基于动态共价键的pH响应自修复水凝胶的制备与评价

以α-甲基丙烯酸(MAA)和2-丙烯酰胺-2-甲基丙磺酸(AMPS)的共聚物P(MAA/AMPS)及聚乙烯醇(PVA)为单体、十水合四硼酸钠为交联剂合成了P(MAA/AMPS)-PVA二重互穿网络的pH响应水凝胶.通过SEM、FTIR、GPC、TGA-DTG和流变仪等表征了水凝胶的表面形貌和化学状态;测定了水凝胶的溶胀性﹑pH响应性﹑自修复性和流变性.结果表明,水凝胶形成了稳定的互穿网络结构且具有pH敏感性、自修复性;PVA羟基与硼酸根离子形成的共价配位硼酸酯键使水凝胶具备自修复性并受介质酸碱性的控制;力学性能测定结果显示,自修复水凝胶(SB用量为2.5％,水凝胶溶胀度为4)拉伸强度668 kPa,断裂伸长率可达665％,修复效率可达81％.     

具有pH响应性的双网络水凝胶的合成与性能研究

以锂藻土(Laponite)为交联剂,丙烯酰胺(AM)在Laponite分散液中进行原位自由基聚合合成第一网络,海藻酸钠(SA)与钙离子(Ca~(2+))进行物理交联形成第二个网络,制备具有高强度和响应性的互穿网络水凝胶。通过改变两个网络高分子的比例及交联密度调节水凝胶的拉伸强度和pH响应性。结果表明,当水凝胶中高分子的质量分数为9%,m(AM)∶m(K2S2O8)=1∶0.25%,Laponite含量占总体系质量的6%,m(SA)∶m(Ca~(2+))=1∶5.6%时制备的双网络水凝胶拉伸强度可达80kPa;同时水凝胶表现出灵敏的pH响应性。     

基于动态硼酸酯键/氢键的自修复水凝胶的制备及性能

通过4-(溴甲基)苯基硼酸(PBA)和1-乙烯基咪唑(IL)的烷基化反应制备了苯硼酸离子液体(PBA-IL)单体。在2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO)氧化纳米纤维素(CNF)的存在下，通过丙烯酰胺(AM)和PBA-IL的一步聚合反应，制备了一种具有半互穿网络结构的自修复导电水凝胶(PAM/PBA-IL/CNF)。通过1HNMR对PBA-IL的化学结构进行表征；通过FTIR、XPS、SEM对水凝胶的化学结构和物理形貌进行表征，并测试了水凝胶的拉伸性能、自修复性能和导电性能。结果表明，PBA-IL单体和水凝胶成功制备，且水凝胶具有典型的多孔结构。PAM/PBA-IL3/CNF水凝胶[3代表PBA-IL含量为30%，以AM、PBA-IL、CNF悬浮液、N,N’-亚甲基双丙烯酰胺(MBA)溶液、过硫酸铵(APS)的总绝干质量为基准]的断裂应力为335.1 kPa、断裂伸长率为1969.5%、断裂能为12.1 kJ/m²、自修复效率为95.43%(150 min)、电导率为6.38 mS/cm。     

pH敏感性水凝胶的制备与作用原理

对pH敏感性水凝胶的合成方法和作用原理进行了综述。pH敏感性水凝胶的合成方法主要包括交联聚合、接枝共聚和互穿网络三种方式；pH敏感性水凝胶具有pH响应性的原因是聚合物网络中含有可离子化的酸性或碱性基团。     

铜纳米线复合有机水凝胶的制备及性能研究

采用乙二醇和水形成二元溶剂体系,并通过聚乙烯醇与十水合四硼酸钠之间产生动态交联作用赋予凝胶耐低温和自修复的功能,在聚丙烯酰胺和聚乙烯醇网络中引入铜纳米线,合成铜纳米线复合有机水凝胶.其在-40℃下储存5 h依旧保持良好的机械性能.基于聚乙烯醇的羟基与四羟基硼酸根离子之间的动态硼酸酯键,凝胶有着优异的自修复性能,其愈合效率可达93％.凝胶的拉伸应变可达15倍,拉伸应力为1.9 MPa,且在500％的宽应变范围内保持优异的电机械稳定性.     

预辐照聚乙烯薄膜接枝丙烯酸/丙烯酰胺制备水凝胶互穿网络的研究

通过二次接枝方法，在预辐射聚乙烯(PE)薄膜上分别接枝丙烯酸(AAc)和丙烯酰胺(AAm)制得了具有pH敏感性和温度敏感性水凝胶互穿网络(IPN)。研究了不同辐照源、单体浓度、阻聚剂的浓度等对接枝率的影响，经测定，所得到的PE-g-Amn／AAc水凝胶膜具有明显的pH敏感性。     

双重动态共价键交联纳米纤维素导电水凝胶及其柔性传感器

自愈合导电水凝胶因其良好的自愈合性能与导电性能,在柔性可穿戴设备中具有巨大的应用前景。以4-甲酰基苯硼酸(Bn)交联聚乙烯醇(PVA)和聚乙烯亚胺(PEI)构建基于硼酸酯键和亚胺键的双重动态交联水凝胶网络,引入聚吡咯修饰的纤维素纳米纤维(PPy@CNF)构建了具有良好自愈合和导电性的PBP-PPy@CNF纳米复合水凝胶。结果表明,当PPy@CNF的质量分数为0.8%时,水凝胶的力学性能最佳,其最大应力可达6.65kPa,断裂拉伸应变可达2080%,电导率为2174μS/m。基于该水凝胶的电阻式传感器具有良好的稳定性和重复性,在应变检测范围0～800%内,灵敏因子GF可分为三个线性响应区域,分别是0～200%(GF₁=2.82)、200%～600%(GF₂=7.15)和600%～800%(GF₃=12.85),该传感器能有效检测人体不同部位的运动,可应用于可穿戴传感设备。     

温度和pH响应型水凝胶的制备及性能研究

采用双丙酮丙烯酰胺、丙烯酰胺和丙烯酸为原料,以N,N'-亚甲基双丙烯酰胺为交联剂,2-酮戊二酸为光引发剂,采用光引发聚合方法制备了具有温度和pH响应型水凝胶。研究了水凝胶在不同温度和pH条件下的溶胀性能。结果表明,随着温度的升高,水凝胶的溶胀率降低,随着pH的增加,水凝胶的溶胀率增加,表现出明显的温度、pH双重响应性。     

聚甲基丙烯酸/丙烯酰胺pH敏感凝胶的合成与溶胀行为研究

以单体丙烯酰胺(AM)、甲基丙烯酸(MAA),交联剂N-N'亚甲基双丙酰胺(BIS)为原料,通过自由基共聚合成了聚甲基丙烯酸/丙烯酰胺[P(MAA-co-AM)]水凝胶.研究了干凝胶在不同pH溶液中的溶胀动力学,结果表明不同AM、MAA单体配比的凝胶溶胀性具有很大差异,其溶胀率都随着溶液的pH增加而增大,在pH=12和pH=2溶液反复变换时显示可逆溶胀-退溶胀和快速响应特性,溶胀-退溶胀过程中搅拌作用对凝胶响应速率有显著影响.吸水平衡P(MAA-co-AM)水凝胶在酸性及碱性条件下均出现收缩,在pH=2下10 min之内凝胶收缩90%以上,随着pH增大逐渐减慢.通过不同浓度的NaCl与CaCl2溶液研究了溶液离子强度以及反离子的电荷数对凝胶溶胀性影响,在NaCl溶液和水中,呈现反复溶胀-退溶胀响应特性.     

粒状聚N-异丙基丙烯酰胺/壳聚糖水凝胶的制备、性能及其应用

用反相悬浮聚合法,合成了具有温度/pH敏感性的聚N-异丙基丙烯酰胺/壳聚糖粒状半互穿网络(PNIPA/CS semi-IPN)水凝胶,研究了该水凝胶在不同温度、不同pH介质以及不同组成下的溶胀率变化.结果表明:该水凝胶的最低临界溶液温度(LCST)与PNIPA水凝胶基本相同,均在33℃左右,pH=3时溶胀率达到最大,具有明显的温度和pH敏感性.壳聚糖(CS)的不同比例也对凝胶的溶胀率产生很大影响.振荡实验表明:凝胶粒子具有温度响应可逆性.同时进行了乳酸吸附与释放的初步研究,当PNIPA/CS质量比为10时,最大吸附达到168.29 mg(g dry gel)-1,释放率为31.74%.     

聚乙烯醇水凝胶自修复性能

高浓度聚乙烯醇（PVA）水凝胶具有一定的修复功能,但其自修复机理及制备工艺参数对其修复性能的影响缺乏研究。本文采用冷冻-解冻法制备了高浓度自修复PVA水凝胶,通过调整PVA水凝胶制备工艺参数（PVA分子量、PVA浓度、冷冻时间、解冻时间、冷冻-解冻次数、修复时间、冷冻温度等）得到了最佳工艺条件,分析了水凝胶自修复机理,并研究了PVA水凝胶的多次自修复性能。研究结果表明：相对分子质量大的PVA制备的水凝胶自修复性能好;其中冷冻时间为2h,解冻时间为1h,一次冷冻-解冻循环制备得到的水凝胶自修复性能最好,最佳修复时间为12h,能较好地进行反复自修复。指出水凝胶自修复性能主要是由其内部可逆氢键的相互作用形成的,其主要影响源于冷冻-解冻处理后水凝胶内部羟基含量及PVA分子的流动性。     

Swelling kinetics of modified poly(vinyl alcohol) hydrogels

Interpenetrating polymer network (IPN) hydrogels composed of poly(vinyl alcohol) (PVA) and monomer, N‐isopropylacrylamide (NIPAAm), diallyldimethylammonium chloride (DADMAC), or methacrylic acid (MAA) were prepared by using the sequential‐IPN method. The equilibrium swelling ratios of PVA/NIPAAm (VANP), PVA/DADMAC (VADC), and PVA/MAA (VAMA) are 412, 370, and 297 at 25°C, respectively. VANP had the highest swelling ratio in time‐dependent swelling behavior, whereas the swelling ratio of VAMA had the lowest. The n values of VANP, VADC, and VAMA are 0.72, 0.81, and 0.96, respectively. Transport of all IPN hydrogels is anomalous and their transport mechanisms are dominated by a combination of diffusion‐controlled and relaxation‐controlled systems. VAMA has the highest activation energy and VANP has the lowest activation energy. The values of all IPN hydrogels are from 4.66 to 16.49 kJ/mol, which proves that all IPN hydrogels are hydrophilic. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3310–3313, 2003     

半纤维素/碳纳米管复合凝胶的溶胀性能

采用 (NH4)2S2O8-Na2SO3为引发剂体系,N,N-亚甲基双丙烯酰胺（BIS）为交联剂,利用自由基聚合法成功制备了半纤维素/碳纳米管复合凝胶。用SEM对凝胶的结构形态进行了研究分析;研究了单体比例、碳纳米管含量和pH值对凝胶溶胀率的影响;并应用溶胀动力学方程对试验数据进行拟合。研究结果表明：半纤维素/碳纳米管复合凝胶的溶胀率随着甲基丙烯酸/半纤维素比例的增加而减小,随着碳纳米管含量的增加而减小;pH≤11时随pH值的增加而增大,pH>11时随pH值的增加而减小。拟合结果表明整个溶胀过程符合Schott二级动力学模型。     

A Novel Polyvinyl Alcohol-Based Hydrogel with Ultra-Fast Self-Healing Ability and Excellent Stretchability Based on Multi Dynamic Covalent Bond Cross-Linking

A novel self-healing poly(vinyl alcohol) (PVA)-based hydrogel is developed by cross-linking PVA chains through multi dynamic covalent bonds by use of a small cross-linker composed by 4-formylphenylboric acid (FPBA) and lysine (Lys). The dynamic borate-imine-imine-borate bond structure between PVA chains endows the hydrogel excellent stretchability and ultra-fast self-healing ability without external stimulation. The self-healing efficiency can attain 94% and the elongation at break can reach up to near 1000% after only 3 min healing. Moreover, the self-healing of the hydrogel through the contact of two faces from both the same cut position and different cut positions has similar excellent efficiency. The hydrogel with the unusual self-healing performance and stretchability is used as an ideal material in strain sensors monitoring human movement and tiny vibrations caused by human voice. Interestingly, the sensor can continue to function normally after self-healing for only ≈3 s. It is expected that this simple strategy of fabricating self-healing hydrogels with multi dynamic bonds will provide new opportunities in the design and preparation of PVA-based hydrogels to expand their potential applications in sensors and other various fields.     

Crosslinked poly(vinyl alcohol)/carboxymethyl chitosan hydrogels for removal of metal ions and dyestuff from aqueous solutions

Hydrogels composed of poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMCh) were synthesized via ultraviolet (UV) irradiation that can be used in several industrial fields. Several analysis tools were used to characterize the physical and thermal properties of CMCh/PVA hydrogels namely FT‐IR, scanning electron microscope (SEM), XRD, thermogravimetric analysis (TGA), and differential scanning calorimetery (DSC). TGA results showed that CMCh/PVA hydrogels are thermally more stable than CMCh and their thermal stability increases as PVA content increases in the hydrogel. Also, DSC results showed that CMCh/PVA hydrogels are at least partial miscible blends. Moreover, the swelling behavior of the CMCh/PVA hydrogels was studied in different buffered solutions and in different salt solutions at various concentrations. CMCh/PVA hydrogels swell much more than CMCh especially at alkaline pH. Both metal and dye uptake were studied for CMCh/PVA hydrogels. The hydrogels adsorb much more dyestuff and metal ions like Cu²⁺, Cd²⁺, and Co²⁺ than CMCh itself. Much dyestuff and metal ions are adsorbed by the hydrogels as PVA content increases in the hydrogel. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel Biodegradable pH/Thermosensitive Hydrogels: Part 1. Preparation and Characterization

A series of biodegradable and pH/thermosensitive hydrogels based on monomethoxyl poly(ethylene glycol) (MPEG), poly(?-caprolactone) (PCL), methylacrylic acid (MAA), and N-Isopropylacrylamide (NIPAAm) were prepared by UV-initiated free radical polymerization method. Swelling behavior and hydrolytic degradable behavior in aqueous medium with different pH values and pH/thermosensitivity of the hydrogels were studied in detail. The prepared biodegradable pH/thermo-sensitive hydrogels based on PCL, MPEG, MAA, and NIPAAm may have great potential application in smart drug delivery system.     

聚丙烯酸/氧化石墨烯自修复水凝胶的合成及性能

通过改进的Hummers方法成功制备了氧化石墨烯(GO)。以Fe3+为交联剂、丙烯酸(AA)为单体、GO为增强剂,采用原位聚合法制备了聚丙烯酸(PAA)/GO自修复水凝胶。考查了不同GO含量下,PAA/GO自修复水凝胶的溶胀性能,并探讨了GO含量、Fe3+含量和H2O含量对PAA/GO自修复水凝胶力学性能的影响,研究了PAA/GO自修复水凝胶的自修复性能。结果表明,Fe3+含量、GO含量和H2O单体含量分别为0.5 %（摩尔分数）、0.5 %（质量分数,下同）、80 %时,具有最佳力学性能（其拉伸强度为743.5 kPa,断裂伸长率为2940.5 %）;GO含量为0.25 %时,PAA/GO自修复水凝胶的吸水性能最大;PAA/GO自修复水凝胶具有优异的自修复性能。     

Aminoglycoside hydrogels based on dynamic covalent bonds with pH sensitivity,biocompatibility, self-healing,and antibacterial ability

Despite aminoglycosides (AGs) have superior antibacterial ability, all approved AGs by FDA are associated with adverse effects such as ototoxicity and nephrotoxicity. To solve these problems, AGs hydrogels based on dynamic covalent bond cross-linking were quickly prepared within 25 s by using AGs, aldehyde hyaluronic acid (A-HA), and adipic acid dihydrazide graft hyaluronic acid (HA-ADH) as materials. FT-IR, thermal analysis, and SEM results exhibited that A-HA/HA-ADH/AGs hydrogels were successfully synthesized with highly porous and interconnected network structure. The water absorption ratio of the hydrogels increased with the decreasing pH and temperature, indicating the hydrogels were pH- and temp-responsive. The pH-dependent degradation also demonstrated pH sensitivity of the hydrogels. Rheology and self-healing analysis assessment displayed that AGs hydrogels had good mechanical property, self-healing ability, and injectability. The hydrogels had no cytotoxicity to L929 cells and their hemolysis ratios were between 0.7% and 1.3%, which reached a nontoxic level. Most importantly, inhibition zones results demonstrated that the hydrogels had excellent and sustained antibacterial performance against Escherichia coli and Staphylococcus aureus. Therefore, A-HA/HA-ADH/AGs hydrogels are potential dressings for wound healing. Further plans including antibacterial and in vivo wound healing assays will be shown in the next work.     

Preparation, characterization, and antibacterial properties of pH-responsive P(MMA-co-MAA)/silver nanocomposite hydrogels

A pH-responsive copolymer hydrogel was synthesized based on methyl methacrylate (MMA) and methacrylic acid (MAA) as monomers, and was adopted as a nanoreactor for assembling Ag nanoparticles. Fourier transform infrared spectroscope (FTIR), scanning electron microscopy (SEM), transmission electron microscope (TEM), UV-visible spectroscopy (UV-Vis) and thermogravimetric analysis (TGA) were used to fully characterize the formation of silver nanoparticles in P(MMA-co-MAA) hydrogels. The experimental results showed that the P(MMA-co-MAA) hydrogels assume a three-networks architecture in morphologies, and that nearly spherical Ag nanoparticles are formed in these hydrogel networks; the size of these Ag nanoparticles varies with the system composition. The swelling kinetics investigations demonstrated that the equilibrium swelling ratio (ESR) of the P(MMA-co-MAA)/Ag hydrogels depended on the content of the MAA and pH of the buffer solutions, and the ESR values were reduced with increasing MAA contents. The antibacterial properties against both S. aureus and B. subtilis bacteria demonstrated that the P(MMA-co-MAA)/silver nanocomposite hydrogels had higher antimicrobial efficacy than the pure P(MMA-co-MAA) counterparts. Therefore, the nanocomposite hydrogels turned out to be a potentially smart material in the range of applications of antibacterial activity.     

Comparative study of PEO and PVA hydrogels for removal of methylene blue dye from wastewater

In this study, poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO) hydrogels were synthesized and evaluated as adsorbent for dye removal from wastewater using methylene blue (MB) in aqueous solution as probe. PEO samples were photochemically prepared by varying irradiation time (1–16 h), while PVA samples were synthetized with different concentration of glutaraldehyde (GA) (0.03–0.48%). The obtained hydrogels were obtained through the analysis of a swelling test, scanning electron microscopy, and adsorption studies. PEO hydrogels adsorption capacity was dependent on the irradiation time, while the PVA hydrogel adsorption capacity reduces with GA concentration. Both hydrogels demonstrated a Langmuir isotherm adsorption model at the equilibrium and pseudo‐second order kinetic fits properly. pH studies showed that when pH reaches 12, the adsorbed MB amount is close to 8 and 2 times higher than pH = 2 both hydrogels. Photochemical preparation of hydrogels shows an easier way of tuning their properties in order to maximize dye removal. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45043.