Ordering processes in polyester thermoplastic elastomers

Synthesis of thermoplastic elastomers derived from poly-tetramethylene glycol (PTME glycol), dimethylterephthalate and different mixtures of ethylene and butylene glycol is described. Extended heating near the crystalline melting point of these systems leads to a measurable increase in the melting point of 15–20°C. This ordering process can be reversed by heating at 250°C or well above the melting point. These results are interpreted in terms of sequence ordering within existing crystallites via interchain transesterification on heating near the melting point. Heating at 250°C is best explained as randomization of the ordered ester units.     

INS,IR, RAMAN, 1H NMR and DFT investigations on dynamical properties of l-asparagine

Results of inelastic neutron scattering (INS), infra-red (IR), Raman and ¹H NMR spectroscopy used for investigations on the l-asparagine dynamics are reported. The crystallographic structure and experimental vibrational spectra are compared with those calculated by the DFT methods applied to the solid state. Very good conformity of the experimental and theoretical structures has been found. The NH₃⁺ torsional vibration mode is observed in the INS spectra at 494 cm⁻¹, while the bands assigned to the vibrations of the strong NH⋯O hydrogen bonds are observed at 2849, 2650, and 2480 cm⁻¹ in the IR spectrum. A ¹H NMR investigation has been carried out at 26.75 MHz in the temperature range 150–300 K. For l-asparagine the activation energy needed for the NH₃⁺ group reorientation is equal 5.6 kcal/mol.     

Structural and dynamical aspects of PEG/LiClO4 in solvent mixtures via NMR spectroscopy

Motivated by the potential usefulness of polyethylene glycol (PEG)/Li⁺ salt mixtures in several industrial applications, we investigated the structure and dynamics of PEG/LiClO₄ mixtures in D₂O and its mixtures with CD₃CN and DMSO-d₆, in a series of PEG-based polymers with a wide variation in their molecular weights. ¹H NMR chemical shifts, T₁/T₂ relaxation rates, pulsed-field gradient NMR diffusion experiments, and 2D HOESY NMR studies have been performed to understand the structural and dynamical aspects of these mixtures. Increasing the temperature of the medium results in a significant perturbation in the H-bonded structure of PEG in its PEG/LiClO₄/D₂O mixtures as observed from the increase in chemical shifts. On the other hand, the addition of molecular cosolvents has a negligible effect. The hydrodynamic structure of PEG shows a pronounced variation at low temperature with increasing molecular weight, which, however, disappears at higher temperatures. Increasing the temperature leads to a decrease in the hydrodynamic structure of PEG, which can be explained on the basis of solvation–desolvation phenomena. The 2D HOESY NMR spectra reveal a new finding of Li⁺-water binding in the PEG/LiClO₄/D₂O mixtures with the addition of molecular solvents, suggesting that the Li⁺ cation diffuses freely in the D₂O mixtures of polymers as compared with the polymer mixtures with DMSO or CD₃CN.     

NMR investigations of rotenoids

Extensive NMR studies of major rotenoids have (1) verified the cis B/C ring fusion of rotenone; (2) confirmed the structure of the reduction-dehydration product of rotenone; (3) provided considerable evidence regarding the preferred conformations of rotenoids; (4) revealed an array of long-range couplings; and (5) pointed up analytically useful solvent effects. Incidentally, these studies also allowed assignment of NMR signals for essentially all protons of the major rotenoids in deuterochloroform.     

NMR investigations of polymer electrets

1H NMR investigations were performed on thin films of poly(vinylidene fluoride) (PVDF) and polyamide 11 (PA 11). The variation of the angle between the static magnetic B_o-field and preferred directions given by drawing and poling leads to characteristic dependences of T_20ff, which can be discussed in terms of Legendre polynomials of the orientational distribution functions of crystallographic c- and b-axis. A good c-axis alignment can be realized by uniaxial drawing. The tendency for b-axis to orient towards the direction of the applied electric field via the orientation of the electric dipoles is evident. The b-axis alignment can be “switched” periodically.     

29Si NMR investigations on oligosilane dendrimers

Starting with the high functionalized trisilane SiClMe(SiCl₂Me)₂ and tetrasilane SiMe(SiCl₂Me)₃ several octa- and decasilane dendrimers containing directly neighboured branchings were prepared. In these compounds the ²⁹Si NMR chemical shifts of the different silyl groups are shifted towards lower field compared with those of analogous groups in tetra- or hexasilanes. This observation is a helpful tool for the characterization of further dendritic oligomers by ²⁹Si NMR. Received: 3 June 1996 / Revised: 3 July 1996 / Accepted: 9 July 1996     

29Si NMR investigations on oligosilane dendrimers

Starting with the high functionalized trisilane SiClMe(SiCl₂Me)₂ and tetrasilane SiMe(SiCl₂Me)₃ several octa- and decasilane dendrimers containing directly neighboured branchings were prepared. In these compounds the ²⁹Si NMR chemical shifts of the different silyl groups are shifted towards lower field compared with those of analogous groups in tetra- or hexasilanes. This observation is a helpful tool for the characterization of further dendritic oligomers by ²⁹Si NMR. Received: 3 June 1996 / Revised: 3 July 1996 / Accepted: 9 July 1996     

Thermogravimetric investigations in dynamical regime on some tetramolybdates or organic bases

A systematic study about the thermal decomposition kinetics in function ofthe substituted bases in (BH)₂Mo₄O₁₃ type compounds shows a decomposition pattern with three or two steps which are controlled by a random nucleation mechanism.The thermal stability as well as the activation energy is studied as a function of the nature of the base, its symmetry and its pK_a.     

Mechanical, electrical and spectroscopic investigations of carbon nanotube-reinforced elastomers

This paper reports investigations carried out on elastomeric matrices filled with multiwall carbon nanotubes. A comparison with carbon black-filled polymers is also made. The state of dispersion of the fillers in the polymer matrix is evaluated through transmission electron and atomic force microscopies. Stress–strain measurements of the composites demonstrate that carbon nanotubes bring significant improvements in the mechanical properties with regard to the pure polymer. Infrared and Raman spectroscopies are shown to bring molecular insights into the structure/property correlations. Electrical properties of the filled materials are also analyzed in order to determine the so-called percolation threshold and the insulator–conductor transition corresponding to the formation of an interconnected filler network throughout the matrix.     

Electron microscopy investigations of polyester-polyurethane elastomers stained with ruthenium tetroxide

Microphase separation of as-reacted polyester-polyurethane samples based on α-hydro-ω-hydroxypoly(oxyethyleneoxyadipoyl)/4,4′-methylenedi(phenyl isocyanate)/1,4-butanediol/2-ethyl-2-hydroxymethyl-1,3-propanediol (mole ratio 1:3,2:1,9:0,1) was studied using transmission electron microscopy. A new staining technique was applied which uses ruthenium tetroxide vapour for the treatment of the polymer. Ruthenium tetroxide reacts preferably with the hard-segment-rich microdomains of the polyester-polyurethane. Therefore, a well-contrasted pattern is formed by staining which reflects the microdomain structure of the polymer. The hard-segment-rich microdomains have irregular, mostly globular shape, and their sizes range from about 2 to 8 nm.     

Electron transfer mechanisms in surface dynamical processes

Some topics concerning on the dynamical electron transfer processes between adparticle and surface are discussed based on recent theoretical studies. They include the band effect on the electron transfer probability, the change from the diabatic to adiabatic behavior seen in the field induced desorption (FID), and the effect of the couplings with the medium degrees of freedom on the electron transfer process. It is elucidated how the competition of the energy parameters, i.e., the band width, the inverse of the scattering time and the interaction energy leads to different features of the electron transfer. Natural crossover of the FID behavior from the diabatic to the adiabatic limit is clarified by the generalized kinematic equation based on the quantum model of the electron transfer. Enhancement of the diabatic behavior by the coupling with the heat bath or sorrounding medium is concluded with the stochastic trajectory method and the time-developing operator method.     

Kinetic investigations on some analytical catalytic processes

Summary Kinetic investigations have been carried out on the rate of oxidation ofp-phenetidine with potassium chlorate in the presence of vanadium as a catalyst and phenol as activator. The activation energy of the reaction was found to be 11400 cal/mol. It has been established that citric acid has an activating effect on the process. It is assumed that this is due to the formation of stable complexes with vanadium with a stronger catalytic effect. The important difference between the action of phenols and citric acid is that while phenols take part directly in the formation of reaction-products, citric acid only increases the activity of the catalyst.

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Zusammenfassung Reaktionskinetische Untersuchungen der Oxydation von p-Phenetidin mit Kaliumchlorat bei Gegenwart von Vanadium als Katalysator und Phenol als Aktivator wurden ausgeführt. Die Aktivierungsenergie der Reaktion beträgt 11400 kal/Mol. Ein aktivierender Effekt von Zitronensäure wurde festgestellt. Es wird angenommen, daß dieser auf der Bildung eines stabilen Vanadiumkomplexes mit verstärkter katalytischer Wirkung beruht. Der wesentliche Unterschied in der Wirkung des Phenols und der Zitronensäure besteht darin, daß sich Phenol unmittelbar an der Bildung von Reaktions-produkten beteiligt, während die Zitronensäure nur die Aktivität des Katalysators verstärkt.

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Résumé On a effectué l'étude cinétique de la vitesse d'oxydation de lap-phénétidine par le chlorate de potassium en présence de vanadium comme catalyseur et du phénol comme activateur. On a trouvé 11400 cal/mol pour valeur de l'énergie d'activation de la réaction. On a établi que l'acide citrique présente un effet d'activation sur le processus. On suppose que ce phénomène est dû à la formation de complexes stables avec le vanadium, présentant un effet catalytique plus marqué. La différence importante entre l'action des phénols et celle de l'acide citrique vient du fait que, tandis que les phénols prennent part directement à la formation des produits de réaction, l'acide citrique augmente seulement l'activité du catalyseur.

     

NMR study of water bound to soft segments in thermoplastic elastomers

The interaction between water absorbed in four hard-soft segment block-copolymers and the polymer chains is investigated by pulsed field gradient echo NMR spectroscopy and Nuclear Overhauser NMR spectroscopy. The results show, depending on the structure and mass fraction of the soft segments, a strong interaction between water and the soft segments. Most likely this is due to a hydrogen bond between water and the ether groups. The self-diffusion of water has been determined and is described as a jumping process between the ether sites with a residence time t and a time between sites t. It is found that the residence time is of the order of a few ns and also that the ratio t/τ decreases with increasing soft segment rigidity.     

PFG NMR investigations of TPA-TMA-silica mixtures

Pulsed-field gradient (PFG) NMR studies of tetrapropylammonium (TPA)-tetramethylammonium (TMA)-silica mixtures are presented, and the effect of TMA as a foreign ion on the TPA-silica nanoparticle interactions before and after heating has been studied. Dynamic light scattering (DLS) results suggest that silica nanoparticles in these TPA-TMA systems grow via a ripening mechanism for the first 24 h of heating. PFG NMR of mixtures before heating show that TMA can effectively displace TPA from the nanoparticle surface. The binding isotherms of TPA at room temperature obtained via PFG NMR can be described by Langmuir isotherms, and indicate a decrease in the adsorbed amount of TPA upon addition of TMA. PFG NMR also shows a systematic increase in the self-diffusion coefficient of TPA in both the mixed TPA-TMA systems and pure TPA systems with heating time, indicating an increased amount of TPA in solution upon heating. By contrast, a much smaller amount of TMA is observed to desorb from the nanoparticles upon heating. These results point to the desorption of TPA from the nanoparticles being a kinetically controlled process. The apparent desorption rate constants were calculated from fitting the desorbed amount of TPA with time via a pseudosecond-order kinetic model. This analysis show the rate of TPA desorption in TPA-TMA mixtures increases with increasing TMA content, whereas for pure TPA mixtures the rate of TPA desorption is much less sensitive to the TPA concentration.     

The interferometric investigations of electromembrane processes

The multi-frequency laser interferometric method for measuring concentration profiles under electrodialysis with ion-exchange membranes including the case of small intermembrane distances and in the presence of ion-conducting spacers is developed. Experimental results obtained by laser interferometric method are in good agreement with the mathematical models of electrodialysis. The amplitude of the concentration field oscillations is shown to increase at the current density exceeding the limiting current density, and these oscillations transfer into the state of dissipative chaos. This instability is presumably a consequence of irregularly distributed heat sources, namely, the Joule heat and the heat of dissociation and recombination of water molecules.     

Precise dipolar coupling constant distribution analysis in proton multiple-quantum NMR of elastomers

In this work we present an improved approach for the analysis of (1)H double-quantum nuclear magnetic resonance build-up data, mainly for the determination of residual dipolar coupling constants and distributions thereof in polymer gels and elastomers, yielding information on crosslink density and potential spatial inhomogeneities. We introduce a new generic build-up function, for use as component fitting function in linear superpositions, or as kernel function in fast Tikhonov regularization (ftikreg). As opposed to the previously used inverted Gaussian build-up function based on a second-moment approximation, this method yields faithful coupling constant distributions, as limitations on the fitting limit are now lifted. A robust method for the proper estimation of the error parameter used for the regularization is established, and the approach is demonstrated for different inhomogeneous elastomers with coupling constant distributions.     

Total synthesis and NMR investigations of cylindramide

Cylindramide (1) was built up from three components: a hydroxyornithine derivative 7, a tetrazolylsulfone 8, and a substituted pentalene subunit 9. Derivative 7 was prepared in a six-step reaction sequence involving the Wittig reaction and a Sharpless asymmetric dihydroxylation starting from N-Boc-3-aminopropanal (12). Tetrazolylsulfone 8 was accessible in four steps from dioxinone 22. The synthesis of the pentalene fragment 9 started from cycloocta-1,5-diene 26, that was converted into enantiopure bicyclo[3.3.0]octanedione 29. The latter was functionalized to give derivative 9. The total synthesis was accomplished by inducing C-C bond formation by Sonogashira coupling of derivatives 9 and 7 followed by olefination with tetrazolylsulfone 8 under Julia-Kocienski conditions, macrocyclization, and subsequent Lacey-Dieckmann condensation to form the tetramic acid unit. As indicated by extensive 1H and 13C NMR spectroscopic investigations (DQF-COSY, ROESY spectra), the stereochemistry of synthetic cylindramide (1) corresponds with that of the naturally occurring product. ROE data were used for molecular modeling of the lowest-energy structures for cylindramide.     

Radiation aging and chemi-crystallization processes in polyoxymethylene

The radiochemical degradation of a polyoxymethylene homopolymer (POM) was used to study the effects of molar mass changes in the crystalline structure. The dose rate was 20 kGy h⁻¹ with doses of up to 30 kGy used. Both WAXS and SAXS were used to analyse the structures. Results showed that, under irradiation, the polymer undergoes random chain scission. The radiochemical yield was found to be G = 1.6 chain scission events per 100 eV. It was found that no crosslinking occurs and that only one chain scission mechanism, leading to the formation of formate groups, operates. Proof for the existence of chemi-crystallization is evidenced by (i) an increase in the crystallinity ratio as well as (ii) a decrease in the amorphous layer thickness. Simple models, derived from Rault’s theory, are used to predict both (i) and (ii) from molar mass values.     

Influence of laser pulse parameters on dynamical processes during azobenzene photoisomerization

When a molecule is subjected to a short intense laser pulse, the ensuing dynamical processes depend qualitatively on the pulse parameters, including duration, frequency, and fluence. Here we report studies of cis to trans photoisomerization of azobenzene following femtosecond-scale laser pulses which are relatively short (10 fs) or long (100 fs) and which have a central frequency matched to either the first excited state (S1, or HOMO to LUMO in a molecular orbital picture) or the second (S2, or HOMO-1 to LUMO). The results presented here demonstrate that photoisomerization involves a rather intricate sequence of connected steps, with the nuclear and electronic degrees of freedom inextricably coupled. One important feature is the de-excitation required for the molecule to achieve its new ground-state after isomerization. If the primary excitation is to S1, then we find that only a single HOMO/LUMO avoided crossing is required and that this crossing occurs halfway along a rotational pathway involving the central CNNC dihedral angle. If the primary excitation is to S2, then the same HOMO/LUMO avoided crossing is observed, but it must be preceded by another avoided crossing that permits transfer of holes from the HOMO-1 to the HOMO, so that the HOMO is then able to accept electrons from the LUMO. We find that this earlier crossing can occur in either of two geometries, one near the cis configuration and the other near the trans. The fact that S2 (pi pi*) isomerization requires two steps may be related to the fact that isomerization yields are smaller for this (UV) excitation than for the S1 (n pi*, visible-light) excitation.