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1.
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   

2.
Herein we report the surface modification of poly(vinylidene fluoride) (PVDF) microporous membrane via thermally induced graft copolymerization with maleic anhydride (Man)/styrene (St) in supercritical carbon dioxide (SC CO2). SC CO2, as a solvent and carrier agent, could accelerate mass transfer of monomers inside polymer matrixes and then facilitate the graft copolymerization on the surface of the membrane and within membrane pores, which were confirmed by FT-IR/ATR and XPS spectra together with SEM photographs. The effects of SC CO2 pressure and temperature and the monomer concentration on the graft copolymerization were investigated. The modified PVDF membranes containing from 0 to 7 wt.% of grafted St–Man copolymer (SMA) were prepared and analysed in terms of surface microstructure, composition, hydrophilicity and biocompatibility. Solid-state 13C CP/MAS NMR and DSC indicated that the grafted SMA on the PVDF membrane had the alternative sequence structure and formed the different phases in the modified membrane, where the grafted SMA was associated with Tg of 122.8 °C and the PVDF matrix with Tm of 161.2 °C. The static contact angle measurements revealed that remarkable and permanent hydrophilicity was obtained upon grafting SMA. The experiments of BSA adsorption and cell growth also showed that the surface of SMA-based PVDF membrane has excellent biocompatibility.  相似文献   

3.
An epoxy‐group‐containing monomer, glycidyl methacrylate (GMA), was grafted onto poly(vinylidene fluoride) powder via preirradiation‐induced emulsion graft polymerization. The existence of graft chains was proven by chemical structure characterization with Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy analysis. The degree of grafting was calculated by means of fluorine content analysis. A kinetic study indicated that, with the emulsion graft polymerization system, the GMA conversion rate was high, exceeding 80%. The variation in the molecular weight of the grafted polymer was measured by gel permeation chromatography, and its crystallinity was investigated with differential scanning calorimetry. The epoxy groups in graft chains were found to be suitable for further chemical modification. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

4.
Acrylic acid (AA)‐grafted poly(vinylidene fluoride) (PVDF) hollow fiber membrane was obtained by ultrasonic wave‐assisted graft polymerization. The grafting density (GD) of AA on the PVDF membrane surface could be controlled by altering the reaction conditions, such as ultrasonic time, ultrasonic power, monomer concentration and initiator concentration. The attenuated total reflectant Fourier transform infrared spectra (FITR‐ATR) and X‐ray photoelectron spectroscopy were used to investigate the chemical composition of modified membranes. The changes of surface morphology and roughness were characterized by field emission scanning electron microscope and atomic force microscopy. Results show that AA was successfully grafted on the membrane surface. With increasing GD, the static water contact angle was decreased from 95.7 to 41.4°, indicating that hydrophilicity of modified membrane was significantly enhanced. Pure water flux before and after bovine serum albumin (BSA) contamination was measured. The modified membrane with the GD of 0.76 mg/cm2 has the highest water flux as high as 350 L/m2·h. When compared with the pristine membrane(M0), the flux recovered ratio was improved from 52.75 to 96.29% at the GD 2.76 mg/cm2 (M3), which suggested the protein fouling could be effectively prevented for the modified membrane. POLYM. ENG. SCI., 2018. © 2018 Society of Plastics Engineers POLYM. ENG. SCI., 59:E446–E454, 2019. © 2018 Society of Plastics Engineers  相似文献   

5.
Abstract

When partially hydrolysed poly(vinyl acetate) (PVAc) is used as a suspending agent in the suspension polymerisation of vinyl chloride monomer, it has significant effects on the morphology of the resulting poly(vinyl chloride) (PVC) particles. At the initial step of polymerisation, PVC molecules are grafted onto the molecules of the suspending agent forming a PVC–PVAc membrane. The properties of this membrane depend on the type of suspending agent, the polymerisation temperature, the mixing efficiency, and other factors. The morphology of the growing PVC particles and the properties of the PVC resin obtained depend in turn on the characteristics of the membrane. A model has been developed relating to the connection between the polymerisation conditions and the characteristics of the suspending agent on one hand, and on the PVC properties on the other hand. The model is based on an analysis of the characteristics of the PVC–PVAc membrane and their effect on PVC properties.  相似文献   

6.
Polydimethylsiloxane (PDMS) membranes were improved by graft polymerization of fluoroalkyl methacrylates (FALMA) and alkyl methacrylates (AMA) by electron beam, and the effect of the solubility and diffusibility of a monomer on graft polymerization and the pervaporation through grafted membrane were investigated. The difference of the grafted amount was small for the monomers with various solubility parameters and log Pow which is the logarithm of the octanol–water partition coefficient. Compared to each other in the same group of FALMA or AMA, the sorpted and grafted amount for a monomer that has low molecular volume was high, and the sorpted and grafted amount for a monomer that has high molecular volume was low. FALMA‐grafted PDMS membranes showed high separation performance compared to PDMS membranes. Among them, 2,2,3,3,3‐pentafluoropropyl methacrylate grafted PDMS membrane, which had a high grafted amount, and F/Si calculated by the grafted amount had high selectivity for trichloroethylene (TCE). The FALMA‐grafted PDMS membranes that had the high TCE concentrations in the sorbed solution exhibited high permselectivity for TCE. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 203–213, 2001  相似文献   

7.
Abstract

Ground tyre rubber (GTR) powder has been treated using a novel surface grafting process allowing the incorporation of various chemical functional groups onto the polymer surface. The GTR was functionalised with methacrylic acid by photoinitiated polymerisation. The process comprises two steps: UV irradiation of GTR in the presence of air, followed by grafting of methacrylic acid (MA) onto the GTR surface. The presence of reactive carboxy groups, which was confirmed by titration, provides the possibility of covalent linkage with reactive groups when the powder is blended with a suitable matrix polymer.

The effectiveness of the process was assessed by examining the tensile and Charpy impact properties of polyamide and epoxy compounds containing ungrafted and grafted GTR. A significant improvement in the tensile properties of polyamide was observed on adding methacrylic acid grafted GTR. The grafted GTR also worked as an impact modifier in epoxy compounds. The best results to date were achieved when methacrylic acid grafted GTR was added to polyurethane formulations.  相似文献   

8.
含氟磺酸型质子交换膜是一类具有高热稳定性、化学稳定性及良好力学性能的离子交换膜,具有极其广阔的应用前景。采用60Co辐照接枝技术,在聚偏氟乙烯(PVDF)基膜上产生自由基聚合位点,进而接枝对苯乙烯磺酰氯单体,经过一定条件酸碱处理得到一种新型偏氟磺酸型质子交换膜。并对其进行红外分析,结果显示PVDF膜上成功接枝上了对苯乙烯磺酰氯单体;定量研究了在相同辐照总剂量、不同剂量率条件下,所得质子交换膜的质子传导率、吸水率及离子交换容量与接枝率的关系,结果表明:当剂量率为40 Gy·min-1时,所得质子交换膜接枝率为52.7%,吸水率为36.85%,80℃时质子传导率达到136 mS·cm-1,离子交换容量为1.274 mmol·g-1。  相似文献   

9.
A novel air‐drying membrane was developed and investigated as an alternative for planar and tube‐shaped drying membranes composed of Nafion®. The new membrane is based on poly(vinylidene fluoride) (PVDF) polymer types grafted with polystyrene sulfonic acid. Modification of the PVDF membrane by chemical grafting was initiated via γ‐irradiation of pre‐made film and tube‐shaped samples. The grafting was conducted while the pre‐irradiated PVDF samples were immersed in styrene monomer solution. Three unique characterization methods were introduced to evaluate the ion exchange and barrier functions of the membrane. This investigation focuses on optimizing the degree of grafting yield, and subsequently the control of the membrane's overall functional performances, through (1) monitoring the PVDF's degree of crystallinity and (2) monitoring the styrene monomer solution temperature, respectively. Different levels of crystallinity were achieved by melt blending the PVDF‐copolymer with PVDF‐homopolymer, in various mixing ratios. Another variable examined in this investigation was the introduction of an ionic complex on the sulfonic acid end groups, and its effect on the membrane functional performance was studied. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

10.
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   

11.
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  相似文献   

12.
A reverse atom transfer radical polymerization (RATRP) with benzoyl peroxide (BPO)/CuCl/2,2-bipyridine (Bpy) was applied onto grafting of poly(methyl methacrylate) (PMMA) and poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA) from poly(vinylidene fluoride) (PVDF) microfiltration (MF) membrane surfaces, including the pore surfaces. The introduction of peroxide and hydroperoxide groups onto the PVDF membranes was achieved by ultraviolet (UV) irradiation in nitrogen, followed by air exposure. RATRP from UV pretreated hydrophobic PVDF membranes was then performed for attaching well-defined homopolymer. The chemical composition of the modified PVDF membrane surfaces was characterized by attenuated total reflectance (ATR) FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS). The surface and cross-section morphology of membranes were studied by scanning electron microscopy (SEM). The pore sizes of the pristine PVDF and the PMMA grafted PVDF membranes were measured using micro-image analysis and process software. With increase of graft concentration, the pore size of the modified membranes decreased and became uniform. Kinetic studies of homogeneous (in toluene solution) system revealed a linear increase in molecular weight with the reaction time and narrow molecular weight distribution, indicating that the chain growth from the membrane surface was a “controlled” or “living” grafting process. The introduction of the well-defined PMMA on the PVDF membrane gave rise to hydrophilicity. Protein adsorption and protein solution permeation experiments revealed that the UV pretreated hydrophobic PVDF membrane subjected to surface-initiated RATRP of methyl methacrylate (MMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) exhibited good antifouling property.  相似文献   

13.
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   

14.
A versatile method is described to synthesize a new family of solvent‐responsive membranes whose response states can be not only tunable but also fixable via ultraviolet (UV) irradiation induced crosslinking. The atom transfer radical polymerization (ATRP) initiator 2‐bromoisobutyryl bromide was first immobilized on the poly(ethylene terephthalate) (PET) track‐etched membrane followed by room‐temperature ATRP grafting of poly(2‐hydroxyethyl methacrylate) (PHEMA) and poly(2‐hydroxyethyl methacrylate‐co‐2‐(dimethylamino)ethyl methacrylate) (P(HEMA‐co‐DMAEMA)) respectively. The hydroxyl groups of PHEMA were further reacted with cinnamoyl chloride (a photosensitive monomer) to obtain photo‐crosslinkable PET‐g‐PHEMA/CA membrane and PET‐g‐P(HEMA/CA‐co‐DMAEMA) membrane. The length of grafted polymer chains was controllable by varying the polymerization time. X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy in attenuated total reflection and thermogravimetric analysis were employed to characterize the resulting membranes. The various membrane surface morphologies resulting from different states of the grafted chains in water and dimethylformamide were characterized by scanning electron microscopy. It was demonstrated that the grafted P(HEMA/CA‐co‐DMAEMA) chains had more pronounced solvent responsivity than the grafted PHEMA/CA chains. The surface morphologies of the grafted membranes could be adjusted using different solvents and fixed by UV irradiation crosslinking. © 2014 Society of Chemical Industry  相似文献   

15.
Acrylic acid was grafted onto the surface of commercial poly(vinylidene fluoride) (PVDF) membrane using plasma polymerization techniques. Graft reaction was confirmed by X-ray photoelectron spectroscopy (XPS) spectra and attenuated total reflectance Fourier transform infrared spectra. Grafting rate was dependent on plasma exposure time. For argon plasma at 30 W, grafting rate decreased after maximum rate was observed at 30 s exposure. PVDF membrane with 30 s plasma exposure and subsequently grafted with acrylic acid (AA-3) showed the greatest O1s/F1s area ratio in XPS spectra. Thus its graft density and degree of polymerization were the largest among the graft membranes. Permeation of riboflavin through all poly(acrylic acid)-g-PVDF membranes showed a decrease in permeability of riboflavin in pH 4–5. © 1996 John Wiley & Sons, Inc.  相似文献   

16.
多孔膜基材对等离子体接枝膜微观结构的影响   总被引:1,自引:0,他引:1  
采用等离子体诱导接枝聚合法,在有机聚偏氟乙烯(PVDF)膜、尼龙(N6)膜和无机多孔阳极氧化铝(PAA)膜上接枝甲基丙烯酸(MAA),系统地研究了多孔膜基材及接枝工艺条件对接枝开关膜微观结构的影响。结果发现,对于PVDF基材膜,单体溶液脱气次数越多接枝率越大。对于不同类别的多孔膜基材,采用相同工艺条件接枝时,N6膜的接枝率高于PVDF膜,PAA膜接枝率最低。在接枝率相近的时候,接枝层在PVDF膜整个断面孔内和表面均存在,而N6膜则主要集中在表层。在PAA膜上接枝时发现,等离子体照射功率的强弱对基材膜的影响很大,当功率超过50W时,PAA膜表层就会被刻蚀而导致膜的质量减轻。  相似文献   

17.
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   

18.
Terpolymer poly(α‐methylstyrene‐co‐glycidyl methacrylate‐co‐4‐acryloyl tetraphenylethylene) (PAGT) was synthesized by radical copolymerization using α‐methylstyrene, glycidyl methacrylate, and trace fluorescent monomer 4‐acryloyl tetraphenylethylene. Thermal decomposition of α‐methylstyrene constitutional units in copolymer chains is known to produce macromolecular radicals at temperatures exceeding 90 °C, which may be melt‐grafted to polypropylene (PP) without other initiators by means of extrusion. In this study, the PP‐g‐PAGT microporous material was prepared by casting and stretching. The structure and properties of the PAGT were characterized by Fourier transform infrared spectroscopy, 1H‐nuclear magnetic resonance, and thermogravimetic analysis. The grafting degree and rheological properties proved that the PAGT chains were successfully grafted onto the PP. The uniformity of the PAGT in the PP‐g‐PAGT was observed using a spectrofluorophotometer. The polarity of the cast membrane was characterized by the water contact angle. The results showed that the PAGT evenly grafted onto the PP, and the polarity and hydrophilicity of the cast membranes were improved. The microporous structure of the separator was observed via scanning electron microscopy. Testing of the performance of the lithium battery showed that the impedance decreased and the ionic conductivity increased with the introduction of PAGT onto PP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46020.  相似文献   

19.
Rubber-modified polystyrene (PS) owes its impact resistance to a morphology of salami domains: in the PS matrix, polybutadiene (PB) domains are dispersed that, in turn, are strongly filled with PS subdomains. This unique structure is created in situ as styrene is polymerized in PB/styrene solutions. The salami domains are built up by graft copolymer chains PB-g-PS. It was suggested previously that these domains assume their characteristic architecture because strongly grafted chains stabilize them on the outside while weakly grafted chains provide their internal substructure. This model is extended in this paper that deals with the polymerisation of methylmethacrylate (MMA) in EP/MMA solutions of a poly(ethylene-co-propylene) copolymer (EP). Intermediate and final products were characterized by 1H NMR spectroscopy, transmission electron microscopy, two-dimensional chromatography and statistical calculations, with a focus on the pivotal stage of phase inversion during the polymerisation where the salami domains are born.  相似文献   

20.
A novel cyclodextrin (CD) derivative, m‐xylenediamine‐β‐cyclodextrin (m‐XDA‐β‐CD), has been synthesized and used to graft β‐CD on membrane surface for the pervaporation separation of butanol isomers. The reaction mechanisms for the m‐XDA‐β‐CD synthesis and the membrane surface grafting are confirmed by FTIR and TGA. The as‐fabricated novel CD‐grafted polyamide‐imide (PAI) membranes show homogeneous morphology and significant improved separation performance as compared to the unmodified PAI membranes and PAI/CD mixed matrix membranes made of physical blends. The effects of chemical modification time and dope concentration on the asymmetric membrane have been studied. The optimal separation performance can be found with the CD‐grafted PAI membrane cast from a 22 wt % dope concentration, which exhibits a total butanol flux of 15 g/m2/h and a separation factor of 2.03. This newly developed membrane with surface‐immobilized CD may open new perspective for the development of next‐generation high‐performance pervaporation membranes for liquid separations. © 2010 American Institute of Chemical Engineers AIChE J, 2011  相似文献   

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