Facile surface modification of PVDF microfiltration membrane by strong physical adsorption of amphiphilic copolymers

To endow the surface of poly(vinylidene fluoride) (PVDF) microfiltration (MF) membranes with hydrophilicity and antifouling property, physical adsorption of amphiphilic random copolymers of poly(ethylene glycol) methacrylate (PEGMA) and poly(methyl methacrylate) (PMMA) (P(PEGMA‐r‐MMA)) onto the PVDF membrane was performed. Scanning electron microscopy (SEM) images showed that the adsorption process had no influence on the membrane structure. Operation parameters including adsorption time, polymer concentration, and composition were explored in detail through X‐ray photoelectron spectroscopy (XPS), static water contact angle (CA), and water flux measurements. The results demonstrated that P(PEGMA‐r‐MMA) copolymers adsorbed successfully onto the membrane surface, and hydrophilicity of the PVDF MF membrane was greatly enhanced. The antifouling performance and adsorption stability were also characterized, respectively. It was notable that PVDF MF membranes modified by facile physical adsorption of P(PEGMA₅₈‐r‐MMA₃₃) even showed higher water flux and better antifouling property than the commercial hydrophilic PVDF MF membranes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3112–3121, 2013     

Improving the charged and antifouling properties of PVDF ultrafiltration membranes by blending with polymerized ionic liquid copolymer P(MMA‐b‐MEBIm‐Br)

This study describes the fabrication and properties of poly(vinylidene fluoride) (PVDF) filtration membranes modified by blending with ionic liquid block copolymer P(MMA‐b‐MEBIm‐Br), which is synthesized via reversible addition‐fragmentation chain transfer polymerization method. The attenuated total reflectance‐Fourier transform infrared spectroscopy and X‐ray photoelectron analyses reveal that the ionic liquid block copolymers are immobilized on PVDF membrane surface. The modified PVDF membrane exhibits excellent charged and antifouling properties because of the charged and hydrophilic properties of the copolymer. Scanning electron microscopy and atomic force microscopy also indicate the morphological characteristics of the membrane and demonstrate that the surface porous structure becomes denser after adding the copolymer. The data of filtration and the zeta potential of the membranes suggest that the charged properties of the ionic liquid block copolymers are mainly responsible for the improvement of the reversible fouling ratio and the decrease in the total fouling ratio of the membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44751.     

Electrospun fiber membranes from blends of poly(vinylidene fluoride) with fouling‐resistant zwitterionic copolymers

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     

Amphiphilic poly(vinyl chloride)‐g‐poly[poly(ethylene glycol) methylether methacrylate] copolymer for the surface hydrophilicity modification of poly(vinylidene fluoride) membrane

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     

Hydrophilic Modification of PVDF Microfiltration Membrane with Poly (Ethylene Glycol) Dimethacrylate through Surface Polymerization

The hydrophilic modification of poly (vinylidene fluoride) (PVDF) membrane with poly (ethylene glycol) dimethacrylate (PEGDMA) through grafting reaction for antifouling was reported. The influence of PEGDMA content, reaction temperature and time, on the structure, morphology, antifouling, and hydrophilicity of PVDF-g-PEGDMA membrane has been investigated. The PEGDMA monomers that were grafted on the surface of PVDF microfiltration membrane were confirmed by Attenuation total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS), and morphology study conducted by SEM revealed the changes before and after modification. The protein adsorption, filtration performance, water content, and dynamic contact angle were used to characterize the antifouling and hydrophilicity of the modified PVDF membranes. Compared with the pristine PVDF membrane, the bovine serum albumin (BSA) adsorption on the PVDF-g-PEGDMA membrane decreased about 80%, and the water contact angle of the membrane dropped to 0°. Besides, the experimental results revealed no significant differences between the membrane samples with respect to pore size.     

Surface modification of polyamide nanofiltration membrane by grafting zwitterionic polymers to improve the antifouling property

A simple two‐step surface modification method of polyamide nanofiltration membrane, involving the activation of amide groups by formaldehyde and the subsequent cerium [Ce (IV)]‐induced graft polymerization of zwitterionic 3‐(methacryloylamino) propyl‐dimethyl‐(3‐sulfopropyl) ammonium hydroxide) (MPDSAH) monomers, was employed to improve membrane antifouling property. The membranes before and after modification were characterized by attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), scanning electron microscopy, and atomic force microscopy. The changes in both surface chemical composition and morphology of membranes confirmed the successful graft polymerizations of MPDSAH onto polyamide nanofiltration membrane. The static water contact angle measurements showed that surface hydrophilicity of the modified membranes was significantly enhanced. As the MPDSAH concentration increased, the water flux of grafted membrane decreased gradually, while salt rejection increased slightly. The fouling experiments with bovine serum albumin solution demonstrated that modified membranes exhibited better resistance to protein fouling. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41144.     

Antifouling and blood‐compatible poly(ether sulfone) membranes modified by zwitterionic copolymers via In situ crosslinked copolymerization

A novel and simple but practical method for the preparation of modified poly(ether sulfone) (PES) membranes was provided by the in situ crosslinked copolymerization of sulfobetaine methacrylate (SBMA) and sodium p‐styrene sulfonate (NaSS) in PES solution followed by a phase‐separation technique. Then, semi‐interpenetrating network membranes modified by the crosslinked copolymers of poly(sulfobetaine methacrylate‐co‐sodium p‐styrene sulfonate) [P(SBMA‐co‐NaSS)] were prepared. The SBMA‐containing copolymer‐modified membranes showed improved protein antifouling properties with flux recovery ratios above 90%. Furthermore, the anticoagulant properties of the NaSS‐containing copolymer‐modified membranes were obviously enhanced; their activated partial thromboplastin time could be prolonged to about 115 s. Thus, the P(SBMA‐co‐NaSS) zwitterionic copolymer‐modified membranes showed improved antifouling properties and blood compatibility and will provide wide choices for their specific applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41585.     

Synthesis of well‐defined amphiphilic block copolymers via AGET ATRP used for hydrophilic modification of PVDF membrane

A well‐defined amphiphilic block copolymer consisting of a hydrophobic block poly(methyl methacrylate) (PMMA) and a hydrophilic block poly[N,N–2‐(dimethylamino) ethyl methacrylate] (PDMAEMA) was synthesized by activator generated by the electron transfer for atom transfer radical polymerization method (AGET ATRP). Kinetics study revealed a linear increase in the graph concentration of PMMA‐b‐PDMAEMA with the reaction time, indicating that the polymer chain growth was consistent with a controlled process. The gel permeation chromatography results indicated that the block copolymer had a narrow molecular weight distribution (Mw/Mn = 1.42) under the optimal reaction conditions. Then, poly(vinylidene fluoride) (PVDF)/PMMA‐b‐PDMAEMA blend membranes were prepared via the standard immersion precipitation phase inversion process, using the block copolymer as additive to improve the hydrophilicity of the PVDF membrane. The presence and dispersion of PMMA‐b‐PDMAEMA clearly affected the morphology and improved the hydrophilicity of the as‐synthesized blend membranes as compared to the pristine PVDF membranes. By incorporating 15 wt % of the block copolymer, the water contact angle of the resulting blend membranes decreased from pure PVDF membrane 98° to 76°. The blend membranes showed good stability in the 20 d pure‐water experiment. The bovine serum albumin (BSA) absorption experiment revealed a substantial antifouling property of the blend membranes in comparison with the pristine PVDF membrane. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42080.     

Preparation of PVDF/poly(tetrafluoroethylene‐co‐vinyl alcohol) blend membranes with antifouling propensities via nonsolvent induced phase separation method

Poly(vinylidene fluoride) (PVDF) was blended with a new amphiphilic copolymer, poly(tetrafluoroethylene‐co‐vinyl alcohol) [poly(TFE‐VA)], via non‐solvent induced phase separation (NIPS) method to make membranes with superior antifouling properties. The effects of the VA/TFE segment ratio of the copolymer and the copolymer/PVDF blend ratio on the properties of the prepared membranes were studied. Membranes with similar water permeabilities, surface pore sizes, and rejection properties were prepared and used in bovine serum albumin (BSA) filtrations with the same initial water flux and almost the same operating pressure, to evaluate the sole effect of membrane material on fouling propensity. While the VA/TFE segment ratio strongly affected the membrane antifouling properties, the effects of the copolymer/PVDF blending ratio were not so drastic. Membrane surface hydrophilicity increased, and BSA adsorption and fouling decreased upon blending a small amount of amphiphilic copolymer with a high VA/TFE segment ratio with PVDF (copolymer/PVDF blending ratio 1:5). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43780.     

Surface modification of PVDF membranes with sulfobetaine polymers for a stably anti-protein-fouling performance

Two sulfobetaine-based zwitterionic monomers, including 3-(methacryloylamino) propyl-dimethyl-(3-sulfopropyl) ammonium hydroxide (MPDSAH) and 2-(methacryloyloxyethyl) ethyl-dimethyl-(3-sulfopropyl) ammonium (MEDSA) were successfully grafted from poly(vinylidene fluoride) (PVDF) hollow fiber membrane outside surface via chemical activation and atom transfer radical polymerization (ATRP). The ATRP time at 2 h under the 2 mol/L of zwitterionic monomers was the minimum period for the complete coverage of grafted sulfobetaine polymers on the PVDF membrane surface. The surface hydrophilicity of the sulfobetaine-modified PVDF membranes was significantly enhanced. The poly-MPDSAH-g-PVDF (GA: 247 μg/cm²) and poly-MEDSA-g-PVDF membranes (GA: 338 μg/cm²) efficiently resisted to the adsorption of both negative and positive charged proteins, and showed excellent anti-protein-fouling performance with flux recovery ratio (RFR) higher than 90% and total fouling (RT) less than 25% during the cyclic filtration of bovine serum albumin solution. After cleaned in membrane cleaning solution for 12 days, the grafted MPDSAH layer on PVDF membrane could maintain without change, however, the poly-MEDSA-g-PVDF membrane lost the grafted MEDSA layer. Therefore, the amide group of sulfobetaine, which made a great contribution to the higher hydrophilicity and stability, was significant in modifying the PVDF membrane for a stably anti-protein-fouling performance. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of antifouling poly(vinylidene fluoride) blended membranes

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     

Thermal and gas permeation properties of copolymers derived from 3‐methacryloxypropyltris(trimethylsiloxy)silane and adamantyl group‐containing methacrylate derivatives

Novel copolymer membranes derived from three types of adamantyl group‐containing methacrylate derivatives and 3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA) were synthesized via free radical polymerization. The thermal and permeation properties of these copolymer membranes were investigated. Copolymer membranes with less than 11.9 mol % adamantane content exhibited good membrane forming abilities that are suitable for permeation measurement. The decomposition temperature of all copolymers increased up to approximately 40–80°C with increasing adamantane content compared with poly(SiMA). Moreover, the glass transition temperature (T_g) of all copolymers increased up to approximately 46–60°C with increasing adamantane content compared with the theoretical value, which was estimated from Fox equation. 1‐Adamantyl methacrylate copolymer had the highest fractional free volume among the three types of adamantly group‐containing methacrylate derivatives. The gas permeability coefficient of this copolymer increased by 22–45% with increasing adamantane content compared with that of poly(SiMA). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43129.     

One‐pot synthesized poly(vinyl pyrrolidone‐co‐methyl methacrylate‐co‐acrylic acid) blended with poly(ether sulfone) to prepare blood‐compatible membranes

In this study, a random copolymer of poly(vinyl pyrrolidone‐co‐methyl methacrylate‐co‐acrylic acid) was synthesized via a one‐pot reaction with the reversible addition–fragmentation chain‐transfer method and was then blended with poly(ether sulfone) (PES) to prepare flat‐sheet membranes that were expected to have anticoagulant and antifouling properties. The synthesized copolymer was characterized by Fourier transform infrared (FTIR) and NMR spectroscopy. The molecular weights and molecular weight distributions were determined by gel permeation chromatography. Elemental analysis was used to calculate the molar ratios of vinyl pyrrolidone (VP), methyl methacrylate (MMA), and acrylic acid (AA) in the copolymer. A liquid–liquid phase‐inversion technique was used to prepare the copolymer‐blended PES membranes. X‐ray photoelectron spectroscopy and attenuated total reflectance–FTIR spectroscopy were used to investigate the copolymer on the membrane surfaces. Compared with the pristine PES membrane, the modified PES membranes showed improved hydrophilicity, low hemolysis ratios, decreased protein adsorption, and suppressed platelet adhesion. Furthermore, the thrombin time and activated partial thromboplastin time indicated that the blood compatibility of the modified PES membranes were improved. The results of the 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay and the cell morphology suggested that the cytocompatibility increased. In addition, the modified membranes showed good protein antifouling properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4284–4298, 2013     

Morphologies of polybutylacrylate/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization Part I. Thermodynamics equilibrium morphology

Heterogeneous latexes were prepared by a semicontinuous seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amounts of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. Phase separation towards the thermodynamic equilibrium morphology was accelerated either by ageing the composite latex at 80 °C or by adding a chain‐transfer agent during polymerization. The morphologies of the latex particles were examined by transmission electron microscopy (TEM). The morphology distributions of latex particles were described by a statistical method. It was found that the latex particles displayed different equilibrium morphologies depending on the composition of the second‐stage copolymers. This series of equilibrium morphologies of [poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate)] (PBA/P(St‐co‐MMA)) system provides experimental verification for quantitative simulation. Under limiting conditions, the equilibrium morphologies of PBA/P(St‐co‐MMA) were predicted according to the minimum surface free energy change principle. The particle morphology observed by TEM was in good agreement with the predictions of the thermodynamic model. Therefore, the morphology theory for homopolymer/homopolymer composite systems was extended to homopolymer/copolymer systems. © 2002 Society of Chemical Industry     

Outstanding antifouling performance of poly(vinylidene fluoride) membranes: Novel amphiphilic brushlike copolymer blends and one-step surface zwitterionization

In this study, we endowed a poly(vinylidene fluoride) (PVDF) membrane with outstanding antifouling ability by blending the hierarchical amphiphilic brushlike copolymer [poly(hydroxyethyl methacrylate)-b-polydimethylsiloxane-b-poly(hydroxyethyl methacrylate)]-g-poly(N,N-dimethylamino-2-ethyl methacrylate) with different initial monomer/initiator feed ratios and performing a one-step surface zwitterionization of spontaneously segregated poly(N,N-dimethyl aminoethyl methacrylate) segments. Interestingly, nanoscale granular micelles were formed on the surface during zwitterionization because of the migration and self-assembly of the amphiphilic copolymer; this contributed to the membrane hydrophilicity and antifouling ability. During the filtration of the model foulant bovine serum albumin (BSA) aqueous solution, the BSA rejection ratio and flux recovery ratio increased remarkably to 94.8 and 100.0%, respectively. Moreover, the modified membranes also possessed stable and durable antifouling properties after three cycles of BSA filtration. Thus, this study provided a versatile method for constructing a PVDF ultrafiltration membrane that could achieve high permeability and good antifouling properties in efficient wastewater treatment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47637.     

Effect of methyl methacrylate on the properties of transparent flame retardant unsaturated phosphate ester copolymer

The effect of methyl methacrylate (MMA) on the properties of transparent flame retardant unsaturated phosphate ester copolymer (poly[UPE‐co‐MMA]) prepared by bulk polymerization technique was investigated. Fourier transform infrared spectra, gel fraction (G) test, and dynamic mechanical analysis revealed the structure and crosslinking density of poly(UPE‐co‐MMA) copolymers. The thermal degradation and flame retardancy of copolymers were indicated by thermogravimetric analysis, limiting oxygen index (LOI), and microscale combustion calorimeter (MCC) test. Besides, the mechanical properties and transparency were tested with testing machines and solid ultraviolet absorption spectra. As the MMA content increased to 50%, the copolymer contained 50 wt% MMA showed the maximal G (88.93%) and transmittance was up to 91.72%. From the poly(UPE‐co‐MMA) copolymers, the tensile strength increased from 14.62 to 26.95 MPa, assigned to the increase of crosslinking density of copolymers. The char yield of poly(UPE‐co‐MMA) was up to 21.18 wt%, which was a result of decomposition of phosphate groups, producing a phosphorus‐rich layer that increased the thermal stability of the residues. LOI and MCC results confirm that the introduction of MMA can retain the flame retardancy of copolymer remarkably. POLYM. ENG. SCI., 59:2103–2109, 2019. © 2019 Society of Plastics Engineers     

Synthesis and characterization of diblock,triblock, and multiblock copolymers containing poly(3‐hydroxy butyrate) units

A poly[(R,S)‐3‐hydroxybutyrate] macroinitiator (PHB‐MI) was obtained through the condensation reaction of poly[(R,S)‐3‐hydroxybutyrate] (PHB) oligomers containing dihydroxyl end functionalities with 4,4′‐azobis(4‐cyanopentanoyl chloride). The PHB‐MI obtained in this way had hydroxyl groups at two end of the polymer chain and an internal azo group. The synthesis of ABA‐type PHB‐b‐PMMA block copolymers [where A is poly(methyl methacrylate) (PMMA) and B is PHB] via PHB‐MI was accomplished in two steps. First, multiblock active copolymers with azo groups (PMMA‐PHB‐MI) were prepared through the redox free‐radical polymerization of methyl methacrylate (MMA) with a PHB‐MI/Ce(IV) redox system in aqueous nitric acid at 40°C. Second, PMMA‐PHB‐MI was used in the thermal polymerization of MMA at 60°C to obtain PHB‐b‐PMMA. When styrene (S) was used instead of MMA in the second step, ABCBA‐type PMMA‐b‐PHB‐b‐PS multiblock copolymers [where C is polystyrene (PS)] were obtained. In addition, the direct thermal polymerization of the monomers (MMA or S) via PHB‐MI provided AB‐type diblocks copolymers with MMA and BCB‐type triblock copolymers with S. The macroinitiators and block copolymers were characterized with ultraviolet–visible spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, cryoscopic measurements, and thermogravimetric analysis. The increases in the intrinsic viscosity and fractional precipitation confirmed that a block copolymer had been obtained. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1789–1796, 2004     

“Smart” membrane materials: Preparation and characterization of PVDF‐g‐PNIPAAm graft copolymer

In this research, a smart membrane material of graft copolymer of poly(vinylidene fluoride) with poly(N‐isopropylacrylamide) (PVDF‐g‐PNIPAAm) was synthesized by atom transfer radical polymerization (ATRP) using poly(vinylidene fluoride) (PVDF) as a macroinitiator and direct initiation of the secondary fluorinated site PVDF facilitates grafting the N‐isopropylacrylamide comonomer. The copolymers were characterized by Fourier transform infrared (FTIR), ¹H NMR, gel‐permeation chromatography (GPC), and X‐ray photoelectron spectroscopy (XPS). The temperature‐sensitive membrane was prepared from the PVDF‐g‐PNIPAAm graft copolymers by the phase inversion method. The effects of temperature on the flux of pure water of membrane was investigated. The results showed that alkyl fluorides were successfully applied as ATRP initiators in the synthetic condition and the flux of pure water through the PVDF‐g‐PNIPAAm membrane depended on the temperature change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1482–1486, 2007     

Improvement of the physical properties of poly(methyl methacrylate) by copolymerization with pentafluorophenyl methacrylate

Copolymers of methyl methacrylate (MMA) and pentafluorophenyl methacrylate (PFPMA) of various compositions were prepared with a free‐radical initiator. When PFPMA was included in the copolymers, the glass‐transition temperatures increased and showed a positive deviation from the Gordon–Taylor equation. A copolymer containing 20 wt % PFPMA exhibited almost zero orientational birefringence, and the photoelastic birefringence became zero when the copolymer contained 13 wt % PFPMA. When 20 wt % PFPMA was incorporated into the MMA copolymer, its water absorption decreased to 0.4 wt % versus 1.8 wt % for poly(methyl methacrylate) (PMMA) under the same condition. The flammability of the PFPMA/MMA copolymer was reduced in comparison with that of the MMA homopolymer. The refractive indices of the PFPMA/MMA copolymers were very close to that of PMMA, and the transmittances of the copolymers were slightly better than that of PMMA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Poly(vinylidene fluoride) hollow‐fiber membranes containing silver/graphene oxide dope with excellent filtration performance

In this study, an antifouling poly(vinylidene fluoride) (PVDF) hollow‐fiber membrane was fabricated by blending with silver‐loaded graphene oxide via phase inversion through a dry‐jet, wet‐spinning technique. The presence of graphene oxide endowed the blended membrane with a high antifouling ability for organic fouling. The permeation fluxes of the blended membrane was 3.3 and 2.9 times higher than those of a pristine PVDF membrane for filtering feed water containing protein and normal organic matter, respectively. On the other hand, the presence of silver improved the antibiofouling capability of the blended membrane. For the treatment of Escherichia coli suspension, the permeation flux of the blended membranes was 8.2 times as high as that of the pristine PVDF membrane. Additionally, the presented blended membrane improved the hydrophilicity and mechanical strength compared to those of the pristine PVDF membrane, with the water contact angle decreasing from 86.1 to 62.5° and the tensile strength increasing from 1.94 to 2.13 MPa. This study opens an avenue for the fabrication of membranes with high permeabilities and antifouling abilities through the blending of graphene‐based materials for water treatment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44713.