紫外接枝聚合聚乙二醇甲基丙烯酸甲酯制备抗污染聚砜超滤膜

以二苯甲酮(BP)为紫外引发剂,将聚乙二醇甲基丙烯酸甲酯(PEGMA)接枝在聚砜超滤膜表面以提高膜的抗污染性能.在二苯甲酮存在的条件下,波长较长(λ300nm)的紫外光(UV)辐射下发生提氢反应,可以有效防止聚砜分子主链的剪切,保持改性膜的分离性能.考察了PEGMA浓度、UV辐射时间和BP浓度对改性超滤膜接枝度、亲水性和抗污染性能的影响.用表面全反射红外光谱(ATR/FTIR)表征改性前后膜表面化学组成的变化.表面改性膜的纯水通量略有降低而牛血清白蛋白(BSA)截留率有所提高.随着接枝度的提高,PEGMA接枝改性膜的抗污染性能增加.     

基于多巴胺自聚合及肝素固定改善钛的血液相容性

利用多巴胺自聚合及肝素固定的方法对纯钛进行表面修饰, 以改善其血液相容性. 采用水接触角测量、 X射线光电子能谱(XPS)和甲苯胺蓝法(TBO)等方法对所修饰的材料进行了表征. 采用溶血实验检测了材料的溶血性能, 并结合活化部分凝血活酶时间(APTT)测试和血小板黏附实验对所修饰材料的血液相容性进行了评价. 结果表明, 多巴胺能够在钛表面实现自聚合, 肝素可以共价接枝在聚多巴胺层上, 经肝素修饰后的材料的表面亲水性显著提高, 而且具有较低的溶血率, APTT时间显著延长, 血小板的黏附数量和被激活程度也显著降低. 因此, 纯钛经多巴胺自聚合以及肝素接枝修饰后的血液相容性得到了显著改善, 有望成为具有抗凝血功能的新型心血管植入材料.     

一种新型的亲水性聚丙烯酸-陶瓷复合膜

通过化学气相沉积和丙烯酸(AA)在大孔陶瓷膜表面的接枝共聚制备了一种新型的亲水性PAA-陶瓷复合膜. 用FT-IR、SEM、EDS、表面接触角等方法对复合膜接枝层的化学组成、表面形态、元素分布和亲水性进行了表征. 通过系统研究气相沉积和接枝反应的主要条件对膜的渗透汽化性能的影响, 发现当TEOS用量为5 mL, 汽化温度为175 ℃时进行气相沉积, 然后在丙烯酸浓度为7.5%的溶液中进行接枝聚合, 制得的复合膜对醇水混合物显示了优良的分离性能.     

一种新型亲水性有机-无机渗透蒸发分离膜——聚丙烯酰胺复合膜的制备

将纳米二氧化硅微孔膜用γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷处理,再通过自由基聚合接枝丙烯酰胺单体制备出一种新型的亲水性有机-无机复合膜.用TGA测定了单体在二氧化硅粉末上的接枝率;用SEM和AFM观察了接枝反应前后膜表面形态的变化;系统研究了接枝单体浓度对膜的渗透蒸发分离性能的影响.结果表明,这种膜用于醇水和丙烯酸水溶液的分离有很好的选择性和渗透性;在丙烯酰胺质量分数为3%的溶液中接枝的膜有较好的分离性;溶液浓度和操作温度对膜渗透性的影响非常特殊.     

聚砜共价键合磷铵两性离子的结构修饰及其血液相容性的研究

利用形成碳-氧键将磷铵两性离子(1)共价键合到聚砜(PSF)材料表面,改善其抗凝血性能.首先对聚砜(PSF)进行氯甲基化反应,生成苄氯结构,然后通过自合成两性离子化合物1中的—OH与氯甲基化聚砜的—CH2Cl反应形成醚键,将两性离子结构接枝在PSF上.用ATR-FTIR、EA和1H-NMR表征了产物结构,并通过水接触角、溶血实验和血小板黏附实验对结构修饰前后材料的亲水性和抗凝血性能进行了比较.改性PSF材料的表面亲水性提高,几种改性PSF材料的溶血率均低于5%,PSF-18.1%1材料的表面几乎没有血小板黏附.结果表明,磷铵两性离子结构修饰的聚砜材料可以显著提高其血液相容性,在血液相容性材料等领域具有潜在的应用价值.     

在聚砜膜表面接枝聚甲基丙烯酸及接枝膜对生物碱化合物的吸附特性

首先将聚砜(PSF)氯甲基化,制得氯甲基化聚砜(CMPSF),CMPSF流延成膜后与乙二胺(EDA)反应,制得表面键合有EDA的氨基化膜(AMPSF)。在此基础上,在水溶液体系中构建氨基-过硫酸盐表面引发体系,使甲基丙烯酸(MAA)发生接枝聚合,制得了功能接枝膜PSF-gPMAA。考察了影响膜接枝过程的主要因素,优化了接枝聚合条件。采用傅里叶红外光谱(FTIR)、光学显微镜(OM)及称重法对接枝膜PSF-g-PMAA进行了表征。最后研究了功能接枝膜对氧化苦参碱和金雀花碱两种生物碱化合物的吸附特性。结果表明,采用氨基-过硫酸盐表面引发体系,可以顺利地实施MAA在PSF膜表面的接枝聚合,接枝度随氨基化膜AMPSF表面氨基键合量的增大而增大,接枝聚合适宜的温度为50℃,溶液中适宜的过硫酸盐用量为单体质量的1.0%。在适宜的条件下可制得PMAA接枝度为4.62mg/cm2的接枝膜。凭借强静电相互作用和氢键作用的协同作用,功能接枝膜PSF-g-PMAA对生物碱化合物可产生强烈的吸附作用,在中性溶液中,对氧化苦参碱和金雀花碱的吸附容量分别可达277μg/cm2和331μg/cm2。     

两亲性共聚物的分子设计与合成及其共混膜性能

从分子结构设计出发,采用自由基聚合、醚化、酯化、原子转移自由基聚合(ATRP)、可逆加成断裂链转移自由基聚合(RAFT)等方法合成了一系列具有不同分子结构(包括接枝、嵌段、交替、超支化等)和链形态(包括直链、梳状、哑铃状、链球状等)的两亲性共聚物,并对这些聚合物进行了谱学表征和性能测试.将这些两亲性共聚物与聚合物膜材料(包括聚偏氟乙烯、聚氯乙烯、聚砜、聚醚砜、聚醚砜酮等)进行溶液共混,通过相转化法制备共混膜,在成膜热力学和动力学分析的基础上,对共混膜的结构和性能进行调控.研究发现,两亲性共聚物在成膜过程中自发地向膜表面迁移富集,并进行自组装,在膜表面形成两亲性共聚物包膜,显著改善了聚合物多孔膜的亲水性和抗污染性能.此外,两亲性共聚物中的功能基团还可赋予共混膜某些功能特性,如生物相容性、环境响应性(pH、温度敏感性)、酶活性等.     

静电纺丝复合反渗透膜的改性制备与脱盐性能

利用静电纺丝技术在无纺布上制备PET纳米纤维膜, 并用交联壳聚糖对其进行改性得到壳聚糖改性纳米纤维复合膜. 以间苯二胺(MPD)和均苯三甲酰氯(TMC)为单体, 采用界面聚合法在壳聚糖改性纳米纤维复合膜的表面制备聚酰胺分离层, 得到新型静电纺丝纳米纤维基复合反渗透膜. 新型复合反渗透膜具有典型的聚酰胺复合反渗透膜的表面脊-谷结构. 从膜的表面形貌、 亲水性、 分离性能等3个方面对水相MPD溶液中阴离子表面活性剂十二烷基苯磺酸钠(SDBS)的含量对膜结构和性能的影响进行了系统研究. 结果表明, SDBS的含量对膜形态结构的均匀性和亲水性有一定影响, 且随着SDBS含量的增加, 膜的脱盐率先增大后减小, 而通量小幅度上升后, 先减小后增大, 呈现规律性变化.     

紫外辐照接枝制备亲水性荷正电纳滤膜

通过在酚酞基聚芳醚酮超滤膜表面紫外辐照接枝亲水性单体二烯丙基二甲基氯化铵(DADMAC)制备了一种表面荷正电的纳滤膜. ATR-FTIR和表面水接触角的研究结果表明膜表面的接枝率和亲水性随着辐照时间和单体在接枝溶液中的浓度的增加而增加. 荷正电纳滤膜对盐溶液有很好的截留, 对盐溶液中的高价阳离子和低价阳离子的截留率分别为95%和65%. 但当溶液中存在高价负离子时, 膜的截留性能会明显下降. 表明静电效应在荷电纳滤膜的分离过程中起了重要的作用.     

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.     

Hydrophilic nanofiltration membranes with self-polymerized and strongly-adhered polydopamine as separating layer

Inspired by the self-polymerization and strong adhesion characteristics of dopamine in aqueous conditions,a novel hydrophilic nanofiltration（NF） membrane was fabricated by simply dipping polysulfone（PSf） ultrafiltration（UF） substrate in dopamine solution.The changes in surface chemical composition and morphology of membranes were determined by Fourier transform infrared spectroscopy（FTIR-ATR）,X-ray photoelectron spectroscopy（XPS）,scanning electron microscopy（SEM） and atomic force microscopy（AFM）.The experimental results indicated that the self-polymerized dopamine formed an ultrathin and defect-free barrier layer on the PSf UF membrane.The surface hydrophilicity of membranes was evaluated through water contact angle measurements.It was found that membrane hydrophilicity was significantly improved after coating a polydopamine（pDA） layer,especially after double coating.The dyes filtration experiments showed that the double-coated membranes were able to reject completely the dyes of brilliant blue,congo red and methyl orange with a pure water flux of 83.7 L/（m²·h） under 0.6 MPa.The zeta potential determination revealed the positively-charged characteristics of PSf/pDA composite membrane in NF process.The salt rejection of the membranes was characterized by 0.01 mmol/L of salts filtration experiment.It was demonstrated that the salts rejections followed the sequence:NaCl2SO₄422,and the rejection to CaCl₂ reached 68.7%.Moreover,the composite NF membranes showed a good stability in water-phase filtration process.     

Mussel‐inspired method to decorate commercial nanofiltration membrane for heavy metal ions removal

Nanofiltration (NF) membranes have been widely used for the treatment of electroplating, aerospace, textile, pharmaceutical, and other chemical industries. In this work, halloysite nanotubes (HNTs) were directly anchored on the surface of commercial nanofiltration (NF) membrane by dopamine modification following advantageous bio‐inspired methods. SEM and AFM images were used to characterize the HNTs decorated membrane surface in terms of surface morphology and roughness. Water contact angle (WCA) was employed in evidencing the incorporation of HNTs and dopamine in terms of hydrophilicity or hydrophobicity. Augmentation of HNTs was found to obviously enhance the hydrophilicity and surface roughness resulting in improved water permeability of membrane. More importantly, the rejection ratios of membrane also increased during the removal of heavy metal ions from wastewater. The permeability and Cu²⁺ rejection ratio of modified NF membrane were as high as 13.9 L·m^?2·h^?1·bar^?1 and 74.3%, respectively. Incorporation of HNTs was also found to enhance the anti‐fouling property and stability of membrane as evident from long‐term performance tests. The relative concentration of HNTs and dopamine on membrane surface was optimized by investigating the trade‐off between water permeability and rejection ratio.     

Preparation of composite hollow fiber membranes: co-extrusion of hydrophilic coatings onto porous hydrophobic support structures

Coating a layer onto a support membrane can serve as a means of surface functionalization of membranes. Frequently, this procedure is a two-step process. In this paper, we describe a concept of membrane preparation in which a coating layer forms in situ onto a support membrane in one step by a co-extrusion process. Our aim is to apply a thin ion exchange layer (sulfonated polyethersulfone, SPES) onto a polysulfone support. The mechanical stability and adhesion of the ion-exchange material to the hydrophobic support membrane (polysulfone) has been studied by a systematic approach of initial proof-of-principle experiments, followed by single layer and double-layer flat sheet casting. Critical parameters quantified by the latter experiments are translated into the co-extrusion spinning process. The composite hollow fiber membrane has low flux as a supported liquid membrane for the copper removal due to the low ion exchange capacity of the SPES. The coating layer of the composite membrane is porous as indicated by gas pair selectivity close to unity. However, our new composite membrane has good nanofiltration properties: it passes mono and bivalent inorganic salts but rejects larger charged organic molecules. The experimental work demonstrates that co-extrusion can be a viable process to continuously prepare surface tailored hollow fiber membranes in a one-step process, even if the support and coating material differ significantly in hydrophilicity.     

Preparation of an efficient nanofiltration membrane based on blending of polysulfone and polysulfone-g-butylacrylate prepared by ATRP

Polysulfone is one of the most common used polymers for preparation of nanofiltration membranes. These membranes are highly susceptible to fouling problems because of their surface hydrophobic nature. In this paper a new approach for modification of polysulfone to overcome the fouling problems was introduced. The modification was carried out via blending of polysulfone with a modified grafted polysulfone using atom transfer radical polymerization (ATRP) method. The modified grafted polysulfone was synthesized via ATRP grafting of n-butylacrylate from chloromethylated polysulfone. The graft copolymers were characterized by FT-IR, NMR, DSG and TGA techniques. Furthermore, surface morphology and performance of the corresponding membrane were studied in detail using SEM and pure water flux and salt rejection experiments, respectively. The results indicated that the prepared modified polysulfone membranes have high surface hydrophilicity and therefore better fouling resistance and very good water permeability.     

Hydrophilic Modification of Microporous Polysulfone Membrane via Surface‐Initiated Atom Transfer Radical Polymerization and Hydrolysis of Poly(glycidylmethacrylate)

Poly(glycidylmethacrylate) (PGMA) brushes were grafted from chloromethylated polysulfone (CMPSF) membrane surface by surface‐initiated atom transfer radical polymerization (SI‐ATRP), and the grafting was followed by hydrolysis of epoxy groups in the grafting chains to improve the membrane's hydrophilic property. Fourier transform infrared spectroscopy (FT‐IR) and X‐ray photoelectron spectroscopy (XPS) measurements confirmed the successful grafting and hydrolysis of PGMA. The grafting degree of the monomer, measured by periodic acid titration and gravimetric analysis, increased linearly with the polymerization time, while the static water contact angle of the membrane grafted with PGMA or hydrolyzed PGMA linearly decreased. In comparison with the PGMA‐grafted membranes, the hydrolyzed PGMA‐grafted membranes possess stronger hydrophilicity as indicated by their contact angle and hydration capacity, and as a result they have an improved antifouling property. Therefore, the control of the hydrophilicity of PSF membrane could be realized through adjusting the polymerization time and transforming the functional groups in the grafting chain.     

Fabrication of PES-based nanofiltration membrane modified by composite PAA-co-PMMA-g-ZnA nanoparticles

In the current research, nanocomposite polyethersulfone-based nanofiltration membranes were prepared by composite PAA-co-PMMA-g-ZnA nanoparticles. NF membranes were fabricated by phase inversion through casting solution technique. The effect of composite PAA-co-PMMA-g-ZnA nanoparticles concentration into the casting solution on physicochemical characteristics of membrane was studied. Scanning optical microscopy images showed uniform particle distribution for the membranes. Scanning electron microscopy images also demonstrated that membrane porosity was enhanced by increase in nanoparticles content ratio. The membrane surface 3D images showed smooth surface for the membranes filled with 0.05, 0.1 and 0.5 wt% nanoparticles. The contact angle results exhibited that membrane hydrophilicity was improved significantly by using of NPs in membrane matrix. The contact angle was decreased from 65.38° for PES membrane to 48.33° for membrane filled with 0.5 wt% nanoparticles. The water permeability was reduced initially by addition of 0.05 wt% nanoparticles into the casting solution and then increased by more nanoparticles loading rate (0.1 wt%). The water permeability was decreased again by more increase in nanoparticles loading range from 0.5 to 1 wt%. The salt rejection was improved strongly from 68.4 % for PES to 88.58 % for membrane filled with 0.5 wt% nanoparticles. The membranes mechanical strength was increased sharply from 2835.5 to 3337.3 kPa with addition of nanoparticles into the casting solution.     

Removal of aromatic compounds in the aqueous solution via micellar enhanced ultrafiltration: Part 1. Behavior of nonionic surfactants

The effects of nonionic surfactants having different hydrophilicity and membranes having different hydrophobicity and molecular weight cut-off on the performance of micellar-enhanced ultrafiltration (MEUF) process were examined. A homologous series of polyethyleneglycol (PEG) alkylether having different numbers of methylene groups and ethylene oxide groups was used for nonionic surfactants. Polysulfone membranes and cellulose acetate membranes having different molecular cut-off were used for hydrophobic membranes and hydrophilic membranes, respectively. The concentration of surfactant added to pure water was fixed at the value of 100 times of critical micelle concentration (CMC). The flux through polysulfone membranes decreased remarkably due to adsorption mainly caused by hydrophobic interactions between surfactant and membrane material. The decline of solution flux for cellulose acetate membranes was not as serious as that for polysulfone membranes because of hydrophilic properties of cellulose acetate membranes. The surfactant rejections for the cellulose acetate membranes increased with decreasing membrane pore size and with increasing the hydrophobicity of surfactant. On the other hand the surfactant rejections for polysulfone membranes showed totally different rejection trends with those for cellulose acetate membranes. The surfactant rejections for the polysulfone membranes depend on the strength of hydrophobic interactions between surfactant and membrane material and molecular weight of surfactants.     

PES中空纤维复合纳滤膜的制备

采用界面聚合法制备聚醚砜（PES）中空纤维复合纳滤（NF）膜,讨论了制备条件对PES中空纤维复合NF膜性能的影响。实验结果表明,聚合反应时间、均苯三甲酰氯浓度、哌嗪浓度和酸吸收剂三乙胺浓度对复合NF膜性能有显著影响,同时二次反应能够提高复合NF膜的截留率,对2g／L的Na2SO4截留率可达到99．2％。