Synthesis and properties of solvent absorptive methyl methacrylate‐divinylbenzene copolymer beads

Methyl methacrylate‐divinylbenzene copolymer beads were synthesized by radical suspension polymerization. The effects of the divinylbenzene concentration and the composition of the toluene/heptane diluent were studied with regard to the polymer bead formation, surface morphology, solvent swelling ratio, and absorption kinetics. The crosslinking density and diluent composition were responsible for solvent swelling. The interaction between the polymer and the diluents is attributed to phase separation, which controls the formation of a network‐type or pore‐type polymer, or a combination. For the optimum bead swelling in toluene, a combined morphology of more flexible polymer networks and a small amount of pores is essential for the desired absorption–desorption behavior. Dynamic swelling behavior of the polymer beads was elucidated. The mechanism of toluene transport into the beads became more a relaxation control. POLYM. ENG. SCI., 47:447–459, 2007. © 2007 Society of Plastics Engineers.     

Porous poly(2-hydroxyethyl acrylate) hydrogels prepared by radical polymerisation with methanol as diluent

Dynamic-mechanical and water sorption properties of porous and non-porous hydrogels have been studied as a function of their porosity and crosslinking density. Porous hydrogels with different crosslinking densities were prepared by co-polymerisation of 2-hydroxyethyl acrylate and ethyleneglycol dimethacrylate in solution in methanol. Pores were formed due to the segregation of the solvent from the polymer network during the polymerisation process. The porosity of the samples was observed by scanning electron microscopy. The pores collapse during the drying process after polymerisation but they reopen when the xerogel is immersed in liquid water. Bulk polymer networks with varying crosslinking densities were also synthesised and used as a reference in the analysis of the porous hydrogels. Water sorption from the gas phase and from the liquid phase was studied by means of equilibrium sorption isotherms and immersion experiments, respectively. Dynamic-mechanical spectroscopy conducted on the xerogels shows that the elastic modulus in the rubber-like state highly depends on the amount of solvent used in the polymerisation what is attributed to the presence of discontinuity surfaces in the xerogel although the pores are closed.     

Liquid sorption in a segmented polyurethane elastomer

The sorption and diffusion of a series of liquids in a segmented polyurethane have been studied to determine how the behavior is affected by the choice of solvent and the heterophase nature of the polymer. The polyurethane was composed of methylene-di-para-phenylene isocyanate (MDI) butanediol, and poly(tetramethylene oxide) (1000) with a mole ratio 3:2:1. Immersion experiments in n-heptane liquid, a poor solvent, and incremental sorption experiments in n-heptane vapor showed normal Fickian havior. In the set of liquids of increasing polarity, which included 1-chloroheptane, three dichloroalkanes and orthodichlorobenzene, the swelling increased to very high levels. Effective values of the molecular weight between crosslinks computed from the Flory Rhener equation, assuming complete phase segregation, varied widely with the different liquids. Agreement could be improved by allowing 30 percent mixing of hard segments with the soft segment phase. The sorption and desorption curves for the highly swelling liquids showed various anomalies some of which might be the result of solvent induced relaxation of hard segment domains.     

Effect of crosslinking density on the physical properties of interpenetrating polymer networks of polyurethane and 2-hydroxyethyl methacrylate-teminated polyurethane

Interpenetrating polymer networks (IPNs) of 2-hydroxyethyl methacrylate-terminated polyurethane (HPU) and polyurethane (PU) with different crosslinking densities of the PU network were prepared by simultaneous solution polymerization. Dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) show that compatibility of component polymers in IPN formation depends on the crosslinking density of the PU network. Physical properties such as density and water absorption rely on the subtle balance between the degree of phase separation and the crosslinking density of the PU network. In spite of the occurrence of phase separation, the tensile moduli and tensile strength of the IPNs increase with the crosslinking density of the PU network. Morphological observation by scanning electron microscopy revealed different fracture surfaces between the compatible and incompatible IPNs. Surface characteristics of the IPNs, indicated as hydrogen bonding index and hard-to-soft segment ratio, are altered considerably by varying surface morphologies. Improved blood compatibility of IPN membranes is due to the variation of the hydrophilic and hydrophobic domain distribution.     

Diffusion of mineral oil in styrene‐butadiene polymer films

Mineral oil diffusion in styrene‐butadiene polymer films was investigated with a simple gravimetric sorption method. Over the selected range of temperatures and film thicknesses for which sorption tests were performed, the diffusion process is described in terms of Fick's third law. Polymer dissolution was found to compete with the diffusion process especially at high temperature. Possible interference due to dissolution on data generated using a gravimetric method, resulted in an estimation of apparent activation energy using diffusion coefficient set calculated with Crank's half‐time relationship. The mineral oil diffusion activation energy was found to be relatively high compared with those of hydrocarbons diffusing in natural and synthesized rubbers or crosslinked polybutadiene as reported in the literature. The influence of polymer T_g, crosslinking density, and polarity on mineral oil ability to penetrate polymer film was evaluated in terms of percent weight increase over time. Maximum absorption after 60‐min sorption time linearly correlates with mineral oil absorption rate for polymers prepared with different structures. This linear relationship suggests that diffusion of solvent in styrene‐butadiene polymers reveals the macroscopic composition and structural polymer modification rather than local changes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Water sorption and diffusion through saturated polyester and their nanocomposites synthesized from glycolyzed PET waste with varied composition

A new system of saturated polyester and their nanocomposites synthesized from glycolyzed PET with varied composition is investigated for the sorption and diffusion studies in water. The kinetics of sorption is studied by using the equation of transport phenomena. The values of ‘n’ from transport equation are found to be below ‘0.5’, showing the non-Fickian or pseudo-Fickian transport in the polymer. The dependence of diffusion coefficient on composition and temperature has been studied for all polymeric samples. The diffusion coefficient of saturated polyester samples decreases with an increase in glycolyzed PET contents. The nanocomposite samples show less diffusion coefficient than pristine polymer and it decreases with an increase in nano-filler up to 4 wt%. The diffusion coefficient increases with an increase in temperature for all the samples. The sorption coefficient shows a little change with variation in composition as well as temperature for all the samples and it is in a range of 1. The activation energy for diffusion and permeation is positive for all the samples. The heat of sorption is also positive for all the samples, indicating Henry type mode of sorption.     

Effect of vapor phase ethylenediamine crosslinking of matrimid on alcohol vapor sorption and diffusion

This work examines the sorption, diffusion, and polymer relaxation behavior for water and C1‐C7 alcohol vapors at 30 °C in ethylenediamine vapor‐phase crosslinked Matrimid. Ethylenediamine is sufficiently volatile that crosslinking can occur by exposing the polymeric film to saturated vapor, in contrast to more conventional means of dissolving the crosslinker in a solvent and immersing the polymeric film in the solution. The vapor‐phase exposure method avoids the use of additional solvent and undesired solvent‐induced swelling. Sorption isotherms demonstrate that water and C1‐C5 alcohols do not appreciably differ for unmodified and crosslinked Matrimid; however, an approximate 90% reduction in sorption was determined for hexanol and heptanol. A minor impact on diffusion coefficients for water, methanol, and ethanol was observed, while those of propanol and butanol were reduced over an order of magnitude. Relaxation kinetics were similarly unchanged for water and C1‐C3 alcohols, while being significantly reduced for butanol and higher alcohols. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44771.     

Poly(ether urethane)/poly(ethyl methacrylate) IPNs with high damping characteristics: The influence of the crosslink density in both networks

Interpenetrating polymer networks (IPNs) with a controlled degree of microphase separation were synthesized from a poly(ether urethane) (PUR) and poly(ethyl methacrylate) (PEMA). The influence of the crosslink density of both networks was investigated in the 70:30 PUR/PEMA IPN. The extent of damping was evaluated by dynamic mechanical thermal analysis. Mechanical properties were studied using tensile testing and hardness measure-ments. Control of crosslinking was successful in tailoring the damping profile. Higher crosslinking in the first-formed network (polyurethane) seemed to increase slightly the area under the linear loss modulus curve, LA, whereas no influence was obvious when changing the crosslink density in the second network. TGA studies revealed improved thermal properties for the IPNs with a higher crosslink density in the PUR network. TEM micrographs confirmed a finer morphology for the materials with a higher crosslink density in the PUR, whereas increasing the crosslink density in the PEMA network resulted in a decrease of phase mixing. © 1996 John Wiley & Sons, Inc.     

Effects of crosslinking density on structure and properties of interpenetrating polymer networks from polyurethane and nitroguar gum

Semi‐interpenetrating polymer networks (semi‐IPNs) of castor oil‐based polyurethane prepolymer and nitroguar gum (NGG) with different crosslinking density of the PU network, coded as UNG films, were prepared through varying the trimethanol propane (TMP)/1,4‐butanediol (BDO) molar ratios in the chain extender mixture. The effects of crosslinking density on the structure and properties of the UNG films was investigated by attenuated total reflection Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical thermal analysis, scanning electron microscopy, crosslinking density measurements, solvent‐extracting tests, and tensile tests. The experimental results revealed that incorporation of TMP crosslinker into the hard segments of polyurethane resulted in a decrease in the aggregation of hard segments. With an increase of the TMP/BDO molar ratios, the semi‐IPN films exhibited the higher crosslinking density, glass temperature (T_g), stiffness, and tensile strength (σ_b). Furthermore, the experimental results also indicated that NGG restricted the formation of crosslinking networks when the TMP content is relatively high, which led to the negative deviation of the theoretically predicted crosslinking density and Dibenedetto's equation. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

丙烯酸聚氨酯涂料成膜过程(Ⅰ)溶剂扩散系数的估算

采用傅里叶变换红外光谱（FTIR）测定了不同时间下丙烯酸聚氨酯涂料体系成膜聚合物的固化度及固化反应速率常数,并将该体系按二元聚合物-溶剂体系进行简化处理,在Vrentas-Duda自由体积理论模型的基础上,利用Di-Benedetto方程关联了溶剂的扩散系数与涂膜的固化度,建立了涂膜中溶剂扩散系数的预测模型.结果表明,本涂膜体系中溶剂扩散系数是溶剂浓度、干燥时间的函数.     

Analysis of reaction injection molding process of polyurethane-unsaturated polyester blends. Part II: Mechanical properties

The mechanical properties of polyurethane-unsaturated polyester interpenetrating polymer networks (IPNs) that were prepared by reaction injection molding (RIM) process were measured with variations In composition, cross-link density, and relative reaction rate. From dynamic mechanical analysis (DMA), it was found that the two component polymers had a good compatibility over the whole composition range. The tensile strengths of the blends were greater than those of the pure components and had a maximum value at 50/50 composition. The modulus of elasticity and surface hardness decreased and the impact strength increased as the polyurethane content was increased, but the changes were not high at low polyurethane content, below 50%. For higher cross-link density, the compatibility was enhanced and the mechanical properties were improved. When the reaction rates of the components were different, some extent of phase separation was found in DMA and the properties were affected adversely.     

Sorption/desorption properties of ethanol,toluene, and xylene in poly(dimethylsiloxane) membranes

Sorption/desorption kinetics and sorption equilibria have been determined for ethanol, toluene, and xylene vapors in a poly(dimethylsiloxane) membrane containing about 32 wt % silica resin at 25°C. Dependence of diffusion coefficient on vapor activity and sorption isotherms have been compared to identify the transport mechanisms of those penetrants in the PDMS membrane. The analysis of Zimm–Lundberg clustering functions showed that all three penetrants had a tendency to form clusters and ethanol molecules might be immobilized by the residual silanol groups within the silica resin in the membrane. The diffusion coefficient of toluene was roughly constant and that of xylene slightly decreased as increasing the vapor activity due to the competing effects of penetrant clustering and solvent swelling of polymer. The diffusion coefficient of ethanol versus activity exhibited a maximum due to the effects of ethanol immobilization and cluster formation. The freevolume effect by solvent swelling to diffusion was obscured by either penetrant clustering or immobilization for the three penetrant–polymer systems. © 1994 John Wiley & Sons, Inc.     

New gasoline and gas barrier from plasticized carbon black reinforced butyl rubber/high‐density polyethylene blends

The effects of the high‐density polyethylene volume fraction on the curing characteristics and network structure of rubber blends have been studied in terms of the torque, scorch time, optimum curing time, Mooney viscosity, number of elastically effective chains, viscosity, interfacial tension, glass‐transition temperature, scanning electron microscopy, internal friction, sound velocity, acoustic attenuation, polymer–solvent interaction parameter, swelling index, and gel fraction. The applicability of the blends for gasoline barriers has been examined through the changes in the electrical resistance and volumetric swelling in gasoline versus time at room temperature. The transport mechanism of the solvent through the crosslinked butyl rubber/high‐density polyethylene blends is governed by Fickian diffusion law. The transport coefficients, namely, the diffusion coefficient, intrinsic diffusion, and permeation coefficient, have been computed. The experimental data for the permeation coefficient are in good agreement with the values calculated by Maxwell's model and far from those of Robeson's model. In addition, some thermodynamics parameters, namely, the standard entropy, standard enthalpy, and standard Gibbs free energy, have been estimated as functions of the high‐density polyethylene concentration of the butyl rubber blends. Furthermore, the applicability of butyl rubber/high‐density polyethylene composites for Freon gas barriers and antistatic charge dissipation has been examined. Finally, the mechanical properties, such as the tensile strength, hardness, stiffness, and elongation at break, of butyl rubber composites with different high‐density polyethylene concentrations have been evaluated. The increase in the mechanical properties is due to the increase in the crosslinking density and the interfacial adhesion of the blend. This proves that these new blends have important technological applications as gasoline and Freon barriers and for antistatic charge dissipation with good mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1237–1247, 2006     

Effect of crosslink density on transport of industrial solvents through polyether based polyurethanes

Polyurethanes based on PPG 2000 with variable concentrations of TDI and TMP were prepared and used for sorption studies, employing homologous series of hydrocarbons such as benzene, toluene and xylene. The sorption was observed to be non-Fickian in nature. The solubility parameter of the polyurethane series was observed to be 9·7(calcm^-3)^1/2. The polymer solvent interaction parameter χ was found to be lowest in benzene, suggesting higher interaction with it. The sorption and diffusion coefficients were observed to increase with a decrease in the degree of crosslinking. Molecular weights between crosslinks were calculated using the Flory–Rehner equation and compared with those obtained theoretically. © 1998 Society of Chemical Industry     

Synthesis and swelling characteristics of responsive carboxybetaine gel

A polyimminium gel, Dimedone‐[N, N′ melaminium] butyrocarboxylate copolymer, comprising of zwitterionic carboxybetaine repeat units was synthesized via a catalyst free facile polycondensation approach. The polymer was studied for its photoluminescence, thermal, and swelling behavior. Swelling behavior was investigated in different solvent mixtures as well as in pure solvents. The extent of swelling was dictated by solvent composition, such as dielectric constant, pH, ionic strength, and other variables for instance, temperature and crosslinking density. Gel was soluble in alkali and could be regenerated on treatment with an acid. This pH responsive behavior could find various industrial applications, especially in wastewater treatment. A preliminary study on sorption of dyes was also carried out. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Temperature‐responsive characteristics of poly(N‐isopropylacrylamide) hydrogels with macroporous structure

Macroporous poly(N‐isopropylacrylamide) (PNIPA) hydrogels were synthesized by free‐radical crosslinking polymerization in aqueous solution from N‐isopropylacrylamide monomer and N,N‐methylenebis (acrylamide) crosslinker using poly(ethylene glycol) (PEG) with three different number‐average molecular weights of 300, 600 and 1000 g mol^?1 as the pore‐forming agent. The influence of the molecular weight and amount of PEG pore‐forming agent on the swelling ratio and network parameters such as polymer–solvent interaction parameter (χ) and crosslinking density (ν_E) of the hydrogels is reported and discussed. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying different molecular weights and compositions of PEG during polymerization. At a temperature below the volume phase transition temperature, the macroporous hydrogels absorbed larger amounts of water compared to that of conventional PNIPA hydrogels, and showed higher equilibrated swelling ratios in aqueous medium. Particularly, the unique macroporous structure provides numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to external temperature changes during the swelling and deswelling process. These macroporous PNIPA hydrogels may be useful for potential applications in controlled release of macromolecular active agents. Copyright © 2006 Society of Chemical Industry     

Coupling between mass diffusion and film temperature evolution in gravimetric experiments

In gravimetric experiments, the swelling and the drying of polymer films is used to investigate the thermodynamic properties and the mutual diffusion coefficient of polymer/solvent systems. Usually thermodynamic equilibrium at the interface between the film and the solvent vapor and thermal equilibrium between the film and the surroundings are assumed. In this paper we show that the second assumption may fail. Indeed, during a swelling or drying experiment, the temperature of the film surface changes due to the latent heat of vaporization, which induces a variation of the activity. When the corresponding variation of the solvent content is of the same order than the variation due to the sorption experiment and when the thermal time constant is significant compared to the characteristic mass diffusion time, this thermal effect must be taken into account when analyzing sorption data. We evaluate the consequence of this thermal effect on gravimetric experiments and develop a complete model to take this phenomenon into account when analyzing sorption data. As an example, the mutual diffusion coefficient for the system PIB (polyisobutylene)/toluene is estimated for various solvent concentrations at 25 °C.     

Pore collapse during the fabrication process of rubber‐like polymer scaffolds

Rubbery polymer scaffolds for tissue engineering were produced using templates of the pore structure. The last step in the fabrication process consists of dissolving the template using a solvent that, at the same time, swells the scaffolding matrix that was a polymer network. Sometimes the polymer matrix is stretched so strongly that when the solvent is eliminated, i.e., the network is dried, it shrinks and is not able to recover its original shape and, consequently, the porous structure collapses. In this work we prepared, using the same fabrication process (the same template and the same solvent), a series of polymer scaffolds that results in collapsed or noncollapsed porous structures, depending on the polymer network composition. We explain the collapse process as a consequence of the huge volume increase in the swelling process during the template extraction due to the large distance between crosslinking points in the scaffolding matrix. By systematically increasing the crosslinking density the porous structure remains after network drying and the final interconnected pores were observed. It is shown that this problem does not take place when the scaffolding matrix consists of a glassy polymer network. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1475–1481, 2007     

Relationship between structure and aromatic solvent permeability of crosslinked polyurethanes based on hyperbranched polyesters

This work investigates the relationship between structure and aromatic solvent permeability of polyurethanes based on trimethylolpropane (TMP) as a classical crosslinker and self‐made hyperbranched polyesters (HBPEs) as newly developed crosslinking agents. For this purpose three groups of samples were synthesized using toluene diisocyanate, poly(tetramethylene glycol) and different pseudo‐generation numbers of crosslinkers in the variable hard segment content. The results obtained from characterization tests indicate that replacing TMP by HBPE leads to an increase of crosslink density resulting in significant reduction of sorption capacity and conversely leads to an increase of the diffusion coefficient due to the lower glass transition temperature (T_g) of soft segments. In this way, the toluene permeability of hyperbranched polyurethane (HBPU) is considerably lower than that of classical polyurethane. The HBPUs with sufficient amount of hard segment have the lowest solvent uptake and diffusion coefficient leading to optimal barrier performance. By increasing the generation number of HBPE, the crosslink density of HBPU increases, but the crystallinity as well as T_g of soft segments decrease. These two contradictory changing trends of the structural characteristics cause a slight decrease in sorption coefficient of membranes and an increase of diffusivity. Therefore the barrier performance of HBPUs is weakened with increasing generation number of crosslinkers. © 2015 Society of Chemical Industry     

Permeation of oxygen through polyurethane–polyepoxide interpenetrating polymer networks

Oxygen permeation studies on polyurethane (PU)/polyepoxide (EP) interpenetrating polymer networks show that the increased crosslinking density owing to additional permanent chain entanglement (resulting from interpenetration) can decrease the coefficients of permeation, diffusion, and oxygen solubility. At 20% PU, at which the crosslinking density is maximum, these coefficients retain minimum values, while the tensile strength retains a maximum value.