聚芳醚砜酮溶液凝固相分离的研究

研究了聚芳醚砜酮的N-甲基吡咯烷酮溶液在凝固剂作用下的凝固相分离条件,测定了相分离时凝固剂种类、凝固液浓度、凝固温度和磺化处理对凝固液的凝固值和溶剂临界浓度的影响。结果表明水的凝固值最小,是一种强凝固剂;随凝固剂浓度和温度的提高,凝固值增大,临界浓度基本不变;磺化处理能够提高凝固值,从而缓和相分离剧烈程度。     

间位芳纶溶解及凝固性能研究

以二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、1-甲基-2-吡咯烷酮(NMP)为溶剂,分别加入LiCl和CaCl_2制备溶解体系,研究了间位芳纶在这几种溶解体系中的溶解性能。再以H_2O-DMAc、H_2O-DMF、H_2O-DMSO、H_2O-NMP为凝固浴,研究了溶剂种类、芳纶溶液质量分数、离子浓度等对间位芳纶溶液的凝固性能的影响。结果显示:Li Cl-DMAc溶解体系具有更强的溶解性能;凝固值随凝固浴中凝固剂H_2O的含量的增加不断减小,而临界浓度几乎没有变化;随着凝固浴温度的增加,凝固值增大,临界浓度减小;凝固值随凝固浴中离子浓度的升高而增大,但临界质量分数则不断降低。另外,间位芳纶溶液的扩散系数随着凝固浴中H_2O的含量的减少不断减小,随着芳纶浓度的增加不断减小。     

3,4'-ODA改性PPTA共聚物溶液性质的研究

为了改善聚对苯二甲酰对苯二胺(PPTA)的溶解性能,在PPTA的聚合过程中添加第三单体3,4'-二氨基二苯醚(3.4'-ODA),得到了PPTA的共聚体溶液.主要讨论不同的溶剂体系(NMP或DMAc)中共聚物溶液的凝固性和稳定性,包括凝固剂的种类,溶剂的浓度,CaCl2的含量和温度对溶液的凝固值和临界浓度的影响.实验结果表明:水是非常强的凝固剂;随着凝固液中溶剂浓度的提高,凝固值增大;随着CaCl2含量的增大凝固值逐渐增大;温度影响不是太大,变化趋势比较缓和;共聚物溶液在室温和60℃下都具有非常好的稳定性.     

聚偏氟乙烯中空纤维膜纺丝凝固浴中有机物含量测定方法的研究

通过紫外光谱扫描分析PVDF中空纤维膜纺丝凝固浴的主要成分,用折光指数法测定了聚偏氟乙稀(PVDF)中空纤维膜纺丝过程中凝固液主要成分N,N-二甲基乙酰胺(DMAc)随时间的变化及其与COD的关系。结果表明,紫外光度法、折光指数法、COD法都可以用于DMAc的测定,其中折光指数法对0~70%体积分数的DMAc溶液有很好的线性相关性;在纺丝过程中,凝固浴的COD与其折射率具有很好的相关性。随着凝固浴中DMAc含量升高,膜孔径和断裂强度变化不大,膜通量降低。可利用折光指数法分析监控纺丝过程中凝固浴组成。     

3，4＇-ODA改性PPTA共聚物溶液性质的研究

为了改善聚对苯二甲酰对苯二胺（PPTA）的溶解性能，在PPTA的聚合过程中添加第三单体3,4’-二氨基二苯醚（3．4＇-ODA），得到了PPTA的共聚体溶液。主要讨论不同的溶剂体系（NMP或DMAc）中共聚物溶液的凝固性和稳定性，包括凝固剂的种类，溶剂的浓度，CaCl2的含量和温度对溶液的凝固值和临界浓度的影响。实验结果表明：水是非常强的凝固剂：随着凝固液中溶剂浓度的提高，凝固值增大；随着CaCl2含量的增大凝固值逐渐增大；温度影响不是太大，变化趋势比较缓和；共聚物溶液在室温和60℃下都具有非常好的稳定性。     

凝固浴组成和温度对PVDF疏水微孔膜结构与性能的影响

利用非溶剂相转化法(NIPS),以聚偏氟乙烯(PVDF)/磷酸三乙酯(TEP)-N,N-二甲基乙酰胺(DMAc)为铸膜液体系,乙醇水溶液为凝固浴制备高性能的PVDF疏水微孔膜。考察了凝固浴中乙醇(EtOH)含量及凝固浴温度对PVDF成膜分相速率、膜结构和膜疏水性的影响。实验结果表明,在20℃的凝固浴温度下,凝固浴中乙醇含量的升高减慢了铸膜液体系的分相速率,提高了PVDF膜的孔隙率;在凝固浴中添加60%(wt)的乙醇,可形成表面荷叶状结构和截面对称的海绵状结构,膜表面的接触角为130.3°,呈很强的疏水性,并具有较优的膜强度。     

PEO改性PVDF/SMA膜结构和性能

将聚氧化乙烯(PEO)添加到聚偏氟乙烯/苯乙烯马来酸酐树脂(PVDF/SMA)膜体系中,通过非溶剂致相分离法(NIPS)制备了添加不同PEO含量的PVDF/SMA共混膜。其中PEO质量分数为2%的共混超滤膜性能最好,水通量为531.1L/(m²·h),牛血清蛋白(BSA)截留率为65.8%,水接触角为63.6°,膜剥离强度为0.2756kN/m。接着以PVDF/SMA膜为主要研究对象测试了凝固浴温度对共混超滤膜的纯水通量以及BSA截留率的影响,该实验的结果表明凝固浴温度的改变对膜性能没有产生明显的影响。因此,选择在常温凝固浴温度下测试不同凝固浴成分对共混膜性能的影响。探究了膜在凝固浴成分分别为N,N-二甲基乙酰胺(DMAc)(质量分数为3%、6%、9%)、氯化钠(NaCl)(0.05mol/L、0.1mol/L、0.2mol/L)和乙醇(质量分数为3%、6%、9%)时的膜性能变化,以及对各个组分得到的膜样本进行扫描电子显微镜(SEM)表征。结果表明,随着DMAc含量增加,膜表面的孔在减少,且膜皮层的厚度增加,使得膜的水通量减少而BSA截留率提高。而随着NaCl浓度...     

聚砜酰胺原液凝固性能研究

研究了凝固浴浓度、原液温度、聚合物相对分子质量、凝固浴中的盐分、共聚物分布序列和第三单体物质的量对聚砜酰胺原液的凝固值和临界浓度的影响。结果表明：凝固浴浓度越高,凝固值越高,而临界浓度基本不变;随着原液温度的提高,凝固值略有提高,临界浓度略有下降;凝固浴中盐分含量越大,凝固值越高,临界浓度越低;聚合物相对分子质量越大,凝固值越低,临界浓度越高;共聚物大分子链越规整,第三单体含量越少,则凝固值越低,临界浓度越高。     

γ-BL/TEP混合溶剂对PVDF膜结构和性能的影响

通过溶解度参数预测,膜渗透性能检测,及扫描电镜(SEM)对膜形貌观察,考察了聚偏氟乙烯(PVDF)在γ-丁内酯(γ-BL)、磷酸三乙酯(TEP)为混合溶剂,乙二醇(EG)、N,N-二甲基乙酰胺(DMAc)及其混合物为凝固浴时,相转化条件及溶剂配比对PVDF膜在孔隙率、纯水通量、BSA截留率,以及拉伸强度等性能方面的影响行为。结果表明,随混合溶剂中TEP质量分数的增加,凝胶浴中溶剂DMAc质量分数增大,PVDF膜皮层逐渐变薄,PVDF结晶球粒粒径变小,孔隙率增加,拉伸强度下降。当混合溶剂中TEP的质量分数为60%,凝胶浴DMAc含量30%时,膜纯水通量达2 100 L/(m2·h),BSA截留率仍保持58.7%,具有良好的超滤性能,可作为制备高通量、较高截留PVDF超滤膜的最佳条件。     

N-甲基吗啉含量测定方法研究

建立测定N-甲基吗啉含量测定的非水滴定法。以醋酐作溶剂,结晶紫作指示剂,照指示剂法用高氯酸滴定液滴定。本法测定值的相对标准偏差RSD均小于2%。本法操作简单,滴定终点清晰,重复性好,可作为测定N-甲基吗啉含量的方法。     

A method for determination of thermodynamics and solubility parameters of polymers in dilute solutions from critical volume fractions

An equation using the critical volume fraction and segment number of polymer was proposed for the partial molar entropy change of a polymer for mixing in dilute solution. The partial molar enthalpy change of polymer for mixing was determined from the thermodynamic equilibrium property of two polymer phases at the critical temperature. The solubility or cohesion parameter of a polymer fraction at the critical temperature was calculated by using the partial molar enthalpy change and repeat unit volume of the polymer. The solubility parameter of high molar mass polymer at the theta temperature was determined by extrapolating solubility parameter values of the polymer fractions to high molar mass by using the solubility parameter-segment number relation of polymer fraction. This relation gives good straight line. The solubility parameter of the polymer at the theta temperature and the exchange energy parameter for polymer-solvent pair were obtained directly from the intercept and the slope of this line, respectively. These equations were applied to the critical point data of polystyrene (PS) in methylcyclohexane (MCH) and in cyclohexane (CH) solutions. The results obtained in this study coincide with the literature values for the solubility parameter of PS and exchange energy parameter for PS in CH solution. It was also found that the partial molar entropy change of a polymer for mixing at theta temperatures has about a constant value.     

Phase behavior and mechanism of formation of protofiber morphology of solution spun poly(acrylonitrile) copolymers in DMF‐water system

Phase diagrams of a series of copolymers of acrylonitrile (AN) and acrylic acid (AAc) were constructed using linearized cloud point correlation. The miscibility region in the phase diagram was found to increase with the increase in AAc content of the copolymers. For various compositions, χ₁₃ (polymer–water interaction parameter) values were estimated by sorption experiment. As the hydrophilic nature of the polymer increased with the increase in the content of acrylic acid, the χ₁₃ interaction parameter was found to decrease from poly(acrylonitrile) homopolymer to its copolymer with 50 mol % acrylic acid (AA50B). The polymer–solvent interaction parameters (χ₂₃) and composition at the critical points for all the polymers were determined by fitting the theoretical bimodal curves to the experimental cloud point curves using Kenji Kamide equations. The polymer composition at the critical point was found to increase by 400% with increasing AAc content. The polymers were solution spun in DMF‐water coagulation bath at 30°C and their protofiber structures were investigated under scanning electron microscopy. The observed morphological differences in protofibers were explained on the changes brought about in the phase separation behavior of the polymer–solvent–nonsolvent systems. The copolymers with higher acrylic acid content could be solution spun into void free homogeneous fibers even at conditions that produced void‐filled inhomogeneous fibers in poly(acrylonitrile) and its copolymers with lower AAc content. The experiments demonstrate the important role of thermodynamics in deciding the protofiber morphology during coagulation process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

基于称量法的聚砜酰胺原液凝固过程

将聚砜酰胺纺丝液从注射器中注入二甲基乙酰胺(DMAc)水溶液中成形并凝固,通过计量凝固样品质量随时间的变化来考察在不同凝固浴条件下的凝固速率,并观察凝固样品的横断面形貌。结果表明:凝固样品质量的变化可以直观地反应不同凝固浴条件下聚砜酰胺-DMAc-H2O三元体系凝固速率的变化;随凝固浴浓度的提高,凝固速度减小,截面由非圆形变为圆形,并趋于均匀化、致密化;凝固温度由15℃升高到60℃,凝固速度加快,并且从30℃开始纤维内部出现很多微小孔洞甚至出现中空,但温度对截面圆整度影响不显著。     

湿纺凝固条件对PAN初生纤维形态结构的影响

分析了凝固浴温度、浓度、表观负拉伸等凝固条件对聚丙烯睛初生纤维形态结构的影响规律及作用机理,得出最佳的凝固工艺参数。结果表明:在其他凝固参数不变时,凝固浴温度、浓度及表观负拉伸均存在各自的临界值,低于或超过此临界值,初生纤维及原丝的性能均下降;采用凝固浴温度60℃、凝固浴质量分数为65％的最佳凝固工艺参数,可获得截面圆形且结构致密的初生纤维,并制得力学性能优异的原丝。     

酚酞基聚醚砜溶液的流变性研究

采用锥板式流变仪研究了酚酞基聚醚砜/二甲基乙酰胺(PES-C/DMAc)的流变性能。结果表明:溶液的质量分数为18%～28%时,PES-C/DMAc溶液属于切力变稀流体,随着PES-C浓度的增加,非牛顿指数降低,零切粘度上升;溶液温度为20～100℃时,随着溶液温度的升高,PES-C/DMAc溶液非牛顿指数上升,零切粘度降低。温度升高,有利于提高溶液的可纺性。根据Arrhenius方程,溶液质量分数为18%～28%,PES-C/DMAc溶液的粘流活化能随浓度的增加而缓慢增加,但变化不大。     

聚醚砜／二甲基乙酰胺溶液流变性的研究

采用锥板式流变仪研究聚醚砜／二甲基乙酰胺(PES／DMAc)溶液的流变性能。结果表明：PES／DMAc溶液(质量分数为18％～28％)属非牛顿流体中的假塑性流体，表观粘度随温度和剪切速率提高而降低，具有切力变稀行为。溶液的剪切应力随浓度升高而增大，同一剪切速率下，随温度的升高而降低，非牛顿指数(n)值随溶液温度的升高而逐渐增大。     

Effects of different coagulation conditions on polyacrylonitrile fibers wet spun in a system of dimethylsulphoxide and water

Polyacrylonitrile (PAN) precursors were prepared by the wet spinning way. The effects of the coagulation conditions, such as coagulation temperature, coagulation ratio, and coagulation concentration, are discussed in detail. While keeping the coagulation bath concentration constant, as the coagulation bath temperature increased, the cross section deviated less from a circular form, and the as‐spun fiber diameter decreased. Measurement to the rate of the boundary movement has been calculated depending on the coagulation rate. While keeping the coagulation bath temperature constant, high coagulation bath concentration can cause more coagulant to diffuse into the solution to the polymer precipitated consequently, which led to a faster coagulation rate. The as‐spun fiber from high coagulation concentration was compacted than those from low concentration. The character of the formed structure reflected the system mobility and capability to crystallize. Improvement in fiber density in the as‐spun fiber resulted in improvements in the tensile strength of the as‐spun fiber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3723–3729, 2007