Synthesis of uniform microspheres with higher content of 2-hydroxyethyl methacrylate by employing SPG (Shirasu porous glass) emulsification technique followed by swelling process of droplets

Relatively uniform microspheres containing a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA), were prepared by employing a swelling method of uniform seed droplets. A uniform seed emulsion composed mainly of styrene (St) was prepared by the Shirasu porous glass (SPG) membrane emulsification technique; this was mixed with a secondary emulsion composed mainly of HEMA/St or HEMA/MMA (methyl methacrylate) prepared by a homogenizer for swelling. The swollen droplets obtained were polymerized at 75°C under a nitrogen atmosphere. The uniform microsphere with a higher content of HEMA was obtained successfully by the swelling method while it failed by a direct emulsification method. The effects of the composition of the oil phase and the inhibitor in the continuous phase on the incorporated fraction of HEMA, the morphology of particles, and monomer conversion were investigated. It was found that the incorporated fraction of HEMA increased with increasing its feed fraction, and more HEMA was incorporated into the microsphere when HEMA/MMA was used as the oil phase of the secondary emulsion rather than HEMA/St. Although the final conversion was very low when the feed fraction of HEMA was higher, it can be increased to more than 80% by using an adequate amount of ethylene glycol dimethacrylate (EGDMA) as a crosslinker and NaNO₂ as an inhibitor in the aqueous phase. Various microspheres with different morphologies such as spherical, snowmanlike, and popcornlike were observed, depending on composition of the oil phase. Furthermore, the porous microsphere with a high content of HEMA was obtained by employing hexanol (HA) as a porogen. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1325–1341, 1997     

Preparation of polyurethaneurea (PUU) uniform spheres by SPG membrane emulsification technique

Uniform polyurethaneurea (PUU) spheres were prepared from 20–40 wt % urethane prepolymer (UP) solution of xylene. Uniform droplets were formed with the Shirasu porous glass (SPG) membranes of 1.42, 5.25, and 9.5 μm pore size, dispersed in an aqueous phase with dissolved stabilizers, and allowed to stand for the chain extension at the room temperature with diamines that were added after the emulsification. The reaction progressed rapidly by an addition of ethyl acetate to the aqueous phase, promoting the diffusion of diamines into the droplets. The reaction of —NCO groups with water did not hamper the emulsification process, which normally occurred in 1 to 2 h, yielding stable droplets with the coefficient of variation around 10%. No instability or coagulation occurred, while standing for the chain extension, and solid, spherical PUU particles of 5–20 μm were obtained after removal of the solvent. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2237–2245, 2000     

Application of porous microspheres prepared by SPG (Shirasu porous glass) emulsification as immobilizing carriers of glucoamylase (GluA)

Fairly uniform spheres of crosslinked polystyrene (PS) and polymethyl methacrylate (PMMA), prepared by a particular emulsification process using SPG (Shirasu Porous Glass) membranes and subsequent suspension polymerization, were applied for immobilizing carriers of Glucoamylase (GluA). A mixture of monomers, solvents, and oil-soluble initiator was allowed to permeate through the micropores of SPG, suspended in an aqueous solution of poly(vinyl alcohol), and polymerized while retaining the narrow size distribution during polymerization. A small amount of acrylic acid or glycidyl methacrylate (GMA) was incorporated for the immobilization of GluA via covalent bonding. Although GluA has been regarded as being difficult to retain its activity after the immobilization process, a porous structure of the carriers definitely favored the immobilization, and a maximum 55% relative activity (RA) was obtained by the physical adsorption to PMMA spheres. The reaction of epoxide in GMA with 6-aminocaproic acid provided a spacer arm for the carboxyl group. An improvement of activity was expected by the incorporation of the spacer arms; however, barely noticeable activity was observed for PMMA carriers either by the physical adsorption or by the covalent bonding. A slight improvement was observed for PS carriers with spacers compared to the carriers without them. The diffusion process of oligosaccharides in the porous carriers seemed to retard the rate of hydrolysis in the case of largest carriers, 60 μm PS-DVB-AA spheres. The activity of immobilized GluA was retained during a long storage period of more than 150 days, some of them even increasing gradually, while the activity of native GluA dropped to zero after 100 days. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2655–2664, 1997     

Synthesis of 100 μm uniform porous spheres by SPG emulsification with subsequent swelling of the droplets

100 μm porous p(styrene-co-divinylbenzene) (PS-DVB) microspheres were synthesized by employing a particular membrane emulsification technique, and subsequent swelling of the seed droplets. DVB dissolving a water-insoluble substance, hexadecane (HD), and an initiator was permeated through a SPG (Shirasu porous glass) membrane, and the uniform (seed) droplets were released to a stabilizer solution acting as the continuous phase. The average droplet size was around 30 μm, and this emulsion was mixed with a secondary emulsion of much smaller size consisting of more hydrophilic components, a mixture of styrene, middle chain alcohol (C6 to C8), dichlorobenzene, and isoamyl acetate, which promotes the degradative diffusion process of the components. After all the droplets in the secondary emulsion virtually disappeared, the seed droplets were swollen to a maximum 110 μm. Polymerization was carried out at 348 K under a nitrogen atmosphere. Uniform porous spheres of 100 μm with the coefficient of variation less than 10% were obtained. Specific surface area was 350 m²/g. Careful controlling of the specific gravity of swollen droplets and the choice of solvents balancing between the good solvency for the polymer and polarity (solubility in water) proved vital in order that the polymerization may proceed without an extensive phase separation in the early stage, which eventually induces breakup of the droplets. The three component system, isoamyl acetate-hexanol-o-dichlorobenzene, provided an adequate cosolvent for these purposes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 931–942, 1997     

Synthesis and property behavior of dioctyl phthalate plasticized styrene–acrylate particles by Shirasu porous glass emulsification and subsequent suspension copolymerization

Two‐phase model styrene–acrylate copolymers were synthesized with a soft phase consisting of methyl acrylate, butyl acrylate, and butyl methacrylate. Besides the styrenic copolymers, copolymers containing a hard phase of methyl methacylate and methyl acrylate were also synthesized. Comonomer droplets with a narrow size distribution and fair uniformity were prepared using an SPG (Shirasu porous glass) membrane having pore size of 0.90 μm. After the single‐step SPG emulsion, the emulsion droplets were composed mainly of monomers, hydrophobic additives, and an oil‐soluble initiator, suspended in the aqueous phase containing a stabilizer and inhibitor. These were then transferred to a reactor, and subsequent suspension polymerization was carried out. Uniform copolymer particles with a mean diameter ranging from 3 to 7 μm, depending on the recipe, with a narrow particle size distribution and a coefficient of variation of about 10% were achieved. Based on the glass‐transition temperatures, as measured by differential scanning calorimetry, the resulting copolymer particles containing a soft phase of acrylate were better compatibilized with a hard phase of methyl methacrylate than with styrene with dioctyl phthalate (DOP) addition. Glass‐transition temperatures of poly(MMA‐co‐MA) particles were strongly affected by the composition drift in the copolymer caused by their substantial difference in reactivity ratios. Incorporation of DOP in the copolymer particles does not significantly affect the glass‐transition temperature of MMA‐ or MA‐containing copolymer particles, but it does affect the St‐containing copolymer and particle morphology of the copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3037–3050, 2003     

Study on preparation of monodispersed poly(styrene‐co‐N‐dimethylaminoethyl methacrylate) composite microspheres by SPG (Shirasu Porous Glass) emulsification technique

Monodispersed poly(styrene‐co‐N‐dimethylaminoethyl methacrylate) [P(St‐DMAEMA)] composite microspheres were prepared by employing a Shirasu Porous Glass (SPG) emulsification technique. A mixture of monomer, hexadecane (HD), and initiator N,N′‐azobis(2,4‐dimethylvaleronitrile) (ADVN) was used as a dispersed phase and an aqueous phase containing stabilizer [poly(vinyl pyrrolidone) (PVP) or poly(vinyl alcohol) (PVA)], sodium lauryl sulfate (SLS), and water‐soluble inhibitor [hydroquinone (HQ), diaminophenylene (DAP), or sodium nitrite (NaNO₂)], was used as a continuous phase. The dispersed phase was permeated through the uniform pores of SPG membrane into the continuous phase by a gas pressure to form the uniform droplets. Then, the droplets were polymerized at 70°C. The effects of inhibitor, stabilizer, ADVN, and DMAEMA on the secondary nucleation, DMAEMA fraction in the polymer, conversion, and morphologies of the particles were investigated. It was found that the secondary nucleation was prevented effectively in the presence of HQ or DAP when PVP was used as the stabilizer. The secondary particle was observed when ADVN amount was raised to 0.3 g (/18 g monomer); however, no secondary nucleation occurred even by increasing DMAEMA fraction to 10 wt %. This result implied that the diffusion of ADVN into the aqueous phase was a main factor responsible to the secondary nucleation more than that of DMAEMA. The hollow particles were obtained when NaNO₂ was used, while one‐hole particles formed in the other cases. By adding crosslinking agent, the hole disappeared and the monomer conversion was improved. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2408–2424, 2001     

Influence of colloidal fouling and feed water recovery on salt rejection of RO and NF membranes

The influence of colloidal fouling and feed water recovery (or concentration factor, CF) on salt rejection of thin-film composite reverse osmosis (RO) and nanofiltration (NF) membranes was investigated. Fouling experiments were carried out using a laboratory-scale crossflow test unit with continuous permeate disposal to simulate the CF and recovery as commonly observed in full-scale RO/NF systems. For feed waters containing only salt (NaCl), permeate flux declined linearly as CF was increased and salt rejection was nearly constant for both RO and NF membranes. On the other hand, a sharp decrease in permeate flux and significant decline in salt rejection with increasing CF were observed under conditions where colloidal fouling takes place. For both RO and NF membranes, the marked permeate flux decline was attributed to the so-called “cake-enhanced osmotic pressure”. The decline in salt rejection when colloidal fouling predominated was much more substantial for NF than for RO membranes. In all cases, the decline in salt rejection was higher under conditions of more severe colloidal fouling, namely at higher ionic strength and initial permeate flux.     

Novel ultrafiltration membranes with adjustable charge density based on sulfonated poly(arylene ether sulfone) block copolymers and their tunable protein separation performance

A novel poly(arylene ether sulfone) (PAES) block copolymer was prepared from previously synthesized fluoride terminated oligomer (A₁₆) and hydroxyl terminated oligomer (B₁₂) by aromatic nucleophilic substitution polycondensation reaction. PAES was subsequently sulfonated under controlled conditions to yield a copolymer (S-PAES) with sulfonic acid groups selectively in the B₁₂ segments and without chain degradation. Non-solvent induced phase separation method was used to prepare a series of ultrafiltration membranes from blends of S-PAES and PAES with varied ratios and, hence, sulfonic acid group densities. Porous membrane morphologies, structure and surface properties were characterized comprehensively using scanning electron microscopy, Fourier transform infrared spectroscopy in the attenuated total reflection mode, as well as contact angle and zeta potential measurements. Studies of membrane performance revealed systematically increasing water permeabilities and reduced protein fouling tendencies with increasing fraction of S-PAES in the membrane. The protein transmission as function of pH value (and hence protein charge) was studied for two model proteins (bovine serum albumin and lysozyme) and found to be controlled by combined size exclusion and charge effects. The selectivity for the separation of the binary protein mixture could be systematically increased with increasing membrane charge density (by increasing S-PAES fraction). Consequently, the trade-off relationship between permeability and selectivity for conventional ultrafiltration membranes where separation is based on size exclusion solely could be overcome. Due to their high stability and tunable functionality, the PAES block copolymers have also large potential as membrane material for other applications.     

Preparation and characterization of polyacrylonitrile-based membranes: Effects of internal coagulant on poly(acrylonitrileco-malefic acid) ultrafiltration hollow fiber membranes

Ultrafiltration hollow-fiber membranes (UHFMs) ofpoly(acrylonitrile-co-malefic acid) (PANCMA) were prepared by a dry-wet phase inversion process. The morphologies of inner surface and cross section for these hollow fibers were inspected with scanning electron microscopy. It was found that, by increasing the amount of solvent DMSO in internal coagulant, the number and size of macrovoid underneath the inner surface decreased. The water flux of the UHFMs also decreased while the bovine serum albumin rejection increased minutely. These results were interpreted based on the ternary phase diagrams for the PANCMA/DMSO/(H₂O+DMSO) system, which was obtained from the experimental cloud point measurements and empirical linearized cloud point relation. It was envisaged that the membrane surface could be further modified by the reaction of acid groups with poly(ethylene glycol).     

Synthesis of poly(vinyl acetate)‐graft‐polystyrene and application to preparation of porous membranes

Poly(vinyl acetate)–TEMPO (PVAc–TEMPO) macroinitiators were synthesized by bulk polymerization of vinyl acetate in the presence of benzoyl peroxide (BPO) followed by termination with 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). Radicals were mainly transferred to the acetoxy methyl groups in PVAc during the polymerization. The PVAc–TEMPO macroinitiators had several TEMPO‐dormant sites and styrene bulk polymerization with the macroinitiators produced poly(vinyl acetate)‐graft‐polystyrene (PVAc‐g‐PS). All the TEMPO‐dormant sites of PVAc–TEMPO macroinitiators participated in the styrene polymerization with almost equal reactivity. Methanolysis of PVAc‐g‐PS broke the PS branches apart from the PVAc backbone chains. Hydrophobic or hydrophilic porous membranes with controlled pore size could be prepared by removing the PVAc domains or the PS domains from the graft copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1658–1667, 2001     

聚丙烯腈UF膜的微孔表面ζ电位和电荷密度

根据Helmholtz-Smoluchowski方程,由实验测定的流动电位计算聚丙烯腈ACP-0053超滤膜的ζzeta电位,并根据Gouy-Chapmann方程,估算出膜的微孔表面电荷密度。表明UF膜微孔表面ζ电位和电荷密度与电解质的种类、浓度有关。UF膜在NaCl与KCl体系的ζ电位相近,在MgCl2与MgSO4体系的ζ电位也相近,即阳离子价态和结构越相近,ζ电位越相近,但当阴离子价态较高时,也有一定影响。由膜微孔表面ζ电位和电荷密度随溶液浓度的变化关系可知,在低浓度区域,膜表面ζ电位和电荷密度较高,并出现一个峰值,之后随浓度增大而缓慢降低。     

Triblock copolymers of methyl methacrylate/N‐vinyl pyrrolidone and their hydrophilication effects on poly(vinylidene fluoride) porous membranes

The new amphiphilic triblock copolymers of poly(N‐vinyl pyrrolidone‐b‐methyl methacrylate‐b‐N‐vinyl pyrrolidone) (P(VP‐b‐MMA‐b‐VP)) were synthesized via a reversible addition fragmentation chain transfer polymerization route. Using these copolymers as additives in casting solutions, the porous blend membranes of poly (vinylidene fluoride) and P(VP‐b‐MMA‐b‐VP) were prepared following a typical nonsolvent induced phase separation process. The influences of P(VP‐b‐MMA‐b‐VP) on the morphologies of the blend membranes were observed by scanning electron microscopy. The chemical compositions in membrane surface layers were measured by X‐ray photoelectron measurement. Water contact angle and water flux experiments were used to evaluate the hydrophilicity and permeation properties of the blend membranes. It was found that the P(VP‐b‐MMA‐b‐VP) copolymers could be retained in membrane stably in membrane formation and application process. The copolymers could enrich in surface layer and endowed the blend membrane with efficient hydrophilicity and higher water permeation flux. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of magnetic field on surface properties of Bacillus cereus CrA and its Extracellular Polymeric Substances (EPS)

The effect of magnetic field on surface properties of Bacillus cereus CrA and its EPS was studied by zeta potential and FT-IR spectrum. The weak magnetic fields of 6.0–10.0 mT promoted the predominant strain B. cereus CrA to form EPS. The weak magnetic field of 2.4–10.0 mT could improve the bio-adsorption efficiency of anions by decreasing the negative charge of the intact strain, while the magnetic field of 17.4 mT could increase the negative charge of the strain’s EPS by 20% and be responsible for the bio-adsorption of cations. Magnetic field could affect the band intensity and the slight shifting of peaks and the fluctuation of the bacterial absorption capability depended on the magnetic density. The magnetic field energy could affect the hydroxyl group and carboxyl group by forming hydrogen bonding, which were responsible for the adsorption ability of the strain and its EPS.     

Preparation and properties of porous gels from poly(l-lactic acid) and poly(d-lactic acid) with ionic liquids as solvents and porogens

We prepared poly(lactic acid) (PLA) porous gel materials by combining poly(l -lactic acid) and poly(d -lactic acid) of three different molecular weights in different mass ratios. Moreover, we used several imidazole-based ionic liquids with different anions as solvents and porogens at room temperature to prepare these materials. The properties of the resulting products were compared with those of materials prepared by sodium chloride as a conventional porogen and 1,4-dioxane as a solvent. The internal morphologies of the different types of materials were observed via scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and wettability analysis. The presented results should provide guidance and reference values for the preparation of PLA materials and for the improvement of their mechanical properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47058.     

Influences of nonionic poly(ethylene glycol) polymer PEG on electrokinetic and rheological properties of bentonite suspensions

The determination of the electrokinetic properties of colloidal systems is very important for the chracterization of these systems. Colloidal systems have high adsorption performance due to the carrying of negative charges and the colloid structure. The control of the electrokinetic properties of the bentonite–water system are important not only from a technological point view; they are also important from a scientific point of view. Knowing the electrokinetic and rheological properties of bentonite minerals is important for the estimation of the behavior of clays under various environmental conditions. The purpose of this study was to interpret the effect of the nonionic poly(ethylene glycol) (PEG) polymer on electrokinetic and rheological properties. Zeta potential and viscosity measurements were done as a function of PEG molecular weights (400, 3000, and 8000) and their concentrations (2.5 × 10^?5 to 1.25 × 10^?2 mol/L). We interpreted the experimental data, taking into account these two parameters. X‐ray diffaction studies were done together with the electrokinetic and rheological measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 341–346, 2002     

Preparation of polyelectrolyte complex membranes based on sodium cellulose sulfate and poly(dimethyldiallylammonium chloride) and its permeability properties

In this study, polyelectrolyte complex (PELC) membranes prepared by the simultaneous interfacial reaction between aqueous solutions of sodium cellulose sulfate (NaCS) as polyanion and poly(dimethyldiallylammonium chloride) (PDMDAAC) as polycation were proposed. The preparation conditions were optimized. The influence of two important factors, molecular weight (MW) of PDMDAAC and reaction time on the membrane formation procedure and permeability was investigated. Membranes with the preparation conditions as NaCS 3.5% (w/v), PDMDAAC (MW = 200–350 kDa) 7.0% (w/v), the reaction time 30 min, hold a favorable performance, and steady state in water flux experiment. To testify the feasibility of the membrane used in salt separation, membrane performances and selectivity of the inorganic salts as well as their relations to the preparation conditions, the operation parameters, the species of inorganic salts, etc., were investigated in the pressure‐driven experiments. The results showed that this single‐layer PELC membrane afforded higher rejections of divalent ions (SO) to that of monovalent ions (Cl⁻), which indicated the potential application of this membrane system in the salt rejection process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Combined effect of relative humidity and temperature on dynamic viscoelastic properties and glass transition of poly(vinyl alcohol)

On the basis of the experimental studies on viscoelastic properties of poly vinyl alcohol (PVA) films at various relative humidity (RH) and temperature conditions by dynamic mechanical analysis (DMA), the influence of both temperature and RH on the glass transition are discussed and an improved property model is developed to relate the dynamic modulus to RH and temperature. The results indicate that (1) with increasing the RH, the storage modulus of PVA decrease remarkably, while both loss modulus and tanδ sharply increase to reach the peak and then markedly drops. The intensity of this variation is highly dependent upon temperature. (2) Moisture increase will cause the glass transition of PVA at isothermal condition and the transition point can be detected by glass transition relative humidity (RH_g) that obtained by isothermal RH scans. (3) Similar to the relationship between T_g and RH, the RH_g of PVA vary linearly with temperature. The state diagram of RH_g versus temperatures is nearly consistent with that of T_g versus RH. (4)The present equation based on model of Mahieux and Reifsnider (Mahieux and Reifsnider, Polymer 2001, 42, 3281) can predict well the dynamic modulus of PVA at various RHs and temperatures. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3161–3167, 2013     

Bone cell viability on methacrylic acid grafted and collagen immobilized porous poly(3‐hydroxybutrate‐co‐3‐hydroxyvalerate)

Porous poly(3‐hydroxybutrate‐co‐3‐hydroxyvalerate) (PHBV) film was prepared by solute leaching of salt/PHBV cast film. The surface chemistry of the PHBV membrane was modified by performing graft polymerization of methacrylic acid (MAA) on ozone treated porous PHBV film, followed by immobilization of type I collagen. The surface characteristics of the modified and nonmodified porous films were measured by water contact angle. The rat osteosarcoma cell line UMR‐106 osteoblast like cells were used as model cells to evaluate the cell viability on surfaces. The initial cell attachment, growth pattern, and proliferation as measured by MTT assay were used to evaluate the bone cell viability on the modified and nonmodified films. Among the PHBV films studied, the nonmodified porous PHBV and the porous PHBV film type I collagen dip coated showed no significant difference in cell attachment and proliferation, while the porous PHBV membrane that was collagen immobilized after MAA grafting showed considerable activity of osteoblast like cells. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1916–1921, 2005     

Polydopamine-coated poly(vinylidene fluoride) membranes with high ultraviolet resistance and antifouling properties for a photocatalytic membrane reactor

We modified poly(vinylidene fluoride) (PVDF) membranes with a polydopamine (PDA) coating for photocatalytic membrane reactor application with appropriate UV resistance and studied the effects of the PDA coating conditions (i.e., coating time and dopamine concentration) and UV irradiation time on the modified PVDF membrane properties. The PVDF membrane that was surface-coated with the appropriate dopamine solution concentration and coating time played a key role in controlling the membrane properties and in protecting the modified membrane against UV radiation. The optimization of the coating condition not only completely protected the modified membrane from free-radical attack initiated through UV irradiation but also improved the membrane hydrophilicity, antifouling properties, filtration performance, and mechanical strength of the membrane. UV irradiation of the membrane that was surface-coated with a high-concentration dopamine solution for a long coating time resulted in a higher mechanical strength than that of the membrane without the application of UV irradiation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47312.     

Effects of Al:Si and (Al + Na):Si ratios on the properties of the international simple glass,part I: Physical properties

Understanding composition-structure-property relationships of high-alumina nuclear waste glasses are important for vitrification of nuclear waste at the Hanford Site. Two series of glasses were designed, one with varying Al:Si ratios and the other with (Al + Na):Si ratios based on the international simple glass (ISG, a simplified nuclear waste model glass), with Al₂O₃ ranging from 0 to 23 mol% (0 to 32 wt%). The glasses were synthesized and characterized using electron probe microanalysis, X-ray photoelectron spectroscopy, small angle X-ray scattering, high-temperature oxide melt solution calorimetry, and infrared spectroscopy. Glasses were crystal free, and the lowest Na₂O and Al₂O₃ glass formed an immiscible glass phase. Evolution of various properties—glass-transition temperature, percentage of 4-coordinated B, enthalpy of glass formation—and infrared spectroscopy results indicate that structural effects differ based on the glass series.