Synthesis and cationic photopolymerization of new fluorinated,polyfunctional propenyl ether oligomers

New fluorinated, polyfunctional propenyl ether functionalized resins were synthesized, and their behavior in cationic photopolymerization was investigated. The photopolymerization proceeded efficiently with a high double‐bond conversion (>90%), giving rise to UV‐cured coatings characterized by low glass‐transition temperatures (?33 °C ≤ glass‐transition temperature ≤ ?15 °C) and hydrophobic surface properties. A fluorinated additive was also employed as a reactive additive in the cationic photopolymerization of trimethylolpropane tripropenyl ether, increasing the double‐bond conversion, polymer network flexibility, thermal stability, and surface hydrophobicity. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6943–6951, 2006     

The crystal and molecular structure of the cycloadduct from an activated carbodiimide and methyl isothiocyanate

The crystal and molecular structures of the cycloadduct from isopropyl[α-(dimethylthio-carbamoyl)isopropyl]carbodiimide and methyl isothiocyanate were determined by single-crystal X-ray methods. The product was established to be 2-(1-isopropyl-3,5-dimethyl-4,6-dithioxo-hexahydro-1,3,5-triazine-2-ylidenamino)-N,N-dimethylthioisoburyramide, in which contrary to expectations based on hybridisation the heterocyclic ring adopts a boat conformation.     

Preparation and properties of phenylene oxide–aryl ether sulphone block copolymers and their blends

We have prepared triblock copolymers of poly(phenylene oxide) (PPO) and polysulphone (PSF) of the form PPO–PSF–PPO in order to assess their intrinsic mechanical properties and their potential as interfacial compatibilizers in polystyrene/PSF blends. For sufficiently long polysulphone block lengths, we observed microphase separation both in the triblock copolymers and in their blends with polystyrene. The triblock polymers, nevertheless, showed very similar microdeformation behavior to the PPO homopolymer, suggesting the phase separation to play a minor role. On the other hand, the compatibility of the poly(phenylene oxide) blocks and polystyrene ensured a high degree of interphase adhesion in blends containing both polystyrene and free PSF, even for relatively high homopolymer molecular weights. © 1996 John Wiley & Sons, Inc.     

Progress and challenge in polymer crazing and fatigue

In this review on polymer crazing and fatigue three aspects have been treated more explicitely: the molecular rearrangements preceding and provoking craze initiation, the competition between disentanglement and chain scission during lateral craze growth, and the distinct fatigue failure mechanism occurring in cyclically loaded PET and PA fibers. An overview on other aspects is given including references to work in progress.     

Über Nahordnung und elastisches Verhalten amorpher Hochpolymerer

Ohne Zusammenfassung     

Synthesis, characterization, adsorption, and interfacial rheological properties of four-arm anionic fluorosurfactants

Four-arm oligo(fluorooxetane) tetraols containing -CF3 and -C2F5 groups were prepared in reasonable yields by cationic, ring-opening polymerization of fluorinated oxetane monomers using a tetrafunctional, alkoxylated polyol as initiator and BF3.THF as catalyst. The tetraols were then converted to ammonium sulfate salts using oleum followed by neutralization with ammonium hydroxide in excellent yields. The four-arm oligo(fluorooxetane) sulfates (1=-CF3, 2=-C2F5) have an architecture characterized by a hydrophobic core of oligo(fluorooxetane) arms with a hydrophilic sulfate shell and initiator. The four-arm anionic oligo(fluorooxetane)s are surface active with critical micelle concentration values approximately 4.2x10(-6) and 2.4x10(-6) mol/L for 1 and 2, respectively. Surface tension isotherms in pH 8 buffered solution were measured and data fitted parametrically to the Davies surface tension isotherm equation. Molecular areas at saturation were estimated to be approximately 89 and approximately 85 A2 with DeltaGads=-12.7 and -13.2 kcal/mol for 1 and 2, respectively. The results are compared to two-arm, bolaamphiphilic analogues of 1 and 2 and a small molecule, long perfluoroalkyl-chain (-C8F17), anionic fluorosurfactant (Kausch, C. M.; Kim, Y.; Russell, V. M.; Medsker, R. E.; Thomas, R. R. Langmuir 2003, 19, 7182). Dynamic surface tension data for 1 and 2 were analyzed using the Ward-Tordai mass transport equation to yield concentration-dependent diffusion coefficients. In the concentration range approximately 10(-6) mol/L, diffusion coefficients were estimated to be approximately 1-3x10(-5) cm2/s. Dilational interfacial rheological parameters for 1 and 2 were measured. Values of |E| and E' were found to be larger than those of the two-arm analogues of the same perfluoroalkyl chain length while E' 'and phi were found to be smaller. The magnitude of these values reflects the difference in adsorption strength and mass transport and/or relaxation between the two different architectures.     

Study of stress-induced changes in poly(ethylene terephthalate) through Fourier transform infrared spectroscopy

The molecular level changes resulting from an external stress applied onto a highly uniaxially oriented poly(ethylene terephthalate) film has been studied. For this purpose, a new technique - Fourier Transform Infrared Spectroscopy - has been employed. Stress-induced differences are visible in a number of bands within the IR spectra of stressed PETP films. From the assignments of these IR bands, it is inferred how external stresses applied on the polymer films are actually transmitted to the molecular level. The intermicrofibrillar chains are the first to be stressed followed by stress transmission on the crystalline regions. These stresses are also responsible for stretching the backbone bonds, for transforming gauche conformations (predominantly present in the amorphous regions) of the ethylene glycol linkages to the trans, and for modifying the interchain interactions.