Morphology of polyurethane–isocyanurate elastomers

The dynamic viscoelastic properties and thermal transition behavior of reaction injection molding (RIM) and cast polyurethane—isocyanurate elastomers have been studied as a function of various segments (soft and hard urethane, and hard isocyanurate) content. RIM and cast elastomers were prepared at different concentrations of soft and hard urethane, and hard isocyanurate segments. RIM elastomers with the higher isocyanate index (lower hard urethane and greater isocyanurate segment content) displayed an unchanged T_g (glass transition temperature of soft segment) and increasing T_gh (glass transition temperature of hard segment) related to the hard urethane and isocyanurate segments. This is due to the phase separation between the soft and the hard segments. Cast elastomers synthesized from the higher amount of 1,4-butanediol (greater hard urethane and less hard isocyanurate segment content) showed an increasing T_gs, decreasing T_gh of hard urethane segments, and an unchanged T_gh of isocyanurate segments. This is related to the phase mixing between the soft and the hard urethane segments and the phase separation of hard isocyanurate and hard urethane segments.     

O2 and N2 gas permselectivity of alternating copoly(vinylidene cyanide–vinyl acetate)

The sorption and permeation of oxygen and nitrogen in and through alternating copoly(vinylidene cyanide–vinyl acetate) [copoly(VDCN–VAc)] (T_g = 176°C) membranes annealed for different periods just below T_g, 160°C, were investigated over the pressure range from 100 to 1000 cmHg. The dual-mode sorption and mobility models were used to analyze the results. A sub-T_g annealing of copoly(VDCN–VAc) caused a slight decrease in the amount of sorption in the membranes. This decrease in the amount of oxygen and nitrogen sorption can be attributed to a decrease in the Langmuir sorption capacity term, C′_H, with increasing sub-T_g annealing period. The densification of copoly(VDCN–VAc) membranes caused simultaneously by the annealing remarkably reduced diffusion coefficients for both gases. The reduction in diffusion coefficients of Langmuir mode, D_H, for both gases was found to be larger than that of Henry's law mode, D_D. Furthermore, permselectivity of oxygen to nitrogen, the ratio of permeability coefficient of oxygen to nitrogen (P O₂/P N₂), reached to 11.8 for the copoly(VDCN–VAc) annealed for 30 h. Evidently the reduction of D_H and D_D for nitrogen with increasing annealing period was much larger than that for oxygen.     

Gas permeation of polymer blends. II. Poly(vinyl chloride)/acrylonitrile–butadiene copolymer (NBR) blends

The transport behavior of He, O₂, N₂, and CO₂ in a series of PVC/NBR polymer blends with varying acrylonitrile (AN) content in the NBR component has been studied at 25° and 50°C. In addition, measurements of density, crystallinity, and thermal expansion coefficients were carried out. The transport behavior of these blends is similar to previous result for PVC/EVA.¹. With increasing AN content in NBR, the permeability (P) and diffusivity (D) of the permeants decreased while the activation energy for diffusion (E_D) increased. For the polymer blends, better additivity of permeability and diffusivity was observed with increasing AN content in the NBR component. The polymer blends also showed increasing volume contraction with increasing AN content in the NBR component. These effects have been discussed as due mainly to increased polymer–polymer interaction causing reduced segmental mobility and increased compatibility of the two polymers. The sorption values calculated from P/D ratios were largely irregular and fluctuated with the blend composition. They were less reproducible than other transport parameters, i.e., P and D measured separately. Several reasons for the irregular sorption behavior were proposed.     

Characterization and transport properties of a novel aliphatic polyamide with an ethyl branch

The CO₂ gas and water vapor transport properties of a novel aliphatic polyamide with an ethyl branch were investigated. The polymer was characterized with density measurements, differential scanning calorimetry, thermogravimetric analysis, and wide‐angle X‐ray diffraction analyses, and the amorphous and glassy nature of the polymer at the ambient temperature were confirmed. The CO₂ sorption isotherm of the polymer appeared to obey the dual‐mode sorption isotherm, which was characteristic of the glassy state. The water vapor sorption below a relative humidity of 0.4 or 0.5 was explained in terms of the Brunauer–Emmett–Teller sorption mechanism, whereas that at a high relative humidity demonstrated a dissolution type of water vapor into the polyamide. The permeability coefficients of He, CO₂, O₂, and N₂ gases through the membrane were as follows: P(He) > P(CO₂) > P(O₂) > P(N₂). The novel polyamide membrane was more permeable to CO₂, O₂, and N₂ gases than nylon 6 and nylon 66 membranes, containing a crystalline and hydrogen‐bonding nature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1955–1960, 2005     

Synthesis of polyurethane–imide (PU–imide) copolymers with different dianhydrides and their properties

This study reports the synthesis of polyurethane–imide (PU–imide) copolymers using 4,4′-diphenylmethane diisocyanate (MDI) polytetramethylene glycols (PTMGs) and different aromatic dianhydrides. Differential scanning calorimetry (DSC) results indicate that PU–imide copolymers had two phase structures containing four transition temperatures (T_gs, T_ms, T_gh and T_mh). However, only PU–imide copolymers were formed by soft PTMG(2000) segments possessing a T_ms (melting point of soft segment). When different aromatic dianhydrides were introduced into the backbone chain of the polyurethane, although the T_gs (glass transition temperature of the soft segment) of some of PU–imide copolymers did not change, the copolymers with long soft segments had low T_gs values. The T_gh (glass transition temperature of hard segment) values of PU–imide copolymers were higher than that of polyurethane (PU). In addition, the high hard segment content of PU–imide copolymer series also had an obvious T_mh (melting point of hard segment). According to thermogravimetric analysis (TGA) and differential thermogravimetric analysis (DTGA), the PU–imide copolymers had at least two stages of degradation. Although the T_di (initial temperature of degradation) depended on the hard segment content and the composition of hard segment, the different soft segment lengths did not obviously influence the T_di. However, PU–imide copolymers with a longer soft segment had a higher thermal stability in the degradation temperature range of middle weight loss (about T_d 5%–50%). However, beyond T_d 50% (50% weight loss at temperature of degradation), the temperature of degradation of PU–imide copolymers increased with increasing hard segment content. Mechanical properties revealed that the modulus and tensile strength of PU–imide copolymers surpassed those of PU. Wide angle X-ray diffraction patterns demonstrated that PU–imide copolymers are crystallizable. © 1999 Society of Chemical Industry     

Gas permeation of polymer blends. IV. Poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) terpolymer

The transport behavior of He, O₂, N₂, and CO₂ in membranes of poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) blends has been studied at 25°C. The blends were further characterized by dynamic mechanical measurements, differential thermal analysis (DTA), density measurements, and x-ray diffraction. The equilibrium sorption of CO₂ and N₂ was measured directly at atmospheric pressure using an electromicrobalance and compared with sorption values obtained as P/D ratios from permeation measurements. The rates of permeation (P) and diffusion (D) increase with increasing ABS content in the blends. The P and D values are not additive, and only slight indications of phase inversion in the blends are observed at 5–10 wt-% ABS in the blends. Experimental densities of the blends are higher than calculated densities assuming volume additivity. The data are interpreted to mean that the PVC/ABS blends form a two-phase system composed of a soft polybutadiene (rubber) phase and a rigid PVC/styrene–acrylonitrile copolymer (SAN) phase of mutually compatible components. DTA and dynamic mechanical measurements also show a two-phase system. Sorption values of CO₂ and N₂ by equilibrium sorption measurements increase with increasing ABS content in the blends without the large fluctuations which have been observed for the sorption values obtained from the time lag method. Comparison of the two types of sorption values (from direct measurements and from P/D ratios) show larger deviations for CO₂ than for N₂. This suggests that the time lag method is not valid for permeants with polar character in heterogeneous two-phase systems where chemical immobilizing effect on the permeant molecules occurs.     

Transport parameters and solubility coefficients of polymers at their glass transition temperatures

Many parameters of polymers exhibit breaks when temperature passes through glass transition. It is also often assumed that fractional free volume (FFV) at the glass transition temperature (T_g) has a standard value (the isofree volume concept). As gas diffusion (D) and permeability (P) coefficients depend on FFV, and mechanism of sorption and permeation is different above and below T_g, a question can be asked if D and P parameters of various gases in polymers have standard values at corresponding T_g, and, if not, how the values of D(T_g) and P(T_g) vary with T_g in different polymers. To examine this problem, two approaches were used: (1) extrapolation to T_g of numerous P and D values measured at ambient temperatures; (2) an analysis of direct data obtained in different polymers at their T_g. In both cases, qualitatively similar results were obtained: the D(T_g) and P(T_g) values increase with growing T_g independently of the nature of gas. Permselectivity P_i(T_g)/P_j(T_g) and selectivity of diffusion D_i(T_g)/D_j(T_g) are reduced when T_g increases. The dependence of the solubility coefficients S(T_g) = D(T_g)/P(T_g) is much weaker than those of D(T_g) and P(T_g). This conclusion was confirmed by the results of direct measurements of S in a wide range of temperature including T_g for several gas/polymer systems. An analysis of the results of positron annihilation studies of free volume in polymers led to the conclusion that the observed increases in the D(T_g) and P(T_g) values with T_g are caused mainly by thermal activation of diffusion processes at T_g. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1691–1705, 2000     

Gas permeabilities of cellulose nitrate/poly(ethylene glycol) blend membranes

The permeability (P) of cellulose nitrate (CN)/poly(ethylene glycol) (PEG) blend membranes for N₂, O₂, and CO₂ has been measured as a function of film composition. The system CN/PEG-300 showed excellent miscibility, and films of the composition from 100/0 to 50/50 could be used for permeability measurements. P for each gas has been found to be almost constant or rather slightly lowered up to ca. 20 wt % PEG-300 content and then increased appreciably with increasing fraction of PEG. The increment of permeability was most remarkable for CO₂, and hence the permselectivity for CO₂ was considerably enhanced. Such a behavior of P has been found to be attributable to the plasticizing effect of PEG molecule lowering the glass transition temperature of the blend polymers. The effect of the molecular weight of PEG and that of closed voids generated in glassy blend membranes fabricated from acetone cast on gas permeabilities have been also discussed.     

Gas permeation of polymer blends. III. Poly(vinyl chloride) (PVC)/chlorinated polyethylene (CPE)

The permeability P, diffusivity D, and activation energy for diffusion, E_D, of He, O₂, N₂, and CO₂ were determined for blends of PVC/chlorinated polyethylene (CPE), where the chlorine content of the CPE components varied: 36 wt-% for CPE-1, 42 wt-% for CPE-2, and 48 wt-% for CPE-3. The difference in thermal expansion coefficients Δα above and below the glass transition temperature T_g of the polymers and the fractional free volume V_g of the polymers at their T_g were determined. Density and crystallinity measurements for the blends were also carried out as in the earlier work (Shur and Rånby, J. Appl. Polym. Sci., 19 , 1337 (1975)). Dynamic mechanical measurements of the blends were made using a torsion pendulum at about 1 Hz. P and D decreased, but E_D increased with increasing CI content of CPE in the blends. P and D for the blends showed no additivity. The permeability indicated phase inversion for blend compositions at about 10% of CPE-1 and CPD-2 by weight. The experimental and the calculated densities were largely the same for PVC/CPE-1 blends; but for PVC/CPE-2 and PVC/CPE-3 blends, the experimental values were higher than the calculated ones. The Δα and V_g values for PVC and the three CPE samples decreased with increasing CI content in the polymers. Dynamic mechanical measurements indicate that PVC/CPE-1 and PVC/CPE-2 blends form largely incompatible blends, while PVC/CPE-3 blends are compatible to some extent. There is some weak interaction between PVC and CPE-3 giving a low level of compatibility. The solubility of gases obtained from time-lag measurements of diffusion for 50/50 blends decreased for He, O₂, and N₂, but increased for CO₂ with increasing Cl content in CPE. The solubility of He, O₂ and N₂ shows a positive correlation with the Lennard-Jones force constant ?/k. However, a deviation from the linear relation between ?/k and In S was observed for CO₂ and the deviation became larger with increasing Cl content in CPE. The abnormally high solubility of CO₂ is probably due to the high polarizability of this gas. The heat of solution ΔH_s indicates that for He the sorption process may be a molecular slip process (endothermic), but for other gases the sorption may proceed by a dissolution process (exothermic). There is a large difference between the calculated solubility for the blends assuming incompatibility and the experimental values from time-lag measurements. This may partly be due to the uncertainty of sorption values obtained from the time-lag method and/or partly to changes of sorption modes by interaction between PVC and CPE in the blends. The resulting transport behavior of the blends is discussed on the basis of the free volume concept and of phase–phase interaction in the blends.     

Solubility of CO2 in Glassy PMMA and PS over a Wide Pressure Range: The Effect of Carbonyl Groups

The equilibrium sorption isotherms of CO₂ in glassy PMMA and PS at 32, 42, and 52C over a wide pressure range from 20 to 340 atm were investigated. The normalized sorption concentration (C) isotherms for the polymers in terms of pressure (P) can be described fairly well by two power laws C=kP ⁿ for below and above critical pressure (P _c). The exponent n is a measure of sorption intensity and is closely associated with the interaction between CO₂ and the polymer. From the temperature variation of n values, a negligible interaction between CO₂ and the polymer is found in the sorption process below P _c whereas the interaction is significant above P _c. For a given temperature, the n value for PMMA is 12 times higher than that for PS as a result of the specific interaction of CO₂ and the carbonyl groups in PMMA. The pre-exponential constant k is a measure of sorption capacity and is closely associated with the heat of sorption. In sorption above P _c, k is found to decrease with increasing temperature due to the exothermic sorption process that leads to a decrease in sorption capacity with temperature. From the sorption isobars of PMMA and PS, we observe that the temperature necessary for chemisorption to occur is lower for PMMA than for PS; this results from the specific interaction of CO₂ and the carbonyl groups of PMMA.     

Effects of different particle deposition parameters on adhesion of resin cement to zirconium dioxide and phase transformation

This study evaluated the effect of air-abrasion parameters such as particle size, distance, and time on adhesion of resin cement to zirconium dioxide (Y-TZP) and t→m phase transformation. Y-TZP blocks (N = 80) (In-Ceram YZ, Vita) (4 mm^3?×?4 mm^3?×?3 mm³) were assigned into eight groups (n = 10): air-abrasion with 30 μm (CoJet Sand, S30) and 110 μm (Rocatec-Plus, S110) silica-coated alumina particles, applied for either for 10–20 s (T = time), from a distance of 10–20 mm (D = distance), composing the following groups: S₃₀T₁₀D₁₀, S₃₀T₁₀D₂₀, S₃₀T₂₀D₁₀, S₃₀T₂₀D₂₀, S₁₁₀T₁₀D₁₀, S₁₁₀T₁₀D₂₀, S₁₁₀T₂₀D₁₀, and S₁₁₀T₂₀D₂₀. Resin composite (RelyX ARC) was bonded to Y-TZP blocks in polyethylene molds. The specimens were aged (10,000 thermal cycles and water storage for 90 days) prior to shear bond test. Failure types were analyzed under stereomicroscope and SEM, and phase transformation was calculated. Data (MPa) were analyzed using 3-way ANOVA and Tukey’s tests. Air-abrasion with 110 μm silica particles (10.96) presented significantly higher bond strength (p = 0.0149) compared to 30 μm (8.96). Time (p = 0.403) and distance (p = 0.179) parameters did not affect the results significantly. Air-abrasion with 110 μm particles (12.3) promoted higher bond strength than that of 30 μm (6.4) when applied for 10 s from a distance of 10 mm (Tukey’s). Failure types were predominantly adhesive. Phase transformation ranged between 30.3 and 35.9% for 30 μm particles and 23.8–43.7% for 110 μm particles. While the size of silica-coated alumina particles were more relevant parameter for resin cement adhesion to Y-TZP, time (up to 20 s) and distance (up to 20 mm) appear to be less pertinent.     

Kinetics and thermodynamics of water adsorption onto rice husks ash filled polypropene composites during soaking

The kinetics and thermodynamics of water adsorption onto rice husks ash filled polypropene composites during soaking were studied at different temperatures, quantities and nature of fillers. Raw rice husk, “white” and “black” rice husks ash and Aerosil were used as fillers of polypropene. The increase of fillers contents in the polymer matrix was found to result in non-linear increase of the amount of adsorbed water. The highest adsorption capacity showed the samples filled with raw rice husks, while the lowest—those filled with black rice husks ash. The adsorption kinetics was limited by intra-particle diffusion in plane sheet particles. The values of the diffusion coefficients D, diffusion constants D ^o, activation energy of the diffusion process Е _а, changes of free energy ΔG ^≠, enthalpy ΔH ^≠ and entropy ΔS ^≠ for the formation of the activated complex from the reagent were calculated. A compensation effect between D ^o and Е _а was observed. Based on the Van’t Hoff equation, the values of the changes of standard free energy ΔG ^o, enthalpy ΔH ^o and entropy ΔS ^o of water adsorption were calculated. The sorption process is exothermal in nature and accompanied with decrease of the entropy. The values of the sorption coefficient S and permeability coefficient P were calculated at 25 and 90 °C.     

Equilibrium solubility of CO2 in rubbery EVA over a wide pressure range: effects of carbonyl group content and crystallinity

The equilibrium CO₂ sorption isotherms and isobars for rubbery EVA containing various amounts of vinyl acetate (VA) over a wide pressure range 10-340 atm and 25-52 °C were investigated. The normalized CO₂ sorption concentration (in cm³ (STP) CO₂/mole VA) isotherms of these polymers as a function of pressure consisted of two distinct regions turning at near P_c. The normalized sorption isotherms in these two distinct regions could be fairly described by two respective power laws: C=K_aP^n_a for above P_c and C=k_bP^n_b for below P_c. The normalized CO₂ sorption isotherms were found to be about the same for four EVA samples having different VA contents for below P_c, suggesting that the sorption process at below P_c may be mainly driven by the presence of carbonyl groups. At above P_c, the degree of crystallinity of the polymer appeared to be a major factor to affect the sorption process, with the higher the degree of crystallinity, the lower the normalized CO₂ sorption concentration in the polymer. The sorption isobars of the polymer as a function of temperature were governed by the interplay of density, viscosity, and diffusivity of CO₂ depending on the pressure studied.     

Gas and vapor sorption in polymers just below Tg

Generally, sorption isotherms for gases like CO₂ in glassy polymers are concave to the pressure axis, whereas in the rubbery state these isotherms are linear for gases or sometimes convex to the pressure axis for more condensable vapors. Examples of CO₂ isotherms are reported here that show at low pressure the curvature characteristic of glasses and then become linear at higher pressures. This is observed when the glass transition temperature T_g is not much greater than the observation temperature T, and plasticization of the polymer by sorbed CO₂ causes T_g to become equal to T within the range of pressures employed in the isotherm measurement. For the sorption of vapors in glassy polymers, this can lead to sigmoidal isotherms, as discussed using an illustration from the literature.     

Microporous polyvinylidene fluoride hollow fiber membrane contactors for CO2 stripping: Effect of PEG-400 in spinning dope

In order to develop the structure of microporous PVDF membranes, PEG-400 was introduced into the polymer dope as a non-solvent additive. The hollow fiber membranes were prepared via a wet phase-inversion process and then used in the membrane contactor modules for CO₂ stripping from water. By addition of different amounts of PEG-400, cloud points of the polymer dope were obtained to examine phase-inversion behavior. From FESEM analysis, the membrane structure changed from a finger-like to an approximately sponge-like morphology with the addition of 4 wt.% of PEG-400. The prepared membranes presented smaller mean pore size (0.13 μm) and significantly higher wetting pressure (550 kPa) compared to the plain membrane. From CO₂ stripping test, at water velocity of 0.4 m/s, the PVDF membranes prepared by 4% PEG-400 demonstrated an approximate CO₂ stripping flux of 4.5 × 10⁻⁵ (mol/m² s) which is 125% higher than the flux of the plain membrane. It could be concluded that structurally developed hydrophobic PVDF hollow fiber membranes can be prepared by a controlled phase-inversion process to enhance the performance of gas–liquid membrane contactor.     

Polymer–CO2 systems exhibiting retrograde behavior and formation of nanofoams

The sorption of compressed gases in polymers causing a reduction in the glass transition temperature (T_g) is well established. There is, however, limited information on polymer–gas systems with favorable interactions, producing a unique retrograde behavior. This paper reports on using a combination of established techniques of in situ gravimetric and stepwise heat capacity (C_p) measurements using high‐pressure differential scanning calorimetry (DSC) to demonstrate the occurrence of this behavior in acrylonitrile–butadiene–styrene copolymer (ABS)–CO₂ and syndiotactic poly(methyl methacrylate) (sPMMA)–CO₂ systems. The solubility and diffusion coefficient of CO₂ in the range 0 to 65 °C and pressures up to 5.5 MPa were determined, which resulted in a heat of sorption of ? 15.5 and ? 15 kJ mol^?1, and an activation energy for diffusion of 28.3 and 32.1 kJ mol^?1 in the two systems, respectively. The fundamental kinetic data and the changes in C_p of the polymer–gas systems were used to determine the plasticization glass transition temperature profile, its relationship to the amount of gas dissolved in the polymer, and hence the formation of nano‐morphologies. Copyright © 2006 Society of Chemical Industry     

Study of CO2 and CH4 Permeation Properties through Prepared and Characterized Blended Pebax-2533/PEG-200 Membranes

This study demonstrates how incorporation of polyethylene glycol (PEG-200) into poly (ether-block-amide) (Pebax-2533) can improve the prepared membrane performance in separating CO₂from CH₄. Additionally, the effect of various PEG-200 loadings on CH₄and CO₂permeability and CO₂/CH₄selectivity values was investigated. The prepared membranes were examined using Fourier transform infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. Permeation experiments of the gasses through the neat Pebax and the blended (Pebax-2533/PEG-200) membranes were carried out at a temperature of 25 ^∘C and pressure range of 2 to 10 bar. The gas permeation experiments indicated that the performance of blended membranes is better than that of the neat membrane. As an example, CO₂permeability and ideal CO₂/CH₄selectivity values for the blended membrane with 40 wt.% of PEG-200 loading are 351.65 and 9.17 Barrer, while those values for the neat membrane are 187.54 and 7.28 Barrer, respectively.

     

Molecular transport of n‐alkanes into PU/PBMA interpenetrating polymer network systems

The methylene diisocyanate (MDI) and toluene diisocyanate (TDI) based polyurethane/polybutyl methacrylate (PU/PBMA‐50/50) interpenetrating polymer network (IPN) membranes have been prepared. The molecular migration of n‐alkane penetrants such as hexane, heptane, octane, nonane, and decane through PU/PBMA (50/50) membranes has been studied at 25, 40, and 60°C using a weight gain method. From the sorption results, diffusion (D) and permeation (P) coefficients of n‐alkane penetrants have been calculated. Molecular migration depends on membrane‐solvent interactions, size of the penetrants, temperature, and availability of free volume within the membrane matrix. Attempts have been made to estimate the parameters of an empirical equation and these data suggest that molecular transport follows Fickian mode. From a study of temperature dependence of transport parameters, activation energy for diffusion (E_D) and permeation (E_P) have been estimated from the Arrhenius relation. Furthermore, sorption results have been interpreted in terms of enthalpy (ΔH) and entropy (ΔS) of sorption. The liquid concentration profiles have been computed using Fick's equation with appropriate initial and boundary conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 739–746, 2003     

Low-pressure CO2 sorption in poly(vinyl benzoate) conditioned to high-pressure CO2

Sorption of CO₂ in poly(vinyl benzoate) was gravimetrically measured at pressures up to 1 atm. Sorption isotherms were determined above and below the glass transition temperature T_g from 5 to 85°C. The isotherms were analyzed by the dual-mode sorption model assuming that the plasticizing effect of sorbed CO₂ is negligible at this pressure range. The solubilities and Henry's law dissolution parameters were compared with those obtained by the high-pressure sorption and permeation measurements. Henry's law dissolution parameters were in good agreement with one another. However, the solubilities first determined here were smaller than those determined by the high-pressure sorption experiment at the same temperature. It was clear that the Langmuir capacity of the present specimen was smaller in spite of similar high-pressure CO₂ exposure. Relaxation of the polymer was expected to be one of the reasons. This expectation was confirmed from the observation and analysis of sorption isotherms after two kinds of treatments. After annealing above T_g, the Langmuir capacity was shown to be decreased to 1/2 or even to 1/3 from the sorption isotherms below 45°C. This means that the conditioning to the high-pressure CO₂ surely has a large effect on the nature of glassy polymer. Just after high-pressure CO₂ exposure at 25°C, increased solubility was observed. Furthermore, the slow decrease of solubility, that is, the decrease of conditioning effect, was also followed from the continual measurements at 25°C. This result reflects not only the characteristic of sorption capacity after high-pressure CO₂ exposure, but also the relaxation of polymer in glassy state.     

Preparation and properties of MDI/H12MDI‐based water‐borne poly(urethane‐urea)s—Effects of MDI content and radiant exposure

Water‐borne poly(urethane‐urea)s (WBPUs) were prepared by a prepolymer mixing process using aromatic diisocyanate (MDI, 4,4′‐diphenylmethane diisocyanate)/aliphatic diisocyanate (H₁₂MDI, 4,4′‐methylenebis cyclohexyl isocyanate), polypropylene glycol (PPG, M_n = 1000), dimethylol propionic acid, and ethylene diamine as a chain extender, and triethylamine as a neutralizing agent. The effect of MDI on the molecular weight, chemical structure, dynamic thermo, and tensile properties of WBPUs was investigated. The yellowness index (YI, photo‐oxidation behavior) change of WBPUs under accelerated weathering exposure was also investigated. The WBPUs containing higher MDI content showed lower molecular weight, which verified the participation of some high reactive isocyanate groups of MDI into side reaction instead of chain growing reaction. As the MDI content increased, the storage modulus and tensile modulus/strength of WBPUs film increased, and their glass transitions of soft segments (T_gs) and hard segments (T_gh) were shifted to higher temperature. The intensity of tan δ peak of all three samples increased with increasing radiant exposure. The YI of H₁₂MDI‐based WBPU sample (WBPU‐0) was not occurred. The YI of WBPUs containing MDI increased with increasing MDI content and radiant exposure. However, the YI of sample WBPU‐25 containing 25 mol % of MDI at 11.3 MJ/m² (radiant exposure) was 6.6 which is a permissible level for exterior applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008