Polyisobutylene-containing block polymers by sequential monomer addition

Novel poly(acenaphtylene-b-isobutylene-b-acenaphtylene) (PAc-PIB-PAc) triblock copolymers exhibiting thermoplastic elastomer (TPE) properties have been prepared. The synthesis involved the addition of acenaphtylene (Ac) to living polyisobutylene dications (PIB) obtained by living isobutylene (IB) polymerization induced by the dicumyl methyl ether (DiCumOMe)/TiCl₄ initiating system at-80°C. The triblocks contain very short polyacenaphtylene (PAc) blocks (M_n9,000) and consequently yield very soft, low modulus TPEs. Efforts to develop conditions for the living carbocationic polymerization (LCPzn) of Ac have failed.For Part VIII of this subseries see J. P. Kennedy, S. Midha, B. Keszler: Macromolecules (in press)     

Thermoplastic elastomers by sequential monomer addition

The living carbocationic polymerization (LC Pzn) of p-methylstyrene (pMeSt) was achieved by the use of the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl₄ initiating system in the presence of triethylamine (Et₃N) electron donor in CH₃Cl/nC₆H₁₄ mixed solvent at-80°C. Next, the synthesis, characterization, and some physical-mechanical characteristics of a series of poly (p-methylstyrene-b-isobutylene-b-p-methylstyrene) (PpMeSt-PIB-PpMeSt) triblocks is described. The latter synthesis involved two steps in one reactor: 1) The generation of diliving polyisobutylene dications (PIB) by the dicumyl chloride (DiCumCl)/TiCl₄ system under similar conditions followed by 2) The addition of pMeSt and growth of living PpMeSt cations. The PpMeSt-PIB-PpMeSt triblocks are soft thermoplastic elastomers (TPEs).Paper L in the series Living Carbocationic Polymerization     

Phase transition in swollen gels

Summary The swelling and mechanical behaviour of networks of copolymers of acrylamide, methylenebisacrylamide and sodium 2-(2-carboxybenzoyloxy)ethylmethacrylate (mole fraction of salt x _s =0–0.2) in water-acetone mixtures was investigated. In the range x _s 0.01 phase transition (collapse) was observed, with both the extent of the collapse and the critical acetone concentration in the mixture at collapse, a _c , increasing with increasing concentration of the salt. A comparison between these results and those obtained for networks with a quaternary ammonium salt led to a conclusion that an exchange of the positive charge of the ammonium salt (NCl) for the negative charge of the sodium salt (COONa) in the side chain decreases the critical content of salt necessary for the collapse, X _s ^c , from 0.03 to 0.01, and the collapse takes place at lower concentrations of acetone. The collapse may also take place in a mixed solvent waterethanol; the dependence of network swelling on the concentration of ethanol is roughly the same as that on the concentration of acetone.     

Dynamic mechanical properties of crosslinked polyisoprene under deformation

Summary Molecular motions of elastomers under deformations were observed through dynamic mechanical measurements. Composite master curves of dynamic moduli E and E and loss tangent tan over a wide range of frequency and in a state of elongation were obtained by the time-temperature superposition procedure. It is found that both moduli increase with strain, . The slope of the dispersion curve of E become more gradual with the increase in , while that of E is almost unchanged. The increment of E is generally larger than that of E, which does not agree with the N. W. Tschoegl prediction, E ^* ()=f() E _o ^* (), where E ^* () and E _o ^* () are complex moduli at the strain of and O, respectively, and f() is the function of only . The difference in the strain dependence of E from E was found to correspond to the strain dependence of the equilibrium modulus.     

Molybdenum nitride for the direct decomposition of NO

The physico-chemical properties of passivated -Mo₂N have been investigated. The material showed high activities for NO direct decomposition: nearly 100% NO conversion and 95% N₂ selectivity were achieved at 450C. The amount of O₂ taken up by -Mo₂N increased with temperature rise and reached 3133.9 molg^–1 at 450C; we conclude that there formation of Mo₂O_xN_y occurred. This oxygen-saturated -Mo₂N material was catalytically active: NO conversion and N₂ selectivity were 89 and 92% at 450C. We found that by means of H₂ reduction at 450C, Mo₂O_xN_y could be reduced back to -Mo₂N and the oxidation/reduction cycle is repeatable; such a behaviour and the high oxygen capacity (3133.9 molg^–1) of -Mo₂N suggest that -Mo₂N is a promising catalytic material for automobile exhaust purification.     

Weak Gel Behaviour of Poly(vinyl alcohol)-Borax Aqueous Solutions

Thermal transition of PVA-borax aqueous gels with a PVA concentration of 60 g/L and a borax concentration of 0.28 M was investigated at temperatures ranging from 15 to 60C using static light scattering (SLS), dynamic light scattering (DLS), and dynamic viscoelasticity measurements. Three relaxation modes, i.e. two fast and one slow relaxation modes, were observed from DLS measurements. Two fast relaxation modes located around 10^–310¹ sec, with one fast mode (_f1) being scattering vector q-dependent and the other fast mode (_f2, with _f2>_f1) being q-independent. The _f1 mode was attributed to the gel mode whilst the _f2 mode could be due to the hydrodynamics of intra-molecular hydrophobic domains formed by uncharged segments of polymer backbones. The slow relaxation mode with relaxation time located around 10¹10³ sec in DLS data was due to the motion of aggregated clusters and was observed only at temperatures above 40C. The amplitude and relaxation time of slow mode decrease as temperature is increased from 40 to 60C. At temperatures below 40C, no slow relaxation mode was observed. The SLS measurements showed PVA-borax-water system had fractal dimensions D _f2.4 and D _f2.0 as temperature was below and above 40C, respectively. The simple tilting test indicated gel behaviour for the PVA-borax aqueous system at temperatures below 40C with a creep flow after a long time exposure in the gravity field. But the dynamic viscoelasticity measurements demonstrated a solution behaviour for PVA/borax/water at temperatures below 40C, the critical gel point behaviour for G() and G() was not observed in this system as those reported for chemical crosslinked gels. These results suggest that the PVA-borax aqueous system is a thermoreversible weak gel.     

Cooperative inclusion of sodium 1-pyrenesulfonate by γ-cyclodextrin

Summary The interaction of -cyclodextrin(-CD) with sodium 1-pyrenesulfonate(PS) was studied spectrophotometrically. -CD was found to cause much larger decrease in the absorption maxima of PS than -CD. The fluorescence spectra of PS in the presence of -CD showed excimer emission, while those of PS with -CD showed only monomer emission, indicating that -CD forms 12 (-CDPS) complexes in which two PS molecules are included in the -CD cavity in a face-to-face fashion. The binding isotherm showed a sigmoidal curve. The association constants were estimated by computer simulation of the binding curve. The 12 (CDPS) complex was found to be much more stable (K=10⁶ M^–1) than the 11 complex (K=1 M^–1). At high concentration of -CD another -CD cooperates in binding two PS molecules, resulting in the formation of a 22 complex.     

Effect of framework aluminum in proton‐ or copper‐exchanged MFI ferrialuminosilicates on their activity for the reduction of nitric oxide with ammonia

Reduction of NO with ammonia in excess oxygen has been carried out on protonform and Cu²⁺exchanged MFI ferrialuminosilicate. Though HZSM5 showed very low activity, the framework Al in Hferrialuminosilicate greatly enhanced the activity. The framework Al in Cu²⁺exchanged ferrialuminosilicate also enhanced the activity to some extent.     

Synthesis of new metal-containing side-chain monomers and polymers

New metal-containing vinyl monomers, hexyl-6-oxy-{4-[4-(4-carboxy cyclopentadienyl manganese tricarbonyl phenyl)phenyl]benzoyloxy}methacrylate and hexyl-6-oxy-{4-[4-(4-ferrocenoyl phenyl)phenyl]benzoyloxy}methacrylate, and the corresponding homopolymers and random copolymers with hydroxy monomer hexyl-6-oxy-{4-[4-(4-hydroxyphenyl)phenyl]benzoyloxy}methacrylate were synthesized. The compounds were characterized by¹H NMR; their thermal behavior was investigated by means of differential scanning calorimetry. Monomers and polymers containing the ferrocene unit melt at lower temperatures than those derived from the cyclopentadienyl managanese tricarbonyl moiety. The melting temperatures of the monomers and polymers ranged from 399 to about 515 K, Both monomers and polymers failed to exhibit mesogenic behavior. Values ofM _n,M _w,M _w/M _n, and degree of polymerization were obtained by gel permeation chromatography. TheM _n ranged from 16,500 for the copolymer containing hexyl-6-oxy-{4-[4-(4-ferrocenoyl phenyl)phenyl] benzoyloxy}methacrylate and hydroxy monomer hexyl-6-oxy-{4-[4-(4-hydroxyphenyl)phenyl]benzoyloxy}methacrylate at a 1:3 ratio to 26,000 for the copolymer containing hexyl-6-oxy-{4-[4-(4-carboxy cyclopentadienyl manganese tricarbonyl phenyl)phenyl]benzoyloxy}methacrylate and hydroxy monomer hexyl-6-oxy-{4-[4-(4-hydroxyphenyl)phenyl]benzoyloxy}methacrylate at a 1:3 ratio.M _w/M _n ranged from 1.6 in the case of the copolymer containing hexyl-6-oxy-{4-[4-(4-carboxy cyclopentadienyl manganese tricarbonyl phenyl)phenyl]benzoyloxy}methacrylate and hydroxy monomer hexyl-6-oxy-{4-[4-(4-hydroxyphenyl)phenyl]benzoyloxy}methacrylate at a 1:3 ratio to 2.2 in the case of poly(hexyl-6-oxy{4-[4-(4-carboxy cyclopentadienyl manganese tricarbonyl phenyl)phenyl]benzoyloxy}methacrylate).     

The ratio of crystallinity and thermodynamical interactions of polycaprolactone with some aliphatic esters and aromatic solvents by inverse gas chromatography

Summary The retention diagrams of benzene, toluene, ethyl benzene, chloro benzene, n-propyl benzene, isopropyl benzene, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate and isoamyl acetate on the polycaprolactone were plotted at temperatures between 70 and 140^oC by inverse gas chromatography technique. Percent crystallinity of polycaprolactone were obtained at temperatures below melting point from the retention diagrams of benzene, toluene and ethyl benzene. It was concluded that the data obtained by inverse gas chromatography were comparable those of obtained by differential scanning calorimetry. Specific retention volume, V_g^o, Flory-Huggins polymer-solvent interaction parameters, ₁₂, the weight fraction activity coefficients of the solvents at infinite dilution, ₁, effective exchange energy parameters, X_eff were determined. Later, the partial molar heat of sorption, H_1,sorp and the partial molar heat of mixing, H₁ were obtained from the slope of the logarithm of specific retention volume, Ln V_g^o versus 1/T plot and from the slope of the logarithm of the weight fraction activity coefficients, ₁versus 1/T plot, respectively.     

Note of the estimation of the Θ temperature and Ψ parameter from the critical temperature data

Summary Critical values of the polymer volume fraction _2,c and the interaction parameter _c have been computed for the case that the equation for the chemical potential of solvent contains terms _{c 2} ³ and _{c 2} ⁴ in addition to ₂ ² . For 0 _c 1/3, the limits for infinite chain length are _2,c = 0 and _c = 0.5. Quite different results are obtained for _c > 1/3, _2,c being finite and _c lower than 1/2. Conclusions for the estimation of the temperature and the entropy-of-dilution parameter are discussed.     

Effects of gas bubbles on the current and potential profiles within porous flow-through electrodes

This paper presents a mathematical model to calculate the distributions of currenti(x), potentialE(x), gas void fraction (x) and pore electrolyte resistivity (x) within porous flow-through electrodes producing hydrogen. It takes into consideration the following effects: (i) the kinetics of the interfacial charge transfer step, (ii) the effect of the non-uniformly generated gas bubbles on the resistivity of the gas-electrolyte dispersion within the pores of the electrode (x) and (iii) the convective transport of the electrolyte through the pores. These effects appear in the form of three dimensional groups i.e.K=i _o L where i_o is the exchange current density, is the specific surface area of the electrode andL its thickness.= ⁰ L where ⁰ is the pore electrolyte resistivity and =/Q where is a constant, =tortuosity/porosity of the porous electrode andQ is the superficial electrolyte volume flow rate within it. Two more dimensionless groups appear: i.e. the parameter of the ohmic effect =K/b and the kinetic-transport parameterI=K. The model equations were solved fori(x),E(x), (x) and (x) for various values of the above groups.Nomenclature specific surface area of the bed, area per unit volume (cm^–1) - b RT/F in volts, whereR is the gas constant,T is the absolute temperature (K) - B =[1–(I ² Z/4)], Equation 9a - C =(1–B ²), Equation 9b - E(L) potential at the exit face (V) - E(0) potential at the entry face (V) - E(x) potential at distancex within the electrode (V) - E _rev reversible potential of the electrochemical reaction (V) - F Faraday's constant, 96500 C eq^–1 - i _o exchange current density of the electrode reaction (A cm^–2 of true surface area) - i(L) current density at the exit face (A cm^–2 of geometrical cross-sectional area of the packed bed) - I K =i _oL(/Q) (dimensionless group), Equation 7d - K =i _oL, effective exchange current density of the packed bed (A cm^–2) Equation 7a - L bed thickness (cm) - q tortuosity factor (dimensionless) - Q superficial electrolyte volume flow rate (cm³ s^–1) - x =position in the electrode (cm) - Z =exp [(0)], Equation 7f - transfer coefficient, =0.5 - =K/b=(i ₀ L ⁰ L)/b (dimensionless group) Equation 7e - (x) gas void fraction atx (dimensionless) - = ⁰ L, effective resistivity of the bubble-free pore electrolyte for the entire thickness of the electrode ( cm²) - (0) polarization at the entry face (V) - (L) polarization at the exit face (V) - =q/, labyrinth factor - constant (cm³ C^–1), Equation 3a - =/Q (A ^–1) conversion factor, Equation 3b - porosity of the bed - (x) effective resistivity of the gas-electrolyte dispersion within the pores ( cm) - ⁰ effective resistivity of the bubble-free pore electrolyte ( cm)     

Synthesis,electroconductivity and third-order nonlinear optical property of poly(2-isopropoxy-5-methoxy-1,4-phenylenevinylene)

Summary Asymmetrically disubstituted poly(2-isopropoxy-5-methoxy-1,4-phenylene-vinylene), PIMPV, was prepared in thin films via organic-soluble precursor polymer method. These polymer films could be easily stretched up to 7 times, and the drawn films of the PIMPV could be doped with FeCl₃ and I₂ to give conductivities of 26.9 and 11.3 Scm^-1, respectively. The third-order nonlinear optical susceptibility of the polymer was determined using third harmonic generation(THG) method at 1907 nm, fundamental wavelength. Measured ⁽³⁰⁾ (-3: , , ) value was 3.7x10^-12 esu.     

Multi-arm star polyisobutylenes

Summary The first synthesis of a multi-arm radial-star polyisobutylene (*-PIB) is described. The synthesis occurred by the addition of excess divinylbenzene (DVB) linking reagent to a living polyisobutylene (PIB) charge i.e., by the arm first method under specific conditions. The radial structure of the *-PIB was proven by determining the molecular weight of a sample by light scattering, then selectively destroying the aromatic polydivinylbenzene (PDVB) core, and finally determining the molecular weight of the surviving alphatic PIB arms. The synthesis strategy, kinetic observations during synthesis, and procedures leading to a representative *-PIB are described. This product whose g/mole with , contained 90.3 mole% (78 wt.%) PIB arms and 9.7 mole% (22 wt.%) aromatic core; thus the number of PIB arms emanating from the core was (number average number of arms)=56 or (weight average number of arms)=110.     

Diffusion-controlled current distributions near cell entries and corners

This paper reports experimental work undertaken to explore diffusion-controlled current distributions immediately downstream of sudden changes in flow cross-sectional area such as may occur at the entry to electrochemical flow cells. Nozzle flows expanding into an axisymmetric circular duct and into a square duct have been investigated using the reduction of ferricyanide ions on nickel micro-electrodes as the electrode process. The spanwise distribution of current has also been studied for the case of the square cell where secondary corner flows are significant.Nomenclature A electrode area (cm²) - c bulk concentration of transferring ions (mol dm^–3) - D cell diameter (cm) - D Diffusion coefficient (cm₂s^–1) - F Faraday number (96 486 C mol^–1) - I limiting electrolysis current (A) - k mass transfer coefficient (cm s^–1) - N nozzle diameter (cm) - u mean fluid velocity (cm s^–1) - x distance downstream from point of entry to cell (cm) - z number of electrons exchanged - electrolyte viscosity (g s^–1 cm^–1) - electrolyte density (g cm^–3) - (Re)_D duct Reynolds number,Du/ - (Re)_N nozzle Reynolds number,Nu/ - (Sc) Schmidt number,/D) - (Sh) Sherwood number,kD/D)     

The surface structure and composition of the low index single crystal faces of the ordered alloy Pt3Sn

The surface composition and structure of 111, 100, and 110 oriented single crystals of the ordered alloy Pt₃Sn (Ll₂ or Cu₃Au-type) were determined using the combination of low energy electron diffraction (LEED) and low energy ion scattering spectroscopy (LEISS). The clean annealed surfaces displayed LEED patterns and Sn/Pt LEISS intensity ratios consistent with the surface structures expected for bulk termination. In the case of the 100 and 110 crystals, preferential termination in the mixed (50% Sn) layer was indicated, suggesting this termination to be the consequence of a thermodynamic preference for tin to be at the surface.     

Critical solution point and chain dimension of branched-polystyrene solutions

Summary Critical solution point and chain dimension were measured for branched polystyrene(BPS) in solution as a function of molecular weight(M) and compared with those for linear polystyrene(LPS). The critical concentration _c of BPS was quite different from that of LPS at a fixed M, but the same at a fixed overlap-concentration ^*, i.e., plots of _c vs. ^* fall on a single straight line for both BPS and LPS (gf_c ^*). Reduced critical temperature _c defined by gt_c=(–T_c)/ [T_c: critical temperature, : the -temperature] was related to _c as _{c c} ² for BPS, whereas _{c c} for LPS.     

Variable‐temperature IR spectroscopic studies of CO adsorbed on Na‐ZSM‐5 and Na‐Y zeolites

CO interacts with extraframework alkali metal cations (M⁺=) of zeolites to form both M⁺CO and M⁺OC species. By using variabletemperature FTIR spectroscopy, these Cbonded and Obonded species were found to be in a temperaturedependent equilibrium. For the same cation, the difference in interaction energy depends upon the zeolite framework. Thus, for the equilibrium process ZNa⁺=CO ZNa⁺OC, where Z represents the zeolite framework, H ⁰ was found to take the values 3.8 and 2.4 kJ mol^– for CO/NaZSM5 and CO/NaY, respectively. The Cbonded species show always the highest cation–CO interaction energy.     

Thermal stability of PP with acetylated sisal fiber: Romero García kinetic method

Summary This work deals the effect of acetylated and non-acetylated sisal fiber 011 thermal degradation of polypropylene. Applying the R-G method at constant conversion levels of 0.1, 0.3, 0.5, 0.7 and 0.9 to thermograms of the PP/untreated sisal fiber blend, E, values of 99, 213, 224, 187, and 145 kJ/mol were obtained, whereas they were 99, 299, 255, 205, 154 kJ/mol for the PP/treated sisal fiber blend. On the other hand, with the R-G method at constant temperature, activation energies within the range of 156-417 kJ/mol were obtained for the PP/treated sisal fiber blend and within the range of 126-344 kJ/mol for the PP/untreated sisal fiber blend. Additionally, the method establishes as dominant the following decomposition mechanisms: three-dimension limiting surface reaction between both phases, diffusion in two and three dimeiisions and first-order random nucleation and nuclei growth.     

Convective Regime of Filtration Combustion of Energetic Materials in a Cocurrent Flow of Their Combustion Products

The convective regime of filtration combustion of energetic materials in a cocurrent flow of their combustion products is studied using a model with extremely simplified kinetics and heat transfer, which shows instability of the process. It is shown that the more accurate twotemperature model describes a steadystate regime. In this regime, the gas temperature on the hot boundary of the heating zone is well below the combustion temperature, and the solidphase temperature is well below the temperature proposed in recent studies on this topic. It is pointed out that the twotemperature approach is unjustified and intragranular nonisothermicity must be taken into account for convective regimes. It is shown that the threetemperature model, which takes into account this effect, does not give a stable steadystate solution.