Swelling behavior of radiation‐polymerized polyampholytic two‐component gels: Dynamic and equilibrium swelling kinetics

Polyampholytic hydrogels, with varying degrees of crosslinking and ionic content, were prepared by radiation polymerization of p‐sodium styrene sulfonate (SSS) and vinyl benzyl trimethylammoniumchloride (VBT). These gels were investigated for their dynamic and equilibrium swelling kinetics. Dynamic swelling of these gels established that the gels containing equal amounts of SSS and VBT strictly follow Fickian diffusion. The hydrogels containing excess of SSS followed the case II type of diffusion, whereas those containing excess of VBT followed anomalous diffusion. Equilibrium swelling kinetics of these gels in aqueous system, ethanol–water mixture, at different pHs, and in the presence of solutions of biological interest was studied. It was seen that gels containing equal amounts of SSS and VBT show the lowest equilibrium swelling. Swelling of the polyampholytic gel decreased with an increase in the radiation dose imparted and the amount of crosslinking agent incorporated in the gel. The gels having an excess of VBT showed higher equilibrium swelling in comparison to those having an excess of SSS. Differential scanning calorimetry (DSC) studies showed that crosslinking of the gels decreases equilibrium swelling but increases the bonded nonfreezable water content of the gels. The organic solvents like ethanol cause abrupt collapse of the polyampholyte gels containing excess of SSS and those containing equal amounts of both the monomers at some critical ratio of water and ethanol in swelling medium. However, the deswelling in the water–ethanol mixture was gradual for gels containing an excess of VBT and the extent of deswelling was also low for these gels in comparison to other gels. The swelled gels of all compositions deswelled when they were transferred to solutions at pH in the range 2–12. Biologically important solutes like urea, glucose, and surfactants like Triton‐X tend to further swell the polymer matrices, whereas NaCl causes their deswelling. The additive effect is more prominent for polyampholyte gels containing excess of either of the monomers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 730–742, 2003     

煤溶胀动力学与热力学的研究

以煤溶胀机理、氢键等为基础,从热力学和动力学方面综述了煤溶胀的本质,讨论了溶剂性质、氧化、温度、煤粉粒度及热处理对溶胀动力学的影响。结果表明：溶胀过程中,表观活化能和速率常数不仅与溶剂分子的空间属性有关,还受溶剂分子形状的影响;混合溶剂的协同效应极大地提升了溶胀速率,增大了表观活化能;抽提煤的干燥条件不同及煤经过氧化后,溶胀机理均会发生明显改变。最后详细介绍了煤溶胀技术对煤分子结构的影响及在煤液化方面的应用。     

Modeling of swelling by fluorescence technique in poly (methyl methacrylate) gels

A novel technique based on in-situ steady-state fluorescence (SSF) measurements is introduced for studying swelling processes in gels formed by free radical cross-linking copolymerization (FCC) of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) in toluene. Gels were prepared at 75°C for various toluene contents with pyrene (Py) as a fluorescence probe. After drying these gels, swelling and desorption experiments were performed in toluene at 50°C by real-time monitoring of Py fluorescence intensity. A correction method was developed to obtain pure swelling curves, by using desorption curves of Py molecules. Li-Tanaka equation was employed to produce swelling parameters. Cooperative diffusion coefficients (D_c) were measured and found to be around 10⁻⁶ cm²/s for gels swollen in toluene. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1777–1784, 1997     

Fast transient fluorescence technique for studying swelling of gels made at various crosslinker contents and exposed to organic vapour

Fast transient fluorescence technique (FTRF) was employed for studying swelling of disc‐shaped poly(methyl methacrylate) (PMMA) gels, which were prepared by free radical copolymerization of methyl methacrylate (MMA) using various ethylene glycol dimethacrylate (EGDM) contents at 60 °C. Pyrene (P) was introduced as a fluorescence probe during polymerization. Swelling experiments were performed by using P‐doped PMMA gels under chloroform vapor. Decay curves of P were measured during in situ swelling experiments. Exponential fits were performed to measure pyrene lifetimes, τ, inside the PMMA gels. It was observed that τ values decreased as swelling proceeded. An equation is derived for low quenching efficiencies to interpret the behaviour of P lifetimes during swelling. The Li–Tanaka equation was used to determine the cooperative diffusion coefficients, D_c, for the gels made at various crosslinker contents. It is observed that D_c values decrease as the crosslinker content is increased. © 2002 Society of Chemical Industry     

随机共聚高分子凝胶溶胀和体积相变行为的分子热力学模型

基于随机共聚高分子溶液的格子模型,建立了一个可以描述温度和pH双重响应的随机共聚高分子凝胶溶胀行为的分子热力学模型。该模型考虑了溶剂与不同高分子的混合、高分子网络的弹性以及包含小分子离子在凝胶内外分布的Donnan平衡和聚合物网络上的大分子离子及其反离子之间的静电相互作用的离子影响对化学势的贡献。与其他模型不同的是,该模型还考虑了高分子的组成f。该模型有两类可调的模型参数,一类是溶剂与不同高分子网络之间的相互作用能参数ε槇ij,另一类是高分子网络自身的尺寸参数Mc。研究结果表明,该分子热力学模型只需较少的模型参数就可较好地描述温度和pH双重敏感的随机共聚高分子凝胶的溶胀行为。     

In situ fast transient fluorescence technique (FTRF) to study swelling of gels made of various crosslinker contents

The fast transient fluorescence technique (FTRF), which uses the strobe master system (SMS), was employed to study the swelling of disc‐shaped PMMA [poly(methyl methacrylate] gels. Seven gels were prepared by free radical copolymerization (FCC) of methyl methacrylate (MMA) with various ethylene glycol dimethacrylate (EGDM) contents. Pyrene (P_y) was introduced as a fluorescence probe during polymerization. After drying these gels, swelling experiments were performed in chloroform at room temperature. P_y lifetimes were measured from fluorescence decay traces during the in situ swelling experiments. An equation was derived for low quenching efficiencies to interpret the behavior of lifetimes in the gel during swelling. It was observed that P_y lifetimes in the gel decreased as swelling proceeded. The Li–Tanaka equation was used to determine the cooperative diffusion coefficients, D_c, which were found to decrease as the crosslinker content was increased. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 464–472, 2003     

醇类化合物对聚丙烯酸树脂表面改性后的溶胀动力学研究

采用紫外光引发合成聚丙烯酸类高吸水凝胶,利用醇的羟基与丙烯酸羧基的酯化反应对其进行表面改性,防止吸水过程中的凝胶粘结,研究了所用醇类表面处理剂的碳链长度、羟基含量对树脂吸水速率的影响,并利用动力学关系式Q(t)=Qmax(1-e^kt)对结果进行理论分析证明,得出处理后的树脂后值在0．12～0．15时,接近于理想的网络溶胀。     

Novel shrinking–swelling hysteresis in DMSO/THF mixtures of copolymer gels containing sulphonate groups

The swelling volume of copolymer gels made from 2-(acrylamido)-2-methylpropanesulphonic acid (AMPS; electrolyte monomer), N,N-dimethylacrylamide (DMAA; comonomer) and N,N′-methylenebis(acrylamide) (BIS; crosslinker) was measured in mixtures of two organic solvents, dimethyl sulphoxide (DMSO) and tetrahydrofuran (THF) at 25°C. A volume phase transition was observed in the gels having 43·18mol% AMPS with different counterions K⁺, Na⁺ and H⁺, when the THF concentration in the mixture increased beyond a certain value. We observed a swelling-hysteresis between the shrinking and swelling curves, i.e. more DMSO was required to make a shrunk gel start to swell again than to cause the volume shrinking. This hysteresis stems from the formation of ion pairs and/or multiplets in the ionizable gels when the medium polarity is decreased. An excess of DMSO is required to reduce the ionization energy for making the shrunk gel swell again in the DMSO/THF mixture. These aggregates and multiplets do not seem to be entirely removed by the swelling process and act as additional physical crosslinks, so that the DMSO concentration required to induce the shrunk gel to swell becomes higher in the next swelling process, showing another hysteresis. The release of bound water from the solvating layer after shrinkage may be another possible reason for this hysteresis. © 1998 Society of Chemical Industry     

煤溶胀影响因素及溶胀技术的应用

以煤溶胀机理、溶胀动力学等为基础,综述了溶剂性质、煤阶、氧化、温度、预处理、溶胀时间、水分、煤粉粒度等对煤溶胀的影响。结果发现:溶剂的供电子数目(EDN)、溶剂碱性、溶剂类型对煤的溶胀有不同的影响。煤阶对煤的溶胀影响较大,表现在随着C的增多,溶胀度也在增大,但当C含量大于85%时,溶胀度急剧降低。氧化煤易于溶胀。升高温度和预处理均有利于煤的溶胀。煤粉粒度越小溶胀度越好。脱除煤中的矿物质后有利于提高煤的溶胀度,但增加幅度不大。最后详细介绍了煤溶胀技术在研究煤分子结构、煤热解、煤液化方面的应用。     

新型少胶粉云母带的研制

本文介绍了一种新型少胶带的胶粘剂、粉云母纸、补强材料的选择以及少胶带的制造工艺。该少胶带与H9110不饱和聚酯亚胺无溶剂浸渍树脂配套使用具有整体性好、介质损耗因数小、电气强度高等优点。     

依兰煤在液化溶剂中的溶胀动力学研究

笔者以依兰煤为原料,研究了依兰煤在室温至2000℃范围内在液化起始溶剂和循环溶剂中的溶胀行为,并确定了依兰煤在试验条件下的溶胀动力学参数。试验结果表明：依兰煤在液化起始溶剂和循环溶剂中的溶胀度随溶胀温度的增加和溶胀时间的延长而增大;依兰煤在这2种溶剂中的溶胀都是受Case-Ⅰ扩散控制为主的过程,其溶胀活化能分别为4．18和4．22kJ·mol^-1。     

Preparation and adsorption selectivity of deltamethrin molecularly imprinted polymers by two-step seed swelling method

Deltamethrin (DM) is one of the most efficient pyrethroid insecticides, which is widely applied to the control of insect pests in tea. In this work, efficient molecularly imprinted polymers (MIPs) were synthesized using DM as the template and acrylamide as the functional monomer, in conjunction with two-step seed swelling polymerization. Scanning electron microscopy, Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller surface area analysis confirmed the staggered pore structure and the presence of binding site in DM MIPs. The adsorption properties of the DM MIPs were also investigated based on assessing equilibrium adsorption as well as kinetic modeling and solid-phase extraction. Isothermal equilibrium adsorption experiments show that the adsorption behavior is consistent with the Freundlich and Halsey models, indicating heterogeneous multilayer specific adsorption. Fitting of the kinetic data demonstrates that chemical adsorption could be the rate-limiting step in DM extraction, which is consistent with a pseudo-second-order kinetic model. Using the imprinted polymers as solid-phase extraction filler, the DM recoveries from various teas were greater than 80% and exceeded those of the structural analogs cypermethrin, lambda-cyhalothrin, and bifenthrin. These results confirm that the MIPs exhibit specific adsorption of this analyte. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47415.     

Determination of the kinetics of diffusion in coals by solvent swelling techniques

A simple technique has been developed for measuring the kinetics of solvent diffusion in coals at various temperatures. The technique is based on a well-known method for measuring the volumetric swelling of coals by solvents. Several coals have been examined in both pyridine and tetrahydrofuran, at temperatures between 298 and 332 K. The diffusion follows the well-established case II rate law at ambient temperatures, implying that the processes are controlled by relaxation in the coal network structure. As temperatures are increased, the process becomes more Fickian in nature. The activation energies for the diffusion-relaxation processes are in the range 31 to 82 kJ mol⁻¹.     

Preparation and pH‐sensitive swelling behavior of physically crosslinked polyampholyte gels

A novel polyampholyte hydrogels were prepared by free radical aqueous copolymerization of ionic complex consisting of acrylic acid (AAc), (N,N‐diethylamino) ethyl methacrylate (DEAEM), and acrylamide (designated as PADA). Without any chemical crosslinker, the formation of PADA network structures was mainly attributed to the electrostatic interaction of AAc (anionic monomer) and DEAEM (cationic monomer). The PADA gels exhibited a typical swelling behavior of polyampholyte gels in buffer solutions. The hysteresis of isoelectric point (pI) for PADA gels was observed after preswollen in alkaline solutions. The swelling behavior of PADA gels in response to change of pH was investigated. It was found that the equilibrium swelling ratio orderly decreased in buffer solutions with alternating pH between 2.2 and 5. An abrupt swelling was observed for the hydrogels at the pH near isoelectric point in the earlier stage of swelling process. The study of swelling kinetics of the hydrogels showed that the swelling process was in agreement with the second‐order swelling kinetics. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3857–3861, 2006     

Synthesis and swelling characteristics of responsive carboxybetaine gel

A polyimminium gel, Dimedone‐[N, N′ melaminium] butyrocarboxylate copolymer, comprising of zwitterionic carboxybetaine repeat units was synthesized via a catalyst free facile polycondensation approach. The polymer was studied for its photoluminescence, thermal, and swelling behavior. Swelling behavior was investigated in different solvent mixtures as well as in pure solvents. The extent of swelling was dictated by solvent composition, such as dielectric constant, pH, ionic strength, and other variables for instance, temperature and crosslinking density. Gel was soluble in alkali and could be regenerated on treatment with an acid. This pH responsive behavior could find various industrial applications, especially in wastewater treatment. A preliminary study on sorption of dyes was also carried out. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Mechanical response and equilibrium swelling of thermoresponsive copolymer hydrogels

Covalently crosslinked thermoresponsive (TR) gels form a special class of hydrogels that swell noticeably below their volume phase transition temperature T_c and shrink above T_c. As the critical temperature is weakly affected by the preparation conditions and molar fractions of monomers and crosslinkers in the pre‐gel solution, a facile method to modulate T_c (which is required for biomedical applications of TR gels and their use as temperature‐triggered actuators) is to incorporate relatively small amounts of neutral monomers whose hydrophilicity differs from that of the basic monomers. Although observations on copolymer gels confirm the effectiveness of this method, the molar fractions of comonomers necessary for the tuning of T_c remain unknown. A model was developed for the mechanical response and equilibrium swelling of TR gels. Adjustable parameters in the governing relations were found by fitting equilibrium swelling diagrams for poly(N‐isopropylacrylamide) homopolymer and copolymer gels. Good agreement is demonstrated between the experimental data and the results of simulation. Based on the model, an analytical formula is derived that expresses the volume phase transition temperature in terms of the molar fraction of comonomers. Its ability to predict the critical temperature is confirmed by comparison with observations on several copolymer gels. © 2020 Society of Chemical Industry     

溶胀技术在煤科学中的研究进展

综述了煤溶胀技术的研究进展,着重从溶胀机理、煤溶胀度的影响因素、煤中氢键与溶胀率关系、溶胀动力学及溶胀煤的表征分析等几个方面论述了溶胀技术在煤科学中的研究进展。     

Heavy metal removal using hydroxypropyl cellulose and polyacrylamide gels,kinetical study

In this article we report the removal of Pb, Ni and Cu using a hydrogel made with hydroxypropyl cellulose (HPC) and polyacrylamide (PAAm). The hydrogel successfully removed those metals, as shown by the results of atomic absorption spectroscopy; the polymer removed 53% of Pb, 52% of Ni and 51% of Cu. Different pHs were tried for these polymers. The highest metal removal was found at 40°C. The adsorption kinetics fitted Langmuir and Freundlich isotherms. Metal particles were detected on the hydrogel with electron microscopy and energy–dispersive X–ray spectroscpy, confirming that the gel removed the metals from the testing solutions. This polymer is a good option for treating wastewater and industrial waters as it removes metals and is composed of nontoxic materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43285.     

Determination of hydrogel swelling factors by two established and a novel non-contact continuous method

Hydrogels were introduced as suitable materials for applications in, e.g., medical, agriculture, or daily life areas. Swelling characteristics of a hydrogel are important and must be precisely known for various fields of application. In medicine, where hydrogels are used as implants or drug delivery systems, precise knowledge of the swelling behavior is essential. Especially in ophthalmology as part of cataract surgery, the visco-elastic properties of the hydrogels could even allow for the restoration of accommodation. The easiest way to describe the swelling is by measuring the swelling ratio, generally done by scaling. Besides that, it can also be done by volume investigations. The similarities and differences are studied on five hydrogel samples made of methyl methacrylate and N-vinyl pyrrolidone. Additionally, a first camera-based approach, potentially providing an automated, quasi-continuous non-contact method for swelling kinetics investigations, is described.