Phase separation during fast (RIM) poly-urethane polymerization

Phase separation dynamics during a reaction injection molding process of an elastomeric polyurethane was studied via FT-IR and rheology. 4, 4′ methylenediphenyl isocyanate and 1, 4 butanediol were mixed with 50 wt% of a 2000 molecular weight poly(proplyene oxide)polyol catalyzed by dibutyltin dilaurate. A small reaction injection molding machine was used to impingement mix the chemicals and inject these directly into a Fourier transform infrared spectrometer or into a rheometer. The reaction conversion was followed by the isocyanate absorbance and the development of inter-urethane hydrogen bonding was related to phase separation dynamics. Isothermal dynamic mechanical modulus build-up during reaction was monitored by a thin gap parallel plate geometry subjected to small amplitude oscillation. An optimum reaction temperature was found, below which phase separation prematurely cuts off high molecular weight build up. Above this temperature phase separation is too slow and incomplete; modulus values are lower. Increasing catalyst reduces this optimum temperature.     

Ultrasonic and dielectric studies of segmented ester polyurethanes

Ultrasonic and dielectric relaxation measurements are reported as a function of frequency and temperature for a series of segmented ester polyurethanes. Glass transitions for the ester block were determined using a combination of differential scanning calorimetry and dilatometry. The activation energy associated with the dipolar relaxation of the ester group was found to be sensitive to changes in the molecular weight and the relative proportions of the ester and isocyanate in the polymers. These data are discussed with reference to the morphological changes which are known to occur in these systems.     

Influence of the gel-liquid phase transition on hematoporphyrin triplet deactivation in liposomes

The deactivation of the triplet state of hematoporphyrin and its dimethyl ester in unilamellar liposomes of dipalmitoyl phosphatidylcholine was studied by nanosecond laser flash photolysis. It was found that the rate of deactivation increases abruptly on raising the temperature in the region of the gel-liquid phase transition of the lipid bilayer (41 degrees C). The rate of change has its maximum at 38.4 +/- 0.5 degree C for both porphyrins. This variation is due to the high lateral mobility of the porphyrins in the liquid-crystal bilayer, which enhances the rates of concentration triplet quenching and triplet-triplet annihilation.     

Structure and property development in poly(p-phenylene terephthalamide) during heat treatment under tension

The evolution of several structural characteristics during isothermal heat treatment of poly(p-phenylene terephthalamide) was studied. In this work, heat treatment was interrupted after different treatment times, with the specimens immediately quenched to room temperature. These specimens were then characterized by tensile testing, wide- and small-angle x-ray scattering, and optical microscopy. Structural parameters obtained from these measurements relate to crystal perfection (via the paracrystalline axial distortion parameter), axial crystallite size, transverse crystallite size, degree of chain misorientation, and degree of pleating. Structural and mechanical parameters were then plotted against heat-treatment time to obtain kinetic isotherms for each parameter. The kinetics of the removal of chain misorientation parallels that of tensile modulus increase under all conditions. Of the other structural parameters, only the kinetics of pleat removal mimics that of modulus change, indicating that pleat removal is the effective cause of increased chain alignment and thereby of increased axial stiffness. ©1995 John Wiley & Sons, Inc.     

Effect of internal mold release agent on flexural and inter laminar shear properties of carbon and glass fabric reinforced thermoset composites

The study is focused on thermoset composites reinforced with carbon and glass woven fabrics. Two types of thermoset resins, for example, epoxy and vinyl ester were used as the matrix. Varying concentrations of internal mold releasing (IMR) agent was used in the resin. The composites were cured both at room temperature and at 80°C. The flexural properties were studied using 3‐point bending test method. Further theinter‐laminar shear strength (ILSS) was investigated using the short beam shear strength test based on 3‐point bending. The flexural modulus of room temperature cured epoxy resin is higher than that of high temperature cured epoxy resin and cured vinyl ester resin. The flexural modulus is lowest for 1% IMR sample in epoxy system and the modulus for 0% and 2% epoxy are not significantly different. Lowest flexural strength and modulus can be observed for the combination of reinforcement and curing conditions for samples containing 1% IMR for the epoxy systems. Carbon fiber is found to be less compatible with the vinyl ester resin system and the addition of IMR to the resin degraded the properties further. Inter‐laminar shear strength for epoxy‐based composites is not much affected by presence of IMR, but in case of vinyl ester based composites there is a decrease in ILSS on addition of IMR agent. The study explains variation in flexural properties on addition of IMR and change of curing conditions. These results can be used for ascertaining variation in mechanical properties in real use.     

万古霉素及其苯异氰酸酯衍生物手性固定相的制备与应用

采用"一锅法",以1,6-二异氰酸正己酯作间隔臂,制备了万古霉素及苯异氰酸酯衍生化的万古霉素手性固定相。对拉米夫定、拉米夫定的L-薄荷醇酯、酞胺哌啶酮和盐酸氟西汀进行了手性分离研究,在极性有机相模式下,研究了流动相甲醇中冰醋酸-三乙胺浓度和比例对手性分离的影响,观察到两种手性固定相具有不同的手性识别能力。在万古霉素手性固定相上4种溶质都获得了基线分离;在苯异氰酸酯衍生化的手性固定相上除盐酸氟西汀外也均获得基线分离。     

Thermal analysis of the structure of segmented polyurethane elastomers

Polyurethanes were prepared from 4,4′-methylenebis (phenyl isocyanate) (MDI), 1,4-butanediol (BD), and poly(tetrahydrofurane) polyether polyol (PTHF) by melt polymerization. The –OH functional group ratio of polyol/total diol was kept constant at 0.4, while the ratio of the isocyanate and hydroxyl groups (NCO/OH) changed between 0.940 and 1.150. The thermal analysis of the polymers by DSC and DMTA measurements indicated several transitions. The three glass transition temperatures observed were assigned to the relaxation of the aliphatic –CH₂– groups of the polyol, and to that of the soft and hard segments, respectively. The glass transition temperature of the soft and hard phase changed with the NCO/OH ratio indicating changes in phase structure and composition confirmed also by the maximum in the number of relaxing soft segments. Changes in the relatively small number of end-groups result in considerable modification of mechanical properties. Strength is determined by molecular mass and interactions, while stiffness depends mainly on phase structure. Surprisingly enough, –OH excess yields stiffer polymers, since the interaction of the –OH groups results in a decrease in the amount of the soft phase. A unique correlation was found between tensile modulus and the number of relaxing soft segments.     

Physical characterisation of amylopectin gels

Amylopectin is a highly and non-randomly branched polysaccharide and is one of the two main components of starch. Aqueous amylopectin solutions of sufficiently high concentration can form physically crosslinked thermoreversible gels upon cooling to below room temperature. We present a detailed investigation into the rheology of these gels and establish the relationship between gel modulus and concentration; this is fitted with the model of Clark and Ross-Murphy. Amylopectin gelation is accompanied by the development of crystallinity. Differential Scanning Calorimetry (DSC) and novel time-resolved Wide Angle X-ray Scattering measurements using synchrotron radiation indicate that the DSC gel melting endotherm provides a measurement of the degree and perfection of the crystallinity in the gel. For gels stored at 4 °C, the crystallinity covered a wide range of perfection and part of the contribution to the growth in the melting endotherm was the result of the formation of a disproportionate number of poorer, less perfect crystallites. Annealing amylopectin gels below their peak melting temperature, following storage at 4 °C increased the perfection of the crystallinity by melting out the poorest crystallites, causing the gels to melt at a higher temperature and over a narrower range.     

Kinetic studies of chromium (VI) binding to carboxylic acid- and methyl ester-functionalized silica/water interfaces important in geochemistry

Real-time kinetic measurements of hexavalent chromium binding to fused silica surfaces functionalized with carboxylic acid and methyl ester terminal groups are performed in situ using resonantly enhanced surface second harmonic generation (SHG) at pH 7 and 300 K. These functional groups were chosen because of their high abundance in humic acids and related biopolymers. Kinetic measurements are conducted in the submonolayer regime using chromate solution concentrations ranging from 1 x 10(-6) to 2 x 10(-5) M. The adsorption rates were analyzed using the standard Langmuir model and the Frumkin-Fowler-Guggenheim model. The desorption kinetics are consistent with a first-order process. These results indicate that hexavalent chromium mobility in carboxylic acid- and ester-rich soil environments increases with decreasing chromate concentrations. Based on the measured half-lives of the adsorbed Cr(VI) species, remobilization of bound hexavalent chromium due to natural or anthropogenic events that lower the chromate concentration in the aqueous phase can occur within minutes.     

A study of structure formation processes occurring with the gelation of polysulfonamide solution in dimethylacetamide

This work investigates spontaneous gelatination of polysulfonamide in the solution of dimethylacetamide by nuclear magnetic relaxation, small-angle light scattering, and refractive index measurement. Two stages of the gelatination process were found to occur. Spherulites are formed in the first stage while the mobility of the solvent molecules decreases sharply. The second stage is characterized mainly by perfection of the inside structure of spherulites without a change in their size. The degree of decreasing mobility of the solvent molecules is much less in this stage than in the first stage.     

Polymer depletion-induced instability of silica suspensions in the presence of flexible and semiflexible polymers

Polymer depletion-induced instability of silica suspensions in dilute toluene solutions of flexible polystyrene (PS) or semiflexible poly(hexyl isocyanate) (PHIC) was investigated by direct observation and oscillatory moduli measurements as functions of silica volume fraction and polymer molecular weight. Addition of the respective polymers to the gelled silica suspensions induces a gel settling. Below the silica volume fraction phi=4 vol%, PS chains compress the volume of the sediment silica phase, whereas PHIC chains expand it and play a role in swelling agents. Thus, PHIC chains lead to the formation of aggregates in the silica suspensions that are larger and less compact than those formed by the PS chains. On the other hand, above phi=4 vol% where the silica suspension occurs gelation, the effect of nonadsorbing polymers on changes in the volume of the silica phase is opposite. Moreover, polymer depletion interaction results in a mechanically stronger gelled phase, leading to the storage modulus G' values larger than those without polymer, but the effects of polymer concentration and polymer molecular weight on the G' values are not clear.     

Degradation induced variation of LC transition of poly(n-undecyl isocyanate)

The first-order thermal transitions including side-chain melting, crystal-LC, biphasic chimney-like, and isotropic transitions of poly(n-undecyl isocyanate) (PUDIC) were investigated by varying its thermal history. After annealing at 140 °C for different periods of time, it leads to different degrees of backbiting degradation into n-undecyl isocyanurate trimer which behaves as a solvent for the rest non-degraded/rigid PUDIC to change into a lyotropic LC from thermotropic transition. Based on the degree of degradation, various amounts of trimers are present and the PUDIC demonstrates different types of thermal transitions found in DSC thermograms due to the variation of the non-degraded PUDIC concentration in solvent trimers. Finally, a phase diagram includes all types of crystallines, LC, and isotropic regions can be drawn according to the DSC thermograms.     

Ringing gels: Their structure and macroscopic properties

The phase diagram of the ternary surfactant system which consists of dimethyltetradecylaminoxide, hydrocarbon, and water contains a highly elastic gel phase which borders on the micellarL ₁-phase. This gel phase is transparent, optically isotropic, and shows the ringing phenomena when it is excited to mechanical vibrations. From SANS and light-scattering measurements it is shown that this phase consists of the same spherical microemulsion droplets which are present in the adjacent micellar solution. Even in the micellar solution the droplets are fairly monodisperse and in the SANS scattering functions a second scattering maximum was observed. Both the light scattering and SANS data can be described quantitatively on the basis of hard sphere interactions between the particles. Furthermore, it is shown that elasticity and shear modulus of the gel phase, which were determined experimentally, correlate with the compressibility modulus as calculated from the scattering data. The elasticity modulus and hence the osmotic compressibility modulus are related to the Laplace pressure inside the globules. For the calculation of this pressure it is possible to take the interfacial tension, which is obtained from a dilute micellar solution against the hydrocarbon which is used for the system. The radius of the particles and the hydrocarbon content in the system can be increased when some of the dimethyltetradecylaminoxide is replaced by dimethyltetradecylphosphinoxide.     

Formation of block copolymers from polyurethanes containing reactive disulfides

Block copolymers containing polyether segments and segments of a vinyl polymer have been synthesized. A low molecular weight polyether terminated with isocyanate groups was condensed with bis-(β-hydroxyethyl disulfide) to give polyurethanes containing reactive disulfide linkages. When this polymer was photolyzed in the presence of a vinyl monomer such as styrene, methyl methacrylate, or acrylonitrile, homolytic cleavage of the disulfide polymerized the monomer, giving block copolymers. The mechanical properties of the products were investigated by means of modulus–temperature measurements.     

Hydrodynamic and Colloidal Interactions in Concentrated Charge-Stabilized Polymer Dispersions

Hydrodynamic and colloidal interactions are explored in concentrated, charge-stabilized colloidal dispersions by measuring the dependence of rheology (e.g., low and high-shear viscosity, high-frequency viscosity, and modulus) and self-diffusivity on salt content, particle size, and concentration. Model, sulfonated polystyrene lactices of varying diameter are prepared and investigated by shear rheology, high-frequency torsional resonance, electrophoresis, titration, and dynamic light scattering. The high-frequency and high-shear viscosity both are dominated by hydrodynamic interactions, but are shown not to be identical, due to the microstructure distortion resulting from high shear rates. The short-time self-diffusion is also shown to be insensitive to direct particle interactions, but has a different concentration dependence than the high-frequency viscosity, further illustrating a predicted violation of a generalized Stokes-Einstein relationship for these properties. The apparent colloidal surface charge is extracted from the high-frequency elastic modulus measurements on concentrated dispersions. The surface charge is in good agreement with results from critical coagulation concentration measurements and perturbation theories, but disagrees with electrophoretic mobility experiments. This indicates that the effective surface charge determined by torsional high-frequency measurements is a more reliable predicter of the salt stability of charge-stabilized dispersions, in comparison to zeta-potentials determined from electrophoretic mobilities. Further, we demonstrate by direct comparison that measurements of the apparent plateau modulus by rotational rheometry underestimate the true, high-frequency modulus and provide unreliable estimates for the surface charge. Copyright 2000 Academic Press.     

Determination of non-linear dynamic properties of carbon-filled rubbers

A forced non-resonance test method is described for determining the dynamic mechanical properties of polymeric materials over wide ranges of strain and frequency. The use of this method for carrying out studies on carbon-filled rubbers is illustrated by results which demonstrate the variation of the dynamic shear modulus and damping factor of a tyre tread material with dynamic strain amplitude, frequency and temperature. Procedures are discussed for the analysis and presentation of such data.

Two methods are described for the determination of loss factor, and results from these are compared in order to assess the validity of phase angle measurements on non-linear materials.

Brief reference is made to dynamic testing under compressive and combined compression and shear modes of deformation. The prediction of performance under this combined loading situation from experimental data obtained in shear is demonstrated.     

Quantitative mapping of elastic moduli at the nanoscale in phase separated polyurethanes by AFM

The micro phase separated nanoscale morphology of phase separated polyurethanes (PUs) was visualized by atomic force microscopy (AFM) height and phase imaging of smooth surfaces obtained by ultramicrotonomy. PUs were obtained from 4,4′-methylenbis (phenyl isocyanate) (MDI), 1,4-butanediol (BD) and poly(tetrahydrofurane) polyether polyol (PTHF). The segmented polyether PUs with varying stoichiometric ratio of the isocyanate and hydroxyl groups were prepared to investigate the effect of molar mass, as well as the type and number of end-groups on their morphology and mechanical performance.The PU samples studied show characteristic “fingerprint” AFM phase images. Novel dynamic imaging modes of AFM, including HarmoniX material mapping and Peak Force Tapping were used to assess the mechanical performance of phase separated polyurethanes quantitatively as a function of their molecular structure. The values of surface elastic moduli were determined with nanoscale resolution and were in excellent agreement for both AFM modes. While tensile testing provides a bulk average value for the elastic modulus of the elastomers, the novel AFM based elastic moduli mappings introduced enable the study of surface stiffness with nanoscale resolution in a quantitative way.     

Cellulose Derivatives Synthesized via Isocyanate and Activated Ester Pathways in Homogeneous Solutions of Lithium Chloride/N,N-Dimethylacetamide

Abstract

Cellulose carbamate and ester derivatives were synthesized in homogeneous solutions of lithium chloride (LiCl)/N,N-dimemyl-acetamide (DMAc) by the reaction of cellulose with ethyl 4-isocyanatobenzoate and the activated esters of N,N-dimethyl-aminobenzoic acids. Comparative reactions were performed with phenyl isocyanate and the activated ester of benzoic acid. All reactions were followed spectroscopically by FTIR, ¹H NMR, and ¹³C NMR. Degrees of substitution were calculated utilizing UV spectroscopy. The isocyanate reactions are facile allowing controllable degrees of substitution and high yields. By contrast, the activated ester pathway inherently results in lower degrees of substitution and lower yields due in part to undesirable side reactions.     

A facile and controllable synthesis of dual‐crosslinked elastomers based on linear bifunctional polydimethylsiloxane oligomers

Dual‐crosslinked supramolecular elastomers with the hybrid network consisting of hydrogen bonds and covalent bonds combine the reversibility of hydrogen bond and mechanical properties of covalent crosslinking network. In this article, isocyanate mixture is used as curing agent to prepare dual‐crosslinked elastomer based on bifunctional polydimethylsiloxane under mild condition. This method can effectively build up a hybrid network with the designed structure. A series of elastomers with same hydrogen bond density and variable covalent crosslinking degree are obtained. Swelling measurements and ¹H‐NMR spectra confirm the feasibility and controllability of curing method, the increasing of bifunctional isocyanate give rise to higher covalent crosslinking degree, improving the solvent resistance. The studies on viscoelastic property show that the introduction of an irreversible covalent crosslinking network stabilize the hybrid network, restrain the chain movement. The mechanical and self‐healing property studies reveal that the covalent crosslink significantly reinforce the whole network, while the reparable strength seems to mainly depend on the hydrogen bond density. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3760–3768     

Quantum-chemical study on reactions of isocyanates with linear methanol associates: VII. Effect of nonspecific solvation on the reaction of methyl isocyanate with linear methanol associates

The effect of nonspecific solvation on the reactivity of methyl isocyanate toward linear methanol associates and thermodynamic parameters of this reaction was studied at the B3LYP/6-311++G(df,p) level of theory in terms of the polarizable continuum model (PCM). Transformations in the liquid phase are more exothermic than in the gas phase. Change of the solvent nature leads to variation of the geometric parameters and intrinsic free energies of the reactants and transition states. Increase in solvent polarity is accompanied by increase in the degree of asymmetry and polarity of transition states. As the dielectric permittivity rises, the polar constituent of the Gibbs energy of solvation decreases, while its nonpolar constituent increases. Owing to the opposite variations of these constituents of the Gibbs energy of activation, the reaction is weakly sensitive to solvent polarity.