Influence of degree of grafting and grafting temperature on the permeabilities of grafted polypropylene membranes

Polypropylene dialysis membranes were prepared using cobalt-60 gamma radiation to directly graft 2-hydroxyethyl methacrylate (HEMA) onto polypropylene (PP) membranes. The surface structures of both the grafted membranes and the PP membrane were observed by using FTIR–PAS and ESCA methods. The X-ray diffraction diagrams of the PP and PP-g-HEMA membranes indicated a transformation process of the β-form toward the α-form crystallinity with increasing degree of grafting. The SEM data of the membrane grafted under a low grafting temperature showed many spheres of PHEMA embedded in the PP matrix, whose size was well distributed and increased with the degree of grafting. The influences of the degree of grafting and grafting temperature on the permeabilities of PP-g-HEMA membranes toward urea and creatinine were studied in a dialyzer. In all cases, the PP-g-HEMA membrane obtained under higher grafting temperature showed higher permeability toward those solutes. The permeation coefficients of urea and creatinine through the PP-g-HEMA membrane obtained at 59°C were about 10.4 and 28.8 times that through the PP membrane, respectively. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:83–89, 1998     

Pervaporation of ethanol—water mixture by Co60 γ-ray irradiation-modified nylon 4 membrane

The ethanol—water separation by pervaporation with γ-ray irradiation-modified nylon 4 membrane was investigated. The membrane was prepared by homografting γ-ray irradiation of vinyl acetate (VAc) monomer onto nylon 4, poly(vinyl acetate) (PVAc)-homo-g-nylon 4 followed by hydrolysis treatment, poly(vinyl alcohol) (PVA)-homo-g-nylon 4. The homografting method shows significant improvement in the degree of grafting of (VAc) onto nylon 4 over the heterografting method. For example, the degree of grafting of the VAc with 30 vol % and total dose of 2 Mrad for the heterografted method and for the homografted method are 14.1 and 42.2%, respectively. The effects of irradiation with or without oxygen in solution, irradiation time, VAc content, degree of grafting, crystallinity, feed concentration, and operating temperature on performances of the PVA-homo-g-nylon 4 membrane were carried out. Comparison of the separation factor of sorption in membrane (α_sorp) and that of pervaporation (α_perv) was made. A separation factor of 7.3 and a 0.691 kg/m² h permeation rate can be obtained by the PVA-homo-g-nylon 4 membrane with a degree of grafting of 42.2% for 90 wt % ethanol feed concentration. Compared with the unmodified nylon 4 membrane, which has the separation factor of 4 and permeation rate of 0.350 kg/m² h, the PVA-homo-g-nylon 4 membrane shows improved a separation factor and permeation rate. © 1993 John Wiley & Sons, Inc.     

Surface modification of nylon‐6 fibers for medical applications

Hydroxyethylmethacrylate (HEMA) is considered to be one of the important vinyl monomers. The ability of polyhydroxyethyl‐methacylate (PHEMA) graft sites to consecutive chemical modification makes the use of nylon‐6 fibers grafted with PHEMA a feasible bed for immobilization of a wide range of biologically active reagents, specially enzymes, drugs, cells, and immunadsorbents. Stemming from the above discussions, in this article, the graft copolymerization of HEMA onto modified nylon‐6 fibers containing Polydiallyldimethylammonium chloride (PDADMAC) in the presence of Cu²⁺–K₂S₂O₈ as a redox initiating system was carried out, with very high rate and almost without homopolymer formation. The factors affecting the grafting reaction (monomer, K₂S₂O₈ and cupric ion concentrations, the amount of PDADMAC as well as the reaction temperature) were studied. Kinetic investigation revealed that the rate of grafting (R_p) of HEMA onto modified nylon‐6 fibers is proportional to [HEMA]¹, [CuSO₄.5H₂O] ^0.7, [PDADMAC]^0.4, and [K₂S₂O₈]^1.4. The overall activation energy was calculated (71 KJ/mol). The fine structure, surface topography, thermal and electrical properties of parent and grafted nylon‐6 fibers were investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3788–3796, 2007     

HEMA‐grafted chitosan for dialysis membrane applications

Chitosan was graft copolymerized with HEMA (2‐Hydroxyethylmethacrylate) for the development of blood‐compatible dialysis membranes. The permeation characteristics of HEMA‐grafted chitosan films for four different solutes creatinine, urea, glucose, and albumin was studied in vitro at 37°C for assessment of the suitability as dialysis membranes. The grafted film CH‐12.5 composition (425% grafting) showed very high permeation to creatinine by reaching the equilibrium within 45 min. The compositions CH‐7.5 and CH‐12.5 showed excellent permeation to glucose when compared to virgin chitosan films. In the case of urea permeation, all the grafted compositions exhibited higher percent permeation than the virgin chitosan films. The copolymer films CH‐7.5 and CH‐12.5 showed enhanced permeability for the high molecular weight solute, albumin. The other grafted copolymer compositions followed almost the same trend as that of chitosan for the low molecular weight solutes as well as the high molecular weight solute. The copolymer films were also found to be highly blood compatible, noncytotoxic, and biodegradable. Hence, the need for developing blood‐compatible chitosan membranes with desirable permeability properties is achieved by the graft copolymerization of HEMA onto chitosan. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2960–2966, 2006     

Nylon 4/PVA blend membrane for dialysis

To improve the hydrophilicity and enhance the transport flux of nylon 4 membrane for dialysis, this study attempts to utilize blending nylon 4 with poly(vinyl alcohol) (PVA). The instability of PVA in water can be obtained more easily than by other methods, such as chemical, γ-ray irradiated crosslinking, or high-temperature treatment used by previous researchers. The effects of maturation time of the casting solution, nylon 4/PVA ratios, and casting solvent compositions on esterification of PVA, salt permeability, water content, partition coefficient, diffusivity, and mechanical strength of membrances are studied. The membrane, prepared by casting solution of nylon 4/PVA = 9/1 wt % formic acid with 24-h maturation time, possesses permeabilities of NaCl and urea, 33.14 and 19.67 × 10^?5 cm²/min, respectively.     

Radiation-induced graft copolymerization of 2-hydroxyethyl methacrylate onto poly(γ-methyl-L-glutamate) membrane in ethanol solution

The radiation-induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto poly(γ-methyl-L -glutamate) membranes was investigated in ethanol. The effects of dose, dose rate, concentration of HEMA, and temperature on the degree of grafting were studied. The initial rate of grafting copolymerization shows the following functional relationship equation: dG₀/dt = k[M]₀D˙^0.56. The average values of the apparent constants at 27 and 37°C for the initial rates of grafting are k₁ = 51 and k₂ = 91 G%h^−0.44 kGy^−0.56 mol⁻¹ L, respectively. The apparent activation energy of grafting copolymerization is E = 10.7 kcal/mol. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1575–1580, 1998     

Surface graft copolymerization of 2‐hydroxyethyl methacrylate onto low‐density polyethylene film through corona discharge in air

The corona discharge technique was explored as a means of forming chemically active sites on a low‐density polyethylene (LDPE) film surface. The active species thus prepared at atmospheric pressure in air was exploited to subsequently induce copolymerization of 2‐hydroxyethyl methacrylate (HEMA) onto LDPE film in aqueous solution. The results showed that with the corona discharge voltage, reaction temperature, and inhibitor concentration in the reaction solution the grafting degree increased to a maximum and then decreased. As the corona discharge time, reaction time, and HEMA concentration in the reaction solution increased, the grafting degree increased. With reaction conditions of a 5 vol % HEMA concentration, 50°C copolymerization temperature, and a 2.0‐h reaction time, the degree of grafting of the LDPE film reached a high value of 158.0 μg/cm² after treatment for 72 s with a 15‐kV voltage at 50 Hz. Some characteristic peaks of the grafted LDPE came into view at 1719 cm^?1 on attenuated total reflectance IR spectra (C?O in ester groups) and at 531 eV on electron spectroscopy for chemical analysis (ESCA) spectra (O_1s). The C_1s core level ESCA spectrum of HEMA‐grafted LDPE showed two strong peaks at ～286.6 eV (? C ? O? from hydroxyl groups and ester groups) and ～289.1 eV (O?C ? O? from ester groups), and the C atom ratio in the ? C? O? groups and O?C? O groups was 2:1. The hydrophilicity of the grafted LDPE film was remarkably improved compared to that of the ungrafted LDPE film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2881–2887, 2001     

Plasma-modified Nylon 4 membrane for dialysis

The effects of plasma treatment conditions, such as supply power, treatment time, gases used in reactor, surface energy, water content, dialysis permeability, partition coefficient, diffusion coefficient, and free volume of Nylon 4 membranes, were studied. The solutes considered for dialysis system were NaCl, urea, and MgCl₂. The permeabilities of NaCl and urea of membranes with plasma treated in argon at 80 W for 20 min are 5.57 × 10^?5 and 5.89 × 10^?5 cm²/min, respectively. Much higher permeabilities of NaCl and urea obtained by oxygen plasma-treated membranes under 20 W and for 20 min are 30.74 × 10^?5 and 17.66 10^?5 cm²/min, respectively, compared to that of untreated Nylon 4 membranes.     

Plasma deposition modified nylon 4 membranes for hemodialysis

The purpose of this research is to prepare high solute permeability membranes for hemodialysis by plasma depositing hydrophilic monomers onto chemically treated or O₂ plasma etched Nylon 4 substrate. The factors that affect the performances of membranes, such as deposition conditions and chemical or plasma etching conditions, were studied. The monomers used in this study were 1-vinyl-2-pyrrolidone (VP), 2-Hydroxyethyl methacrylate (HEMA), and Methyl methacrylate (MMA). The permeabilities of NaCl, urea, vitamin B₁₂, and albumin were measured, as were the water content, hydration, diffusivity, partition coefficient, and protein adsorption ratio of fibrinogen to albumin by membrane surface of plasma deposited membranes. The permeabilities of NaCl, urea, vitamin B₁₂, and albumin of HEMA 5 w-1 h plasma deposited onto chemical treated Nylon 4 membranes were 2.896 ± 0.192, 3.301 ± 0.325, 0.010 ± 0.007, and 0.000 x 10^?5 cm²/min, respectively. The mole ratio of adsorbed fibrinogen to adsorbed albumin (F/A) is 0.26 ± 0.05, which is much lower than that of the pure Nylon 4 membrane (0.94 ± 0.06) and the Gambro® membrane (0.90 ± 0.15). The HEMA deposited membrane possesses the highest feasibility as hemodialysis material among those plasma deposited membranes considered.     

Radiation-induced graft copolymerization of 2-hydroxyethyl methacrylate onto chloroprene rubber membrane. II. Characterization of grafting copolymer

The cobalt-60 radiation-induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto a chloroprene rubber (CR) membrane has been studied in ethanol. The structure, morphology, crystallinity, thermal stability, and hydrophility of graft copolymer were characterized by means of Fourier transform infrared photoacoustic spectroscopy, scanning electron microscopy, wide-angle X-ray diffraction, differential thermal gravimetric analysis, and contact angle test methods, respectively. The permeabilities of urea, creatinine, and creatine through the CR and CR-g-HEMA membranes are investigated in a dialysis cell, and the permeation mechanism is also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1745–1750, 1998     

Methoden zur Herstellung und Charakterisierung von Kunststoffen mit verbesserter Blutverträglichkeit

Tubings of different internal diameter (ID) were prepared from 10 different polymers (CPE, EPDM, ETFE, EVA, LDPE, PP, PTFE, PUR, PVC and Silicone):

• tubings of 4–5 mm ID for in vitro- and ex vivo-blood compatibility tests with human blood,
• tubings of 0.3–0.4 mm ID for ex vivo-evaluations for blood compatibility via measuring the bleeding time after introduction of the tubing into the ear vein of rabbits.

The tubings were surface modified by grafting with N-vinyl-N-methyl acetamide (VIMA). For both the original and the grafted tubing correlations were established between the physical characterization (degree of grafting, critical surface tension, ESCA, FT-ATR-IR, SEM) and the in vitro and the ex vivo blood compatibility tests. The in vitro blood compatibility tests consist of an incubation of 4–5 mm tubing with citrated human blood and subsequent determinations of clotting parameters. The human ex vivo blood compatibility tests were performed on human arm veins followed by investigation of the internal surface of the tubing. The results could be correlated with the in vitro tests with human blood. A comparison with conventional tubing on the market (PVC and Silicone) as a standard shows, that PTFE/VIMA, LDPE/VIMA, PUR and EVA have better blood compatibility properties than the standard whereas untreated PTFE and LDPE are ranked below the standard.     

Graft copolymerization of methyl acrylate onto nylon1010 initiated by potassium diperiodatonickelate(IV)

In this article, the graft copolymerization of methyl acrylate (MA) onto nylon1010 by using potassium diperiodatonickelate(IV) [Ni(IV)]–nylon1010 redox system as initiator was studied in alkaline medium. The effect of different factors on grafting parameters was investigated. The structure of the graft copolymer was determined by infrared (IR), X-ray diffraction, and scanning electron microscope (SEM). It was found that Ni(IV)–nylon1010 system is an efficient redox initiator for this graft copolymerization. A single-electron transfer mechanism is proposed to explain the formation of radicals and the initiation. The graft copolymer was used as the compatibilizer in blends of poly(methyl methacrylate) (PMMA) and nylon1010. The SEM photographs indicate that the graft copolymer greatly improved the compatibility of the blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2636–2640, 2001     

MMA/TPX homograft membrane for oxygen enrichment

Utilizing the factors of degradation and crosslinking of TPX polymer and high O₂/N₂ selectivity of MMA, the performances of MMA homografted TPX membrane are efficiently improved compared to those of pure TPX membrane. The degradation and crosslinking of TPX polymer solution with or without dissolved oxygen during irradiation were observed and proved in existence by the gas permeability, mechanical, and viscosity change study. High O₂/N₂ permeability ratio of 7.6 and fairly high oxygen permeability of 28 × 10^?10 cm³ cm/cm² s cm Hg of the membrane which was cast from the degassing polymer solution, with 20% degree of MMA grafting, can be obtained. Also the membrane for high oxygen permeability of 63 × 10^?10 cm³ cm/cm² s cm Hg with an O₂/N₂ permeability ratio of 4.5, which was cast from the polymer solution with dissolved oxygen, can be obtained under the condition of 60 h irradiation time and about 7% degree of grafting. O₂/N₂ selectivity of TPX membrane can be improved by homografting method with lower MMA grafting degree than that of heterografting method.     

Temperature effect on the permeation through poly(2-hydroxyethyl methacrylate) membrane

The temperature dependence of permeability through highly syndiotactic poly(2-hydroxyethyl methacrylate) [P(HEMA)] membrane is reported for highly polar organic solutes such as ureas, methyl substituted ureas and amides, and for NaCl and Na₂SO₄. The membranes used were equilibrated in distilled water at each temperature before measurements. From the linear correlationship between the excess heat capacities, ?C_p^o(excess) in aqueous solution at infinite dilution and the permeability parameter PM^1/3, it is found that the water structure perturbing capability of the polar organic solutes is a controlling factor in the permeation mechanism at relatively low temperature, where P(HEMA) membrane has higher water content and more structured water. In addition, it is found that the poor separation for urea of cellulose acetate membrane in the reverse osmosis practice is due to the higher water structure-breaking capability of urea.     

Chemical initiated-grafted nylon 4 membranes

To improve the performance of nylon 4 membranes, this study attempts to utilize chemical initiation which induces different hydrophilicities vinyl monomers grafted onto nylon 4 membranes. Sodium styrene sulfonate, chloromethyl styrene, styrene, and glycidyl methacrylate were used as grafting monomers. The factors that affect the degree of grafting considered were chemical initiators, pH values, kinds and concentrations of monomers, reaction time, and temperatures. The mechanical strength and the transport properties of these chemical-initiated grafted nylon 4 membranes were also investigated. Both the water flux and the salt rejection of sodium styrene sulfonated-grafted membrane were increased significantly, compared to our previous paper,¹ and the casein rejections of all of the four grafted nylon 4 membranes studied exceeded 90%. The quaternized nylon 4-g-poly(chloromethyl styrene) membranes were prepared and possessed high water uptake behavior and high transfer number (0.99) for electrodialysis. The sulfonating process was also applied to improve the hydrophilicity of nylon 4-g-poly(glycidyl methacrylate) membrane so that the water flux and the salt rejection were both increased.     

Study on antithrombosis dialytic membrane prepared by preirradiation grafting

A new antithrombosis dialytic membrane with a hydrophilic–hydrophobic microphase structure was prepared by preirradiation grafting of β‐hydroxyethyl methacrylate (HEMA) and styrene (St) onto ethylene–vinyl acetate (EVA). The influence of some effects, such as preirradiation dose, dose rate, grafting reaction temperature, reaction time, and monomer component, on the degree of grafting was determined, and the properties of the grafted films were investigated. Compared with the conventional EVA‐grafted hydrophilic monomer, the EVA films grafted with HEMA and St have superior antithrombogenicity; the antithrombogenicity and permeability of EVA‐g‐(HEMA‐co‐St) were 30 and 20 times higher than those of the ungrafted films, respectively, when the volume ratio (HEMA versus St) was about 7:3. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1321–1327, 2000     

SBS/VP homograft membrane for oxygen enrichment

The grafting of 4-vinyl pyridine (VP) onto styrene-butadiene-styrene triblock copolymers (SBS) by homografting irradiation with dissolved oxygen was studied. Homograft membranes of various degree of grafting were prepared from a casting solution of grafted copolymer in benzene. The mechanical properties of membranes, gas permeability, and the effect of operating temperature on gas permeation were investigated. The degree of grafting of 8.4% was the largest at an irradiation time of about 15.5 h. It was smaller at both shorter and longer duration because of the interference of dissolved oxygen. It was found that the tensile strength and elongation of SBS-g-VP were similar to those of SBS. The stress relaxation of SBS-g-VP was slower than that of SBS, and this might be due to the formation of rigid microphase separation domain of poly(4-vinyl pyridine), which acted as permanent crosslinking points to reduce the stress relaxation. Using the properties of high flux of SBS and high O₂/N₂ selectivity of poly(4-vinyl pyridine), the performance of gas permeation of 4-vinyl pyridine homografted SBS membrane was studied. The selectivity of SBS-g-VP membrane increased with increasing degree of grafting. However, it was done at the expense of a decrease in the gas permeability. When the operating temperature of gas permeation increased, the permeability of oxygen and nitrogen increased, and the O₂/N₂ permeability ratio decreased. The activation energy (Ep) for gas permeation through different degree of grafting of SBS-g-VP membrane (obtained by the Arrhenius law) increased with increasing degree of grafting. For ungrafted SBS membrane, Ep was 5.5 kcal/mol for oxygen and 7.2 kcal/mol for nitrogen. For 8.4% grafting degree SBS-g-VP membrane, Ep for oxygen and nitrogen, were 6.5 and 8.1 kcal/mol, respectively.     

Pervaporation of aqueous alcohol mixtures through a membrane prepared by grafting of polar monomer onto nylon 4

A hydrophilic pervaporation membrane was prepared via a homografting polymerization of N,N′-(dimethylamino)ethyl methacrylate (DMAEM) onto nylon 4 backbone, DMAEM-g-N4. The water permselectivity was improved by the ammonium quaterization of the pendant N,N′-dimethylamino group on the DMAEM-g-N4 membrane using demethyl sulfate, DMAEMQ-g-N4. The separation factor and permeation rate for both chemically modified nylon 4 membranes were higher than those of the unmodified nylon 4 membrane. The effects of feed composition, feed temperature, and molar volume of the alcohols on pervaporation performance were investigated. Optimum pervaporation was obtained by a DMAEMQ-g-N4 membrane with a degree of grafting of 12.7% for a 90 wt % ethanol feed concentration, giving a separation factor of 36 and a permeation rate of 564 g/m²h. © 1995 John Wiley & Sons, Inc.     

Graft copolymerization of nylon 6 with methyl methacrylate using dimethylaniline/Cu2+ ion system

The ability of dimethylaniline (DMA)/Cu²⁺ ion initiator to induce grafting of methyl methacrylate (MMA) onto nylon 6 was investigated under a variety of conditions. It was found that the graft yield is dependent on the concentration of the Cu²⁺ ion, of DMA, and of MMA. While the graft yield increases as the monomer concentration increases, there are optimal concentrations of DMA and Cu²⁺ ion. Below or above these concentrations, lower grafting occurred. The type of cupric salt also affects grafting to varying degrees. While the presence of CuSO₄ and Cu(NO₃)₂ accelerates grafting, the presence of CuCl₂ offsets the reaction. Increasing the reaction temperature and reaction time favorably influences grafting. Addition of acetic acid enhances grafting, whereas formic acid decreases grafting. Preswelling of nylon with formic acid leaves the susceptibility of nylon toward grafting practically unaltered. Studies of the copolymerization reaction was not confined to the graft yield but was extended to homopolymer formation and total conversion.     

Effect of graft copolymerization of 2-hydroxyethyl methacrylate on the properties of polyester fibers and fabric

Graft copolymerization of hydroxyethyl methacrylate (HEMA) onto poly(ethylene terephthalate) (PET) fibers using benzoyl peroxide (BP) as initiator was carried out in water and in water/organic solvent as a reaction medium. The effect of initiator concentration, reaction time, temperature, and reaction medium as well as addition of FeSO₄ to the polymerization medium was studied. Percent grafting was enhanced significantly by increasing BP concentration up to 0.016 mol/L and then decreased upon further increase in initiator concentration. Increasing the monomer (HEMA) concentration up to 0.48 mol/L improves significantly the graft yield. Raising the polymerization temperature up to 85°C causes a significant increase in grafting yield; further increase in temperature leads to decrease in graft yield. Incorporation of Fe⁺² ions in the polymerization system decrease the graft yield. The same situation is encountered when water/solvent mixture is used as reaction medium. Solvent employed were methanol, toluene, and benzene.