环境对水解的疏水改性聚丙烯酰胺的分子行为和性能的影响

以介观模拟耗散颗粒动力学(DPD)方法为主,结合部分实验,研究了环境条件包括p H、盐度以及外加表面活性剂十二烷基磺酸钠(SLS)对疏水改性水解聚丙烯酰胺(HMHPAM)的分子行为和体相及界面性质的影响.将均方根末端距量化表征的聚合物伸展程度与其体相黏度结合起来,通过调整相互作用参数分别讨论了无机盐的水化作用和静电作用对聚电解质HMHPAM分子行为的影响,确定HMHPAM的最佳应用环境.进一步研究了表面活性剂SLS对HMHPAM界面性质和体相性质的影响,提出了作用机制.     

电荷密度和疏水性对疏水改性聚丙烯酰胺与牛血清蛋白相互作用的影响

对比研究了牛血清蛋白(BSA)与部分水解的未改性聚丙烯酰胺(PAM-AA)、疏水改性聚丙烯酰胺(PAM-C12)和含有丙烯酸基团的疏水改性聚丙烯酰胺(PAM-C12-AA)之间的相互作用.等温滴定量热实验结果表明,除PAM-C12外,其他聚合物与BSA的结合焓均为放热,随AA含量的增加,放热焓值增大.与PAM和PAM-C12相比,PAM-C12-AA能够诱导BSA二级结构和微环境的明显变化,表明疏水性和电荷密度均对聚合物与BSA相互作用有重要影响.另外,不同浓度的PAM-C12-AA与BSA的作用方式不同,当聚合物的浓度略高于临界胶束浓度(CMC)时,由于聚合物的量较少,BSA分子改变其构型从而最大程度地与聚合物结合;当聚合物的浓度远高于CMC时,更多的聚合物链结合到BSA分子的正电荷"patch"上,PAM-C12-AA与BSA的紧密聚集体利于BSA二级结构的稳定.     

疏水改性聚丙烯酰胺溶液的分子模拟

设计了几种不同的非离子型改性聚丙烯酰胺(HM-PAM)和阴离子型改性聚丙烯酰胺(HM-HPAM). 通过分子动力学模拟(MD)方法研究了在聚合物链上加入不同疏水改性单体对提高聚丙烯酰胺耐盐性的影响, 考察了盐浓度对疏水改性聚丙烯酰胺的回旋半径(R_g)、 特性黏数([η])、 径向分布函数(RDF)和均方位移(MSD)的影响以及聚合物的微观结构与特性黏数之间的关系. 研究结果表明, 引入疏水改性单体后, 改性聚丙烯酰胺具有较好的耐盐性. 通过研究非键作用与氢键相互作用可知, 体系中溶质和溶剂间的相互作用及氢键作用越弱, 溶液的特性黏数越大. O-H原子对的RDF结果表明, 聚合物链的伸展与聚合物链及官能团间的相互作用有关. 当RDF峰较弱时, 聚合物链与水的作用越弱, 越有利于聚合物链保持舒展状态, 溶液的特性黏数也就越大. 另外, 从聚合物链的MSD曲线发现, 聚合链的移动性与特性黏数呈负相关.     

疏水缔合聚丙烯酰胺与双子表面活性剂的相互作用

制备了一种脂肪酸酯双磺酸盐型双子表面活性剂, 利用粘度法、界面张力法和原子力显微镜研究了疏水缔合聚丙烯酰胺与双子表面活性剂在溶液中的相互作用. 实验结果表明: 疏水缔合聚丙烯酰胺在溶液中能够通过自组装形成疏水微区并发展成网络结构, 疏水微区与表面活性剂在溶液中能形成混合胶束; 当一定量的表面活性剂加入时, 对疏水缔合聚丙烯酰胺的自组装起促进作用, 而过多双子表面活性剂的加入又会对聚合物分子的自组装起抑制作用, 从而显著影响疏水缔合聚丙烯酰胺的溶液性质, 随着表面活性剂浓度的增加, 聚合物溶液粘度先增加、再降低; 同时, 疏水缔合聚丙烯酰胺对双子表面活性剂的界面性能也有较大影响, 聚合物的加入使双子表面活性剂降低油/水界面张力的能力下降, 油/水界面张力达到平衡所需时间延长.     

聚乙烯醇调控水溶性共轭聚噻吩的光学性质

针对发光共轭聚合物稀溶液在干燥形成固体时的荧光淬灭问题, 通过高分子聚乙烯醇(PVA)的氢键网络调控水溶性共轭聚噻吩在溶液中的聚集行为和构象, 并采用不同的干燥方式实现了调控其固体光学性质的目的. 紫外-可见光吸收、荧光发射光谱测试表明, 在水溶液中PVA可以分散共轭聚合物链, 并增强其共平面性; 高温干燥后, 聚噻吩薄膜与无PVA添加的聚噻吩溶液的荧光性质相似; 而采用冷冻干燥法, 薄膜则保留了添加PVA后混合溶液的发光特性. 该结果表明, PVA对聚噻吩在溶液状态下的聚集/分子构象的调控行为随干燥方式的不同得到了不同程度的保留——高温加热干燥仅维持了PVA对聚噻吩的分散作用; 而冷冻干燥则完整保留了PVA与聚噻吩的分子间相互作用, 将溶液中分子的分散状态和构象同时固定. 本研究从干燥方式的角度为固态共轭聚合物聚集行为及发光性质的调控提供了新的策略.     

表面活性剂对驱油聚合物界面剪切流变性质的影响

利用双锥法研究了表面活性剂十二烷基苯磺酸钠(SDBS)和十六烷基三甲基溴化铵(CTAB)对油田现场用部分水解聚丙烯酰胺(PHPAM)和疏水改性聚丙烯酰胺(HMPAM)溶液的界面剪切流变性质的影响,实验结果表明:HMPAM分子通过疏水作用形成界面网络结构,界面剪切复合模量明显高于PHPAM.SDBS和CTAB通过疏水相互作用与HMPAM分子中的疏水嵌段形成聚集体,破坏界面网络结构,剪切模量随表面活性剂浓度增大明显降低.同时,界面膜从粘性膜向弹性膜转变.低SDBS浓度时,少量SDBS分子与PHPAM形成混合吸附膜,界面膜强度略有升高;SDBS浓度较高时,界面层中PHPAM分子被顶替,吸附膜强度开始减弱.阳离子表面活性剂CTAB通过静电相互作用中和PHPAM分子的负电性,造成聚合物链的部分卷曲,从而降低界面膜强度.弛豫实验结果证实了表面活性剂破坏HMPAM网络结构的机理.     

疏水缔合聚合物重均分子量的测定

采用毛细管法和荧光探针法研究了疏水缔合聚合物在不同甲酰胺浓度和盐浓度的溶剂中的特性黏数和疏水缔合作用强度.找到可以消除缔合作用和聚电解质效应的溶剂条件,用静态光散射法测定疏水缔合聚合物的重均分子量.结果表明,NaCl能够有效的屏蔽聚电解质效应,但是不能消除缔合作用,而且由于NaCl增加了溶液的极性,会进一步促进疏水缔合作用,疏水缔合聚合物以聚集体形态存在溶液中,因此,在NaCl溶剂中测得的疏水缔合聚合物的重均分子量不是真实分子量;而甲酰胺可以完全破坏疏水缔合作用,使聚合物分子以单分子态分散在溶液中,进而测得疏水缔合聚合物的真实分子量.当溶剂中的NaCl浓度为0.2 mol/L、甲酰胺体积分数为50%时,可准确测定疏水缔合聚合物的重均分子量.当缔合作用消除后再改变甲酰胺浓度,测得的重均分子量不再变化;聚电解质效应消除后,盐离子浓度的变化不会再改变测得的重均分子量结果.     

新型疏水缔合聚合物P(AM/POEA)与表面活性剂的相互作用

采用粘度法、荧光探针和透射电镜研究了新型疏水缔合聚合物P(AM/POEA)和表面活性剂SDS和CTAB在水溶液中的相互作用. 聚合物P(AM/POEA)结构中, 疏水体(2-苯氧乙基丙烯酸酯)呈嵌段状无序地分布在聚丙烯酰胺主链上. 这类聚合物很容易和表面活性剂相互作用, 通过疏水缔合, 形成混合胶束状聚集体, 导致溶液粘度剧增. 随聚合物溶液中SDS的加入, 溶液粘度发生大幅度起伏变化, 出现最大值. 粘度最大值对应的表面活性剂浓度c_S,max位于表面活性剂CMC附近, 并发现它的位置不随聚合物微结构而变化. 然而它们缔合作用的增粘程度却与聚合物疏水体含量X_H及疏水嵌段尺寸N_H有关. 在实验浓度范围内, X_H和N_H愈大, 溶液的粘度越高. 此外用透射电镜直接观察到聚合物/表面活性剂体系中聚集体的交联结构形貌.     

疏水改性聚丙烯酰胺的增粘机理研究

通过与聚丙烯酰胺（PAM）对比,使用荧光光谱、紫外光谱、原子力显微镜以及流变性实验对疏水改性聚丙烯酰胺(HMPAM)的溶液行为和微观结构进行了研究.通过荧光实验I3/I1值的变化确定了HMPAM的临界缔合浓度.结合荧光、紫外及流变性实验,对HMPAM在溶液中通过疏水缔合形成疏水微区、超分子聚集体及发展到空间网络的结构变化进行了研究.用原子力显微镜证实了HMPAM溶液中网络结构的存在.对HMPAM表现出的特殊流变性从微观上找到了依据,提出了HMPAM的增粘机理.     

聚氰基丙烯酸乙酯空心纳米纤维的制备

通过溶液聚合法制备了具有空心结构的聚氰基丙烯酸乙酯纳米纤维,纤维直径为50~100 nm.研究了3种溶液体系对形成聚氰基丙烯酸乙酯纳米纤维形貌与直径的影响,并探讨了其形成机理.通过调控溶液体系内外环境可得到不同形貌的聚合物纤维,且纤维表面表现出疏水性质.该方法适用于平整且具有粗糙结构的表面.所形成的聚氰基丙烯酸乙酯纳米纤维涂层可用于基底的疏水改性.     

Ion conducting properties of poly(ethylene oxide)-based electrolytes incorporating amorphous silica attached with imidazolium salts

Poly(ethylene oxide) (PEO)-based polymer electrolytes containing amorphous silica attached ionic liquid (IL) were studied in order to improve electrochemical and interfacial properties. An imidazolium salt such as IL was attached to modified ceramic fillers. The modified ceramic fillers were amorphous silica with the immobilized 1-methyl-3-propyl-imidazolium bromide (MPIm-AS). PEO-based polymer electrolytes were prepared by using the solution casting technique. In order to investigate the ionic conductivity, studies on the modified filler addition effects on the ion-conducting behavior of polymer electrolytes having specific amounts of MPIm-AS were carried out. The addition of MPIm-AS in polymer electrolytes has resulted in higher ionic conductivity at room temperature. The structure, crystallinity, and morphology of the solid polymer electrolytes were evaluated using X-ray diffraction, differential scanning calorimetry, and scanning electron microscope measurement. The ionic conductivity was measured by an AC impedance method. The enhanced conductivity was dependent on the decreased crystallinity and the changed morphologies of composites.     

Synthesis of a Water Dispersion of the PEDOT:PSS/Pd Composite and Its Use for the Fabrication of an Electrochemical Sensor for Hydrazine

Conditions are studied for the synthesis of water dispersions of polymer composites containing palladium and the possibility of their use for the fabrication of modified electrodes is estimated. Water dispersions of the polymer poly(3,4-ethylenedioxythiophene), including a polystyrene sulfate polyanion (PEDOT:PSS) and Pd particles, were obtained by the redox reaction of Pd(II) with the polymer. The electrochemical behavior of composite PEDOT:PSS/Pd films in the medium of a phosphate buffer solution with pH 6.86 is studied. It is shown that, in the presence of hydrazine in a phosphate buffer solution, one wave of hydrazine oxidation on metal inclusions, Pd particles, is observed on the electrode. Specific features of the process of hydrazine oxidation are studied and a possibility using the obtained material for the creation of an electrochemical sensor for hydrazine is demonstrated.     

In situ Raman spectroelectrochemical study of electrocatalytic processes at polyaniline modified electrodes: Redox vs. metal-like catalysis

Two processes of electrocatalytic oxidation of solution species at conducting polymer modified electrodes have been studied for the first time with in situ Resonance Raman spectroelectrochemical technique at a red laser excitation (λ = 632.8 nm), namely electrooxidation of hydroquinone at a sulfonated polyaniline modified electrode in an acidic solution and electrooxidation of ascorbic acid at polyaniline modified electrode in a pH-neutral solution. In both cases, characteristic Raman features have been identified for different redox forms of conducting polymers and changes in the net redox state of a polymer layer during electrooxidation of solution species have been studied. It has been shown that an increase in the concentration of oxidizable species causes an increase of the net content of a reduced form of polyaniline in the modifying layer. From this, the redox (vs. metal-like) mechanism of electrocatalysis at conducting polymer modified electrodes has been deduced.     

聚苯胺纳米纤维修饰石墨箔电极的制备及电化学性能

以石墨箔(GF)为工作电极, 采用循环伏安法(CV), 通过电化学聚合, 制备了聚苯胺(PANI)纳米纤维修饰GF电极(Nano-PANI/GF). 利用红外光谱(FTIR)研究了Nano-PANI/GF修饰电极上聚合物的组成, 利用扫描电镜(SEM)观测了Nano-PANI/GF修饰电极的表面形貌. 利用循环伏安法研究了Nano-PANI/GF修饰电极在0.1 mol/L磷酸盐缓冲溶液(pH=6.9)中的电化学活性, 发现Nano-PANI/GF修饰电极在中性溶液中有良好的电化学活性. Nano-PANI/GF修饰电极对抗坏血酸(AA)电化学氧化的催化作用结果表明, 在0.2 V(vs. SCE)电位下, 在浓度范围1.7~2.0×10³ μmol/L内, 抗坏血酸的氧化电流与浓度呈良好线性关系, 线性方程式为y=0.00013x+0.0031. 修饰电极对抗坏血酸的最低检测限为1.7 μmol/L(S/N=3).     

Electron Communication Between Electrode and Dye-Linked L-Proline Dehydrogenase in Organized Layer-by-Layer Multilayer Film

Multilayer film was fabricated on an electrode surface by alternate layer-by-layer(LBL) adsorption of polycationic redox polymer(PEI-Fc) and dye-linked L-proline dehydrogenase(L-proDH).The electrochemistry of the PEI-Fc/L-proDH multilayer modified electrode was investigated by cyclic voltammetry,and the enzyme catalysis mediated by the redox polymer was studied in a solution containing L-proline.It was observed that electron communication between L-proDH and the electrode was achieved with the help of PEI-F...     

Silver nanoparticle decorated poly(2-aminodiphenylamine) modified carbon paste electrode as a simple and efficient electrocatalyst for oxidation of formaldehyde

This work describes the promising activity of silver nanoparticles on the surface of a poly(2-amino diphenylamine) modified carbon paste electrode (CPE) towards formaldehyde oxidation. Electrodeposition of the conducting polymer film on the CPE was carried out using consecutive cyclic voltammetry in an aqueous solution of 2-aminodiphenylamine and HCl. Nitrogen groups in the polymer backbone had a Ag ion accumulating effect, allowing Ag nanoparticles to be electrochemically deposited on the surface of the electrode. The electrochemical and morphological characteristics of the modified electrode were investigated. The electro-oxidation of formaldehyde on the surface of electrode was studied using cyclic voltammetry and chronoamperometry in aqueous solution of 0.1 mol/L NaOH. The electro-oxidation onset potential was found to be around -0.4 V, which is unique in the literature. The effect of different concentrations of formaldehyde on the electrocatalytic activity of the modified electrode was investigated. Finally, the diffusion coefficient of formaldehyde in alkaline media was calculated to be 0.47 × 10^-6 cm²/s using chronoamperometry.     

疏水改性聚丙烯酸溶液的流变特性研究

本文通过沉淀聚合制备了具有不同主链结构的疏水改性聚丙烯酸(HMPA),由Huggins方程确定了HMPA在溶液(水,盐/水,醇/水)中的特性粘数[η]和Huggins常数KH,采用流变学法研究了HMPA溶液的疏水缔合行为和流变特性.研究表明,HMPA溶液具有典型的剪切变稀行为,主链结构对HMPA溶液的缔合行为和流变特性有显著影响.主链含有疏水链段的HMPA在乙二醇/水溶液中形成类似弹性体的凝胶网络结构,具有较大的活化能,其表观粘度具有明显的温度敏感性.     

Characterization of stainless steel electrode modified by a thin film of polyaniline containing pt particles and its electrocatalytic activity for methanol oxidation

The catalytic behavior of stainless steel (SS) electrode modified by a thin film of polyaniline (PANI) containing platinum particles was studied for electrooxidation of methanol and compared with a platinated Pt/PANI electrode in acidic aqueous solution. Cyclic voltammetry (CV), chronoamperometry, CO stripping techniques were used to investigate electrochemical properties and electrocatalytic activity of SS/PANI/Pt and Pt/PANI/Pt electrodes. The morphology and particle size of Pt catalysts were characterized by Transmission Electron Microscopy (TEM) measurement. The effects of various parameters such as thickness of polymer film, medium temperature and stability of the modified electrodes on methanol oxidation were also investigated. The results indicated that the modified SS electrode exhibited a considerably high electrocatalytic activity on the methanol oxidation as well as the modified Pt electrode.     

Poly(lactic acid) composites with poly(lactic acid)‐modified carbon nanotubes

This work reports the study of the effect of chemical functionalization of carbon nanotubes on their dispersion in poly(lactic acid). The nanotubes were functionalized by the 1,3‐dipolar cycloaddition reaction, generating pyrrolidine groups at the nanotube surface. Further reaction of the pyrrolidine groups with poly(lactic acid) was studied in solution and in the polymer melt. The former involved refluxing the nanotubes in a dimethylformamide/polymer solution; the latter was carried out by direct melt mixing in a microcompounder. The carbon nanotubes collected after each process were characterized by thermogravimetry and by X‐ray photoelectron spectroscopy, showing evidence of polymer bonded to the nanotube surface only when the reaction was carried out in the polymer melt. The composites with polymer modified nanotubes present smaller average agglomerate area and a narrower agglomerate area distribution. In addition, they show improved tensile properties at low CNT concentration and present lower electrical resistivity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3740–3750