. The mean slope increases, and an uncritical linear regression would yield an h_real-value which is higher than before and which would be in the opposite direction to the requirements of a reliable column specification. Generally the linear regression analysis has to be moved to higher k regions in cases of curvature, especially as it is also shown that h_real is an estimation of the traditional HETP value, H∞, that would be obtained when k approaches infinity. This theoretically expected relation is a strong motivation for the use of h_real as a column specification, since the b_0.5-value associated with H∞ is expected to be practically independent of b.     

Formation of “Quasi” Contact or Solvent‐separated Ion Pairs in the Local Environment of Probe Molecules Dissolved in Ionic Liquids

The change from “quasi” contact to “quasi” solvent‐separated ion‐pair configuration in the local environment of a probe molecule in ionic liquids depends on the varying interaction strength of the chosen anions. The ion speciation in these Coulomb fluids could be shown by combining infrared spectroscopy, density functional theory calculations, and natural bond orbital analysis using a low‐self‐clustering probe molecule.     

Reply to “Comment on the Comparative Use of the Electron Density and Its Laplacian”

In our reply to the preceding comment by Richard Bader we show that the statements of the author are not justified and that he contradicts his own previous work.     

ChemInform Abstract: Instability of the Al42‐ “All‐Metal Aromatic” Ion and Its Implications.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Stoichiometric Valence and Structural Valence—Two Different Sides of the Same Coin: “Bonding Power”

Two valencies instead of one! Stoichiometric valence and structural valence are two distinct properties of atoms. The former, ^stoichV, is derived from the composition of a compound and has integer values; the latter, ^structV, depends on the structure of a compound and has non‐integer values. The scheme shows a representation of valence states of antimony and oxidation of Sb^III to Sb^V, as a function of the eccentricity parameter Φ _i.

     

Insights into the Formation and Structures of Molecular Gels by Diimidazolium Salt Gelators in Ionic Liquids or “Normal” Solvents

Insights are provided into the properties of molecular gels formed by diimidazolium salts both in “normal” solvents and ionic liquids. These materials can be interesting for applications in green and sustainable chemistry in which ionic liquids play a significant role, like catalysis and energy. In particular, two positional isomers of a diimidazolium cation have been examined with a wide range of anions for their ability to form gel phases. In particular, di‐, tri‐, and tetravalent anions bearing aliphatic or aromatic spacers were paired with the divalent cations. The properties of the organo‐ and ionogels formed have been analyzed by means of several different techniques, including calorimetry, rheology, resonance light scattering, UV/Vis absorption, polarizing optical microscopy, and powder X‐ray diffraction measurements. The investigations performed enabled us to obtain a wide range of conductive materials characterized by a high thermal stability and a low corrosiveness of the gelator (organogels) or of both gelator and solvent (ionogels). The information gained should be useful in the broader quest to identify and promote their applications.     

Synthesis of ω‐phosphonated poly(ethylene oxide)s through the combination of kabachnik–fields reaction and “click” chemistry

The synthesis of new ω‐phosphonic acid‐terminated poly(ethylene oxide) (PEOs) monomethyl ethers was investigated by the combination of Atherton–Todd or Kabachnik–Fields reactions and the “click” copper‐catalyzed 1,3‐dipolar cycloaddition of azides and terminal alkynes. The Atherton–Todd route fails to give the corresponding phosphonic acid‐terminated PEOs due to competitive cleavage of the P? N bond during the dealkylation step. In contrast, the Kabachnik–Fields route leads with very good yields to ω‐phosphonic acid‐PEO through “click” reaction of azido‐PEO onto dimethyl aminopropargyl phosphonate prepared by Kabachnik–Fields reaction between propargylbenzylimine and dimethyl phosphonate, followed by acidic hydrolysis. The reported methodology, precluding the use of anionic polymerization of ethylene oxide, leads to novel well‐defined phosphonic acid‐terminated PEOs from commercially available products in good yields. Moreover, such a strategy can be adapted to anchor phosphonic acid functionality onto a wide range of polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

“One-pot” synthesis of poly(amide-imide)s derived from trimellitic acid monoesters and multiring aromatic diamines

Aromatic processable poly(amide-imide)s have been prepared according to the Yamazaki and Higashi phosphorylation reaction from flexible aromatic diamines and a mixture of isomeric 1,2,4-benzenetricarboxylic acid monoethylesters following a novel “one-pot” procedure. The polymerization was performed in 1-methyl-2-pyrrolidone/LiCl solutions using triphenylphosphite and pyridine as condensing agents to form amide bonds. Cyclization of the intermediate poly(amide-amic ethylester) occurred by eliminating ethanol under the polymerization conditions used, thus leading to the formation of imide rings. The influence of several parameters which regulate the degree of polymerization and the formation of the imide rings, such as reaction temperature, triphenylphosphite/monomers molar ratio, and pyridine concentration was carefully investigated. In particular, the catalytic activity of pyridine in the imidization reaction has been demonstrated. ¹³C-NMR spectroscopy has been used to show the absence of constitutional regularity in the prepared PAIs thus indicating equal reactivity toward polycondensation of the two different carboxyl groups of the 1,2,4-benzenetricarboxylic acid monoethylesters. © 1996 John Wiley & Sons, Inc.     

Splitless injection–development and state of the art. Including a comparison of matrix (“dirt”) effects in conventional and PTV splitless injection

Kurt Grob introduced splitless injection in 1969. He elaborated most of the working guidelines including the techniques required for reconcentrating the broad intial bands, i.e. the solvent effects and cold trapping. He also designed a vaporizing injector suited for splitless injection. Nevertheless, splitless injection is still often carried out using inappropriate conditions, and many of today's vaporizing injectors are not suited for splitless injection. No autosampler is available that introduces the sample at the appropriate position. Conventional splitless injection is compared to PTV splitless injection for the range of samples that cannot be handled by the anyway superior oncolumn injection, i.e. sample with high loads of involatile byproducts. There is a clear preference for PTV splitless injection as matrix effects observed in conventional splitless injection were found to be substantially reduced or even eliminated.