Effect of degree of crosslinking on water transport in polymer microparticles

The water transport in microparticles of poly(2-hydroxyethyl methacrylate) crosslinked with small amounts of ethylene glycol dimethacrylate was investigated as a function of time. Dynamic swelling curves were obtained and analyzed with a simple, empirical, exponential expression, where the exponent n indicates the mechanism of water transport. It was determined that the mechanism changed from Fickian to non-Fickian transport as the nominal crosslinking ratio increased from X = 0.007 to X = 0.124 mol EGDMA/mol HEMA. Smaller particles attained their equilibrium swelling value faster. The velocity of the penetrant front was determined with optical microscopy, and it was found to decrease from 22.2 to 11.2 μm/min as the crosslinking ratio increased.     

Biocidal polystyrene beads. IV. Functionalized methylated polystyrene

Crosslinked chloromethylated polystyrene beads were reacted with hydantoin and imidazolidinone derivatives to produce functionalized beads which could be rendered biocidal upon reaction with free chlorine or bromine. The biocidal efficacies of the N‐chlorinated, and in one case, the N‐brominated polymeric beads against Staphylococcus aureus and Escherichia coli O157:H7 in aqueous suspension have been determined. Synthetic methods and test data have been presented. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 368–372, 2004     

Synthesis,transport, and sorption properties and free volume of polystyrene derivatives containing Si and F

Gas permeation, sorption, and free volume was studied in a series of glassy vinylic type Si‐containing polymers. They included p‐substituted derivatives of polystyrene, which were compared with polystyrene, and poly(vinylphenyldimethyl silane). The strongest increase in permeability and diffusion coefficients were observed for the polymer containing the Si(CH₃)₃ group directly attached to phenylene ring. An introduction of spacers between phenylene ring and Si(CH₃)₃ group results in much lower gas permeability. Positron annihilation study of free volume in these polymers showed that lifetime spectra are composed of four components. It implies that size distribution of free volume in these polymers, which are characterized by a modest level of gas permeability, is bimodal, a feature previously observed only for extra large free volume and permeability materials such as poly(trimethylsilyl propyne). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1612–1620, 2000     

Anomalous penetrant transport in glassy polymers V. Cyclohexane transport in polystyrene

Transport of liquid cyclohexane through well characterized, initially glassy, crosslinked polystyrene slabs was investigated. The samples were produced by bulk polymerization of styrene and divinyl benzene using benzoyl peroxide as an initiator at 90°C for 48 h; they had initial crosslinking ratios, X, between 0.005 and 0.025 mol DVB/mol styrene, initial thickness of 0.25 mm to 1.80 mm, and the aspect ratio was maintained above 10 to achieve one-dimensional transport. The results of cyclohexane uptake as a function of time were used to elucidate the effects of degree of crosslinking and sample geometry on the mechanisms of penetrant transport. These results were interpreted in terms of relaxational and diffusional mechanisms.     

Anomalous swelling of a polystyrene matrix in organic solvents

Swelling behavior of a commercial linear polystyrene, containing a small amount (<5% wt) of mineral oil, has been studied in three different classes of organic solvents (alkanes, alcohols and carboxylic acids) using both gravimetry and light microscopy. A comparison has been made with the results presented in earlier publications using a different linear polystyrene, without mineral oil. It is shown that the polystyrene containing mineral oil absorbs much higher amounts of solvent at lower temperatures then at higher temperatures. This anomalous behavior sharply contrasts with the polystyrene without mineral oil, which at lower temperatures absorbs much less solvent. Light microscopy of the diffusion layer reveals that in the polymer with mineral oil precipitation occurs during diffusion at low temperatures, but not at high temperatures. These results clearly show that the presence of small amounts of mineral oil (in quantities below the detection limit of FTIR) can cause significant changes in the sorption behavior of polymers. These results are interpreted by pre‐existing nano‐inhomogeneities, formed by the mineral oil, limited miscibility of oil in the polymer phase and high miscibility of solvent in the oil phase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Friedel-Crafts crosslinking methods for polystyrene modification: 1. Preparation and kinetics

A two-step polymerization and grafting-crosslinking reaction was developed for modification of polystyrene. Styrene was first polymerized in dichloroethane at 25°C using SnCl₄ as catalyst. The cationically prepared polystyrene was then grafted with 1,4-dimethyl-2,5-dichloromethyl benzene in dichloroethane at 50°C in a Friedel-Crafts reaction system. The kinetics of the reaction were followed by titrating the evolved HCI from the reaction system. The maximum reaction rate was found to vary with both the initial concentration of 1,4-dimethyl-2,5-dichloromethyl benzene and the initial concentration of SnCl₄. Determination of the concentration of junctions of the grafted polystyrene samples and analysis of their u.v. spectra were used to determine the progress of the reaction, and to propose a reaction mechanism.     

Solvent and relative humidity effect on highly ordered polystyrene honeycomb patterns analyzed by Voronoi tesselation

Highly ordered honeycomb‐patterned polystyrene surfaces are efficiently prepared by static breath figure method. The structured arrays can be obtained by casting a dilute solution polymer on glass substrates under various conditions. Tetrahydrofuran and chloroform are used as solvent to form cavities of several micrometers. The analysis of the surfaces indicates nonlinear relation between concentration and pore size in this system. Voronoi tessellations of the polystyrene surfaces at different relative humidity (RH) are achieved, and each conformational entropy determined. Optimum parameters of concentration and RH are obtained for both solvents. Analysis of hole size distribution and conformational entropy demonstrates the high order of the films obtained. This is a promising method for the fabrication of homogeneous and highly porous films from polystyrene. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44004.     

Effect of size,surface charge,and hydrophobicity on the translocation of polystyrene microspheres through gastrointestinal mucin

Microspheres (MS) have been proposed for use as oral vaccine delivery vehicles (VDV); however, due to poor and variable absorption their clinical utility is limited. The effects of size, ζ-potential, and surface hydrophobicity on the translocation (P_T) permeabilities of polystyrene (PS) MS with varying surface functional groups (amidine, carboxyl, carboxylate-modified [CML], and sulfate) were determined through gastrointestinal (GI) mucin. P_T were determined, under steady-state conditions, using a modified Ussing-type diffusion chamber and a mucin packet developed for use with the Transwell-Snapwell system. P_T followed the Stokes-Einstein relationship, demonstrating the limited ability of larger MS (>0.5 μm) to diffuse through the mucin layer. P_T also varied according to the surface characteristics. Even though the ζ-potential did not correlate with the transport of MS through mucin, surface ionization appears to be important in MS translocation. The PS-amidine MS were significantly less hydrophobic and had a higher P_T than that of the other MS, suggesting that hydrophobicity is also a significant factor in MS transport through mucin. While these results suggest that mucin may be a significant barrier to the oral absorption of vaccines and VDVs in vivo, the rate-limiting barrier for the absorption of MS will be the intestinal mucosa. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1481–1492, 1997     

Hypercrosslinked polystyrene microspheres with bimodal pore size distribution and controllable macroporosity

A combination of suspension polymerization and postcrosslinking was used to prepare hypercrosslinked polystyrene (H‐PS) microspheres with controllably bimodal pore size distribution in the presence of toluene and polypropylene (PP) as a coporogen. The proportion of PP in the coporogen was changed to investigate the influence of the coporogen composition on the pore structure of the H‐PS microspheres. The addition of a small amount of PP achieved the aim of a clearly bimodal pore size distribution and the control of the macroporosity of the H‐PS microspheres, which have potential application in the preparation of catalyst supports. The specific surface area of the H‐PS microspheres could be adjusted in the range 380–790 m²/g by changes in the concentration of PP in the coporogen. Moreover, the H‐PS microspheres displayed all the characteristics of Davankov‐type resins by their ability to be swollen in both thermodynamically poor solvents such as water and good solvents such as toluene. Finally, the possible mechanism of porosity formation during polymerization and postcrosslinking was also examined by a combination of pore structure data and the appearance of the microspheres before and after postcrosslinking. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Methylamino‐group‐modified hypercrosslinked polystyrene resin for the removal of phenol from aqueous solution

Chemical modification was performed for macroporous crosslinked chloromethylated polystyrene. The obtained HJ‐K01 resin was used to remove phenol from aqueous solution, and its adsorption behaviors for phenol were compared with commercial Amberlite XAD‐4. The results indicate that methylamino groups were successfully uploaded onto the surface of the HJ‐K01 resin and the adsorption capacity of phenol onto the HJ‐K01 resin was much larger than that onto XAD‐4. Furthermore, the original phenol solution was suitable for the adsorption, the adsorption isotherms could be fitted by the Freundlich model, and its kinetic curves could be characterized by a pseudo‐second‐order rate equation. The fixed‐bed column adsorption demonstrated that the HJ‐K01 resin was an excellent resin for the removal of phenol. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Kinetic study on the first stage during thermal degradation of polystyrene

The kinetic parameters of the first stage of polystyrene degradation have been investigated to elucidate the reaction mechanisms using the flow reactor system. The decrease in molecular weight of polystyrene was recorded at minute intervals over the temperature range 310°–390°C. Generally, the first and second stages were observed by thermogravimetric analysis (t.g.a.), however in the early stage of the degradation volatile yields of at least 5% occurred. Therefore, using t.g.a. analysis it is difficult to detect this earlier stage. It became evident that the first stage in the earlier part of the reaction could be detected by g.p.c. analysis. We have observed the hidden kinetic parameters of the nature of the first stage of the polystyrene degradation. The results indicate that the main chains were degraded randomly with the small quantitative volatile groups in the first stage and the rates of decrease in molecular weight in the first stage against reaction temperatures were evaluated as log k_s = 12.0 ? 41300/RT.     

Anomalous penetrant transport in glassy polymers VI. Effect of temperature on transport

Transport of liquid cyclohexane through well characterised, initially glassy, crosslinked polystyrene slabs was Investigated at 20, 30, 40, and 50°C. The samples used were produced by bulk polymerization of styrene and divinyl benzene (DVB) at 90°C for 43 hr using benzoyl peroxide as an initiator. The samples tested had initial cross-linking ratios, X, between 5 and 25 × 10^?3 mol DVB/mol styrene. The initial thickness of the samples tested varied from 0.25 mm to 1.80 mm, and the aspect ratio (length to thickness ratio) was maintained above 10;1 in order to analyze the results by one-dimensional transport equations. Cyclohexane uptake was followed as a function of time along with dimensional changes in the thickness and area of the samples. The results of penetrant uptake as a function of time were analyzed using a simplified exponential expression and employing all the data points from the beginning of the experiment until the time of observation of the maximum in uptake. Good correlations were established between the penetrant uptake and the transport temperature. These results were interpreted in terms of competitive relaxational and diffusional mechanisms.     

Hydrophilic polystyrene/maleic anhydride ultrafine fibrous membranes

Polystyrene/maleic anhydride (PSMA) was synthesized to reach a viscosity‐average molecular weight of 700 kDa and fabricated into ultrafine fibrous membranes consisting of fibers with an average diameter of 300 nm. These ultrafine PSMA fibers were rendered insoluble in organic solvents by reactions with hydrazine and ethylenediamine (ED). The highly efficient incorporation of diamines into the fibrous membranes was easily achieved by brief immersions in either dilute (0.5 wt %) hydrazine for 1 min or ED ether solution for 2 min. Heating at 150°C for 5 min produced crosslinked PSMA with very little or no solubility in acetone with the retention of the fibrous membrane structure. The ED‐crosslinked membranes were particularly stable to both bases and acids as well as hydrophilic solvents, had a 46° water contact angle, and absorbed 22 times the amount of water as the as‐spun fibrous membrane. This post‐fiber‐formation crosslinking approach was robust, highly efficient, and fast and required very little crosslinking reagent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterization and dual functionalization of polystyrene with propionic anhydride and cyanate derivatives

First, Friedel–Crafts reactions were used for the acylation process. For this, polystyrene (PS) was reacted with propionic anhydride in the presence of Lewis acid catalyst. The amount of acyl group linked PS as a result of acylation has been identified as volumetric. Second, the bromination and lithiation reactions of acylated PS containing carbonyl groups were realized. Also, the lithiated PS containing acyl groups has been modified a second time with various isocyanates and isothiocyanate derivatives in the presence of n?BuLi catalyst. Some important reaction parameters were assigned in order to optimize the process. The structure all of the products were characterized by Fourier transform infrared, ¹H NMR (Proton Nuclear Magnetic Resonance), and thermogravimetric methods. In addition, reaction yields were determined according to the result of elemental analysis. Dual functionalization yields were realized between 62.2% and 69.9%. For kinetic analysis, the TG/DTG (Thermal Gravimetric Analysis/Differantial Thermal Analysis) data obtained at three different heating rates were processed by Kissinger–Akahira–Sunose method. The results demonstrated that the acylation reaction, bromination and lithiation reactions, and dual functionalization reactions with cyanate derivatives can be carried out to obtain a significantly functionalized polymer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1351‐1362, 2013     

Gas sorption and transport in syndiotactic polystyrene with nanoporous crystalline phase

In this contribution we analyse sorption and transport of several gases in semicrystalline syndiotactic polystyrene with nanoporous crystalline δ form. Investigation was performed on amorphous samples and on samples characterized by different degrees of crystallinity. Sorption isotherms of carbon dioxide, nitrogen and oxygen in the crystalline phase have been determined starting from experimental results obtained for semicrystalline and amorphous samples. Corresponding isosteric heats of sorption were evaluated for the crystalline and amorphous phase. Permeation tests were also performed to gather information on mass transport properties of semicrystalline samples, evaluating average diffusivities of carbon dioxide and oxygen, in the limit of small concentrations as function of degree of crystallinity.     

Friedel-Crafts crosslinking methods for polystyrene modification: 2. Tg′Tll and T′ll transitions of grated polystyrene

Polystyrene was grafted with 1,4-dimethyl-2,5-dichloromethyl benzene in dichloroethane solution at 50°C using SnCl₄ as a catalyst. Thermal analysis of grafted polystyrene samples using differential scanning calorimetry revealed two liquid-liquid transitions, T_ll and T′_ll, in addition to the glass transition, T_g′ and the decomposition temperature, T_d. The effect of the number of junctions per polystyrene chain on T_g′T_ll and T′_ll is examined and analysed.     

The effect of hydrogen content on ballistic transport behaviors in the ni-nb-zr-h glassy alloys

The electronic transport behaviors of (Ni(0.39)Nb(0.25)Zr(0.35))(100-) (x)H(x) (0 ≤ x < 23.5) glassy alloys with subnanostructural icosahedral Zr(5)Nb(5)Ni(3) clusters have been studied as a function of hydrogen content. These alloys show semiconducting, electric current-induced voltage (Coulomb) oscillation and ballistic transport behaviors. Coulomb oscillation and ballistic transport occur at hydrogen contents between 6.7 and 13.5 at% and between 13.5 and 21.2 at%, respectively. These results suggest that the localization effect of hydrogen in the clusters plays an important role in various electron transport phenomena.     

Improvement in silicon-containing sulfonated polystyrene/acrylate membranes by blending and crosslinking

Silicon-containing sulfonated polystyrene/acrylate-poly(vinyl alcohol) (Si-sPS/A-PVA) and Si-sPS/A-PVA-phosphotungstic acid (Si-sPS/A-PVA-PWA) composite membranes were fabricated by solution blending and physical and chemical crosslinking methods to improve the properties of silicon-containing sulfonated polystyrene/acrylate (Si-sPS/A) membranes. FTIR spectra clearly show the existence of various interactions and a crosslinked silica network in composite membranes. The potential of the composites to act as proton exchange membranes in direct methanol fuel cells (DMFCs) was assessed by studying their thermal and hydrolytic stability, swelling, methanol diffusion coefficient, proton conductivity and selectivity. TGA measurements show that the composite membranes possess good thermal stability up to 190 °C, satisfying the requirement for fuel cell operation. Compared to the unmodified membrane, the composites exhibit less swelling and a superior methanol barrier. Most importantly, all of the composite membranes have significantly lower methanol diffusion coefficients and significantly higher selectivity than those of Nafion^® 117. The Si-sPS/A-20PVA-20PWA membrane is the best applicant for use in DMFCs because it exhibits an optimized selectivity value (5.93 × 10⁵ Ss cm⁻³) that is approximately 7.8 times of that of the unmodified membrane and is 27.8 times higher than that of Nafion^® 117.     

Effect of physical aging on the properties of films of amorphous poly(ether ether ketone) (PEEK)

Physical aging of films of poly(ether ether ketone) kept for 2 months at 120°C was studied. The extent of aging was evaluated with different techniques. Aged samples show different thermal behavior and exhibit different mechanical, transport, and viscoelastic properties. An attempt was made to establish the accuracy of different techniques and their reliability in detecting the extent of physical aging. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2635–2641, 1997     

二乙烯基苯对低密度聚苯乙烯密度及尺寸的影响

研究了悬浮聚合法合成氏密度聚苯乙烯（LDPS）微粒子过程中，二乙烯基苯（DVB）的加入对树脂粒径及密度的影响。结果表明，二乙烯基苯从单体分散阶段开始影响单体液滴的分散尺寸，加入DVB后，单体液滴尺寸变小，最终产物粒径变小。且在实验条件下，随DVB量增加，最终LDPS粒径减小，当用明胶做分散剂，二乙烯基苯与苯乙烯之比（DVB／St）大于1时，粒径减小变化趋于平缓；当有致孔剂存在时，LDPS的密度随DVB量增加而减小。