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1.
A poly(vinylidene fluoride)‐graft‐poly(N‐isopropylacrylamide) (PVDF‐g‐PNIPAAm) copolymer was synthesized, and flat‐sheet membranes were prepared via the phase‐inversion method with N,N‐dimethylformamide (DMF) as the solvent and water as the coagulation bath. The effects of the coagulation‐bath temperature on poly(vinylidene fluoride) (PVDF)/DMF/water and PVDF‐g‐PNIPAAm/DMF/water ternary systems were studied with phase diagrams. The results showed that the phase‐separation process could be due to the hydrophilicity/hydrophobicity of poly(N‐isopropylacrylamide) at low temperatures, and the phase‐separation process was attributed to crystallization at high temperatures. The structures and properties of the membranes prepared at different coagulation‐bath temperatures were researched with scanning electron microscopy, porosity measurements, and flux measurements of pure water. The PVDF‐g‐PNIPAAm membranes, prepared at different temperatures, formed fingerlike pores and showed higher water flux and porosity than PVDF membranes. In particular, a membrane prepared at 30°C had the largest fingerlike pores and greatest porosity. The water flux of a membrane prepared in a 25°C coagulation bath showed a sharp increase with the temperature increasing to about 30°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

2.
In the present study, the temperature sensitive PVDF‐g‐NIPAAm HFM was prepared by grafting N‐isopropylacrylamide (NIPAAm) on poly(vinylidene fluoride) (PVDF) hollow fiber membrane (HFM) using a novel approach, alkaline treatment method. The structures of PVDF‐g‐NIPAAm HFM were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. The effects of alkaline treatment time and grafting yield on the mechanical properties of PVDF HFM were measured and analyzed. In addition, the temperature sensitive behavior of PVDF‐g‐NIPAAm HFM and the effect of grafting yield on the temperature sensitive behavior were investigated by the flux of pure water and the rejection of ovalbumin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 833–837, 2006  相似文献   

3.
Graft copolymer (PVDF‐g‐PNIPAAm) having poly(vinylidene fluoride) (PVDF) backbones and poly(N‐isopropylacrylamide) (PNIPAAm) side chains was synthesized via radical copolymerization and its hollow fiber membrane was fabricated from dry–wet spinning technique with N, N‐dimethylformamide as the solvent and poly(ethylene glycol) (10,000) as the additive. The effects of spinning condition (take‐up speeds) on the structures and performances of resulting fiber membranes were systematically considered. The structures and performances of fiber membranes were characterized by element analysis, X‐ray photoelectron spectroscopy, water contact angle measurement, scanning electron microscope, atom force microscope, and filtration experiments. The results indicate that PNIPAAm side chains tended to enrich on the membrane surface and pore surface and especially tended to aggregate on the inner surface due to the effect of bore fluid. The hollow fiber membrane exhibits an obvious temperature‐sensitive property. The pure water flux increases remarkably around 32°C, while the retention of albumin egg decreases accordingly, when the permeation temperature rises from 20 to 45°C. As the take‐up speed increases, both the inner and outer diameters of fiber membranes decrease. A higher take‐up speed favors higher pure water permeation flux, which allows larger molecules to permeate through the fiber membrane. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers  相似文献   

4.
A straightforward strategy is described to synthesize poly(?‐caprolactone)‐graft‐poly(N‐isopropylacrylamide) (PCL‐g‐PNIPAAm) amphiphilic graft copolymers consisting of potentially biodegradable polyester backbones and thermoresponsive grafting chains. PCL with pendent chlorides was prepared by ring‐opening polymerization, followed by conversion of the pendent chlorides to azides. Alkyne‐terminated PNIPAAm was synthesized by atom transfer radial polymerization. Then, the alkyne end‐functionalized PNIPAAm was grafted onto the PCL backbone by a copper‐catalyzed azide–alkyne cycloaddition. PCL‐g‐PNIPAAm graft copolymers self‐assembled into spherical micelles comprised of PCL cores and PNIPAAm coronas. The critical micelle concentrations of the graft copolymers were in the range 7.8–18.2 mg L?1, depending on copolymer composition. Mean hydrodynamic diameters of micelles were in the range 65–135 nm, which increased as the length of grafting chains grew. PCL‐g‐PNIPAAm micelles were thermosensitive and aggregated upon heating. © 2014 Society of Chemical Industry  相似文献   

5.
The copolymer poly(vinylidene fluoride)‐graft‐poly(4‐vinylpyridine) (PVDF‐g‐P4VP) was prepared through the graft copolymerization of poly(vinylidene fluoride) with 4‐vinylpyridine. Through the blending of the PVDF‐g‐P4VP copolymer with poly(N‐isopropylacrylamide) (PNIPAm) in an N‐methyl‐2‐pyrrolidone solution, PVDF‐g‐P4VP/PNIPAm membranes were fabricated by phase inversion in aqueous media. Elemental analyses indicated that the blend concentration of PNIPAm in the blend membranes increased with an increase in the blend ratio used in the casting solution. Scanning electron microscopy revealed that the membrane surface tended to corrugate at a low PNIPAm concentration and transformed into a smooth morphology at a high PNIPAm concentration. The surface morphology and pore size distribution of the microfiltration membranes could be regulated by the blend concentration of the casting solution, temperature, pH, and ionic strength of the coagulation bath. X‐ray photoelectron spectroscopy revealed a significant enrichment of PNIPAm on the membrane surface. The flux of aqueous solutions through the blend membranes exhibited a pH‐ and temperature‐dependent behavior. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4089–4097, 2006  相似文献   

6.
Poly(propylene) (PP) membrane grafted with poly(N‐isopropylacrylamide) (PNIPAAm), which is known to have a lower critical solution temperature (LCST) at around 32°C, was prepared by the plasma‐induced graft polymerization technique. Graft polymerization of PNIPAAm onto a PP membrane was confirmed by microscopic attenuated total reflection/Fourier transform IR spectroscopy. The grafting yield of PNIPAAm increased with the concentration of N‐isopropylacrylamide monomer and the reaction time of graft polymerization. The average pore size of the PP membrane also affected the grafting yield. From the field emission scanning electron microscopy (FE‐SEM) measurement, we observed a morphological change in the PP‐g‐PNIPAAm membrane under wet conditions at 25°C below LCST. The permeability of water through the PP‐g‐PNIPAAm membrane was controlled by temperature. The PP‐g‐PNIPAAm membrane (PN05 and PN10) exhibited higher water permeability (Lp) than the original PP substrate membrane below LCST. As the temperature increased to above LCST, Lp gradually decreased. In addition, the graft yield of PNIPAAm and the average pore size of the PP substrate influenced water permeability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1168–1177, 2002; DOI 10.1002/app.10410  相似文献   

7.
In this study, a comblike amphiphilic graft copolymer containing poly(vinyl chloride) (PVC) backbones and poly(oxyethylene methacrylate) [poly(ethylene glycol) methylether methacrylate (PEGMA)] side chains was facilely synthesized via an atom transfer radical polymerization method. Secondary chlorines in PVC were used as initial sites to graft a poly[poly(ethylene glycol) methylether methacrylate] [P(PEGMA)] brush. The synthesized PVC‐g‐P(PEGMA) graft copolymer served as an efficient additive for the hydrophilicity modification of the poly(vinylidene fluoride) (PVDF) membrane via a nonsolvent‐induced phase‐inversion technique. A larger pore size, higher porosity, and better connectivity were obtained for the modified PVDF membrane; this facilitated the permeability compared to the corresponding virgin PVDF membrane. In addition, the modified PVDF membrane showed a distinctively enhanced hydrophilicity and antifouling resistance, as suggested by the contact angle measurement and flux of bovine serum albumin solution tests, respectively. Accordingly, the PVC‐g‐P(PEGMA) graft copolymer was demonstrated as a successful additive for the hydrophilicity modification, and this study will likely open up new possibilities for the development of efficient amphiphilic PVC‐based copolymers for the excellent hydrophilicity modification of PVDF membranes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

8.
Thermoresponsive graft copolymers of ε‐caprolactone and N‐isopropylacrylamide were synthesized by a combination of ring‐opening polymerization and the sequential atom transfer radical polymerization (ATRP). The copolymer composition, chemical structure, and the self‐assembled structure were characterized. The graft length and density of the copolymers were well controlled by varying the feed ratio of monomer to initiator and the fraction of chlorides along PCL backbone, which is acting as the macroinitiator for ATRP. In aqueous solution, PCL‐g‐PNIPAAm can assemble into the spherical micelles which comprise of the biodegradable hydrophobic PCL core and thermoresponsive hydrophilic PNIPAAm corona. The critical micelle concentrations of PCL‐g‐PNIPAAm were determined under the range of 6.4–23.4 mg/L, which increases with the PNIPAAm content increasing. The mean hydrodynamic diameters of PCL‐g‐PNIPAAm micelles depend strongly on the graft length and density of the PNIPAAm segment, allowing to tune the particle size within a wide range. Additionally, the PCL‐g‐PNIPAAm micelles exhibit thermosensitive properties and aggregate when the temperature is above the lower critical solution temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41115.  相似文献   

9.
A graft copolymer of poly(vinylidene fluoride) (PVDF) with a glucose‐carrying methacrylate, 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐D ‐glucofuranose, was synthesized via the atom transfer radical polymerization technique with commercial PVDF as the macroinitiator. After a treatment with 88% formic acid, the isopropylidenyl groups of the precursor graft copolymer [poly(vinylidene fluoride)‐g‐poly(3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐ D ‐glucofuranose)] were converted into hydroxyl groups, and this produced an amphiphilic graft copolymer (PVDF‐g‐PMAG) [poly(vinylidene fluoride)‐g‐poly(3‐O‐methacryloyl‐α,β‐D‐glucopyranose)] with glycopolymer side chains and a narrow molecular weight distribution (weight‐average molecular weight/number‐average molecular weight < 1.29). This glucose‐carrying graft copolymer was characterized with Fourier transform infrared, proton nuclear magnetic resonance, gel permeation chromatography, and thermogravimetric analysis. A novel porous membrane prepared from blends of PVDF with PVDF‐g‐PMAG via an immersion–precipitation technique exhibited significantly enhanced hydrophilicity and an anti‐protein‐adsorption property. The surface chemical composition and morphology of the membrane were studied with X‐ray photoelectron spectroscopy and scanning electron microscopy, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

10.
Stimuli‐responsive biocompatible and biodegradable materials can be obtained by combining polysaccharides with polymers exhibiting lower critical solution temperature (LCST) phase behavior, such as poly(N‐isopropylacrylamide) (PNIPAAm). The behavior of aqueous solutions of sodium alginate (NaAl) grafted with PNIPAAm (NaAl‐g‐PNIPAAm) copolymers as a function of composition and temperature is presented. The products obtained exhibit a remarkable thermothickening behavior in aqueous solutions if the degree of grafting, the concentration, and the temperature are higher than some critical values. The sol–gel‐phase transition temperatures have been determined. It was found that at temperatures below LCST the systems behave like a solution, whereas at temperatures above LCST, the solutions behave like a stiff gel, because of PNIPAAm segregation. This behavior is reversible and could find applications in tissue engineering and drug delivery systems. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

11.
Poly(vinylidene fluoride) (PVDF) membranes have been widely used in microfiltration and ultrafiltration because of their excellent chemical resistance and thermal properties. However, PVDF membranes have exhibited severe membrane fouling because of their hydrophobic properties. In this study, we investigated the antifouling properties of PVDF blended membranes. Antifouling PVDF blended membranes were prepared with a PVDF‐g‐poly(ethylene glycol) methyl ether methacrylate (POEM) graft copolymer. The PVDF‐g‐POEM graft copolymer was synthesized by the atom transfer radical polymerization (ATRP) method. The chemical structure and properties of the synthesized PVDF‐g‐POEM graft copolymer were determined by NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography. To investigate the antifouling properties of the membranes, we prepared microfiltration membranes by using the phase‐inversion method, which uses various PVDF/PVDF‐g‐POEM concentrations in dope solutions. The pure water permeabilities were obtained at various pressures. The PVDF/PVDF‐g‐POEM blended membranes exhibited no irreversible fouling in the dead‐end filtration of foulants, including bovine serum albumin, sodium alginate, and Escherichia coli broth. However, the hydrophobic PVDF membrane exhibited severe fouling in comparison with the PVDF/PVDF‐g‐POEM blended membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

12.
Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) [P(NIPAM‐co‐HEMA)] copolymer was synthesized by controlled radical polymerization from respective N‐isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) monomers with a predetermined ratio. To prepare the thermosensitive and biodegradable nanoparticles, new thermosensitive graft copolymer, poly(L ‐lactide)‐graft‐poly(N‐isoporylacrylamide‐co‐hydroxyethyl methacrylate) [PLLA‐g‐P(NIPAM‐co‐HEMA)], with the lower critical solution temperature (LCST) near the normal body temperature, was synthesized by ring opening polymerization of L ‐lactide in the presence of P(NIPAM‐co‐HEMA). The amphiphilic property of the graft copolymers was formed by the grafting of the PLLA hydrophobic chains onto the PNIPAM based hydrophilic backbone. Therefore, the graft copolymers can self‐assemble into uniformly spherical micelles ò about 150–240 nm in diameter as observed by the field emission scanning electron microscope and dynamic light scattering. Dexamethasone can be loaded into these nanostructures during dialysis with a relative high loading capacity and its in vitro release depends on temperature. Above the LCST, most of the drugs were released from the drug‐loaded micelles, whereas a large amount of drugs still remains in the micelles after 48 h below the LCST. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

13.
Poly(vinylidene fluoride) (PVDF) powders were grafted with N‐vinyl pyrrolidone using the pre‐irradiation induced graft polymerization technique. The effects of reaction time, absorbed dose, and monomer concentration on the degree of grafting were investigated, and the grafted PVDF powders were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The grafted PVDF powders were also cast into microfiltration (MF) membranes via the phase‐inversion method. The contact angle and water uptake were measured. The membrane morphology was studied by scanning electron microscopy, and the water filtration properties of the membranes were tested. The antifouling properties were determined through measurements of the recovery percentage of pure water flux after the MF membranes were fouled with bovine serum albumin solution. The results confirmed that the existence of poly(N‐vinyl pyrrolidone) (PVP) graft chains improved the hydrophilicity and antifouling properties of the MF membranes cast from PVDF‐g‐PVP powders. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

14.
A highly hydrophilic hollow fiber poly(vinylidene fluoride) (PVDF) membrane [PVDF‐cl‐poly(vinyl pyrrolidone) (PVP) membrane] was prepared by a cross‐linking reaction with the hydrophilic PVP, which was immobilized firmly on the outer surface and cross‐section of the PVDF hollow fiber membrane via a simple immersion process. The cross‐linking between PVDF and PVP was firstly verified via nuclear magnetic resonance measurement on PVP solution after cross‐linking. The hydrophilic stability of the modified PVDF membrane was evaluated by measuring the pure water flux after different times of immersion and drying. The anti‐fouling properties were estimated by cyclic filtration of protein solution. When the cross‐linking time was as long as 6 hr and the PVP content reached 5 wt %, the pure water flux (Jv) was constant as ~ 600 L m?2 hr?1. The hydrophilicity of the PVDF‐cl‐PVP membrane was significantly enhanced and exhibited a good stability. The PVDF‐cl‐PVP membrane showed an excellent anti‐protein‐fouling performance during the cyclic filtration of bovine serum albumin solution. Therefore, a highly hydrophilic and anti‐protein‐fouling PVDF hollow fiber membrane with a long‐term stability can be prepared by a simple and economical cross‐linking process with PVP. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

15.
Several different composition temperature‐ and pH‐sensitive poly(acrylic acid‐gN‐isopropylacrylamide) (P(AA‐g‐NIPAM)) graft copolymers were synthesized by free‐radical copolymerization utilizing macromonomer technique. The phase behavior and conformation change of P(AA‐g‐NIPAM) in aqueous solutions were investigated by UV–vis transmittance measurements, fluorescence probe, and fluorescence quenching techniques. The results demonstrate that the P(AA‐g‐NIPAM) copolymers have temperature‐ and pH‐sensitivities, and these different composition graft copolymers have different lower critical solution temperature (LCST) and critical phase transition pH values. The LCST of graft copolymer decreases with increasing PNIPAM content, and the critical phase transition pH value increases with increasing Poly(N‐isopropylacrylamide) (PNIPAM) content. At room temperature (20°C), different composition of P(AA‐g‐NIPAM) graft copolymers in dilute aqueous solutions (0.001 wt %) have a loose conformation, and there is no hydrophobic microdomain formation within researching pH range (pH 3 ~ 10). In addition, for the P(AA‐g‐NIPAM) aqueous solutions, transition from coil to globular is an incomplete reversible process in heating and cooling cycles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

16.
Poly(N‐isopropylacrylamide) (PNIPAAm)/poly(ethylene oxide) (PEO) semi‐interpenetrating polymer networks (semi‐IPNs) synthesized by radical polymerization of N‐isopropylacrylamide (NIPAAm) in the presence of PEO. The thermal characterizations of the semi‐IPNs were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). The melting temperature (Tm) of semi‐IPNs appeared at around 60°C using DSC. DEA was employed to ascertain the glass transition temperature (Tg) and determine the activation energy (Ea) of semi‐IPNs. From the results of DEA, semi‐IPNs exhibited one Tg indicating the presence of phase separation in the semi‐IPN, and Tgs of semi‐IPNs were observed with increasing PNIPAAm content. The thermal decomposition of semi‐IPNa was investigated using TGA and appeared at around 370°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3922–3927, 2003  相似文献   

17.
Polyaniline‐graft‐Poly(N‐isopropylacrylamide) copolymers were synthesized by atom‐transfer radical polymerization (ATRP) of N‐isopropylacrylamide using polyaniline macro‐initiators. Polyaniline‐chloroacetylchloride and polyaniline‐chloropropionylchloride macroinitiators were obtained by the reaction of amine nitrogens of polyaniline with chloroacetyl chloride and 2‐choloropropionyl choloride, respectively. Both macroinitiators and graft copolymers were characterized by FT‐IR and 1H‐NMR spectroscopy. The cyclic voltammetry (CV) and UV‐Vis spectroscopy studies showed that these copolymers are electroactive. The solubility test revealed that the polyaniline‐graft‐poly (N‐isopropylacrylamide) copolymers are water soluble or water/methanol soluble. The Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) images showed the growing of poly (N‐isopropylacrylamide) chains on polyaniline backbone. Investigation of thermal behavior of graft copolymers by thermal gravimetry analysis (TGA) confirmed the results obtained from AFM and SEM images. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

18.
The poly(vinylidene fluoride) (PVDF)/poly(N‐isopropylacrylamide) (PNIPAM) blend membranes with different PNIPAM contents are prepared by phase inversion of PNIPAM and PVDF in aqueous medium. The membranes are characterized by thermal gravimetric analyses, elemental analysis, Fourier transform infrared spectrometer, X‐ray photoelectron spectroscopy, and scanning electron microscope photographs. The results indicate that PNIPAM chains are largely distributed in membrane pore other than membrane surface, and furthermore, with the increase of PNIPAM content, the porous size, porosity, and water flux through the membrane increase, the hydrophilicity and antiprotein fouling are enhanced. The blend membrane exhibits temperature‐sensitive permeability to aqueous solutions, with the most drastic change being observed at the lower critical solution temperature (LCST) of PNIPAM (around 32°C). Below the LCST, the blend membrane shows a high protein rejection and a low water flux; above the LCST, the blend membrane shows a low protein rejection and a high water flux. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers  相似文献   

19.
Nonwoven super‐hydrophobic fiber membranes have potential applications in oil–water separation and membrane distillation, but fouling negatively impacts both applications. Membranes were prepared from blends comprising poly(vinylidene fluoride) (PVDF) and random zwitterionic copolymers of poly(methyl methacrylate) (PMMA) with sulfobetaine methacrylate (SBMA) or with sulfobetaine‐2‐vinylpyridine (SB2VP). PVDF imparts mechanical strength to the membrane, while the copolymers enhance fouling resistance. Blend composition was varied by controlling the PVDF‐to‐copolymer ratio. Nonwoven fiber membranes were obtained by electrospinning solutions of PVDF and the copolymers in a mixed solvent of N,N‐dimethylacetamide and acetone. The PVDF crystal phases and crystallinities of the blends were studied using wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). PVDF crystallized preferentially into its polar β‐phase, though its degree of crystallinity was reduced with increased addition of the random copolymers. Thermogravimetry (TG) showed that the degradation temperatures varied systematically with blend composition. PVDF blends with either copolymer showed significant increase of fouling resistance. Membranes prepared from blends containing 10% P(MMA‐ran‐SB2VP) had the highest fouling resistance, with a fivefold decrease in protein adsorption on the surface, compared to homopolymer PVDF. They also exhibited higher pure water flux, and better oil removal in oil–water separation experiments. © 2018 Society of Chemical Industry  相似文献   

20.
The physical properties of poly(vinyl chloride) (PVC) and poly(N‐isopropylacrylamide) [poly(NIPAAm)] blend systems, and their corresponding graft copolymers such as PVC‐g‐NIPAAm, were investigated in this work. The compatible range for PVC–poly(NIPAAm) blend systems is less than 15 wt % poly(NIPAAm). The water absorbencies for the grafted films increase with increase in graft percentage. The water absorbencies for the blend systems increase with increase in poly(NIPAAm) content within the compatible range for the blends, but the absorbencies decrease when the amount of poly(NIPAAm) is more than the compatible range in the blend system. The tensile strengths for the graft copolymers are larger than the corresponding blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 170–178, 2000  相似文献   

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