PVC-溶剂-非溶剂相混合参数表征

<正>聚合物-溶剂-非溶剂(沉淀剂)三元相混合参数是影响浸没沉淀相转化法成膜的一个关键因素,溶剂/非溶剂的选择影响成膜机理:瞬时液-液分相和延时液-液分相。顺时液-液分相是指铸膜液浸入凝胶浴后迅速分相,有利于形成大孔结构;延时液-液分相是指铸膜液浸入凝胶浴后一定时间后才开始分相成膜倾向于形成海绵状结构[1]。这是由于当在铸     

湿法成膜法制备聚氨酯微孔膜过程中的非溶剂效应

通过湿法成膜制备了聚氨酯(PU)微孔膜,从实验和量化计算两个方面研究了不同非溶剂对PU铸膜液成膜速率及膜结构的影响。实验结果表明:各非溶剂对PU铸膜液成膜速率的影响从大到小依次为水、甲醇、乙醇、异丙醇,而铸膜液在醇类非溶剂中更易形成形貌均一、分布均匀的多孔结构,其中采用乙醇和异丙醇非溶剂体系得到的PU微孔膜,不但具有相似的形貌而且其成膜速率相近。量化计算结果表明:成膜速率与溶剂-非溶剂间所形成氢键的强度密切相关。     

溶剂/非溶剂体系对聚醚砜微孔膜性能和结构的影响

以N,N-二甲基乙酰胺(DMAc)、N-甲基吡咯烷酮(NMP)和N,N-二甲基甲酰胺(DMF)为溶剂,乙醇(EtOH)、异丙醇(IPA)、正丁醇(BuOH)、一缩二乙二醇(DegOH)、聚乙二醇400(PEG400)为非溶剂添加剂,研究了溶剂/非溶剂体系对聚醚砜(PES)膜的结构和性能的影响.改变铸膜液体系中的非溶剂含量对膜的结构和性能有很大影响,但是这种影响不是以非溶剂的绝对含量来衡量的,而取决于非溶剂/溶剂的比值.改变溶剂的组成和配比也改变了溶剂/非溶剂体系,体系的溶度参数越接近PES的溶度参数,与PES的相容性越好,但是膜的通量较小.实验结果表明,采用NMP(或DMAc)与DMF以适当比例混合作溶剂,比采用单一NMP(或DMAc)作为溶剂制得的膜通量要大.通过改变溶剂配比,可实现对膜的表面开孔率、孔径、断面结构等参数的微控.     

非溶剂对浇铸SPEEK膜性能的影响

首次采用磺化聚醚醚酮/N,N-二甲基甲酰胺(SPEEK/DMF)和非溶剂(四氯乙烯或对二甲苯)组成的铸膜液制备了SPEEK膜.采用交流阻抗法和隔膜扩散法分别考察了膜的质子传导性和透水性能.结果表明,由于在SPEEK/DMF中添加非溶剂,膜的透水率增加了约30％,质子导电率提高了50％左右.非溶剂的加入影响了铸膜液中聚合物的形态、尺寸和团聚情况,从而影响了成膜后膜的性能.本研究提出的控制膜微相结构的新方法将有助于提高SPEEK膜燃料电池性能.     

非溶剂添加剂对聚醚砜酮中空纤维纳滤膜结构和性能的影响

以新型杂萘联苯聚醚砜酮(PPESK)为膜材料,N-甲基-2-吡咯烷酮(NMP)为溶剂,乙二醇甲醚(EGME)、冰醋酸(AA)以及AA/EGME作为复合添加剂,采用干-湿相转化技术制备了中空纤维非对称纳滤膜,重点考察了非溶剂添加剂对中空纤维膜结构和性能的影响。结果表明非溶剂添加剂的加入导致了中空纤维膜孔结构由指状转变为海绵状,从而引起中空纤维膜性能的变化。当聚合物质量分数为23%,铸膜液溶剂体系为m(AA)∶m(EGME)∶m(NMP)=5.7∶16.5∶54.8时,中空纤维膜对PEG600的截留率高于96%,纯水通量为211 L/(m2.h)。     

聚合物膜的研制

以聚丙烯腈(PAN)／聚乙烯醇(PVA)合金为膜材料，用液-固相转化法成膜制备PAN/PVA体系的非对称型合金微滤膜。研究了铸膜液浓度、聚合物共混配比、铸膜液温度溶剂蒸发时间、凝胶浴温度对膜结构和膜性能的影响。结果表明：采用了液-固相转化法成膜，可制成孔径为0．5～5．0μm的非对称性PAN/PVA合金微滤膜。     

聚偏氟乙烯／蒙皂石超滤膜的制备及性能研究

以聚偏氟乙烯(PVDF)为原料,无机层状材料蒙皂石(MMT)为添加剂,通过溶胶-凝胶相转化法研制成PVDF/MMT超滤膜.考察了MMT质量分数在0%~9%范围内对铸膜液黏度、膜孔隙率、孔径、水通量、PEG20000截留率等性能的影响,以及相图和DSC曲线的变化.实验结果表明,MMT的加入使铸膜液的黏度增加,铸膜液呈现非牛顿流体中的假塑性流体的特性;当MMT加入质量分数为7%时,PVDF/MMT超滤膜水通量可达94.32 L·m-2·h-1,对PEG20000的截留率达95.2%.MMT的添加对成膜过程也有影响,从相图分析,加入MMT改变了液–固双节点的位置,铸膜液对非溶剂的容纳能力降低;而从DSC测试曲线得知PVDF/MMT膜的结晶度低于PVDF膜.     

PI/NMP/H_2O三元体系相行为与纤维成形研究

介绍了湿法纺丝中凝固剂/溶剂/聚合物三元体系热力学理论及三元相图双节线和旋节线的计算方法;在聚酰亚胺/N-甲基-2-吡咯烷酮/水(PI/NMP/H2O)三元体系中,采用黏度法计算了PI-NMP相互作用参数(χ23),平衡溶胀法测得PI-H2O相互作用参数(χ13),结合NMP-H2O相互作用参数,并根据FloryHuggins溶液理论绘制出不同温度下PI/NMP/H2O三元体系的理论相图,并研究了不同凝固浴温度下PI纤维纺制中的相分离及成形过程。结果表明:在25,40,60℃时,χ23分别为0.489 6,0.480 1,0.473 4,χ13分别为1.52,1.47,1.30;随着凝固浴温度升高至60℃时,纤维表面逐渐变得致密光滑,断面形态由肾形变为规则的圆形;凝固浴温度升高时,相图中亚稳态区域扩大,纤维成形过程更加缓和,有利于制备结构致密的PI纤维。     

醋酸丁酯酯化反应体系组分在PEBA膜中的吸附性能

采用实验和模型计算两种方法研究了醋酸丁酯酯化反应体系组分在涂布法制备的用于渗透汽化分离的PEBA膜材料中的吸附行为.分别用Flory-Huggins和ONIQUAC模型预测了全浓度范围内的水/有机物二元混合液在PEBA膜中的吸附量.用溶解度参数法得到Flory-Huggins模型中的相互作用参数;用纯溶剂与膜的平衡吸附数据拟合得到UNIOUAC模型中溶剂与膜的二元相互作用参数,而溶剂之间的二元相互作用参数可用文献中汽液平衡数据关联拟合.结果表明PEBA膜材料的亲有机物性能良好,对于四种组分的选择吸附性顺序为:醋酸正丁酯>正丁醇>醋酸>水,并且两种模型的计算结果基本一致.     

羟丙基纤维素/水/甘油体系三元相图的计算机模拟

通过凝固点降低法和平衡溶胀法分别测定了甘油与水、羟丙基纤维素与甘油的相互作用参数,结合羟丙基纤维素与水的相互作用参数,利用Flory-Huggins聚合物溶液理论,以及Matlab计算机程序,首次计算出羟丙基纤维素/水/甘油三元体系的双节线和旋节线,并绘制出羟丙基纤维素/水/甘油体系的三元相图。     

Liquid–liquid phase separation in polysulfone/polyethersulfone/N‐methyl‐2‐ pyrrolidone/water quaternary system

To construct a phase diagram of the polysulfone (PSF)/polyethersulfone (PES)/N‐methyl‐2‐pyrrolidone (NMP)/water quaternary system, cloud point measurements were carried out by a titration method. The miscible region in the PSF/PES/NMP/water quaternary system was narrow compared to the PSF/NMP/water and PES/NMP/water ternary systems. The binary interaction parameters between PSF and PES were estimated by water sorption experiments. The calculated phase diagram based on the Flory–Huggins theory fit the experimental cloud points well. In addition to the usual polymer–liquid phase separation, polymer–polymer phase separation, which resulted in a PSF‐rich phase and a PES‐rich phase, was observed with the addition of a small amount of nonsolvent. The boundary separating these two modes of phase separation could be well described and predicted from the calculated phase diagrams with the estimated binary interaction parameters of the components. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2113–2123, 1999     

聚醚砜制膜液的相分离：Ⅰ.三元体系

本文对聚醚砜在不同溶剂和不同非溶剂中所构成三元体系的相分离进行研究。采用浊点滴定法测定了在常用溶剂和非溶剂中的浊点数据，溶剂对ＰＥＳ的溶解能力，依次为：甲酰胺〈二甲基业砜〈Ｎ，Ｎ－二甲基甲酰胺〈《Ｎ，Ｎ－二甲基乙酰胺〈Ｎ－甲基吡咯烷酮；以二甲基甲酰胺为溶剂，非溶剂的沉淀能力依次为：Ｈ２Ｏ〉丙三醇〉甲醇〉乙二醇〉乙醇〉丙二醇〉丙醇，线性浊点不能较好描述三元体系的浊点关系。     

Analysis of nonsolvent–solvent–polymer phase diagrams and their relevance to membrane formation modeling

Calculations have been carried out, based on Flory–Huggins solution theory, to analyze the behavior of the ternary nonsolvent–solvent–polymer phase diagram for typical membrane-forming systems. Consideration is given to the behavior of the spinodal as well as binodal curves, tie-line slopes, and critical points as a function of various parameters, most especially those related to the concentration dependency of the interaction parameters. Implications regarding membrane structure formation are discussed, and the suitability of different functional forms for the interaction parameter concentration dependence is also analyzed. The net result of these calculations is to demonstrate the importance of the various parameters in controlling the phase-diagram behavior and particularly to show the critical role of the concentration dependence of the solvent–polymer interaction parameter in affecting the nature of the miscibility gap.     

Liquid-liquid phase separation in polysulfone/solvent/water systems

The cloud point curves for polysulfone (PSf)/solvent/water systems were determined by a titration method. A small amount of water was needed to induce liquid-liquid demixing and the temperature effect was small. From numerical calculations, it was found that the binary interaction parameters for the PSf/solvent/water system enlarges the homogeneous region in the phase diagram with a smaller nonsolvent-polymer interaction parameter χ₁₃, a greater nonsolvent-solvent interaction parameter χ₁₂, and a smaller solvent-polymer interaction parameter χ₂₃ and the effect of polymer molecular weight was negligible except in the range of low molecular weight. The phase diagrams, calculated with constant χ₁₂ that was chosen from the concentration-dependent interaction parameter g₁₂ value of the concentration range, were similar to the results obtained with g₁₂. The slope of the tie lines indicated that demixing of the ternary system occurred at relatively similar nonsolvent concentration in both phases. A value of 2.7 for the water-PSf interaction parameter was obtained by fitting the experimental cloud point curve with the calculated binodal lines. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2643–2653, 1997     

Novel surface modifying macromolecules (SMMs) blended polysulfone gas separation membranes by phase inversion technique

In this article an attempt was made to fabricate defect‐free asymmetric polysulfone (PSf) membranes for the separation of oxygen and nitrogen. The approach is based on the enhanced delayed demixing by blending surface modifying macromolecules (SMMs) in the casting solution and by immersing the cast film in isopropanol for a certain period before it is immersed in water. Different SMMs, including hydrophobic and charged SMMs, were synthesized, characterized, and blended to the host PSf. It was found that the charged SMM could indeed contribute to the removal of defective pores from the skin layer and enhancement of oxygen/nitrogen selectivity. The experimental results were further interpreted based on the shift of the phase boundary line on the polymer/solvent/nonsolvent triangular diagram, which occurred when SMMs were blended to PSf, due to the change in the polymer/nonsolvent interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Evaporation rate and equilibrium phase separation data in relation to casting conditions and performance of porous cellulose acetate reverse osmosis membranes

Quantitative data on solvent evaporation rates and equilibrium phase separation compositions corresponding to different film casting conditions are given, and the results are discussed with reference to reverse osmosis data on membrane performance. A typical evaporation rate curve plotted on a semilog scale consists of an initial linear part from whose slope evaporation rate constants b have been determined. For a given casting solution composition and temperature, an optimum value of b exists for best membrane performance, and identical values of b result in same membrane performance. Treating the casting solution as a polymer–solvent–nonsolvent ternary system, the data on equilibrium phase separation compositions have been plotted in a triangular diagram for solution temperatures of ?10°, 0°, and 24°C. The data indicate that even small changes in solution temperature can bring about significant changes in solution structure and hence membrane performance, and useful conclusions on solution structure can be drawn from such phase equilibrium diagrams. The data and correlations presented here offer a quantitative confirmation of the governing significance of the solution structure-evaporation rate concept relating to the mechanism of phase separation and pore formation in the surface region during the process of making reverse osmosis membranes.     

Phase separation phenomena of polysulfone/solvent/organic nonsolvent and polyethersulfone/solvent/organic nonsolvent systems

The precipitation values (PVs) of several organic nonsolvents in polysulfone (PSf)/solvent and polyethersulfone (PESf)/solvent systems were measured in temperatures ranging from 10 to 80°C by the direct titration method and compared with those of water in the same systems. The solvents used were N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAC); the organic nonsolvents employed were methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, ethylene glycol, and diethylene glycol as well as acetic acid and propionic acid. The compositions of nonsolvent, polymer, and solvent at the precipitation points for different polymer concentrations up to 10 wt % were also determined at 30°C with respect to both the polymers and six nonsolvents presented. These results were used to obtain the polymer precipitation curves in the polymer-solvent-nonsolvent triangular phase diagrams and to determine the theta composition of solvent-nonsolvent for a polymer. The results show that the precipitation value of nonsolvent in polymer/solvent systems depends on both the nature of polymer, solvent, and nonsolvent used and the temperature. The effect of temperature on the precipitation value was observed to be dramatically different for different polymer/solvent/nonsolvent systems. These results were explained on the basis of polar and nonpolar interactions of the polymer, solvent, and nonsolvent system. The results indicate that the precipitation values of the type presented in this paper not only give a relative measure of the nonsolvent tolerance of the polymer/solvent system involved and the strength of solvent and nonsolvent for the polymer, but also determine the relative location of the polymer precipitation curve in the triangular phase diagram. © 1993 John Wiley & Sons, Inc.     

Isothermal ternary phase diagram of the polylactic acid-dichloromethane-hexane system

The ternary phase diagram of polylactic acid, dichloromethane (solvent) and hexane (nonsolvent) is experimentally developed at room conditions based on naked eye observations over 14-day periods. The experimental procedure is explained in detail, allowing it to be applied to similar ternary systems. Three regions are distinguishable in this diagram: single phase, liquid–liquid phase separated and solid–liquid phase separated. This diagram is then assessed based on the lever rule concept in ternary phase diagrams. Phase separation kinetics are also evaluated using turbidity studies to quantitatively monitor the cloudiness of the samples over time. The results show that, a small increase in polylactic acid concentration on the order of a few weight percent can drastically increase the phase separation rate. The application of polylactic acid in various fields has been increasing, and this work provides fundamental information essential for solvent-based processing (e.g., nonsolvent induced phase separation and immersion-precipitation) of this polymer in the system composed of dichloromethane and hexane.     

Polymerization of methyl methacrylate in the presence of a nonpolar hydrocarbon solvent. I. Construction of a complete ternary phase diagram through an in situ polymerization

This article presents the ternary phase diagram for methyl methacrylate (MMA), poly(methyl methacrylate) (PMMA), and n‐hexane system at 70°C. It was constructed by both theoretical calculations and online laser light scattering (LLS) technique. In situ polymerization of MMA in a nonpolar nonsolvent carried out in a LLS cell provides a new means for the accurate detection of the cloud points of highly viscous polymer mixtures, with polymer weight fractions over 0.6. The ternary phase diagram measured in this study can be used to design the reaction conditions for the precipitation and/or dispersion polymerization in a nonpolar nonsolvent medium where polymerization kinetics as well as polymer particle morphologies are strongly affected by thermodynamic phase separation phenomena. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of Casting Solution on Morphology and Performance of PVDF Microfiltration Membranes

The effects of preparation‐influencing parameters such as polymer concentration, thickness of casting solution, and type of solvent on morphology and performance of poly(vinylidene difluoride) (PVDF) microfiltration membranes for the treatment of emulsified oily wastewater were investigated. Flat‐sheet membranes were prepared from a casting solution of polymer and additive in various solvents by immersing the prepared films in nonsolvent‐containing mixtures of water and 2‐propanol. The membranes were characterized using scanning electron microscopy. Increasing the polymer concentration and membrane thickness significantly affected the pore size, leading to permeate flux decrease. An attempt was made to correlate the effect of the solvent on membrane morphology and performance employing solubility parameters between solvent and nonsolvent).