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1.
Azacrown ether chitosan (CTSC) was synthesized by the reaction of chitosan with N‐allyl benzo 15‐crown‐5 crown ether. Azacrown ether crosslinked chitosan (CCTSC) was prepared by the crosslinked reaction of CTSC and epichlorodydrin. Their structures were confirmed by infrared spectral analysis and X‐ray diffraction analysis. The adsorption properties of CTSC and CCTSC for metal ions were also investigated. The experimental results showed that the two chitosan derivatives not only had a good capacity to adsorb Pd2+ and Ag+ but also was highly selective for Pd2+ and Ag+ in the coexistence system containing other metal ions. At 20°C ± 1°C and pH = 4, the adsorption capacity of CTSC and CCTSC for Pd2+ was 186.1 and 173.1 mg/g, respectively; and for Ag+ was 90.2 and 56.5 mg/g, respectively. The selectivity coefficients were K = 6.99, K = ∞, K = 35.38, K = ∞ for CTSC and K = 10.66, K = ∞, K = 85.45, K = ∞ for CCTSC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2705–2709, 2006  相似文献   

2.
Two new chitosan azacrown ethers bearing hydroxyl groups (CTS‐DH and CTS‐DO) were synthesized by the reaction of 3‐hydroxyl‐1,5‐diaza‐cycloheptane and 3‐hydroxyl‐1,5‐diaza‐cyclooctane with epoxy‐activated chitosan. Their structures were characterized by elemental analysis, infrared spectra analysis, and X‐ray diffraction analysis. The adsorption and selectivity properties of the hydroxyl azacrown ethers chitosan derivatives for Ag+, Cr3+, Cd2+, and Pb2+ were also investigated. The experimental results showed that the two novel chitosan azacrown ethers have good adsorption capacity for Ag+, and also showed that the grafted chitosan azacrown ethers have high selectivity for the adsorption of Ag+ in the presence of Pb2+ and Cd2+. The selectivity coefficients of CTS‐DH and CTS‐DO were K = 21, K = 42, K = 20.5, K = 41, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1793–1798, 2001  相似文献   

3.
A new type of crosslinked chitosan was prepared using Dihydroxy azacrown ether as the crosslinking agent. Its structure was confirmed by elemental analysis, Fourier transform infrared (FTIR) spectra analysis, solid‐state 13C nuclear magnetic resonance (NMR) analysis, and X‐ray diffraction analysis. Its static adsorption properties for Ag+, Cd2+, Hg2+, and Co2+ were studied. The experimental results showed that the Dihydroxy azacrown ether crosslinked chitosan has good adsorption capacities and high selectivity for adsorption of Ag+ with the coexistence of Hg2+ and Co2+. The selectivity coefficients of crosslinked chitosan are k/ = 5.47, k/ = 4.64, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 530–535, 2002  相似文献   

4.
A novel macrocyclic polyamine derivative of chitosan was synthesized by a reaction between chitosan and epoxy‐activated macrocyclic polyamine. The copolymer that is obtained contains amino functional groups in its skeleton and secondary amine and more polar hydroxyl groups. Four types of analyses were used to characterize the chemical modifications of the chitosan: elemental, FTIR spectra, solid‐state 13C‐NMR, and X‐ray diffraction. The adsorption properties of the macrocyclic polyamine grafted chitosan for Ag+, Cu2+, Co2+, and Cr3+ were also investigated. The experimental results showed that the new macrocyclic polyamine derivative of chitosan has high adsorption capacity and good selectivity for Ag+ in the presence of Ag+, Co2+, and Cr3+. The selectivity coefficients were K = 6.16, K = 14.81, and K = 2.42, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 924–929, 2003  相似文献   

5.
The synthesis of a new dihydroxyl mesocyclic diamine grafting chitosan is presented. This derivative is formed by reaction of dihydroxyl azacrown ether with expoxy‐activated chitosan. The obtained copolymer contains amino functional groups in its skeleton and the secondary amine, and more polar hydroxyl groups. Elemental analysis, fourier transform infrared analysis, as well as solid‐state carbon‐13 nuclear magnetic resonance analysis were used to characterize chemical modifications of the chitosan. The adsorption properties of the dihydroxyl mesocyclic diamine grafted chitosan for Ag+, Pb2+, Cd2+, and Cr3+ were studied. The experimented results showed that the novel chitosan derivative has good adsorption capacity and high selectivity for Ag+ in the presence of Pb2+, Cd2+, and Cr3+, and its adsorption selectivity is better than that of chitosan. The selectivity coefficients were K = 12.25, K = 6.12, and K = 0.52, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2677–2681, 2002  相似文献   

6.
The air separation through triheptyl cellulose (THC)/ethyl cellulose (EC) blend membranes containing no more than 20 wt % THC at the temperature range from 298 to 358 K was investigated using a variable volume method. The air-separation ability for the THC/EC membranes were greater than that for the THC-free pure EC membrane. P for the THC/EC membranes was between 1.06–8.89 × 10?9 cm3 (STP) cm/cm2 s cmHg and P/P 3.04–3.66. The THC/EC membrane showed a unique trend in its P/P ? P relationship, i.e., the magnitude of P/P increased simultaneously with that of P. The THC/EC membrane yielded a maximum oxygen concentration in the oxygen-enriched air (OEA) of 39.5% at an OEA flux of 6.99 × 10?4 cm3 (STP)/s cm2 for a pressure difference of 0.43 MPa at 358 K. After 300 h of measurement at 0.40 MPa and 313 K, the efficiency of the concentrating oxygen was almost constant. © 1994 John Wiley & Sons, Inc.  相似文献   

7.
A series of poly(phthalazinone ether sulfone ketone) (PPESK) copolymers containing different component ratios of bis(4‐fluorodiphenyl) ketone and bis(4‐chlorodiphenyl)sulfone with respect to a certain amount of 4‐(4‐hydroxyphenyl)‐2,3‐phthalazin‐1‐one were synthesized by polycondensation. Glass transition temperatures of these polymers were adjusted from 263°C to 305°C by changing the ratios of reactants. Gas permeability and selectivity of the dense membranes of the polymers for three kinds of gases (CO2, O2, and N2) were determined at different temperatures. The result indicated that the membrane of PPESK (S/K = 1/1, mol ratio) had an excellent gas separation property. Permeability of the polymer membranes for CO2, O2, and N2 was P = 4.121 barrier, P = 0.674 barrier, and P = 0.0891 barrier, respectively. Separation factors of α and α were 7.6 and 46, respectively. New material was made into a composite membrane with silicone rubber for blocking up leaks and defects on the surface of its nonsymmetrical membrane. As a result of the test, permeability of the composite membrane was J = 7.2 × 10−6 cm3 (STP) cm−2 S−1 cm−1 Hg and J = 0.99 × 10−6 cm3 (STP) cm−2 S−1 cm−1 Hg, whereas the α was still higher than 7. These showed that PPESKs had a bright prospect as the potential membrane material for high‐temperature gas separation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2385–2390, 1999  相似文献   

8.
Different amounts of (N,N′‐disalicylideneethylenediamin)cobalt (CoS) were blended to a cobalt (II)‐neutralized sulfonated EPDM (Co(II)S‐EPDM) ionomer membrane to enhance its oxygen‐enriching ability. Various influence factors on permeabilities and selectivities of the composite membranes, such as the gas pressure difference, the CoS content, and the testing temperature have been investigated. Oxygen permeability coefficients (P) and oxygen/nitrogen separation factors (α) increased simultaneously by decreasing the gas pressure difference or by increasing the CoS content. In comparison with the EPDM matrix, P and α of Co(II)S‐EPDM–CoS (85/15) composite membrane increased from 11.0 Barrer and 4.38 to 37.0 Barrer and 9.60. Obvious enhancement in the oxygen‐enriching property shows that the dual actions of cobaltous ion crosslinking and addition of an abundant cobalt complex may be an effective way to improve a rubbery polymer membrane. As high as 15 wt % of the CoS could be blended. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1071–1077, 1999  相似文献   

9.
Mean permeability coefficients for CH4 and CO2 ( and ) in cellulose acetate (CA, DS = 2.45) were determined at 35°C (95°F) and at pressures up to about 54 atm (800 psia). The measurements were made with pure CH4 and CO2 as well as with CH4/CO2 mixtures containing 9.7, 24.0, and 46.1 mol % CO2. In the measurements with the pure gases, was found to decrease with increasing pressure, as expected from the “dual-mode” sorption model. By contrast, passes through a minimum and then increases with increasing pressure, probably due to the plasticization (swelling) of CA by CO2. The values of and determined with the mixtures containing 9.7 and 24.0 mol % CO2 decrease with increasing total pressure; this behavior is adequately described by the extended “dual-mode” sorption model for mixtures. By contrast, the values of and obtained with the mixture containing 46.1 mol % CO2 pass through a minimum and then increase as the total pressure is raised, probably also due to the plasticization of CA by CO2. The CO2/CH4 selectivity (≡/) of the CA membrances decreases with increasing total pressure and, at constant pressure, decreases with increasing CO2 concentration in the feed mixture. The effects of exposing the CA membranes to high-pressure CO2 prior to the permeability measurements (“conditioning” effects) on and have also been studied. © 1996 John Wiley & Sons, Inc.  相似文献   

10.
Surface fluorination of poly(trimethylsilylpropyne) (PTMSP) membranes by CF4 plasma was studied. The surface fluorination of the membranes was carried out in an atmosphere of CF4 in a capacitively coupled discharge apparatus with external electrodes. Dramatic increase in selectivity (P/P) was observed. The effect of fluorination conditions such as duration of treatment and discharge power on the permeabilities of the membranes was studied. X-ray photoelectron spectrometric data of modified PTMSP membranes showed a drastic alternation in the surface layer. The P and P/P of the membranes were observed to be dependent on the F/C atomic ratio. At F/C > 1, the P/P value of the membranes could be more than four. © 1993 John Wiley & Sons, Inc.  相似文献   

11.
A new class of amphiphilic dendritic ABA triblock copolymers, which is based on organic linear polyethylene oxide (PEO) and inorganic dendritic carbosiloxane (CSO) was synthesized. The strategy used in synthesizing these materials is based on divergent method using hydrosilylation‐alcoholysis cycles. The reaction conditions and structural features of dendrimers were analyzed by different physicochemical techniques such as: GPC, NMR, UV spectroscopy, DSC, and viscometry. The generational limit of dendrimer after the first generation, OSC‐D‐PEO‐D‐CSO, forced us to employ HSiCl2CH3 as branching reagent. Also further hydrosilylation of the third generation yielded an irregular structure species. Self‐assembling and morphological studies of first, OSC‐D‐PEO‐D‐CSO, and second, OSC‐D‐PEO‐D‐CSO, generations in aqueous medium were monitored by using fluorescence, TEM and DLS techniques. However, the dendritic block copolymer with third generation, OSC‐D‐PEO‐D‐CSO, could not be dispersed in aqueous phase. The diameters of denderitic micelles had a narrow distribution in the ranges of 69 and 88 nm, respectively. Although the micelles were stable even in first generation, partition equilibrium constants of pyrene and critical micelle concentration in both of dendritic micelles imply that the micellar behaviors of the supramolecules strongly depend on the hydrophobic block's size in which increasing generation effectively promoted the micelle formation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

12.
This study investigates the sorption and transport properties of hydrocarbon membranes based on poly(vinyl alcohol) network and poly(styrene sulfonic acid‐co‐maleic acid) (PSSA‐MA). The water and methanol self‐diffusion coefficients through an 80 wt % PSSA‐MA interpenetrating SIPN‐80 membrane measured 3.75 × 10?6 and 5.47 × 10?7 cm2/s, respectively. These results are lower than the corresponding values of Nafion® 115 (8.89 × 10?6 cm2/s for water and 8.63 × 10?6 cm2/s for methanol). The methanol permeability of SIPN‐80 membrane is 4.1 × 10?7 cm2/s, or about one‐fourth that of Nafion® 115. The difference in self‐diffusion behaviors of Nafion® 115 and SIPN‐80 membranes is well correlated with their sorption characteristics. The solvent uptake of Nafion® 115 increased as the methanol concentration increased up to a methanol mole fraction of 0.63, and then decreased. However, the solvent uptake of the SIPN‐80 membranes decreased sluggishly as the methanol concentration increased. The λ values of water and methanol (i.e., λ and λ) in Nafion® 115 are quite close, indicating no sorption preference between water and methanol. In contrast, the λ value is only one‐third λ for a SIPN‐80 membrane. Accordingly, the SIPN membranes are regarded as candidates for direct methanol fuel cell applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

13.
Facilitated transport of oxygen was investigated in ethyl cellulose membranes containing cobalt(II) meso‐tetrakis (substituted phenyl) porphyrins [CoTPP, CoT(2‐Cl)PP, CoT(4‐Cl)PP, CoT(4‐MeO)PP, and CoT(2,4‐2MeO)PP] as fixed oxygen carriers. The oxygen permeability (P) and oxygen/nitrogen selectivity (P/P) of the membranes containing oxygen carriers increase with a decrease in the upstream gas pressure, but the nitrogen permeability (P) is almost independent of the upstream nitrogen pressure. This indicates that the fixed oxygen carriers in the polymer membranes can reversibly interact with oxygen and facilitate oxygen transport in the membranes. The study on the influences of the substituents in the cobalt(II) porphyrins and the fifth ligand (imidazole or pyridine) on the membrane permeation behaviors shows that the porphyrin complex with an electron‐accepting substituent in the meso‐phenyl ring or with imidazole as the fifth ligand could increase the permeability and oxygen/nitrogen selectivity of the membranes much more than that with an electron‐donating substituent or with pyridine as the fifth ligand. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 484–488, 2000  相似文献   

14.
The novel positively charged poly(ether ether ketone)s (PEEKs) with pendant quaternary ammonium groups were synthesized by copolymerization of 3, 3′‐dimethylaminemethylene‐4,4′‐biphenol (DABP), 3,3′,4,4′‐tetramethylbiphenol, and 4,4′‐bisfluorobenzophenone followed by reaction with iodomethane. The resulting copolymers were used to prepare thin film composite (TFC) nanofiltration (NF) membranes via the dip‐coating method. The effects of different parameters such as copolymer concentration and curing time on the membrane performance (flux and rejection of inorganic salts) were investigated. The optimum parameters were that 1.5 wt % quaternary ammonium PEEK containing 1.8 quaternary ammonium groups per unit with 0.5 wt % DMSO coated on the polysulfone (PSf) support membrane and cured at 100°C. The results of the performance testing showed that the trend for rejection was R > R > RNaCl > R (R = rejection), which was a typical positively charged membrane. The best performance of these composite nanofiltration membranes was 91.3% rejection for 500 ppm MgCl2 and 62.5 L/m2 h water permeability at 0.4 MPa. The MWCO of the membrane was 800 Da. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

15.
Different values are reported in the literature for the intrinsic birefringence of the crystalline (Δn) and the amorphous (Δn) phases in nylon 6. Mostly, these values have either been determined by extrapolation (and then it is assumed that Δn = Δn) or calculated theoretically. In this study, intrinsic birefringence values Δn and Δn for nylon 6 were determined using the Samuels two-phase model which correlates sonic modulus with structural parameters. Three series of fiber samples were used: (1) isotropic samples of different degrees of crystallinity for estimation of E and E moduli at two temperatures. The following modulus values were obtained: 1.62 × 109 and 6.66 × 109 N/m2 for 28.5°C, and 1.81 × 109 and 6.71 × 109 N/m2 for ?20°C; (2) anisotropic, amorphous fiber samples for estimation of Δn = 0.076 and E = 1.63 × 109 N/m2 at 28.5°C; (3) semicrystalline samples of various draw ratios for estimations of Δn = 0.089 and Δn = 0.078. All measurements were carried out with carefully dried samples to avoid erroneous results caused by moisture.  相似文献   

16.
A novel membrane effective in the separation of ethanol-water mixtures by pervaporation was made by combining zeolite NaA and poly(vinyl chloride) modified by 2-(2′-butoxyethoxy)ethyl thiolate. Under ambient conditions, a separation factor (α) of 29 and pervaporability (P) of 4 × 10?4 g m?1 h?1 were obtained for the azeotropic mixture whereas, in the absence of zeolite, the respective values were 7 and 7 × 10?5. A mechanism was proposed relating the preferential water transport at ≈? 50% zeolite content to an interfacial “phase” between the zeolite and the modified polymer.  相似文献   

17.
Mixtures of hexamethyldisiloxane [HMDSiO, (CH3)3SiOSi(CH3)3] and oxygen are plasma polymerized at different oxygen pressures (P = 1.3–11.4 Pa) and a fixed monomer pressure (Pm = 2.6 Pa). The discharge power is kept at 100 W throughout the work. Nanometer‐size holes in the deposited films are characterized by variable‐energy positron annihilation lifetime spectroscopy (PALS). Additional information on the film composition and structure is obtained by X‐ray photoelectron spectroscopy and IR absorption spectroscopy. The ortho‐positronium lifetime τ3 and intensity I3 increase with the P up to 6.2 Pa and then decrease with the P. PALS measurements after annealing at 400°C show that films prepared at high oxygen pressure have a less stable structure than a film deposited at a lower oxygen pressure. These results are discussed in comparison with plasma deposition of pure HMDSiO, as are the possible effects of oxygen radicals on the film structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 974–980, 2001  相似文献   

18.
Dynamic adsorption behaviors between Cr(VI) ion and water‐insoluble amphoteric starches was investigated. It was found that the HCrO ion predominates over the initial pH ∼ 2–4, the CrO ion predominates over the initial pH ∼ 10–12, and both ions coexist over the initial pH ∼ 6–8. The sorption process occurs in two stages: the external mass transport process occurs in the early stage and the intraparticle diffusion process occurs in the long‐term stage. The diffusion coefficient of the early stage (D1) is larger than that of the long‐term stage (D2) for the initial pH 4 and pH 10. The diffusion rate of HCrO ion is faster than that of CrO ion for both processes. The D1 and D2 values are ∼ 1.38 × 10−7–10.1 × 10−7 and ∼ 0.41 × 10−7–1.60 × 10−7 cm2 s−1, respectively. The ion diffusion rate in both processes is concentration dependent and decreases with increasing initial concentration. The diffusion rate of HCrO ion is more concentration dependent than that of CrO ion for the external mass transport process. In the intraparticle diffusion process, the concentration dependence of the diffusion rate of HCrO and CrO ions is about the same. The external mass transport and intraparticle diffusion processes are endothermic and exothermic, respectively, for the initial pH 4 and pH 10. The kd values of the external mass transport and intraparticle diffusion processes are ∼ 15.20–30.45 and ∼ −3.53 to −12.67 kJ mol−1, respectively. The diffusion rate of HCrO ion is more temperature dependent than that of CrO ion for both processes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2409–2418, 1999  相似文献   

19.
The morphology of low-density polyethylene (LDPE) modified by in situ sorption and thermal polymerization of acrylic acid (AA) in the matrix was examined. The microstructure of the LDPE/poly(acrylic acid) (PAA) materials after Eu3+ and UO ion exchange was investigated. The phase behavior of these materials was analyzed using X-ray diffraction, scanning electron microscopy (SEM), and thermal measurements (DSC). The X-ray dif-fraction studies showed that PAA is located at amorphous region of the matrix. The LDPE/PAA surface, as investigate by SEM, was apparently homogeneous before and after Eu3+ and UO ion exchange, respectively. Two Tg values were found for the LDPE/PAA material before and after Eu3+ ion exchange. Also, three and four Tg values were found for LDPE/PAA after UO ion exchange depending on the amount of UO in the modified matrix. This indicates microphase domains in the LPDE/PAA-, LPDE/PAA/Eu3+-, and LPDE/PAA/UO -modified materials, although a lack of visible phase separation in the micrographs was observed. © 1996 John Wiley & Sons, Inc.  相似文献   

20.
Poly(3‐mesityl‐2‐hydroxypropyl methacrylate) (PMHPMA) was synthesized in a 1,4‐dioxane solution with 2,2′‐azobisisobutyronitrile as the initiator at 60°C. The homopolymer and its monomer were characterized with 1H‐ and 13C‐NMR, Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography, and elemental analysis techniques. According to size exclusion chromatography analysis, the number‐average molecular weight, weight‐average molecular weight, and polydispersity index of PMHPMA were 65,864 g/mol, 215,375 g/mol, and 3.275, respectively. According to thermogravimetric analysis, the carbonaceous residue value of PMHPMA was 14% at 500°C. The values of the specific retention volume, adsorption enthalpy, sorption enthalpy, sorption free energy, sorption entropy, partial molar free energy, partial molar heat of mixing, weight fraction activity coefficient of solute probes at infinite dilution (Ω), and Flory–Huggins interaction parameter (χ) were calculated for the interactions of PMHPMA with selected alcohols and alkanes by the inverse gas chromatography method at various temperatures. According to Ω and χ, selected alcohols and alkanes were nonsolvents for PMHPMA at 423–453 K. Also, the solubility parameter of PMHPMA (δ2) was found to be 24.24 and 26.33 (J/cm3)0.5 from the slope and intercept of (δ/RT) ? χ/V1 = (2δ2/RT1 ? δ/RT at 443 K, respectively [where δ1 is the solubility parameter of the probe, V1 is the molar volume of the solute, T is the column temperature (K), and R is the universal gas constant]. The glass‐transition temperature of PMHPMA was found to be 386 and 385 K by inverse gas chromatography and differential scanning calorimetry techniques, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 101–109, 2006  相似文献   

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