Electric field sensitivity of conducting hydrogels with interpenetrating polymer network structure

In this article, we reported the synthesis, structure and electric field sensitivity of polyacrylate/polyaniline (PAA/PANI) and poly(2-acrylamido-2-methyl propylsulfonic acid-acrylic acid)/polyaniline [P(AMPS-AA)/PANI] conducting hydrogels with an interpenetrating polymer network (IPN) structure. Scanning electron microscope showed that the conducting hydrogels presented porous structures consisting of PANI nanofibers. The results of Fourier-transform infrared and X-ray diffraction revealed that the PANI was in its conductive emeraldine state and partial crystallization. The unique morphology and molecular structure of the conducting hydrogels were expected to show unusual electric field responses. The conducting hydrogels were subjected to an electric field in NaCl solution for bending behaviors. It was demonstrated that the electric field response was improved by increasing aniline dosage, applied voltage and concentration of aqueous NaCl solution. The bending mechanism was attributed to polyelectrolyte hydrogel matrix and emeraldine PANI nanofibers.     

温敏性纤维素/聚N-异丙基丙烯酰胺复合水凝胶的固体核磁共振表征及动力学研究

利用半互穿网络方法将具有温度响应的高分子聚N-异丙基丙烯酰胺(PNIPAM)与天然纤维素复合得到温敏性水凝胶. 通过固体核磁共振的 ¹H, ¹³C CP/MAS(交叉极化/魔角旋转)和QCP(定量交叉极化)等实验手段对复合凝胶的结构进行了定性及定量研究, 并利用固体静态变温核磁共振实验和偶极滤波-自旋扩散实验研究了复合凝胶中PNIPAM分子链段的动力学行为.     

Conducting hydrogels based on semi‐interpenetrating networks of polyaniline in poly(acrylamide‐co‐itaconic acid) matrix: synthesis and characterization

In this work, acrylamide/itaconic acid copolymeric hydrogels are prepared by free radical polymerization initiated by redox initiators of potassium persulfate and N ,N ,N ′,N ′‐tetramethyl ethylene diamine; N ,N ′methylene bisacrylamide was employed as a crosslinking agent. Aniline monomer was absorbed in the network of poly(acrylamide‐co‐itaconic acid) P(AAm‐co‐IA) hydrogel and followed by gamma radiation induced polymerization at room temperature. The novel semi‐interpenetrating network was comprised of linear polyaniline immersed in P(AAm‐co‐IA) matrix. Electrical conductivity of the hydrogels was measured using four‐probe technique. The conductivities for the prepared hydrogels are found to increase from 5.5 × 10^?7 S cm^?1 for P(AAm‐co‐IA) alone to 4.4 × 10^?3 S cm^?1 for semi‐interpenetrating polymer network P(AAm‐co‐IA)/polyaniline. Thus, a new composite hydrogel with good conductive properties also displaying enhanced mechanical strength and pH sensitivity was prepared. Copyright © 2017 John Wiley & Sons, Ltd.     

Flexible,stretchable and conductive PVA/PEDOT:PSS composite hydrogels prepared by SIPN strategy

Stretchable conductive hydrogels have received significant attention due to their possibility of being utilized in wearable electronics and healthcare devices. In this work, a semi-interpenetrating polymer network (SIPN) strategy was employed to fabricate a set of flexible, stretchable and conductive composite hydrogels composed of polyvinyl alcohol (PVA) in the presence of glutaraldehyde as the crosslinker, HCl as the catalyst and poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) as the conductive medium. The results from FTIR, Raman, SEM and TGA indicate that a chemical crosslinking network and interactions of PVA and PEDOT:PSS exist in the SIPN hydrogels. The swelling ratio of hydrogels decreased with increasing content of PEDOT:PSS. Due to the chemical crosslinking network and interactions of PVA and PEDOT:PSS, PVA networks semi-interpenetrated with PEDOT:PSS exhibited excellent tensile and compression properties. The tensile strength and elongation at breakage of the composite hydrogels with 0.14 wt% PEDOT:PSS were 70 KPa and 239%, respectively. The compression stress of the composite hydrogels with 0.14 wt% PEDOT:PSS at a strain of 50% was about 216 KPa. The electrical conductivity of the hydrogels increased with increasing PEDOT:PSS content. The flexible, stretchable and conductive properties endow the composite hydrogel sensor with a superior gauge factor of up to 4.4 (strain: 100%). Coupling the strain sensing capability to the flexibility, good mechanical properties and high electrical conductivity, we consider that the designed PVA/PEDOT:PSS composite hydrogels have promising applications in wearable devices, such as flexible electronic skin and sensitive strain sensors.     

Structural design of stimuli‐responsive bioconjugated hydrogels that respond to a target antigen

Stimuli‐responsive bioconjugated hydrogels that can respond to a target antigen (antigen‐responsive hydrogels) were prepared by introducing antigen‐antibody bindings as reversible crosslinks into the gel networks. The preparation conditions of the antigen‐responsive hydrogels and the mechanism of the antigen‐responsive behavior were investigated, focusing on bioconjugated hydrogel structures. This article also focuses on the effect of semi‐interpenetrating polymer network (semi‐IPN) structures on the antigen‐responsive swelling/shrinking behavior of bioconjugated hydrogels with antigen‐antibody bindings. The preparation conditions and the network structures of the bioconjugated hydrogels are discussed in relation to designing antigen‐responsive hydrogels. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2144–2157, 2009     

Preparation and characterization of biodegradable gelatin-PAAm-based IPN hydrogels for controlled release of maleic acid to improve the solubility of phosphate fertilizers

In this study, interpenetrating polymer network (IPN) hydrogel systems including maleic acid (MA) were constituted to improve the solubility of phosphate fertilizers. A series of full and semi-IPN hydrogels were prepared from various gelatin/polyacrylamide mixtures by using two different cross-linkers. The effects of polymer composition on the morphological structures and swelling behaviors of the hydrogels were investigated. The swelling values of all hydrogels were found to be in between 435% and 830%. MA release from load0ed hydrogels was followed and it was determined that MA-loaded hydrogels efficiently decreased pH and improved the solubility of Ca₃(PO₄)₂ in releasing medium.     

k-型卡拉胶/聚乙烯吡咯烷酮共混水凝胶的辐射制备及性质研究

采用辐射技术制备了κ-型卡拉胶(KC)/聚乙烯基吡咯烷酮(PVP)共混水凝胶,研究了共混凝胶内KC含量、PVP的分子量和辐照剂量等对KC/PVP共混水凝胶性质的影响.实验发现,KC与高分子量的PVP(k-90)共混后在一定剂量范围内辐照可得到高强度、高溶胀行为的KC/PVP共混水凝胶,随着共混凝胶内KC含量的增加,凝胶强度及溶胀性能均显著提高.分析表明,KC与高分子量的PVP共混后,在较低剂量下KC的降解被抑制,从而获得一种由物理交联的KC和化学交联的PVP形成的互穿网络(IPN)凝胶.     

聚合物水凝胶基超级电容器的研究进展

可伸展性和可压缩性是超级电容器作为现代柔性可穿戴电子设备的关键性能。聚合物水凝胶因其优异的力学性能、独特的网络状结构等优点,成为新一代高性能超级电容器的理想材料。它不仅可作为高效储能的柔性电极材料,而且可作为准固态电解质材料,在克服传统液体电解质系列缺陷的同时,获得更加轻薄、安全、稳定的柔性全固态储能器件。本文以聚合物水凝胶的化学组成为线索,分别介绍了聚合物水凝胶在超级电容器电极和电解质两方面的应用研究进展,并进一步对聚合物水凝胶在该领域的发展趋势进行了展望。     

Improved oxygen permeability and mechanical strength of silicone hydrogels with interpenetrating network structure

<正>The interpenetrating polymer network(IPN) silicone hydrogels with improved oxygen permeability and mechanical strength were prepared by UV-initiated polymerization of monomers including methacryloxypropyl tris(trimethylsiloxy)silane(TRIS),2-hydroxyethylmethacrylate(HEMA) and N-vinyl pyrrolidone(NVP) in the presence of free radical photoinitiator and cationic photoinitiator.The polymerization mechanism was investigated by the formation of gel network.The structure of IPN hydrogels was characterized by Fourier transform infrared spectroscopy(FTIR), differential scanning calorimetry(DSC) and transmission electron microscopy(TEM).The results showed that the IPN hydrogels exhibited a heterogeneous morphology.The mechanical properties,surface wettability and oxygen permeability were examined by using a tensile tester,a contact angle goniometer and an oxygen transmission tester,respectively.The equilibrium water content of the hydrogels was measured by the gravimetric method.The results revealed that the IPN hydrogels possessed hydrophilic surface and high water content.They exhibited improved oxygen permeability and mechanical strength because of the incorporation of TRIS.     

Swelling characterization of novel ternary semi‐IPNs: acrylamide/1‐vinylimidazole/PEG hydrogels

New ternary semi interpenetrating polymer networks (semi‐IPNs) systems containing acrylamide (AAm), 1‐vinylimidazole (VI) and poly (ethylene glycol) (PEG) have been prepared. AAm/VI hydrogels and semi‐IPN's, poly (AAm/VI/PEG) with 0.25, 0.50, 0.75 and 1.00 g of PEG (per 1.00 g AAm) were prepared by free radical solution polymerization in aqueous solution of AAm with VI as comonomer and a multifunctional crosslinker such as 1,4 butanediol dimethacrylate (BDMA). Swelling experiments were performed in water at 25°C, gravimetrically. The influence of VI and PEG content in hydrogels were examined. AAm/VI and AAm/VI/PEG hydrogels showed large extents of swelling in aqueous media, the swelling being highly dependent on the chemical composition of the hydrogels. Percentage swelling ratio of AAm/VI hydrogels and AAm/VI/PEG hydrogels was shown as 650–4167%. The values of equilibrium water content (EWC) of the hydrogels are between 0.8990 and 0.9750. Diffusion behavior was investigated. Water diffusion into hydrogels was found to be non‐Fickian in character. Copyright © 2007 John Wiley & Sons, Ltd.     

聚乙烯醇/聚吡咯复合导电水凝胶应变传感器的制备及性能

以聚乙烯醇(PVA)为原料, 植酸(PA)和氨基-聚倍半硅氧烷(NH₂-POSS, NP)为交联剂, 通过冻融循环法制得PVA/PA/NP复合水凝胶, 再以其为模板, 通过吡咯的原位聚合制得PVA/PA/NP-PPy复合导电水凝胶, 克服了聚吡咯材料易脆、 疏水的特性, 进一步改善了水凝胶的导电性和灵敏性. 循环拉伸实验结果表明该水凝胶具有良好的自回复能力, 电导率高达7.53 S/m, 从I-V曲线可知其作为柔性可穿戴应变传感器的最高检测电流可达 9.029 mA, 灵敏度因子可达6.796, I-T曲线表明该传感器可以准确地通过电流信号变化来监测人体的各种微小运动.     

磁性半互穿网络智能水凝胶的合成及性质评价

以甲基丙烯酸(MAA)、N-异丙基丙烯酰胺(NIPAAm)、丙烯酰胺(AM)为原料,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,利用IPN技术并结合磁性的γ-Fe2O3增强剂,在水溶液中制备了半互穿网络水凝胶(PMAA/PAM-NIPAAm/γ-Fe2O3),研究了水凝胶的溶胀性﹑热稳定性和电磁性。实验表明,水凝胶形成稳定的IPN互穿网络结构且该水凝胶具温度、pH双重敏感性和顺电磁性。所合成的水凝胶在低临界溶解温度31℃以下,具有明显正向温敏性,高于此温度,水凝胶的温度敏感性会逐渐减弱。产品成功克服了NIPAAm类水凝胶的温缩性。     

Effect of Sodium Alginate on the Properties of Thermosensitive Hydrogels

Sodium alginate (SA ) was combined with poly(N ‐isopropylacrylamide) (PNIPAAm ) to prepare thermosensitive hydrogels through semi‐interpenetrating polymer network (semi‐IPN ) and fully interpenetrating polymer network (full‐IPN ). The thermosensitive, swelling, mechanical, and thermal properties of pure PNIPAAm , SA /PNIPAAm semi‐IPN , and Ca‐alginate/PNIPAAm full‐IPN hydrogels were investigated. The formation of semi‐IPN and full‐IPN significantly improved the hydrogels’ swelling capability and mechanical properties without altering their thermosensitivity. 5‐Fluorouracil (5‐Fu) was selected as a model drug to study the release behaviors of the hydrogels. It was found that in vitro controlled drug release from semi‐IPN hydrogels showed an initial release burst, followed by a slower and sustained release, before reaching equilibrium. Full‐IPN hydrogels showed slow and sustained release during the whole process. Temperature and pH were found to affect the rate of drug release. Ca‐alginate/PNIPAAm full‐IPN hydrogels have potential application as drug delivery matrices in controlled drug release.     

一种高透明、可拉伸导电水凝胶的制备及其在电容传感器中的应用

导电水凝胶由于具备良好的电学特性、可调节的机械性能、易于加工性和生物相容性等,是制备柔性电子设备的理想基材。本文使用马来酸与丙烯酰胺作为共聚单体,氯化锂作为导电离子,N,N'-二甲基双丙烯酰胺作为交联剂,使用光引发剂,采用原位光聚合的方式制备了一种导电水凝胶。制得的水凝胶可见光透过率高达93%,最大拉伸形变~380%,导电率最大为12 S/m。鉴于其优异的综合性能,实验中使用导电水凝胶制备了电容传感器并应用于人体活动监测。结果表明,制备的导电水凝胶电容传感器对不同程度的手指弯曲形变和不同力度的手指触碰均表现出灵敏的响应行为,为未来可穿戴柔性电子产品的发展起到了一定的推动作用。     

高强度PAMPS-PAAm互穿网络凝胶及其溶胀性能

通过考察不同单体浓度或离子强度下凝胶的力学性能和溶胀特性,对聚2-丙烯酰胺-2-甲基丙磺酸(PAMPS)与聚丙烯酰胺(PAAm)形成的互穿网络凝胶的高强度性能和作用机理进行了研究.结果表明:PAMPS-PAAm互穿网络凝胶的力学强度对c(AMPS)存在一个最佳值(1 mol/L),且随c(AAM)的增大而显著增大(0.5～4 mol/L).当c(AMPS)=1 mol/L、c(AAM)＝4 mol/L时,互穿网络凝胶的最大抗压强度达6.46 MPa;改变凝胶体系内水的离子强度,PAMPS-PAAm凝胶在0.25 mol/kg离子强度时的抗压强度与纯水状态下相比增加了29%.     

Effect of kappa-carrageenan on the properties of poly(N-vinyl pyrrolidone)/kappa-carrageenan blend hydrogel synthesized by γ-radiation technology

A series of hydrogels in the form of rods were prepared from kappa-carrageenan (KC) and poly (N-vinyl pyrrolidone) (PVP) by gamma radiation with ⁶⁰Co γ source at room temperature. The properties of the prepared hydrogels, such as the gel strength, gel fraction and swelling behavior were investigated. Incorporation of KC into the PVP/water system increased obviously the gel strength and equilibrium degree of swelling (EDS) of PVP hydrogel. The experimental analyses showed that the crosslinking reaction of PVP was quicker than the degradation of KC at a low dose (less than 30 kGy), and the degradation of KC was inhibited in the PVP/KC mixture system. So an interpenetrating polymer network (IPN) hydrogel composed of PVP (a chemical crosslinking network) and KC (a physical crosslinking network) was proposed here. The existence of different classes of water in this IPN system was shown by water melting curves using DCS.     

PVA-PAMPS-PAA三元互穿网络型水凝胶的合成及其性能研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)以及聚乙烯醇(PVA)为原料,制备了PVA-PAMPS-PAA三元互穿网络型(T-IPN)水凝胶.红外分析表明,PVA与PAA以及PAMPS之间形成了较强的氢键,使得PVA分子上的C—O伸缩震动吸收峰移向了低波数处.X射线衍射以及电镜分析表明,当PVA用量较低时,PVA能均匀的穿插于凝胶网络中,形成完善的互穿网络结构,当PVA用量过高时,部分的PVA结晶而使得凝胶出现相分离.研究了该三元互穿网络型水凝胶的溶胀性能,结果表明,该水凝胶的平衡溶胀比在200至340之间,并且随着AA以及AMPS用量的增加,凝胶的溶胀速率以及平衡溶胀比均升高.该三元互穿网络型水凝胶在酸性溶液中和在碱性溶液中表现出截然不同的消溶胀性能;并且随着溶液pH的升高,凝胶在pH=9.0附近出现体积突变,表现出pH敏感性.通过研究T-IPN水凝胶的抗压缩性能发现,利用线型高分子、柔性高分子网络以及刚性高分子网络制备的三元互穿网络型水凝胶能在高溶胀比下保持较高的强度.溶胀比为180的T-IPN水凝胶,其最大抗压缩强度可达12.1 MPa.进一步研究发现,凝胶的组成以及溶胀比均对凝胶的抗压缩强度和压缩应变均存在较大的影响.     

聚丙烯酸酯/环氧树脂互穿网络聚合物的研究Ⅲ.橡胶态弹性模量和互穿缠结

采用一步法（Ｓｉｍｕｌｔａｎｅｏｕｓｌｙ）合成了双组分的聚丙烯酸酯／环氧树脂互穿网络聚合物（ＩＰＮｓ）．选择预溶胀方法制备了聚丙烯酸酯和环氧树脂两种组分网络．测定了各种组分比的ＩＰＮ和不同溶胀度下的组分网络的动态力学性能，从橡胶态弹性理论出发讨论了ＩＰＮ和预溶胀网络之间在橡胶态弹性模量上的关系，并据此指出互穿缠结增加了网络的有效“交联密度”，因此，它对ＩＰＮ的橡胶态弹性模量有较大的贡献．密度测量的结果也提供了另一方面的证据     

Synthesis and characterization of κ‐carrageenan/poly(N,N‐diethylacrylamide) semi‐interpenetrating polymer network hydrogels with rapid response to temperature

In this study, a novel classical thermo‐ and salt‐sensitive semi‐interpenetrating polymer network (semi‐IPN) hydrogel composed of poly(N,N‐diethylacrylamide) (PDEAm) and κ‐carrageenan (KC) was synthesized by free radical polymerization. The structure of the hydrogels was studied by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR and SEM revealed that the semi‐IPN hydrogels possessed the structure of H‐bonds and larger number of pores in the network. Compared to the PDEAm hydrogel, the prepared semi‐IPN hydrogels exhibited a much faster response rate to temperature changes and had larger equilibrium swelling ratios at temperatures below the lower critical solution temperature (LCST). The salt‐sensitive behavior of the semi‐IPN hydrogels was dependent on the content of KC. In addition, during the reswelling process, semi‐IPN hydrogels showed a non‐sigmoidal swelling pattern. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and Properties of IPN Hydrogels Based on Konjac Glucomannan and Poly（acrylic acid）

As a random copolymer of β-(1,4) linked D-mannose and D-glucose, konjac gluco- mannan (KGM) is a naturally occurring water-soluble polysaccharide, and has been paid attention in the field of drug controlled release carriers potentially used in colon1,2. …