聚偏氟乙烯在不同温度乙醇中的结晶行为

将聚偏氟乙烯(PVDF)的N,N-二甲基甲酰胺(DMF)浓溶液逐滴滴入大量的非溶剂无水乙醇中,研究PVDF在不同温度乙醇中的结晶行为,考察温度对PVDF晶型、结晶形貌和热行为的影响。采用傅里叶变换红外光谱仪(FT-IR)、X线衍射仪(XRD)、扫描电子显微镜(SEM)和差示扫描量热仪(DSC)表征样品性能。结果表明:PVDF在乙醇中结晶时主要形成α晶和少量的β晶,且α晶的含量随温度升高而增大;样品中的许多较小片状或球状的黏结结构,实质为PVDF的初级小晶体;在不同温度乙醇中结晶的PVDF具有相似的熔融曲线,但在较高温度下结晶时,会导致结晶度下降。     

聚偏氟乙烯/偏氟乙烯-三氟氯乙烯共聚物的共混相容性及结晶性

将聚偏氟乙烯(PVDF)颗粒与偏氟乙烯-三氟氯乙烯共聚物(P(VDF-CTFE))物理共混后采用溶液浇注的方法制备成共混薄膜.通过差示扫描量热仪、X线衍射、傅里叶变换红外光谱和扫描电镜等方法对PVDF/P(VDF-CTFE)共混薄膜的相容性、结晶行为及表面形貌进行分析.研究结果表明:PVDF/P(VDF-CTFE)体系中P(VDF-CTFE)作为一种无规共聚物在与PVDF共混时有一定的相容性,影响着PVDF的结晶-熔融热力学特征;PVDF/P(VDF-CTFE)共混结晶时,P(VDF-CTFE)的存在有利于形成β型晶体;PVDF均匀地分散在P(VDF-CTFE)相中,而且随着PVDF含量的减少,分散点的PVDF球晶数量越少.     

稀释剂对混合相分离法制备聚偏氟乙烯膜的影响

以聚偏氟乙烯(PVDF)为基材,分别选用N,N-二甲基乙酰胺(DMAc)、苯丙酮为溶剂和稀释剂,通过将热致相分离(TIPS)和非溶剂致相分离(NIPS)相混合的方法制备了PVDF膜。研究结果表明,随稀释剂含量的增加,膜断面结构由大球晶转变为双连续的结构,膜上表面(空气面)致密层厚度减小,膜下表面(玻璃面)孔径逐渐变小。同时膜纯水通量随稀释剂含量增加而增大,牛血清蛋白(BSA)截留率和拉伸强度由于膜结构的变化而略有降低。     

两亲聚合物改性聚偏氟乙烯膜及其渗透性能

采用大分子单体法合成了含有聚氨酯丙烯酸酯链段和聚甲基丙烯酸甲酯链段的两亲聚合物。将两亲聚合物添加到聚偏氟乙烯(PVDF)原材料中通过相转化法制得聚合物分离膜。通过红外光谱(FT-IR)表征了大分子单体的结构,用凝胶渗透色谱(GPC)仪测定了两亲聚合物的分子量;利用扫描电子显微镜(SEM)观察了膜表面形貌;研究了超滤膜的纯水渗透通量、截留性能、膜表面亲水性和耐污染性等性能。研究表明,随着两亲聚合物含量从0增加到15%,纯水渗透通量由纯PVDF膜的23 L/(m2.h)提高到122 L/(m2.h),膜表面水接触角下降,膜渗透通量衰减实验表明膜的耐污染性得到提高。     

链结构对聚偏氟乙烯介电性质的影响

对已商品化的粘弹、压电、介电联用谱仪进行改进,使其测试精度由1%提高到2‰。利用改进了的仪器对聚偏氟乙烯(PVDF)及偏氟乙烯(95)/氟乙烯(5)共聚物进行了介电性质研究,发现由于5%氟乙烯存在,致使共聚物较之PVDF,其链结构规整性降低,α型介电松弛消失,非晶松弛强度减弱,T_(?)升高3℃,局域松弛活化能增大5.8kJ/mol及松弛时间延长。     

聚偏氟乙烯粘结剂溶液干燥条件对锂电池用石墨负极附着力的影响

聚偏氟乙烯（PVDF）溶液的干燥条件对其结晶性、粘结强度有很大影响,对制备锂离子电池的电极材料亦有影响．为此,设计了一种薄膜剥皮试验来评估PVDF附着于石墨的机械强度;以XRD和电池循环来测量不同热处理条件下PVDF粘结剂的影响．结果表明,在高于PVDF熔点的温度处理的样品,PVDF具有更高的结晶性和附着力,从而改善了石墨电极的循环性能,还观察到前150次循环过程中的容量逐步上升现象．PVDF的逐渐溶胀被认为是出现该现象的原因．     

聚偏氟乙烯/聚醚砜共混中空纤维膜的研究--聚醚砜和聚乙烯吡咯烷酮含量的影响

用聚偏氟乙烯纺制的中空纤维膜，在干燥过程中会产生大量的收缩，通过与聚醚砜共混，使膜的收缩率大幅降低。同时我们还研究了不同的聚醚砜含量、铸膜液浓度和添加剂含量对膜结构和性能的影响。     

氧化多壁碳纳米管、PEG及PVP添加剂对PVDF膜性能的影响

通过引入亲水性添加剂是改善膜聚偏氟乙烯(PVDF)膜亲水性和膜结构的一种有效方法.在本研究中,利用氧化碳纳米管(O-MWNTs)和聚乙二醇(PEG)及聚乙烯吡咯烷酮(PVP)修饰PVDF膜.对添加剂对PVDF膜的结构、渗透性能、亲水性、结晶行为等影响进行了详细研究.结果表明:加入O-MWNTs可以提高PVDF膜的渗透通量、亲水性和机械性能.当铸膜液中添加0.6% O-MWNTs和5% PEG 200或者0.6% O-MWNTs和3% PVP时,所制PVDF膜渗透通量分别达到222.9±12.5 L·^-2·h^-1·bar^-1和 256.9±14.8 L·m^-2·h^-1·bar^-1.添加剂PEG200可以强化O-MWNTs的分散性,并能够促进相转化过程中溶剂与非溶剂间物质交换.PVP作为致孔剂能够促进孔生长和纯水通量提高.     

Temperature-sensitive goldnanotube array membranes modified with poly(N-isopropylacrylamide)

A kind of temperature-sensitive nanotube array membrane was developed by modifying gold-nanotube array membranes with poly(N-isopropylacrylamide) (PNIPAm). The permeation ability of the mem-branes at different temperatures was investigated using sodium fluorescein and quantum dots as probes. The results showed that the pore diameter of nanotube was changed due to the reversible re-sponse of PNIPAm-modified membranes to temperature, and then the permeation ability of the mem-branes was changed. The permeation of fluorescence probes was slow and even almost blocked at 25℃ (below the lower critical solution temperature, LCST), since PNIPAm formed expanded structures and decreased the pore size. While at 40℃ (above the LCST), the permeation was increased, since PNIPAm became compact structures and the pore diameter was increased. Furthermore, the permea-tion ability of the temperature-sensitive nanotube array membranes could be adjusted reversibly and it is possible to use the membranes in nanofluidic devices, nanogates, etc.     

Structure and properties of solid-state synthesiz ed poly (3,4-propylenedi oxythiophene) /nano-ZnO composite

Poly（3,4-propylenedioxythiophene）/nano-Zinic Oxide（PProDOT/ZnO） composites with the content of 3-7 wt%nano-ZnO were synthesized by the solid-state method with FeCl₃ as oxidant.The structure and morphology of the composites were characterized by Fourier transform infrared（FTIR）spectroscopy,ultraviolet-visible（UV-vis） absorption spectroscopy,X-ray diffraction（XRD） and transmission electron microscopy（TEM）.The electrochemical performances of the composites were investigated by galvanostatic charge-discharge,cyclic voltammetry and electrochemical impedance spectroscopy（EIS）.The photocatalytic activities of the composites were investigated by the degradation of methylene blue（MB） dyes in aqueous medium under UV light irradiation.The results from FTIR and UV-vis spectra showed that the PProDOT/ZnO composites were successfully synthesized by solid-state method,and nano-ZnO had great influences on the conjugation length and oxidation degree of the polymers.Furthermore,the PProDOT/5 wt%ZnO had the highest conjugation and oxidation degree among the composites.The results of XRD analysis indicated that there were some FeCl₄^- ions as doping agent in the PProDOT matrix,and the content of ZnO had no effect on diffraction pattern of PProDOT.Morphological studies revealed that the pure PProDOT and composites had similar morphological structure,and all the composites displayed an irregular sponge like morphology.The results of electrochemical tests showed that the PProDOT/5 wt%ZnO had a higher electrochemical activity with a specific capacitance value of 220 F g^-1 than others.The results from photocatalytic activities of the composites indicated that the PProDOT/5 wt%ZnO had better photocatalytic activity than other composites.     

壳聚糖/聚乙烯醇复合纳米纤维膜的制备

用静电纺丝技术制备壳聚糖/聚乙烯醇复合纳米纤维膜,探讨了不同浓度、分子量及聚乙烯醇添加比例对纳米纤维膜成形的影响,运用扫描电镜对纳米纤维膜的形貌进行了分析,同时对其力学和亲水性能进行了测试.结果表明:当分子量为5×105g/mol、质量分数为4%、聚乙烯醇的添加比例为40%时,所制备复合纳米纤维膜具有良好的形貌,具有一定的力学性能,且呈疏水性.     

PVDF/Al_2O_3杂化膜的制备与性能表征

为了改善聚偏氟乙烯(PVDF)超滤膜的性能,采用溶胶-凝胶法,通过PVDF与异丙醇铝(AIP)的原位聚合,制备了不同Al2O3含量的PVDF/Al2O3杂化超滤膜.并采用扫描电镜、红外光谱、超滤实验、接触角和机械性能测试等手段对膜的结构和性能进行了表征.结果表明:AIP在注膜液中发生了水解聚合反应,生成铝氧聚合物掺杂在杂化膜中,并与PVDF发生键联;当AIP添加量为12%时,杂化膜的纯水通量比纯PVDF膜提高了83.36%,其对BSA的截留率由88.27%提高到96.64%,且膜的亲水性、机械性能和抗污染性都得到改善.     

聚苯撑乙炔与电子受体共聚物的合成及光伏研究

利用钯催化剂(Pd(PPh3)2Cl2)和相转移催化剂(PTC),采用Heck交叉偶联缩聚反应合成了聚(苯撑乙炔撑-苯并噻二唑)系列交替共聚物(PPE-BT),比较了聚合物的紫外吸收光谱和荧光光谱特征。PPE-BT与给体MEH-PPV构成器件时,其能量转换效率为2.54×10-3,说明电子在PPE-BT和PPE-DCNTB中的迁移率较小。     

PBs/PET共混体系的制备与表征

以丁二酸、丁二醇为原料,通过直接缩聚反应合成了高分子量聚丁二酸丁二醇酯。并将聚丁二酸丁二醇酯 (PBS)同聚对苯二甲酸乙二醇酯 (PET)在不同温度下熔融共混。测定了不同组分共混物的熔点和水降解性。聚合物熔融峰随着共混时间的增加渐渐的下移。这说明PBS和PET热降解和酯交换反应随着共混温度的增加而同时发生。共混物的降解性与芳香组分的含量和链段长度都有关。     

氯甲基杂萘联苯聚醚砜的制备及表征

采用杂萘联苯聚醚砜(PPES)与氯甲醚反应,制备了氯甲基杂萘联苯聚醚砜(CMPPES).用FTIR、1H-NMR等测试手段对聚合物的结构进行了表征,用氧瓶燃烧法对产物中氯含量进行了测定.为了获得不同氯甲基进程的产物,考察了溶剂、反应温度、氯甲醚用量、不同催化剂及其用量对产物中氯含量的影响,得到了特定氯含量的适宜的合成工艺条件.     

Investigation of performances and mechanism of fluoride removal by Fe (III)-loaded ligand exchange cotton cellulose adsorbent

Novel adsorbent, Fe(III)-loaded ligand exchange cotton cellulose adsorbent [Fe(III)LECCA], was used to investigate the adsorption performances and mechanism of fluoride removal from aqueous solutions. The adsorbent was found to adsorb fluoride rapidly and effectively. The fluoride removal was influenced by pH. Adsorption model followed first-order reaction at different temperature, theapparent adsorption activated energyE, was 6.37 kJ·mol⁻¹, and adsorption enthalpy ΔH was 5.35 kJ·mol⁻¹. The adsorption capacity of fluoride on adsorbent was 3.2 mmol·g⁻¹ (dry weight). The maximal integer coordination ratio of fluoride with Fe(III) LECCA was 3∶1. The ligand exchange mechanism of adsorption was elucidated through chemical methods and IR spectral analysis. Foundation item: Supported by the National Natural Science Foundation of China (29977010) and Shanghai Priority Academic Discipline Biography: ZHAO Ya-ping (1974-), female, Ph.D., research direction: water and wastewater treatment.     

Wet spinning of PVA composite fibers with a large fraction of multi-walled carbon nanotubes

PVA composites fibers with a large fraction of multi-walled carbon nanotubes modified by both covalent and non-covalent functionalization were produced by a wet-spinning process.Model XQ-1 tensile tester,thermogravimetric analysis,scanning electron microscopy,differential scanning calorimetry,and wide-angle X-ray diffraction were used to characterize the properties of PVA/MWNT composite fibers.The TGA results suggested that MWNTs content in composite fibers were ranged from 5.3 wt%to 27.6 wt%.The mechanical properties of PVA/MWNT composite fibers were obviously superior to pure PVA fiber.The Young's modulus of composite fibers enhanced with increasing the content of MWNTs,and it rised gradually from 6.7 GPa for the pure PVA fiber to 12.8 GPa for the composite fibers with 27.6 wt%MWNTs.Meanwhile,the tensile strength increased gradually from 0.39 GPa for the pure PVA fiber to 0.74 GPa for the composite fibers with 14.4 wt%MWNTs.Nevertheless,the tensile strength of the composite fibers decreased as the MWNTs content up to 27.6 wt%.SEM results indicated that the MWNTs homogeneously dispersed in the composite fibers,however some agglomerates also existed when the content of MWNTs reached27.6 wt%.DSC results proved strong interfacial interaction between MWNTs and PVA chain,which benefited composite fibers in the efficient stress-transfer.WXAD characterization showed that the orientation of PVA molecules declined from 94.1%to 90.9%with the increasing of MWNTs content.The good dispersibility of MWNTs throughout PVA matrix and efficient stress-transfer between MWNTs and PVA matrix may contributed to significant enhancement in the mechanical properties.     

聚乳酸-聚乙二醇嵌段共聚物及其交联聚氨酯弹性体的性能研究

通过改变聚乙二醇的用量,将丙交酯与聚乙二醇共聚制成嵌预聚体,用二苯基甲烷二异氰酸酯扩链后再用三羟甲基丙烷交联,制得系列聚氨酯型新颖性体。通过对其性能研究表明,随着ＰＥＧ含量的增加,共聚物的特性粘度降低,玻璃化转变温度降低,拉伸强度先升后降;聚氨酯弹性体的玻璃化转变温度降低,拉伸强度降低,而降解速度去加快。     

PVDF/Al2O3杂化膜的结构及性能表征

为了改善超滤膜的使用性能,采用溶胶-凝胶法,在聚偏氟乙烯(PVDF)注膜液中直接添加异丙醇铝(AIP),制备了不同Al2O3含量的PVDF/Al2O3杂化超滤膜.并用扫描电镜、红外光谱、超滤实验、接触角和机械性能测试等手段对膜的结构和性能进行了表征.结果表明: 由于AIP发生水解聚合反应,生成铝氧聚合物掺杂在杂化膜中,并与PVDF发生键联.当AIP添加量为12%时,杂化膜的通量比纯PVDF膜提高了83.36%,截留率由88.27%提高到96.64%,同时膜的亲水性、机械性能和抗污染性都得到改善.     

Enhanced flame-retardant performance of poly (lactic acid) (PLA) composite by using intrinsically phosphorus-containing PLA

The intrinsically phosphorous-containing flame-retardant poly(lactic acid)(P-PLA) was synthesized through the chain extension of L-lactide and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) derivative, then P-PLA was melt blended with neat PLA to produce flame-retardant PLA composite(FR-PLA). The flame-retardant properties of FR-PLAs were investigated by Limiting Oxygen Index(LOI), UL-94, and Cone Calorimeter Tests, the results indicated that the flame-retardant properties of PLA composites were significantly improved with the addition of P-PLA due to its excellent ability to carbonize and dilute combustible gases. The LOI value of FRPLA10 composite(consisting of 90 wt% neat PLA and 10 wt% P-PLA) increased from 20.5 to 27.8 and UL-94 rating reached up to V-1, the peak heat release rate and total heat release of FR-PLA composite were lower than those of neat PLA. The flame-retardant mechanism of FR-PLA depended on both condensed and gaseous phases,which was confirmed by the FTIR, Raman and TG-FTIR. Besides, the tensile strength of FR-PLA10 slightly decreased from 72.4 to 61.8 MPa, which met the requirements of most practical applications. Therefore, the modification method used in this work presented a feasible approach to prepare FR-PLA composite with satisfactory mechanical property.