一种新的制备有机-无机杂化膜的方法——前驱体水解聚合法制备聚偏氟乙烯-硅杂化膜

首次提出一种制备有机-无机杂化膜的新方法,即将正硅酸乙酯(TEOS)直接添加到聚偏氟乙烯(PVDF)铸膜液中,在入水凝胶时,PVDF逐渐固化成膜,而TEOS同时也与水发生水解聚合反应,生成硅氧聚合物,这就为形成无机高分子与PVDF互穿网络结构或分子链相互缠绕创造了机遇,为制备力学性能优良的聚偏氟乙烯-硅杂化膜提供了可能.实验初步考察了正硅酸乙酯的添加量对聚偏氟乙烯-硅杂化膜的超滤性能和力学性能的影响,对杂化膜进行了能谱分析.结果表明:1)能谱实验证明杂化膜表面有Si元素存在,表明TEOS在凝胶过程中发生水解聚合反应,生成硅氧聚合物留在杂化膜中;2)在无致孔添加剂存在时,随TEOS添加量的增加,杂化膜的纯水通量增大,而对牛血清蛋白的截留率呈现持续下降的趋势;当TEOS含量为8%时,与无TEOS的PVDF膜相比,杂化膜的拉伸强度σt和弹性模量E几乎增加一倍;3)在有致孔添加荆PVP K30和无水LiCl存在时,杂化膜的纯水通量随TEOS添加量的增加呈先升后降然后再上升的趋势,对牛血清蛋白的截留率呈现持续下降的趋势.当TEOS添加量为12%时,与无TEOS的PVDF膜相比,超滤性能相近,但杂化膜的拉伸强度σt和弹性模量E增加近一倍.     

氟树脂对聚偏氟乙烯膜疏水性的影响

采用N,N-二甲基甲酰胺(DMF)为溶剂,以氟树脂为疏水助剂,制备聚偏氟乙烯(PVDF)膜.采用不同偶联剂对疏水助剂氟树脂进行改性,研究了改性氟树脂对PVDF膜疏水性的影响.研究结果表明:添加疏水助剂氟树脂可改善PVDF膜的疏水性.当经偶联刺G502改性的氟树脂添加量为10%时,PVDF膜与水的静态接触角达到120°.通过集灰实验表明添加改性氟树脂的PVDF膜具有较好的疏水性.     

前体水解聚合制备无机-有机杂化膜时TEOS对PVDF成膜过程的影响

通过测定铸膜液黏度、凝胶速率以及绘制浊点相图来研究正硅酸乙酯(TEOS)对聚偏氟乙烯(PVDF)成膜过程的影响.实验发现,随着铸膜液中TEOS添加量的增加,铸膜液的黏度持续降低;三元相图显示更少的凝胶剂就能达到铸膜液的分相点,两者的综合作用使得PVDF膜的凝胶速率加快.TEOS对成膜过程的影响使得膜结构有一定的改变:铸膜液不含添加剂时形成的是海绵状致密膜,随着TEOS含量的增加孔的数量增多,孔径变大;含有添加剂时形成的是指状孔结构,随着TEOS含量增加指状孔生长更充分.     

聚偏氟乙烯膜的超疏水改性研究

为提高疏水膜的疏水性能,使其可在膜蒸馏、膜吸收等领域有更广泛的应用.采用溶液相转移法制备超疏水性聚偏氟乙烯(PVDF)分离膜,考察了铸膜液中PVDF和非溶剂(低分子二醇类化合物PG)的浓度对膜润湿性能的影响.结果表明,通过改变铸膜液中PVDF、PG的浓度,能使PVDF膜的表面静态接触角从75.1°提高到161.7°,滚动角仅为15.8°.还研究了PVDF复合膜的制备条件对膜润湿性能的影响,结果表明,在一定的非溶剂浓度范围,增加复合膜涂覆液中非溶剂PG的加入量,有利于得到较高的复合膜表面接触角,但膜丝在涂覆液中的浸泡时间也需要相应延长.当非溶剂PG的质量分数为39.1%、浸泡时间为50 s时,复合膜表面接触角达到了155°.     

前驱体水解聚合法制备聚偏氟乙烯-硅杂化膜 (Ⅱ)膜性能变化的原因分析

利用前驱体水解聚合法制备的杂化膜的力学性能有较大提高,膜的透过和截留性能亦有较大改变,采用红外、DSC、TG和电镜等手段分析引起聚偏氟乙烯(PVDF)-硅杂化膜性能变化的原因,实验用的前躯体为正硅酸乙酯(TEOS).TEOS加入到PVDF铸膜液中以后,杂化后膜的热分解温度上升了20℃,膜断面结构由指状向海绵状变化,这些都有利于膜机械性能的改善.但TEOS对PVDF的结晶度影响很小,PVDF的β晶形有所减弱.同时由于膜液中TEOS的存在,导致膜表面孔增大,膜的截留性能持续降低.     

聚偏氟乙烯均聚物和共聚物的结晶行为研究

通过研究PVDF均聚物和PVDF与六氟丙烯的共聚物的结晶行为,来掌握与六氟丙烯共聚后,PVDF结晶行为的变化.研究结果表明,在结晶过程中,均聚物和共聚物都形成具有球晶结构的α晶型.相比于均聚物,共聚物的结晶(熔融)温度、平衡熔点和结晶度均下降.两种聚合物在等温结晶时,随着结晶温度提高,结晶速率下降.在相同的过冷度下,共聚物的结晶速率低于均聚物.     

异形聚偏氟乙烯中空纤维膜的研制

利用特殊结构的纺丝喷头,通过溶液相转移法,研制具有异形结构如:一字形多芯、品字形多芯结构的聚偏氟乙烯(PVDF)中空纤维膜.系统研究了纺丝入水距离、异形膜形状对膜形态结构与性能的影响.结果表明:随纺丝入水距离的增大,异形膜的超滤水通量、透气系数、膜蒸馏通量、抗压密系数、断裂强力及破裂压力减小;异形膜中品字形三芯中空纤维膜的断裂强力较单芯中空纤维膜有很大的提高,而且破裂压力和抗压密系数在异形膜中最大,纺丝成形稳定性最佳.     

品字形聚偏氟乙烯中空纤维膜的制备

采用溶液相转移法,通过特殊结构的纺丝喷头,制备了品字形PVDF中空纤维膜,讨论了PVDF固含量和芯液组成对品字形膜形态结构和性能的影响。结果表明,随PVDF固含量的增大,品字形膜支撑层空穴变小,膜丝外形融合程度减小,海绵体结构更致密,超滤水通量、透气系数和膜蒸馏通量相应减小,膜丝断裂强力增大;随芯液中溶剂DMAc含量的增加,品字形膜支撑层空穴变小,融合部分海绵体变致密,超滤水通量、透气系数减小,膜蒸馏通量略微提高,膜丝断裂强力增大;优化后的品字形膜的水通量较单芯膜有所降低,但断裂强力显著提高,接近单芯膜的3倍。     

聚偏氟乙烯膜研究进展

系统地总结了聚偏氟乙烯膜结构和性能的影响因素．不同的添加剂对膜结构的影响也不同．一般而论,低沸点添加剂的加入使膜的支撑层具有海绵状孔结构;而无机盐、水溶性高聚物的加入,会使溶剂与沉淀剂的交换速率加快,使膜的支撑层具有指状孔结构．沉淀剂的凝固强度越高、溶剂与沉淀剂的亲和力越强,越易形成指状孔结构的膜．通过对聚偏氟乙烯膜的改性,可以提高膜的实用性能.     

温敏型聚偏氟乙烯膜材料的合成及表征

以经碱处理的聚偏氟乙烯(PVDF)和N-异丙基丙烯酰胺(NIPA)作为聚合单体,分别采用偶氮二异丁腈(AIBN)和过氧化苯甲酰(BPO)作为引发剂,合成了PVDF-g-PNIPA接枝共聚物.设计了反应时间、单体配比和反应温度三因素三水平的正交试验,并通过红外光谱和核磁共振谱对产物进行表征,计算接枝率.讨论了反应条件及不同的引发剂对接枝率的影响.结果表明:AIBN引发剂在较高温度、较长反应时间下有着更高的接枝率;而BPO引发剂在较低温度、较短反应时间下比相同条件下的AIBN更优秀.     

N-异丙基丙烯酰胺水凝胶对聚偏氟乙烯中空纤维膜的智能改性研究

采用表面改性的方法(强碱处理)制备具有温度敏感聚偏氟乙烯(PVDF)中空纤维智能膜,并对其环境响应性进行了研究.结果表明,对于温度敏感膜可以分别通过控制温度的变化,有效的控制纯水通量和卵清蛋白的截留率.     

聚偏氟乙烯中空纤维膜化学接枝改性研究

通过化学接枝反应在聚偏氟乙烯(PVDF)中空纤维膜表面接枝了2-丙烯酰胺-2-甲基丙磺酸并讨论了反应体系、单体浓度反应温度和时间等因素对接枝率的影响.试验表明,接枝AMPS可有效提高PVDF中空纤维膜的耐污染性,并且改性后中空纤维膜的通量随溶液离子强度的增加而增加.     

Preparation of polyurethane/poly(vinylidene fluoride) blend hollow fibre membrane using melt spinning and stretching

Melt spinning and stretching process was used to prepare polyurethane/poly(vinylidene difluoride) (PU/PVDF) blend hollow fibre membrane in this study. Rheological properties of melts of PU, PVDF and their blends were studied by observing their melting viscosity changing with shear rate and temperature. Morphologies of PU/PVDF blend hollow fibre membranes with different mass ratios were also observed by SEM and results showed that PU/PVDF mass ratio of 3:1 was relatively better condition for membrane preparation. The forming mechanism of the interfacial microvoids in PU/PVDF blends was also investigated and PU/PVDF blend hollow fibre membrane with water flux of ～2174 L m^?2 h^?1 was finally obtained under the pressure of 0·1 MPa.     

聚偏氟乙烯微孔膜的改性和应用研究进展

简要介绍了聚偏氟乙烯（PVDF）微孔膜的制备原理、平板式和中空纤维式两类膜的制备方法，及其改性研究的最新进展和应用现状，并展望其研究与应用的发展趋势。     

LiCl添加剂对超临界CO_2诱导相转化所形成的PVDF膜结构的影响

研究了无机盐添加剂LiCl对超临界CO2诱导相转化所制得的微孔PVDF膜的形貌和晶体结构的影响.对不含盐的体系,PVDF膜显示出液一液分相和结晶作用两种过程的形貌特性,即由互相连接的PVDF粒状微晶包围的蜂窝状孔结构.而对含盐体系,PVDF膜内部形成了大孔结构.随着LiCl加入量的增加,大孔尺寸先增大后减小.宽角X-射线衍射分析表明,由不含盐体系所制得的膜中PVDF晶体结构为α型(Ⅱ型),而由含盐体系所制得的膜中PVDF晶体结构则为β型(Ⅰ型).感应耦合等离子体质谱分析表明,约16%～22%的LiCl仍然残留在PVDF膜中.     

Enhancing the antifouling property of poly(vinylidene fluoride)/SiO2 hybrid membrane through TIPS method

PVDF/SiO₂ hybrid membranes with outstanding antifouling property were prepared from PVDF/glycerol triacetate system via thermally induced phase separation method, and characterized by scanning electron microscope, energy dispersive X-ray spectrometer analyses, differential scanning calorimeter, and wide angle X-ray diffraction. Their properties such as permeability, porosity, pore size distribution, and mechanical performance were also determined. The results show that SiO₂ nanoparticles modified by 3-aminopropyltriethoxysilane can be uniformly dispersed in membranes due to improved compatibility between PVDF solution and nanoparticles. The addition of SiO₂ particles to PVDF/glycerol triacetate mixture has a strong effect on crystallinity of the resulting hybrid membrane, which does not affect the type of PVDF crystal structure. Water flux recovery ratio is significantly increased from 11.7 % for pure PVDF membrane to 93.8 % for PVDF/SiO₂ hybrid membrane with addition of 8 wt% modified SiO₂. This remarkable promotion is related to the implantation of SiO₂ nanoparticles into the inner surface of membrane, which effectively restrains the adsorption of bovine serum albumin on the pore walls and improves antifouling property of the final membranes. Additionally, pure water flux of the hybrid membrane is increased by 276 %, i.e., from 85 to 320 L m^?2 h^?1, tensile strength is increased by 26.5 %, and elongation at break is increased by 85.4 % compared with that of pure membrane.     

50 MeV lithium ion beam irradiation effects in poly vinylidene fluoride (PVDF) polymer

Irradiation effects of 50 MeV⁷Li⁺³ ion beam induced in bulk PVDF polymer have been studied with respect to their optical, chemical, structural and electrical behaviour by using UV-visible, FT-IR spectroscopy, XRD technique and electrical frequency response using LCR bridge. The ion fluences ranging from 1.27 X 10¹¹ to 2.15 X 10¹³ ions cm^-2 have been used to study dose effects of irradiation in PVDF. The recorded UV-visible spectra clearly shows five characteristic peaks at 315, 325, 360, 425 and 600 nm. Due to irradiation, the optical absorption initially decreases but then increases with higher fluences. In the FT-IR spectra, no appreciable change has been observed after irradiation, indicating that this polymer is chemically stable. There is exponential increase in admittance with log of frequency but the effect of irradiation is not quite appreciable. The value of tan δ and relaxation frequency are changed appreciably due to irradiation. The diffraction pattern of PVDF indicates that this polymer is in semi-crystalline form; a decrease in the crystallinity and crystallite size has been observed due to irradiation     

温敏聚偏氟乙烯中空纤维膜的制备和结构表征

制备了聚偏氟乙烯(PVDF)接枝N-异丙基丙烯酰胺(NIPAAm)共聚物(PVDF-g-PNIPAAm),进而采用干-湿法纺丝工艺,首次纺制出温敏PVDF-g-PNIPAAm中空纤维膜.通过红外光谱(FT-IR)、X射线衍射(XRD)、差示扫描量热仪(DSC)、扫描电镜(SEM)等对中空纤维膜的结构和形态进行了表征与研...