采用聚合左旋多巴涂覆及MPEG-NH2接枝对PVDF膜亲水改性的研究

通过涂覆3-羟基-L-酪氨酸(左旋多巴,L-DOPA)和再接枝氨基聚乙二醇单甲醚(Methoxypolyethylene glycol amine,MPEG-NH2)的方式对疏水聚偏氟乙烯(PVDF)膜进行表面亲水改性.在Tris缓冲溶液中,左旋多巴通过氧化反应形成聚合物,粘附在膜表面形成涂覆层,再通过氨基与聚合左旋多巴的共价结合将MPEG-NH2刷状聚合物接枝到PVDF膜表面.实验通过水接触角、傅里叶红外光谱、扫描电子显微镜等测试手段,分析和对比膜改性前后的特征和表面形貌,同时考察原膜、涂覆改性膜和接枝改性膜对乳化油的分离效率和抗污染能力.实验结果表明,左旋多巴涂覆和后续MPEG-NH2接枝改性虽然减小了PVDF膜孔径和纯水通量,但能明显提高膜表面的亲水性和过滤效率,并在乳化液分离实验中提高膜的抗污染性能和膜清洗通量恢复率.     

利用聚合多巴胺及PEG对PVDF中空纤维膜进行表面功能化的研究

通过涂覆多巴胺对PVDF中空纤维膜进行亲水改性,并利用聚合多巴胺(PDOPA)的强附着性进一步进行氨基聚乙二醇(mPEG-NH2)接枝改性,实现微滤膜表面功能化.实验研究了不同反应条件下涂覆和接枝效果,并以乳化油溶液进行过滤对比分析.实验结果表明,经过480min多巴胺涂覆改性,PVDF中空纤维膜亲水性能提高,接触角由原膜的84.9°降低为50.1°,膜表面水滴渗透速度加快;涂覆时间影响膜的纯水通量,30min涂覆时间,纯水通量较原膜提高6.4%;过滤乳化油废水时,改性后的膜通量衰减速率减缓,稳定通量增加,抗污染性能提高.在PDOPA涂覆改性膜基础上进行mPEG-NH2接枝后,亲水性进一步提高,乳化油去除率提高13%.通过多巴胺涂覆与mPEG-NH2接枝,均有效提高了PVDF中空纤维膜在处理乳化油方面的性能.     

射线辐照接枝丙烯酸改性PVDF超滤膜

采用Co-60γ射线共辐照方法对聚偏氟乙烯(PVDF)超滤膜进行接枝丙烯酸(AAc)辐照改性,研究了在一定辐照剂量下AAc体积分数对接枝率的影响,以期达到改善其亲水性的目的.试验表明,在吸收剂量为25 KGy时,接枝率在较低浓度时随AAc体积分数的增大而线性增大,AAc体积分数大于0.40后,接枝率基本不再变化;采用表面水接触角、全反射红外光谱(ATR-IR)分析了膜的表面性质及变化,采用扫描电子显微镜(SEM)观测了膜的表面形态.结果表明,辐照改性后膜表面接触角大幅下降,且随接枝AAc体积分数升高而降低;辐照改性后PVDF超滤膜表面膜孔数量减少,纯水通量降低,截留率提高.     

聚偏氟乙烯微孔膜一步法亲水化改性研究

采用高能电子束预辐照接枝的方法,研究了液相丙烯酸(AAc)和苯乙烯磺酸钠(SSS)双元混合体系对聚偏氟乙烯(PVDF)微孔膜的接枝改性,用一步法直接制备了含有羧酸基团和磺酸基团的强亲水性PVDF微孔膜.考察了辐照剂量、反应时间、反应温度、单体浓度、单体配比以及反应溶液pH值等对接枝率的影响.采用FT-IR、接触角和水通量表征改性前后的膜表面性质和膜性能.结果表明,接枝改性后膜的亲水性增强,接触角随接枝率的增加而降低,水通量随接枝率的增加呈现出先升后降的变化,这主要是由于高接枝率时膜表面和膜孔被接枝链堵塞.     

PVDF中空纤维膜改性研究(1)交联PVP制备亲水化PVDF中空纤维膜

利用聚乙烯吡咯烷酮(PVP)的自交联以及与聚偏氟乙烯(PVDF)的互交联,实现了PVDF微孔膜的亲水化改性.考察了溶液浓度、反应时间等因素对改性PVDF膜性能的影响,采用FT-IR、NMR、接触角和水通量等测试方法表征改性前后PVDF膜的性能.结果表明,自交联PVP的强吸水性使得改性后的PVDF膜(PVDF-cl-PVP膜)亲水性显著提高,与水的接触角45 s内即可降至0°,膜的纯水通量为600 L/(m2·h).PVDF与PVP的互交联以及PVP的自交联结构使得PVP牢牢固定于PVDF微孔膜外表面及膜内部孔通道表面,实现了PVDF微孔膜的永久亲水化.PVDF-cl-PVP膜经纯水反复清洗后仍能保持很高的亲水性.经PVP改性后,PVDF膜的通量恢复率提高了16％,表明PVDF-cl-PVP膜的抗污染性得到显著提高.     

pH敏感型甲基丙烯酸接枝聚偏氟乙烯微滤膜的制备和表征

以强碱、强氧化剂溶液对聚偏氟乙烯(PVDF)微孔滤膜表面极化改性后,用自由基聚合的方法将α-甲基丙烯酸接枝到PVDF微孔滤膜表面,得到pH值敏感型微孔滤膜.结果表明:接枝率确定的情况下,水通量随着被过滤溶液pH值的变化而明显变化;接枝率的逐步升高,水通量呈现先增大后减小的趋势.接枝膜经扫描电子显微镜和原子力显微镜测试表明,接枝膜表面孔数减少,孔径变小,并且观察到孔内有絮状物,证明接枝甲基丙烯酸的存在.为了兼顾改性膜的水通量和pH值敏感性能,需要将膜的接枝率控制在1.9%～6.1%之间.     

聚偏氟乙烯中空纤维医用膜的研制

利用非溶剂相转化法,制备不同聚偏氟乙烯(PVDF)改性膜.研究PVDF与聚乙二醇(PEG)-400固含量对膜性能的影响,并将PVDF改性膜与市售血液透析膜F60S的性能进行了对比分析.结果表明,随着PVDF固含量的增加,膜分离孔径和纯水通量逐渐减小,BSA截留率和机械性能提高;随着PEG-400固含量的增加,膜分离孔径先减小后增大,BSA截留率先增加后减小,纯水通量逐渐提高,机械性能下降.PVDF/PEG膜分离孔径与纯水通量比F60S膜略低,BSA截留率、机械性能、血液相容性与F60S膜相比均具优势.     

等离子体引发表面两性离子化制备抗污染性PVDF膜

为了提高聚偏氟乙烯(PVDF)膜的抗污染性能,采用等离子体技术将甲基丙烯酸二甲胺乙酯(DMAEMA)接枝到PVDF膜表面,使其与3-溴丙酸(3-BPA)发生季铵化反应,得到两性离子化改性膜(PVDF-g-PCBMA).利用傅利叶红外光谱仪(FTIR-ATR)、扫描电子显微镜(SEM)、接触角测定仪分析改性前后PVDF膜表面化学官能团、结构形态以及亲疏水性的变化.通过动态过滤实验来考察原膜、改性膜对牛血清蛋白(BSA)和海藻酸钠(SA)的抗污染性能.结果表明,相比于原PVDF膜,PVDF-g-PCBMA膜的接触角从88.3°降至39.0°,亲水性得到了较大的提高;另外,其在BSA和SA溶液的过滤实验中通量衰减率降低、清洗后的清水通量恢复率升高,体现了两性离子化改性膜良好的抗污染性能.     

臭氧引发接枝制备聚偏氟乙烯亲水膜

利用臭氧的强氧化性,对溶解在N-甲基吡咯烷酮中的聚偏氟乙烯进行处理引入过氧基团,然后通过热引发接枝聚合亲水性聚乙二醇甲基丙烯酸酯(PEGMA),通过相转变法(phase inversion)制备具备亲水特性的PVDF分离膜.通过红外光谱、热重分析和接触角测试对接枝改性后的聚偏氟乙烯的结构和性能进行表征.红外光谱显示在1 734 cm-1处出现PEGMA的特征吸收峰,表明已成功接枝上PEGMA.接枝后的PVDF膜接触角降低到42°,表现出很好的亲水性;同时研究了接枝条件对改性膜亲水性的影响,随接枝单体浓度增加其亲水性增大;改性前后的聚偏氟乙烯膜的表面形貌通过扫描电子显微镜(SEM)分析表明,在相同成膜条件下改性后分离膜表面形貌发生很大变化,改性后制备的分离膜有较大的膜孔出现;水通量测试和牛血清蛋白吸附实验进一步表明,接枝改性可以明显改善PVDF分离膜的亲水性和抗污染性能.     

低温等离子体液相接枝NVP改性PAN膜

采用液相等离子体接枝技术改性聚丙烯腈(PAN)膜,在PAN膜表面引入亲水性单体氮乙烯吡咯烷酮(NVP).通过傅立叶红外光谱、DSC、XPS对PAN改性膜进行了表征,研究了单体浓度、温度、接枝时间对PAN改性膜纯水通量的影响,考察了在不同单体接枝温度下,PAN改性膜对NaCl、MgSO4混合盐体系的分离性能.     

聚偏氟乙烯膜亲水化改性研究进展

强疏水性聚偏氟乙烯(PVDF)膜的亲水化改性是当前分离膜研究的热点之一.对PVDF膜近年来在共混改性、表面化学改性、表面接枝改性等方面的研究进行了综述,并针对PVDF分离膜改性领域今后的研究提出建议,指出膜材料共混改性是今后发展的主要方向.     

聚偏氟乙烯膜表面丙烯酸接枝改性研究

采用自由基接枝聚合反应制备了丙烯酸改性的聚偏氟乙烯膜,研究了单体浓度对接枝率的影响,测定了改性后样品的红外光谱、表面接触角、水通量、蛋白吸附等.结果表明,通过自由基接枝聚合,丙烯酸接枝到膜的表面,明显提高膜的亲水性.接枝后膜的水通量也非常明显下降,特别是在高丙烯酸浓度下.改性的膜的通量对溶液的pH值有明确的响应关系,表明接枝链在水中的溶胀对膜的性能有显著的影响.蛋白吸附实验表明,改性后的膜相比未改性膜有较高的吸附量,而且在酸性情况下,膜的吸附量较大,这主要与丙烯酸和蛋白质之间的相互作用有关.     

On the preparation and application of novel PVDF–POSS systems

Novel systems based on poly(vinylidene fluoride) (PVDF) and polyhedral oligomeric silsesquioxane (POSS) have been prepared by grafting amino-containing POSS (POSS–NH₂) onto the surface of modified PVDF (PVDFm). Namely, the approach consists of a preliminary modification of PVDF by a chemical treatment with an alkaline solution, in order to obtain unsaturations, and a subsequent surface reaction of PVDFm with POSS molecules characterized by an amino group as reactive side. The level of polymer unsaturation, measured by Raman spectroscopy, turned out to be finely tuned by varying the dehydrofluorination reaction time. The surface grafting of POSS has been studied by SEM-EDS analysis, Raman and XPS spectroscopy. Indeed, while the level of modification of PVDFm has been found to decrease as a consequence of the reaction with POSS, thus indicating a likely saturation of double bonds by silsequioxane molecules, the Si concentration turned out to increase with increasing the concentration of the polymer surface unsaturation. The feasibility of the application of POSS grafting onto the surface of membranes, based on PVDFm, has also been verified.     

Zwitterionic sulfobetaine-grafted poly(vinylidene fluoride) membrane with highly effective blood compatibility via atmospheric plasma-induced surface copolymerization

Development of nonfouling membranes to prevent nonspecific protein adsorption and platelet adhesion is critical for many biomedical applications. It is always a challenge to control the surface graft copolymerization of a highly polar monomer from the highly hydrophobic surface of a fluoropolymer membrane. In this work, the blood compatibility of poly(vinylidene fluoride) (PVDF) membranes with surface-grafted electrically neutral zwitterionic poly(sulfobetaine methacrylate) (PSBMA), from atmospheric plasma-induced surface copolymerization, was studied. The effect of surface composition and graft morphology, electrical neutrality, hydrophilicity and hydration capability on blood compatibility of the membranes were determined. Blood compatibility of the zwitterionic PVDF membranes was systematically evaluated by plasma protein adsorption, platelet adhesion, plasma-clotting time, and blood cell hemolysis. It was found that the nonfouling nature and hydration capability of grafted PSBMA polymers can be effectively controlled by regulating the grafting coverage and charge balance of the PSBMA layer on the PVDF membrane surface. Even a slight charge bias in the grafted zwitterionic PSBMA layer can induce electrostatic interactions between proteins and the membrane surfaces, leading to surface protein adsorption, platelet activation, plasma clotting and blood cell hemolysis. Thus, the optimized PSBMA surface graft layer in overall charge neutrality has a high hydration capability and the best antifouling, anticoagulant, and antihemolytic activities when comes into contact with human blood.     

高分子微滤膜等离子体处理接枝N-异丙基丙烯酰胺

用低温等离子体预处理的方法，将N-异丙基丙烯酰胺(NIPAAm)接技在PE微滤膜上。研究了等离子体处理工艺、接枝聚合条件对接枝率的影响，结果表明，等离子体处理产生的活性种具有长寿命，水对接枝聚合反应具有加速效应。SEM观察到接枝膜表面存在接枝物。接枝膜的水通量在32℃附近出现了不连续的变化，聚(N-异丙基丙烯酰胺)(PNIPAAm)接枝链起到了化学阀的作用．     

Surface modification of nanoporous alumina membranes by plasma polymerization

The deposition of plasma polymer coatings onto porous alumina (PA) membranes was investigated with the aim of adjusting the surface chemistry and the pore size of the membranes. PA membranes from commercial sources with a range of pore diameters (20, 100 and 200?nm) were used and modified by plasma polymerization using n-heptylamine (HA) monomer, which resulted in a chemically reactive polymer surface with amino groups. Heptylamine plasma polymer (HAPP) layers with a thickness less than the pore diameter do not span the pores but reduce their diameter. Accordingly, by adjusting the deposition time and thus the thickness of the plasma polymer coating, it is feasible to produce any desired pore diameter. The structural and chemical properties of modified membranes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and x-ray electron spectroscopy (XPS). The resultant PA membranes with specific surface chemistry and controlled pore size are applicable for molecular separation, cell culture, bioreactors, biosensing, drug delivery, and engineering complex composite membranes.     

不同接枝率对PVDF-g-PNIPAAm温敏膜性能影响研究

以聚偏氟乙烯(PVDF)为基材,分别采用直接引发原子转移自由基聚合(ATRP)和碱处理后自由基聚合的方法接枝N-异丙基丙烯酰胺(NIPAAm),合成出不同接枝率的PVDF-g-PNIPAAm共聚物,然后用相转化法制备出PVDF-g-PNIPAAm共聚温敏膜.用核磁共振(1H NMR)和X射线光电子能谱(XPS)分别对共...     

PVDF/SMA共混膜的制备与性能

通过马来酸酐和苯乙烯合成了苯乙烯/马来酸交替共聚物(SMA),并按不同质量比与聚偏氟乙烯(PVDF)共混,通过溶液相转化成膜法制备了PVDF/SMA共混膜。采用红外光谱、扫描电镜、膜通量测试等对不同铸膜液所形成膜的结构和性能进行了研究。结果表明,随着铸膜液中交替共聚物含量增大,所成膜及膜表面交替共聚物含量增大,膜孔尺寸增大,膜孔隙率升高,纯水通量增大,蛋白质截流能力下降,膜表面亲水性和耐蛋白污染能力增强。