聚乙烯醇基水凝胶聚合物电解质超级电容器的研究

以2-丙烯酰胺基-2-甲基丙磺酸（AMPS）作引发剂引发交联聚乙烯醇（PVA）-戊二醛（GA）制备水凝胶聚合物电解质并组装成超级电容器.分别由红外光谱、交流阻抗、循环伏安与恒电流充放电曲线测定该凝胶聚合物电解质及超级电容器的电化学性能.结果表明,该聚合物电解质电导率可达1.23 mS/cm（室温）.而且,以1.0 g AMPS引发0.05mL GA（5 %）与1.0 g PVA交联,制得的凝胶聚合物电解质超级电容器比电容可达139F/g,50次充放电后其值仍于80%以上.     

Polymer-Based Superhydrophobic Coating Fabricated from Polyelectrolyte Multilayers of Poly(allylamine hydrochloride) and Poly(acrylic acid)

Superhydrophobic films mainly based on poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) polyelectrolyte multilayer have been deposited onto cleaned glass substrate by a layer-by-layer dip coating method. 3 bilayers of the PAH and PAA was directly coated onto the substrate as an underlying layer for subsequent coating. Desired surface roughness on the polyelectrolyte bilayers was created by etching the bilayers in hydrochloric acid solution so as to create the open pore having suitable size at the surface. Then, nanoparticles such as SiO₂ and TiO₂ of various sizes were deposited onto the etched polyelectrolyte bilayers. Finally, the surfaces were further modified with semifluorinated silane followed by cross-linking at 180 °C for 2 h to obtain desirable surface morphological features. The effect of etching time and addition of nanoparticles on surface morphology was investigated using an atomic force microscope (AFM). Wetting ability of the prepared film was determined by measuring water droplet contact angle using a goniometer. Adhesion between the superhydrophobic films and the substrate was evaluated by using a standard tape test method (D3359). The adhesion was improved by reducing the organic content in the films.     

A unified analytical treatment of the acid-dissociation equilibria of weakly acidic linear polyelectrolytes and the conjugate acids of weakly basic linear polyelectrolytes

 The influence of added sodium chloride concentration levels on the acid-dissociation equilibria of a weakly acidic linear polyelectrolyte and a conjugate acid of weakly basic linear polyelectrolyte has been investigated potentiometrically by use of polyacrylic acid (PAA) and poly(N-vinylimidazole) (PVIm) as examples of polyelectrolytes. Both equilibria are strongly influenced by the degree of dissociation of the polyacids as well as the concentration levels of sodium chloride due to an electrostatic effect originating from the negatively or positively charged polymer surfaces. These have been analyzed in a unified manner by taking accounts of two-phase properties of the charged linear polyions. Distribution of counterions and coions between a polyelectrolyte phase formed around the polymer skeleton and a bulk solution phase has been rationalized by a Donnan’s relation. Introduction of a volume term for the polyelectrolyte phase permits definition of averaged concentrations of mobile ions in the vicinity of the polyion molecules, which enables us to define hypothetical intrinsic acid-dissociation constants in the polyion domain. The intrinsic constants estimated by extrapolation of apparent acid-dissociation constants at zero-charge state are in good agreement with the acid-dissociation constants of the monomer analogs of the polymers, i.e., acetic acid for PAA and imidazole for PVIm, respectively. The difference between the apparent and intrinsic acid-dissociation constants for PVIm was much higher than that for PAA at defined degree of dissociation of the polyacids, even though the separations of the functionalities fixed on the linear polymers are approximately equal to each other. Received: 4 February 1997 Accepted: 26 May 1997     

Polyelectrolyte complexes of linear copolymers and hydrogels based on 2‐[(methacryloyloxy)ethyl]trimethylammonium chloride and N‐isopropylacrylamide

The formation of polyelectrolyte complexes of linear copolymers and hydrogels based on copolymers of 2‐[(methacryloyloxy)ethyl]trimethylammonium chloride with N‐isopropylacrylamide (MADQUAT–NIPAAM) and poly(acrylic acid) (PAA) has been studied. The composition of the copolymer has been found to affect the composition of the polyelectrolyte complexes significantly, and the molecular weight of PAA influences their aggregation stability. Hydrogels of MADQUAT–NIPAAM immersed in solutions of PAA undergo contraction because of the formation of gel–polymer complexes. The rate of contraction and the final swelling degree of the gel–polymer complexes depend on the concentration of PAA in solution and its molecular weight. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1506–1513, 2004     

大豆分离蛋白接枝氨基封端聚2-丙烯酰胺基-2-甲基丙磺酸的合成及溶液性质研究

用巯基乙胺为链转移剂,过硫酸铵为引发剂合成了氨基封端的聚2-丙烯酰胺基-2-甲基丙磺酸(H2N-PAMPS).再用1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)和N-羟基琥珀酰亚胺(NHS)在室温下催化H2N-PAMPS的端氨基与大豆分离蛋白(SPI)的羧基反应形成酰胺键,得到接枝物SPI-g-NH-PAMPS.用1H-NMR、傅利叶红外光谱、13C-NMR对H2N-PAMPS和接枝物SPI-g-NH-PAMPS进行结构表征.用zeta电位仪、紫外可见光光谱,荧光光谱,动态激光光散射对SPI及其接枝物SPI-g-NH-PAMPS的水溶液性质进行了研究.结果表明,与SPI相比,SPI-g-NH-PAMPS的溶解性、表面疏水性、乳化性等有所改善,接枝物SPI-g-NH-PAMPS聚集体粒径增大,形成独特的核壳结构.     

Swelling Behavior of pH-Sensitive Copolymers Containing 2-Acrylamido-2-Methyl Propane Sulfonic Acid and Acrylic Acid Crosslinked with Vinyl Trimethoxy Silane Crosslinker

Copolymers of 2-acrylamido-2-methyl propane sulfonic acid and acrylic acid were crosslinked in the presence of different mol% of either vinyl trimethoxy silane (VTMS) as the crosslinking agent under acidic conditions or N,N-methylenebisacrylamide (MBA) as crosslinker using solution radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Soluble fractions of the crosslinked networks were reduced by varying the MBA and VTMS concentrations. The surface morphology of the crosslinked polymers was observed by scanning electron microscope. The influence of pH on the swelling behavior of gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity.     

聚丙烯酸/聚丙烯酰胺水溶液复合特性的研究

通过酸度、电导率、粘度、接触角的测定,研究了聚丙烯酸 (PAA) /聚丙烯酰胺 (PAM) 水溶液复合物及复合物膜的结构和性能。结果表明,酸度、温度、浓度和复合比影响PAA/PAM的复合水溶液中大分子链的构象和流体力学体积,适度的氢键作用可以形成均相的复合溶液。经过热处理和未经热处理的聚合物膜表现出了不同的亲水性能。     

Complexation of poly(acrylic acid) and poly(ethylene oxide) investigated by enhanced Rayleigh scattering method

The method of enhanced Rayleigh scattering spectroscopy (ERS) was developed to investigate the complexation of poly(acrylic acid) (PAA) and poly(ethylene oxide) (PEO) in semidilute polymer solutions. Based on the Ornstein‐Zernike equation, the relationship between macromolecular static correlation length and ERS intensity was presented. Moreover, the ERS spectra were calculated by the moving window two‐dimensional (MW2D) correlation spectroscopy to get detailed information of the polymer complexation. The results indicated that the ERS spectroscopy characteristics of the polymer mixtures have similar trend, and the ERS intensity promptly increases as the macromolecular chains contract. The increase of ERS intensity showed that the degree of complexation between PAA and PEO increases when the pH value decreases. The complexation results from the collapse of macromolecular chains, which is induced by the PAA chains contracting and the enhanced association between PAA and PEO chains because of the hydrogen bond formation. In addition, the association resulting from the complexation of PAA and PEO in solution was demonstrated by the MW2D correlation spectroscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1847–1852, 2010     

pH敏感的聚(L-谷氨酸)-交联聚丙烯酸水凝胶的合成与性能研究

通过在聚L-谷氨酸侧链部分接枝甲基丙烯酸2-羟乙酯得到含有双键的聚(L-谷氨酸),将其与丙烯酸共聚得到由聚(L-谷氨酸)侧链接枝并交联聚丙烯酸的pH敏感水凝胶.研究水凝胶在不同pH的缓冲溶液中的溶胀性、溶胀动力学,并通过SEM观察水凝胶的微观结构.结果表明,水凝胶在低pH环境下的溶胀率明显低于高pH环境中的溶胀率,不同...     

Electrochemical synthesis of soluble sulfonated poly(3-methyl thiophene)

Electrochemical polymerization of poly(3-methyl thiophene) films (3-MTy) which are self-doped with SO₃⁻ was investigated. The sulfonated poly(3-methyl thiophene) films synthesized from the solution which contained different amounts of HSO₃F. The sulfonated polymer films were found to be soluble in DMF and KOH. The solubility values increased and the conductivity values decreased with the increase in sulfonation ratio. The resulting polymers were characterized by cyclic voltammetry, UV-Vis, FT-IR, elemental analysis, dry conductivity measurements and SEM techniques.     

Influence of the degree of ionization and molecular mass of weak polyelectrolytes on charging and stability behavior of oppositely charged colloidal particles

Positively charged amidine latex particles are studied in the presence of poly(acrylic acid) (PAA) with different molecular masses under neutral and acidic conditions by electrophoresis and time-resolved dynamic light scattering. Under neutral conditions, where PAA is highly charged, the system is governed by the charge reversal induced by the quantitatively adsorbing polyelectrolyte and attractive patch-charge interactions. Under acidic conditions, where PAA is more weakly charged, the following two effects come into play. First, the lateral structure of the adsorbed layers becomes more homogeneous, which weakens the attractive patch-charge interactions. Second, polyelectrolyte adsorption is no longer quantitative and partitioning into the solution phase is observed, especially for PAA of low molecular mass.     

基于聚(2-甲基-2-噁唑啉)和聚丙烯酸的混合刷在毛细管电泳在线富集溶菌酶中的应用

制备了一种对溶菌酶具有可控吸附性能的混合刷涂层毛细管,用于毛细管电泳在线富集溶菌酶以提高其检测灵敏度。首先,分别通过阳离子开环聚合和可逆加成-断裂链转移（RAFT）聚合合成聚（2-甲基-2-噁唑啉）（PMOXA）和聚丙烯酸（PAA）,然后将甲基丙烯酸缩水甘油酯（GMA）分别与PMOXA和PAA通过自由基共聚和RAFT聚合合成出聚（2-甲基-2-噁唑啉）-r-甲基丙烯酸缩水甘油酯（PMOXA-r-GMA）和聚丙烯酸-b-聚甲基丙烯酸缩水甘油酯（PAA-b-PGMA）。将PMOXA-r-GMA和PAA-b-PGMA的混合溶液以一定比例加入到毛细管内,通过加热即可制备出基于PMOXA和PAA的混合刷涂层毛细管。X射线光电子能谱（XPS）对毛细管原材料的表面组成研究结果表明,当混合溶液质量浓度为20 g/L、PMOXA-r-GMA和PAA-b-PGMA质量比为1：1时,所得涂层中羧基的含量随着PAA链长的增加而增加;异硫氰酸荧光素标记溶菌酶（FITC-溶菌酶）吸附实验结果显示,通过改变环境的pH和离子强度（I）可以调控涂层毛细管对溶菌酶的吸附和释放,在pH 7（I=10^-5mol/L）条件下,毛细管可以吸附大量的溶菌酶,当条件变为pH 3（I=10^-1mol/L）时,吸附的溶菌酶可以被释放出来。将这种具有溶菌酶可控吸附性能的涂层毛细管用于毛细管电泳在线富集溶菌酶,当PAA链长是PMOXA链长的2.2倍时,溶菌酶的灵敏度增强因子为17.69,检出限为8.7×10^-5g/L;同一天内对溶菌酶连续测定5次以及连续测定5天,峰面积的日内、日间相对标准偏差（RSD）分别为2.9%和4.1%,迁移时间的日内、日间RSD分别为0.9%和2.1%。涂层的制备只需一步,简单易行,而且涂层具有很好的稳定性。本研究为毛细管电泳分析痕量蛋白质提供了一种简单有效的方法。     

Two-step surfactant binding of solvated and cross-linked poly(N-isopropylacrylamide-co- (2-acrylamido-2-methyl propane sulfonic acid))

 A solvated and cross-linked copolymer of N-isopropylacrylamide (IPAAm) and 2-(acrylamido)-2-methyl propane sulfonic acid (AMPS) was synthesized and its interaction with cationic surfactant lauryl-pyridinium chloride (C₁₂PyCl) was investigated. The solvated copolymer exhibited a lower critical solution temperature (LCST) in water, which was extensively shifted to a higher temperature due to the increase of hydrophilicity introduced by AMPS. In C₁₂PyCl solution, LCST of the copolymer was dramatically decreased due to the binding of C₁₂PyCl to AMPS unit, forming a stoichiometric complex. However, in the concentrated C₁₂PyCl solution, its LCST increased due to the non-stoichiometric complex formation. This phenomenon was further examined in the cross-linked copolymer, analyzed by binding isotherms. Two-step binding of surfactant was demonstrated followed by gel shrinking and re-swelling. This binding mechanism was further discussed regarding the effect of charge density and the hydro-phobicity of the main-chain backbone in terms of electrostatic and hydrophobic interactions. Received: 13 May 1997 Accepted: 13 August 1997     

Preparation and Characterization of Styrene/Butyl Acrylate Emulsifier-Free Latex with 2-Acrylamido-2-Methyl Propane Sulfonic Acid as a Reactive Emulsifier

A kind of emulsifier-free latex (FL) was successfully synthesized from styrene (St) and butyl acrylate (BA) with 2-acrylamido-2-methyl propane sulfonic acid (AMPS) as a reactive emulsifier. The particle size of latex particles, stability against electrolytes, minimum film forming temperature (MFT) and water contact angle (CA) were evaluated and compared with a conventional latex (CL). Test results show that FL has larger particle size, better stability against electrolytes and lower MFT value compared with CL; higher AMPS content leads to smaller particle size and smaller water CA.     

Application of Ultrasonic Attenuation Measurements in the Studies on Macromolecular Conformational Behaviors——Phase Behavior of the Aqueous Solution of Poly(vinyl methyl ether) Sensitive to Temperature and the Modification of the Behavior by Using Pol

Introduction Studies on the conformational and aggregation be-haviors of macromolecules in aqueous solution and at solid/liquid interfaces have been highlighted in colloid and interface science since the early 1990s.1-3 It was mentioned in the first part of this series of studies that development of new methods, which are characterized by being in time and non-destructive and can be used for monitoring the conformational and aggregation be-havior of macromolecules, is of critical importance fo…     

Application of Ultrasonic Attenuation Measurements in the Studies on Macromolecular Conformational Behaviors

——Phase Behavior of the Aqueous Solution of Poly(vinyl methyl ether) Sensitive to Temperature and the Modification of the Behavior by Using Poly(acrylic acid) The phase behavior of the aqueous solution of poly(vinyl methyl ether) (PVME) sensitive to temperature and the modification of the behavior by using poly(acrylic acid) (PAA) have been studied by ultrasonic attenuation measurements and fluorescence probe techniques. It has been observed that PVME solution is transparent at room temperature and becomes turbid upon heating. The solution turns clear again as soon as the temperature is decreased to room temperature. The heating and cooling process can be repeated for many times. The phase behavior of the solution sensitive to temperature is attributed to the conformational changes of the polymer. PVME may adopt an open coil conformation at room temperature. With this conformation, the polymer is well miscible with the solvent, water, and thereby the system is a real solution. The polymer may adopt a compact coil conformation when the temperature is higher than a specific value, which is called the LCST (the lower critical solution temperature) of PVME. In this case, the polymer tangles to each other and forms various aggregates, which can scatter incident light and ultrasonic waves greatly, resulting in the phase separation. Introduction of PAA decreases the temperature sensitivity of the phase behavior of the polymer. The nature of the inhibition is attributed to the complexation of PAA with PVME and the strong hydrophilicity of PAA. Results from fluorescence probe studies are in accordance with those from ultrasonic attenuation measurements, indicating again that the ultrasonic attenuation method can be successfully used for the qualitative studies of polymer conformations and complexation between polymers.     

Polyelectrolyte complexes of soluble poly-2-[(methacryloyloxy)ethyl]trimethylammonium chloride and its hydrogels with poly(acrylic acid)

The complex formation of poly-2-[(methacryloyloxy)-ethyl]trimethylammonium chloride (PMADQUAT) with poly(acrylic acid) (PAA) of different molecular weights has been studied in aqueous solutions by potentiometric, viscometric, turbidimetric and FTIR spectroscopic methods. The formation of insoluble non-stoichiometric polyelectrolyte complexes has been shown. The stability of polyelectrolyte complexes in solutions of different pH and ionic strength has been evaluated. The formation of polyelectrolyte complexes between hydrogels of PMADQUAT and linear PAA of different molecular weights has been studied. It was shown that the molecular weight of PAA considerably affects the kinetics of interaction as well as the final state of gel-polymer complex.     

pH- and Ionic-Strength-Induced Structural Changes in Poly(acrylic acid)-Lipid-Based Self-Assembled Materials

Summary: The effect of a polyanion introduced as a lipid conjugate (poly(acrylic acid)- dimyristoyl-sn-glycero-3-phosphoethanolamine, PAA-DMPE) on the structure of a self-assembled, biomembrane mimetic has been evaluated using synchrotron small-angle X-ray scattering (SAXS). At high grafting density (8–11 mol.%), the PAA chains were found to produce significant changes in structure in response to changes in pH and electrolyte composition. At low pH and in the absence of salt (NaCl), the neutral PAA chains adopt a coil conformational state that leads to the formation of a swollen lamellar structure. Upon the addition of salt at low to intermediate pH values, two lamellar phases, a collapsed and an expanded structure, coexist. Finally, when the polymer is fully ionized (at high pH), the extended conformation of the polymer generates a cubic phase. The results of this study contribute to an understanding of how polyelectrolytes may ultimately be harnessed for the preparation of self-assembling materials responsive to external stimuli.     

Effects of different acid functional groups on proton conductivity of polymer‐1,2,4‐triazole blends

Proton transfer reactions under anhydrous conditions have attracted remarkable interest due to chemical energy conversions in polymer electrolyte membrane fuel cells. In this work, 1H‐1,2,4‐triazole (Tri) was used as a proton solvent in different polymer host matrices such as Poly(vinylphosphonic acid) (PVPA), and poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) (PAMPS). PVPATri_x and PAMPSTri_x electrolytes were investigated where x is the molar ratio of Tri to corresponding polymer repeat unit. The interaction between polymer and Tri was studied via FTIR spectroscopy. Thermogravimetry analysis and differential scanning calorimetry were employed to examine the thermal stability and homogeneity of the materials, respectively. PVPATri_1.5 showed a maximum water‐free proton conductivity of 2.3 × 10^?3 S/cm at 120 °C and that of PAMPSTri₂ was 9.3 × 10^?4 S/cm at 140 °C. The results were interpreted in terms of different acidic functional groups and composition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3315–3322, 2006     

Preparation and absorption spectrum studies of aromatic and alicyclic poly(amide acid) ammonium salts in water and DMF and in films

A series of ammonium salts of poly(amide acid)s (PAS) were prepared from various poly(amide acid)s (PAA) with tertiary amines. The solubility of poly(amide acid) ammonium salts prepared from PAA(PMDA/ODA) in water is related to the ion concentration of tertiary amines. In order to elucidate the influence of the chemical structures of poly(amide acid)s and poly(amide acid) ammonium salts on their absorption spectra, pyromellitic dianhydride (PMDA), 3,3′,4,4 ′-biphenyltetracarboxylic dianhydride (BPDA), and 3,3′,4,4 ′-benzophenonetetracarboxylic dianhydride (BTDA) were chosen to react with p-phenylenediamine (PDA) and (4,4′-diaminodicyclohexyl)methane (DCHM) to give three kinds of aromatic PAAs and three kinds of alicyclic PAAs. The corresponding PASs were prepared by the reaction of PAAs with triethanolamine (TEA). Their ultraviolet–visible (UV–vis) absorption spectra were investigated compared to those of model compounds. A transparent film without absorption above 320 nm was obtained for PAS(PMDA/DCHM). The difference in absorption spectra of PAS(PMDA/PDA) from that of PAS(PMDA/DCHM) can be related to the existence of intra- and intermolecular charge transfer (CT) for PAS(PMDA/PDA). The absorption spectra of PASs with PDA in films are red shifted compared to those of corresponding PAAs in films, while the absorption spectra of PASs in water are blue shifted compared to those of corresponding PAAs in DMF. No differences in the absorption spectra of PAAs and PASs were found in DMF/H₂O (9/1) mixed solvent. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1329–1340, 1998