四乙基氢氧化铵改性聚偏氟乙烯接枝聚丙烯酸油水分离膜的制备

使用四乙基氢氧化铵(TEAH)液相本体改性聚偏氟乙烯(PVDF), 以过氧化苯甲酰(BPO)为引发剂, 将丙烯酸(AA)接枝到改性PVDF骨架上, 合成了聚偏氟乙烯接枝聚丙烯酸(PVDF-g-PAA)共聚物, 通过浸没沉淀法制备了PVDF-g-PAA亲水性油水分离膜. 通过傅里叶变换红外光谱(FTIR)、 扫描电子显微镜(SEM)和过滤试验分析了膜的结构和分离性能. 研究了不同接枝条件对PVDF-g-PAA膜接枝率的影响. 同时, 通过膜接枝率与膜表面接触角的关系确定最佳接枝条件. 结果表明, TEAH使PVDF脱去HF产生碳碳双键且PAA接枝到改性的PVDF骨架上, 膜内外孔隙分布均匀; PVDF-g-PAA膜的接触角随着接枝率的提高而降低. 接枝单体AA含量为45%, 接枝温度为85 ℃, 接枝4 h制备的PVDF-g-PAA膜的接枝率为20.1%, 孔隙度为65.3%, 平均孔径为78.0 nm, 接触角为57.5°, 且在60 s内接触角降至14.3°; 纯水通量提高到571.33 L/(m²·h), 截留率和水通量恢复率分别达到94.3%和88.7%, 且通量衰减率仅为9.8%. 与纯PVDF膜相比, PVDF-g-PAA膜的分离性能显著提高.     

Surface modification of PVDF porous membranes

A novel method for the surface modification of PVDF porous membranes was introduced. Styrene-(N-(4-hydroxyphenyl) maleimide) alternating copolymer SHMI-Br was blended with PVDF to fabricate SHMI-Br/PVDF membranes. The C-Br bond on the SHMI-Br/PVDF membrane was served as initial site of ATRP, and P(PEGMA) brush was grafted on the PVDF membrane. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR/FTIR) was used to prove the P(PEGMA) brushes were successfully grafted onto the SHMI-Br/PVDF membrane surface. Introduction of P(PEGMA) brushes on the PVDF membrane surface enhanced the hydrophilicity effectively. When the PEGMA degree of grafting was 16.7 wt%, the initial contact angle of PVDF membrane decreased from 98° to 42°. The anti-fouling ability of PVDF membrane was improved significantly after P(PEGMA) brush was grafted. Taking the PEGMA degree of grafting 16.7 wt% as an example, the flux of protein solution was about 151.21 L/(m² h) when the pH value of the BSA solution was 4.9. As the pH value was increased to 7.4, the flux was changed to 180.06 L/(m² h). However, the protein solution flux of membrane M3 (PEGMA: 0 wt%) was only 73.84 L/(m² h) and 113.52 L/(m² h) at pH 4.9 and 7.4, respectively.     

PVDF Hollow fiber Membrane with High Flux and High Rejection Ratio Prepared by Irradiation Induced Grafting of PAA

Summary: A modified poly (vinylidene fluoride) (PVDF) hollow fiber membrane with higher flux and flux recovery rate was prepared by γ-radiation induced grafting of acrylic acid (AA). The influence of radiation dose and monomer concentration on the grafting degree was investigated. The results indicated that the grafting degree increased in the lower monomer volume fraction until the monomer volume fraction exceeded 20%. The grafting degree increased with the increase of radiation dose. Structural and morphological of the original and grafted membrane surface were characterized by FT-IR, scanning electron microscopy (SEM). The results indicated that acrylic acid was grafted onto PVDF hollow fiber membrane and the grafted membrane was more hydrophilic than original PVDF. There was a slight increase of breaking strength and yield stress with the increase of the grafting degree of AA. The pure water flux increased initially but decreased subsequently with the raise of grafting degree. When the grafting degree was 4.4%, the maximum pure water flux reached 1496.3 L/m² × h, 1.79 times of original membrane. The pure water flux, flux recovery rate and rejection ratio for bovine serum albumin could improve simultaneously in a low grafting degree (<4.4%).     

改性聚偏氟乙烯接枝磺化聚(苯乙烯-co-丙烯酸)膜的研制

以过氧化苯甲酰(BPO)作引发剂,通过溶液接枝聚合法把苯乙烯/丙烯酸同时接枝到原硅酸钠改性的聚偏氟乙烯(PVDF)膜上,磺化后得到聚偏氟乙烯接枝磺化聚(苯乙烯-co-丙烯酸)膜(PVDF-g-P(SSA-co-AA)).研究了苯乙烯和丙烯酸的不同比例对膜的接枝反应及其相对湿度对膜电导率和含水量的影响.用傅立叶变换红外光谱(FTIR)检测原硅酸钠改性的PVDF膜经过接枝和磺化后所发生的结构变化,并用扫描电镜(SEM)观察PVDF膜接枝前后的形貌以及接枝磺化后产物PVDF-g-P(SSA-co-AA)膜的形貌及硫和硅分布.结果表明,原硅酸钠改性的PVDF膜与苯乙烯/丙烯酸同时发生接枝聚合反应,环境的相对湿度在20%～80%范围,对添加10wt%Na4SiO4的PVDF-g-P(SSA-co-AA)膜的电导率的影响基本不变,并达到0.0198S·cm-1.原硅酸钠改性的PVDF膜结构在接枝前后和磺化前后发生变化,确认磺化反应不只是在膜表面,同时渗入膜中进行.     

Thermo- and pH-responsive polypropylene microporous membrane prepared by the photoinduced RAFT-mediated graft copolymerization

Thermo- and pH-responsive polypropylene microporous membrane prepared by photoinduced reversible addition–fragmentation chain transfer (RAFT) graft copolymerization of acrylic acid and N-isopropyl acrylamide by using dibenzyltrithiocarbonate as a RAFT agent. Attenuated total reflection-Fourier transform infrared spectroscopy (ATR/FT-IR), X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FE-SEM) were used to characterize the structural and morphological changes on the membrane surface. Results of ATR/FT-IR and XPS clearly indicated that poly(acrylic acid) (PAAc) and poly(N-isopropyl acrylamide) (PNIPAAm) were successfully grafted onto the membrane surface. The grafting chain length of PAAc on the membrane surface increased with the increase of UV irradiation time, and decreased with the increase of the concentration of chain transfer agent. The PAAc grafted membranes containing macro-chain transfer agents, or the living membrane surfaces were further functionalized via surface-initiated block copolymerization with N-isopropyl acrylamide in the presence of free radical initiator, 2,2′-azobisisobutyronitrile. It was found that PNIPAAm can be grafted onto the PAAc grafted membrane surface. The results demonstrated that polymerization of AAc and NIPAAm by the RAFT method could be accomplished under UV irradiation and the process possessing the living character. The PPMMs with PAAc and PNIPAAm grafting chains exhibited both pH- and temperature-dependent permeability to aqueous media.     

Gas-phase and liquid-phase pre-irradiation grafting of AAc onto LDPE and HDPE films for pervaporation membranes

A study has been made on gas-phase and liquid-phase pre-irradiation grafting of acrylic acid onto LDPE and HDPE films for pervaporation membranes of ethanol-water mixtures. It was found that the degree of grafting, percent volume change of grafted membranes and length of grafting chains depend on the methods of grafting, crystal state of substrate films and diffusion rate of the monomer in the films. The pervaporation characteristics of grafted membranes is influenced directly by the surface hydrophilicity of grafted membranes, temperature of the feed, degree of grafting, crosslinking of grafted chains and alkaline metal ions in the functional groups. The potassium ion exchange membrane of HDPE synthesized by gas-phase grafting has better pervaporation efficiency. At 80 wt% ethanol in the feed, 25°C feed temperature and 70% degree of grafting a grafted membrane has a 0.65 kg/m²h flux and a separation factor of 20.     

Microfiltration membranes prepared from polyethersulfone powder grafted with acrylic acid by simultaneous irradiation and their pH dependence

Polyethersulfone (PES) powder was grafted with acrylic acid (AAc) by simultaneous γ-ray irradiation. The kinetics of the radiation induced graft polymerization was studied and the grafted PES powder was characterized. Then, microfiltration (MF) membranes were prepared from PES-g-PAAc powder with different degrees of grafting (DG) under phase inversion method. The swelling behavior and the mean pore size of MF membranes were measured, and the filtration property was tested. The results showed that the pore size and the flux of MF membranes increased with the increase in DG. And, MF membranes’ properties were dependent on the pH value.     

Electrochemical properties of polyethylene membrane modified with carboxylic acid group

Two cation-exchange membranes modified with the carboxylic acid group for battery separator were prepared by radiation-induced grafting of acrylic acid (AA) and methacrylic acid (MA) onto a polyethylene (PE) film. The surface area, thickness, volume, water uptake, ion-exchange capacity, specific electric resistance, and electrolyte flux were evaluated after PE film was grafted with AA and MA. It was found that KOH diffusion flux of AA-grafted PE membrane and MA-grafted PE membrane increased with an increase in the degree of grafting. AA-grafted PE membrane had a higher diffusion flux than MA-grafted PE membrane. Electrical resistance of two cation-exchange membranes modified with AA and MA decreased rapidly with an increase in the degree of grafting.     

Ion-containing reverse osmosis membranes obtained by radiation grafting method

Cationic membranes obtained by radiation grafting of acqueous acrylic acid onto low density polyethylene films followed by alkaline treatment to confer ionic character in the graft chains, were tested for reverse osmosis desalination of saline water. Selected physical properties of such membranes were investigated. The grafted membranes prossess good mechanical and electrical properties. Water uptake for the alkali-treated membrane was much higher than that of the alkali-untreated one. The effect of operation time, degree of grafting, applied pressure and feed concentration on the water flux and salt rejection for the grafted membranes was investigated. Such cationic membranes showed good durability, thermal and chemical stability, acceptable water flux and salt rejection which may make them acceptable for practical use in reverse osmosis desalination of sea water.     

Plasma-induced graft copolymerization of poly(methacrylic acid) on electrospun poly(vinylidene fluoride) nanofiber membrane

Electrospun nanofibrous membranes (ENM) which have a porous structure have a huge potential for various liquid filtration applications. In this paper, we explore the viability of using plasma-induced graft copolymerization to reduce the pore sizes of ENMs. Poly(vinylidene) fluoride (PVDF) was electrospun to produce a nonwoven membrane, comprised of nanofibers with diameters in the range of 200-600 nm. The surface of the ENM was exposed to argon plasma and subsequently graft-copolymerized with methacrylic acid. The effect of plasma exposure time on grafting was studied for both the ENM and a commercial hydrophobic PVDF (HVHP) membrane. The grafting density was quantitatively measured with toluidine blue-O. The degree of grafting increased steeply with an increase in plasma exposure time for the ENM, attaining a maximum of 180 nmol/mg after 120 s of plasma treatment. However, the increase in the grafting density on the surface of the HVHP membrane was not as drastic, reaching a plateau of 65 nmol/mg after 60 s. The liquid entry permeation of water dropped extensively for both membranes, indicating a change in surface properties. Field emission scanning electron microscopy micrographs revealed an alteration in the surface pore structure for both membranes after grafting. Bubble point measurements of the ENM reduced from 3.6 to 0.9 um after grafting. The pore-size distribution obtained using the capillary flow porometer for the grafted ENM revealed that it had a similar profile to that of a commercial hydrophilic commercial PVDF (HVLP) membrane. More significantly, water filtration studies revealed that the grafted ENM had a better flux throughput than the HVLP membrane. This suggests that ENMs can be successfully engineered through surface modification to achieve smaller pores while retaining their high flux performance.     

光接枝法制备新型pH开关核孔膜

用表面光接枝方法制备了具有pH开关特性的丙烯酸接枝PET核孔膜 .XPS、SEM和AFM的表征结果证明 ,接枝膜具有非对称结构 ,丙烯酸接枝层主要在膜的向光侧表面 ,膜背侧和膜孔内没有变化 .膜孔周围的接枝链在湿态下沉入膜孔 ,接枝层对膜孔顶部产生封盖 .接枝链的体积随环境pH值的不同而变化 ,从而控制接枝膜的滤过特性 .在低接枝程度时 ,接枝链体积变化对膜孔径的影响小 ,不具有pH开关特性 ,但是接枝提高了膜的亲水性 ,通量得到提高 ;接枝程度达到一定程度时 (如 0 5 %) ,膜孔径受接枝链体积变化的影响显著 ,接枝膜表现出pH开关效应 .在pH大于 5时 ,接枝膜通量恒定 ,基本不受溶液pH值影响 .当pH值小于 4时 ,膜通量随溶液酸性的增加迅速升高 .接枝膜的开关幅度JpH =2 JpH =6 8,随接枝程度的增加而增加 .膜的通量和开关幅度可以通过接枝程度来调节     

超亲水聚偏氟乙烯中空纤维膜的制备及性能

采用超声辅助接枝聚合技术,将甲基丙烯酸缩水甘油酯(GMA)接枝到聚偏氟乙烯(PVDF)膜表面,制备PVDF-g-GMA膜;再利用氨基诱导环氧基团发生开环反应,将苏氨酸(Thr)接枝到PVDF-g-GMA膜表面,制备了具有两性离子结构表面的PVDF-g-GMA-Thr膜。通过衰减全反射傅里叶变换红外光谱(ATR-FTIR)、X射线光电子能谱(XPS)、接触角测试仪、场发射扫描电子显微镜(FESEM)和牛血清白蛋白(BSA)过滤实验等系统研究了改性前后PVDF膜表面的化学组成、润湿性能、表面形貌和抗污染性能。研究结果表明,随着PVDF-g-GMA接枝Thr反应时间的增加,PVDF-g-GMA-Thr膜的亲水性能明显提高,接触角从90°降为0°,呈现出超亲水性能。同时PVDF-g-GMA-Thr膜的水通量明显提高,当Thr诱导开环反应时间为12 h时,PVDF-gGMA-Thr膜的水通量高达686 L/(m²·h),与PVDF原膜相比,水通量提高了204. 5%。在BSA的过滤测试中,与PVDF膜相比,PVDF-g-GMA-Thr膜呈现出良好的截留性能和抗污染性能,BS...     

四甲基氢氧化铵改性聚偏氟乙烯一步接枝聚苯乙烯磺酸油水分离膜的制备及性能

利用四甲基氢氧化铵(TMAH)聚偏氟乙烯(PVDF)进行改性,以过氧化苯甲酰(BPO)为引发剂,将苯乙烯磺酸(SSA)接枝到改性的PVDF骨架上,制得聚偏氟乙烯接枝聚苯乙烯磺酸(PSSA-g-PVDF)油水分离膜。 研究了TMAH质量分数对PSSA的接枝率和油水分离膜性能的影响,同时采用傅立叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)和视频光学接触角测量仪测试了膜的结构和表面接触角。 结果表明,TMAH使PVDF脱去部分氟化氢(HF)产生碳碳双键,硫元素均匀地分布在分离膜中。 PSSA的接枝率随着TMAH的质量分数增加而升高,分离膜的水通量随接枝率的升高先增加后降低。 当TMAH质量分数为20%,分离膜的接触角在30 s内降低到37.2°,接枝率和水通量分别为22.1%、643.3 L/(m·h),截留率和水通量恢复率分别达到90.6%和93.7%,衰减率为7.1%。 循环测试显示膜的水通量恢复率和油水通量恢复率均在90%以上。     

In-vitro hemocompatibility evaluation of a thermoplastic polyurethane membrane with surface-immobilized water-soluble chitosan and heparin

The surface of a thermoplastic polyurethane (TPU) membrane was treated with low temperature plasma (LTP) and was then grafted with poly(acrylic acid) (PAA), followed by the grafting of water-soluble chitosan (WSC) and heparin (HEP). The surface was characterized with static contact-angle and X-ray photoelectron spectroscopy (XPS). The results showed that the surface densities of peroxides and PAA reached a maximum when treated with LTP for 90 s. A higher pH of the reacting solution led to higher graft densities of WSC and HEP. After WSC and HEP grafting, the hydrophilicity of the TPU membrane was increased. The adsorption of proteins on HEP-grafted TPU membranes was effectively curtailed. In addition, HEP grafting also reduced platelet adhesion, elevated thrombin inactivation, and prolonged the blood coagulation time. According to the L929 fibroblast cell growth inhibition index, the HEP-grafted TPU membranes exhibited non-cytotoxicity. Overall results demonstrated that the HEP immobilization could not only improve the hydrophilicity but also the hemocompatibility of the TPU membrane, while maintaining the ascendant biocompatibility.     

Hydrophilic modification of polyethersulfone membranes by low temperature plasma-induced graft polymerization

A complete and permanent hydrophilic modification of polyethersulfone (PES) membranes is achieved by argon plasma treatment followed by polyacrylic acid (PAA) grafting in vapor phase. Both Ar plasma treatment alone and post-PAA grafting rendered a complete hydrophilicity to the PES membranes. The hydrophilicity of the membranes treated with only the Ar plasmas is not, however, permanent. In contrast, the PES membranes treated with Ar plasma and subsequent acrylic acid (AA) grafting are permanently hydrophilic. High energy resolution X-ray photoelectron spectroscopy (XPS) confirmed the grafting of PAA to all surfaces of the membrane. Furthermore, water bubble point measurements remain unaffected. The pore sizes of the grafted membranes at higher grafting yield are slightly decreased. The modified membranes are less susceptible to protein fouling than the unmodified membranes and the pure water flux for the modified membranes was tremendously increased by plasma treatment. Furthermore, the modified membranes are easier to clean and required little caustic to recover permeation flux.     

Studies on Permeation of Bovine Serum Albumin (BSA) Through Photo-Modified Functionalized Asymmetric Membrane

UV-initiated photo-modification by hydrophilic functional moieties (viz. acrylic acid, acrylamide) is performed on the photo-responsive Polyether sulfone (PES) membrane. Characterization of the modified membranes has been done by porometry, Fourier Transform-IR (FTIR), contact angle, thermogravimetry, X-ray diffraction and gel permeation chromatography. The grafting of acrylamide is higher compared to acrylic acid, as is evidenced from weight increase, as well as porometry studies. The separation abilities of Bovine Serum Albumin (BSA) have been experimented through all the membranes and results show that modified membranes possess a better separation ability compared to virgin polyether sulfone. The separation order follows the trend: PES-g-(AM) > PES-g-(AA) > PES. pH dependence conformational changes of BSA macromolecule influence the separation. The increase in pH results in the decreasing trend in separation. The water flux recovery ratio (FRR) for the virgin PES membrane is minimum compared to other two grafted membranes.     

Grafting of regenerated cellulose membrane by surface‐initiated atom transfer radical polymerization and its pH‐resposive behavior

Regenerated cellulose (RC) membranes which have pH modulated permeability have been prepared by anchoring the hydroxyl groups on the membrane surface with 2‐bromoisobutyryl bromide, followed by grafting with acrylic acid (AA) using atom transfer radical polymerization (ATRP). The obtained membranes were analyzed by X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared attenuated total reflection spectrometer (ATR‐FTIR), scanning electron microscopy (SEM), TGA and the results showed that AA had been grafted onto the membrane surfaces successfully. Then the pH modulated permeability properties were tested by water flux measurement. All results show that the pH modulated permeability properties of a RC membrane can be obtained by surface‐initiated ATRP. Copyright © 2010 John Wiley & Sons, Ltd.     

阴离子型接枝微粒PDAC/PSA的制备及对谷氨酸的吸附性能初探

采用自由基聚合法在溶液聚合体系中将功能单体丙烯酰氧乙基三甲基氯化铵(DAC)接枝于聚苯乙烯伯胺微球(PSA)表面,制备了接枝微粒PDAC/PSA,考察了主要因素对接枝聚合的影响,并初步探究了其对L-谷氨酸的吸附特性。结果表明,在反应温度25℃、单体质量分数为6%、引发剂占单体质量的1.2%的条件下,可制得接枝度为431mg/g的接枝微粒,其对L-谷氨酸的吸附量达140mg/g。     

Exploring the heteroatom effect on polyelectrolyte multilayer assembly: the neglected polyoniums

Different positive polyelectrolytes having the same charge density, molecular weight, and molecular weight distribution were employed for polyelectrolyte multilayer (PEMU) assembly. The polycations differed only in the heteroatom on which the positive charge resided: poly(vinyl benzyl trimethyl ammonium) chloride, poly(vinyl benzyl trimethyl phosphonium) chloride, and poly(vinyl benzyl dimethyl sulfonium) chloride. While the ammonium repeat unit has been employed on numerous occasions for PEMU assembly, the phosphonium and sulfonium units are relatively neglected. The polyanions, poly(styrene sulfonate), PSS, or poly(acrylic acid), PAA, were typical pH-independent or pH-dependent polymers, respectively. All three polyoniums were quite similar in showing linear layer-by-layer buildup with PSS and exponential growth with PAA, under the conditions employed. Hydration and wettability were also similar between polyoniums.     

Radiation-induced grafting of vinyl benzyl trimethyl ammonium chloride onto nylon-6 fabric

Vinyl benzyl trimethyl ammonium chloride (VBTAC) was grafted onto nylon-6 fabric in the presence of 2- hydroxy ethyl methacrylate (HEMA) by the simultaneous irradiation method in the presence of air with ⁶⁰Co γ-radiations. An increase in grafting was observed with increasing dose. Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) confirmed the grafting of VBTAC. Morphological changes after grafting were confirmed by scanning electron microscopy (SEM). The X-ray diffraction (XRD) pattern showed changes in crystallinity on grafting. The initial studies carried out with grafted nylon fabric showed behavioural changes in the burning properties.