水凝胶-水凝胶复合材料的制备与表征

将聚乙二醇400(PEG400)溶胀的交联N-乙烯吡咯烷酮(NVP)水凝胶微粒浸渍在含有引发剂过氧化苯甲酰(BPO)的甲基丙烯酸-2-羟基乙酯(HEMA)单体中并加热引发聚合反应,制备水凝胶-水凝胶复合材料,研究了产物的溶胀行为,并采用SEM、DSC对产物进行了表征。结果表明,水凝胶-水凝胶复合材料的饱和含水量随交联NVP水凝胶颗粒的含量及饱和含水量增大而增大,两种水凝胶之间的界面结构可分为包埋、部分互穿网络以及完全部分互穿网络等三种,其原因在于HEMA单体部分进入交联NVP水凝胶微粒并进行原位聚合的程度不同;处于分散相的水凝胶与处于连续相的水凝胶的吸水倍率不同,导致水凝胶-水凝胶复合材料吸水溶胀时不同相结构之间互相制约,处于分散相的水凝胶的大分子链不能充分伸展,非冻结水的熔融峰被自由水的熔融峰掩盖,表现为DSC谱图上非冻结水的熔融峰被自由水的熔融峰掩盖。     

聚乙烯吡咯烷酮/壳聚糖共混水凝胶的制备与水的状态

以戊二醛作为交联剂,制备了聚乙烯吡咯烷酮（PVP）/壳聚糖（CHI）共混水凝胶,共混物的玻璃化转变温度T_g随CHI含量的升高而升高,SEM图谱观察到PVP/CHI凝胶表面呈现随CHI∶PVP比而变化的微相分离.凝胶溶胀率随着PVP含量升高、PVP分子量降低、CHI脱乙酰度增大而升高.DSC分析表明,非冷冻状态下,CHI∶PVP为1∶2时,游离水、可冻结结合水、非冻结结合水含量分别为42.7%、43.3 %、14.0 %;CHI∶PVP为1∶8时,凝胶中含非冻结结合水少,DSC曲线上只有一个明显的失水吸热峰,由游离水与可冻结结合水叠加而成.-123℃冷冻条件下凝胶的DSC升温曲线在0、38、53℃观察到一组明显的焓化峰,这是由于低温时冻结为结晶相的游离水、可冻结结合水,随温度升高吸热又转化为游离水、可冻结结合水所致.     

印迹水凝胶作为氟尿嘧啶载体的药物缓释性能

以氟尿嘧啶为模板药物,以甲基丙烯酸羟乙酯为骨架单体,以甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁腈为引发剂合成印迹水凝胶,并通过扫描电镜、红外光谱及差示热量扫描等测试手段对凝胶进行了表征,结果表明：制备的印迹水凝胶表面无孔、光滑,氟尿嘧啶与其中的单体通过氢键结合成了复合物,同时经处理后凝胶中已不再残留未反应的单体。印迹水凝胶的吸水溶胀性能实验结果显示其吸水溶胀性能随制备中模板药物的含量的增加而增强,同时同一凝胶的溶胀速度与溶胀率随体系pH值的升高而增强。在氟尿嘧啶溶液中测定水凝胶的药物负载量,结果显示：印迹水凝胶的药物负载能力明显强于非印迹水凝胶,同时印迹水凝胶（8∶1）对药物的负载能力强于印迹水凝胶（4∶1）,药物负载量高达0.0914 mg/g。在模拟体液中测试水凝胶对药物的释放效果结果显示：印迹水凝胶对药物的缓释作用明显优于非印迹水凝胶,并且印迹水凝胶（8∶1）对药物的缓释效果优于印迹水凝胶（4∶1）,对药物的释放平缓,同时,释放体系pH值的升高不利于印迹水凝胶的药物缓释效果。     

温敏性水凝胶的合成及表征

以羟丙基甲基纤维素与丙烯酰氯为原料,制备了羟丙基甲基纤维素丙烯酸酯;以偶氮二异丁腈为引发剂、以羟丙基甲基纤维素丙烯酸酯为大分子交联剂、N-异丙基丙烯酰胺为单体在N,N-二甲基甲酰胺中70℃下通过自由基聚合反应24 h,制备了温度敏感性水凝胶。用DSC对其相转变温度进行了表征,并测定了不同温度下达到溶胀平衡时水凝胶的溶胀比,进行了水凝胶的去溶胀动力学及干凝胶的再溶胀动力学研究。在聚合过程中,加入羟丙基甲基纤维素丙烯酸酯制得的水凝胶:相转变温度由30℃降为29℃;在10℃时溶胀比由29降为24.8;去溶胀速率加快,例如:该水凝胶在10 m in内失水率由56%降为16%,在30 m in内失水率由86%降为19%;并且减慢了凝胶的再溶胀速率。     

聚乙烯醇水凝胶的熔融,再凝胶和再熔融

本文在不同升温速率下，考察了由三氟醋酸乙烯衍生出的间规立构聚乙烯醇（Ｓ－ＰＶＡ）水凝胶的熔融行为。聚合物浓度大于５ｇ／Ｌ的水凝胶，在０－４０℃冻结，熔融温度随升温速率的降低而增加。在低速升温时，因为交联点起了重要作用，对热更稳定。在凝胶和微晶中，相分离随着逐步解体缓慢出现。在１０－３０℃和４５－６０℃的温度范围内，Ｓ－ＰＶＡ水凝胶的ＤＳＣ谱图中得到则明显的放热峰。     

空心玻璃微珠对聚丙烯酸水凝胶溶胀性能的影响

为了研究空心玻璃微珠(HGM)的加入对合成聚丙烯酸(PAA)水凝胶的吸水溶胀性、耐盐性及pH敏感性的影响,以丙烯酸(AA)为单体、聚乙二醇为有机致孔剂、HGM为无机致孔剂、过硫酸铵为引发剂、N,N-亚甲基双丙烯酰胺为交联剂,通过自由基溶液聚合制备了5种不同HGM投料量的PAA水凝胶,并对其结构、热稳定性、表面形貌以及其在纯水、生理盐水和pH缓冲液中的溶胀行为进行了表征。结果表明,HGM的加入并不影响PAA水凝胶的化学组成和热稳定性,但有利于凝胶致孔;适量HGM的加入有助于大幅提高PAA水凝胶的吸水溶胀性、耐盐性和pH敏感性;当HGM的投料量为单体AA质量的10%时,PAA水凝胶的孔结构最丰富,其吸水平衡溶胀比可达345 g/g,吸盐水平衡溶胀比为47 g/g,pH敏感性在5种水凝胶中最佳。     

聚丙烯酸镁/丙烯酸钠双交联水凝胶的制备及性能研究

以丙烯酸镁(Mg A)和丙烯酸钠(SA)为单体、N,N'-亚甲基双丙烯酰胺(MBA)为共价交联剂,通过溶液聚合方法制备了系列聚丙烯酸镁/丙烯酸钠(PAMgA/x-PASA)双交联水凝胶,并测试分析了共聚水凝胶材料的结构、吸水特性和力学性能。结果表明,MBA作用下丙烯酸镁和丙烯酸钠形成了双交联结构的共聚水凝胶,显著提高了丙烯酸盐水凝胶的吸水溶胀比、保水性和重复吸水能力。当SA质量分数为20%时,水凝胶的吸水溶胀比达550%,较单一离子交联的聚丙烯酸镁提高近4倍; 12 h干燥后的保水率约60%;而多次干燥-吸水溶胀以后,水凝胶的吸水溶胀比仍高达300%。此外,丙烯酸钠和MBA的加入对水凝胶的拉伸强度影响不大,但显著提高了材料的断裂伸长率,可从395%提高到690%。     

合成型两性水凝胶研究进展

两性水凝胶因其良好的环境响应特性,而成为吸水保水材料领域的研究热点。以阴离子单体与阳离子单体共聚制备两性聚电解质水凝胶和内盐型两性离子单体聚合制备聚甜菜碱型水凝胶为重点,介绍了两性水凝胶的制备、溶胀特性以及性能改进等方面的国内外研究现状及发展趋势。     

温敏性P(NIPAAm-co-Am)/MMT水凝胶复合材料的研究

以N-马来酰化壳聚糖为交联剂,N-异丙基丙烯酰胺(NIPAAm)、丙烯酰胺(Am)、蒙脱土(MMT)为原料,过硫酸铵和N,N,N’,N’-四甲基乙二胺为引发剂和促进剂,采用水溶液自由基聚合反应合成了温敏性的P(NIPAAm-co-Am)/MMT水凝胶复合材料,研究了复合材料的温敏性、溶胀动力学、退溶胀动力学性能。研究表明:P(NIPAAm-co-Am)/MMT水凝胶复合材料具有良好的温敏性,不同蒙脱土含量的水凝胶的相转变温度(VPTT)均在37℃。由于水凝胶的大孔状结构,均表现出快速的溶胀动力学和退溶胀动力学。     

壳聚糖纤维/壳聚糖/海藻酸钠水凝胶溶胀性能与抑菌性能

制备了壳聚糖(CS)/海藻酸钠(SA)复合水凝胶,并通过加入吸水性壳聚糖长纤维、45%壳聚糖水刺无纺布、80%壳聚糖水刺无纺布、100%壳聚糖水刺无纺布、100%壳聚糖针刺无纺布这五种纤维,增强复合水凝胶的力学性能,探究了复合水凝胶的吸水溶胀性能与抑菌性能。结果表明,加入纤维后水凝胶在蒸馏水中的溶胀比明显降低,在碱性环境中,水凝胶的溶胀比显著上升,在偏中性环境中,水凝胶的溶胀比最低;加入纤维后,复合水凝胶仍具有一定的抑菌性,无纤维添加的水凝胶呈现出的抑菌能力一般,而加入了吸水性壳聚糖长纤维的具有最佳的抑菌性能。     

水在凝胶中的存在状态及其对凝胶力学性能的影响

以偶氮二异丁腈为引发剂,通过化学引发聚合合成甲基丙烯酸β-羟乙酯（HEMA）/N-乙烯基吡咯烷酮（NVP）二元共聚物和HEMA /NVP /甲基丙烯酸甲酯（或甲基丙烯酸丁酯）三元共聚物水凝胶,通过示差扫描量热法（DSC）结合热重法（TG）研究了不同单体配比的共聚物水凝胶中水的状态,证明了凝胶中存在3种不同状态的水：非冻结结合水、可冻结结合水和可冻结自由水.结果发现可冻结水的含量主要由NVP含量所决定,NVP单元基本不能键合水,而非冻结水的含量主要受HEMA含量和疏水性单体甲基丙烯酸酯含量影响.疏水性单体的引入使材料的力学强度提高,对凝胶体系具有增塑作用的是非冻结水而不是可冻结的结合水和自由水.     

PVA水凝胶中水的状态研究

用环氧氯丙烷作交联剂,制备了聚乙烯醇（PVA）亲水水凝胶。并用示差扫描量热法（DSC）对不同含水量的此种亲水水凝胶进行了测试,获得了各种状态水进入水凝胶聚合物网络体系的先后顺序情况,并研究了PVA水凝胶中三种状态水的含量随水凝胶含水量的变化而变化的规律。     

室温交联PVA水凝胶的制备与性能研究

以环氧氯丙烷为交联剂,采用室温化学交联法制备了聚乙烯醇(PVA)水凝胶,研究了交联温度和交联时间对PVA溶胀性能和力学性能的影响,借助差示扫描量热法(DSC)和扫描电子显微镜(SEM)对PVA水凝胶进行分析表征。结果表明,当交联时间为3d且交联温度为50℃时PVA水凝胶的综合性能最佳。PVA的玻璃化转变温度为-54.50℃,PVA水凝胶中包含有自由水、束缚水和非冷冻水。     

DSC studies on states of water in crosslinked poly(methyl methacrylate-co-n-vinyl-2-pyrrolidone) hydrogels

Mixtures of methyl methacrylate (MMA) with N-vinyl-2-pyrrolidone (VP) of various composition in the presence of fixed concentration of ethylene glycol dimethacrylate (EDMA) have been copolymerized to 100% conversion by γ-irradiation. The resultant solid xerogels were swollen in water to yield hydrogels of equilibrium water contents ranging from 15 to 76wt%. The state of water in the poly(MMA-co-VP) hydrogels has been studied by differential scanning calorimetry (DSC) and the percentages of free freezing, freezable bound and nonfreezing water were found to vary with the xerogel composition, i.e. the degree of hydration of the hydrogels. At low equilibrium swelling, most of the water exists as a non-freezing type, whereas at higher equilibrium swelling the majority of water exists as free freezing water. The maximum number of non-freezing water molecules per VP unit in the hydrogel is about 7.5.     

Biocomposite formation using β-cyclodextrin as a biomaterial in poly(acrylamide-<Emphasis Type="Italic">co</Emphasis>-acrylic acid): preparation,characterization, and salinity profile

A biocomposite of poly(acrylamide-co-acrylic acid) hydrogel with β-cyclodextrin as a biomaterial was prepared through one-pot synthesis in water as a green solvent. The formation of biocomposite was confirmed by advanced techniques such as FTIR spectroscopy, XRD, DSC, TGA, and FE-SEM. In this report, straight forward and efficient synthetic protocol for biocomposite formation responded without any environmental hazard. Swelling capacity of P(AM-co-AA) and biocomposite was studied by addition of different saline solutions including monovalent, divalent, and trivalent salts. By addition of β-cyclodextrin, the swelling and saline water-absorbing properties of the biocomposite hydrogel were significantly improved. In this regard, the possible formation mechanism of the composite hydrogel is also discussed. It is deduced that the biocomposite formation can be the result of intermolecular interactions between polymer and β-cyclodextrin. The water-soluble polymer seems to have entered into the inner cavity of β-cyclodextrin to form supramolecular biocomposite structure. The results indicate that the order of water uptake decreases with increase in valency of the salts. It is believed that this is an effective method to prepare supramolecular biocomposite hydrogel materials. Its applications can be extended in marine water industries as a basis for antifouling coating, waste water treatment, and even in medical field. Hence, the synthesized materials can be biodegradable, environment-friendly, and biocompatible inspired by the green chemistry concept.     

Preparation and swelling properties of a starch-g-poly(acrylic acid)/organo-mordenite hydrogel composite

A novel hydrogel composite was prepared via inverse suspension polymerization using starch, acrylic acid and organo-mordenite micropowder with the crosslinker, N,N′-methylenebisacrylamide and the initiator, potassium persulfate. Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy, scanning electron microscopy, and energy dispersive spectroscopy confirmed that the acrylic acid was grafted onto the backbone of the corn starch, that the organo-mordenite participated in the polymerization, and that the addition of organo-mordenite improved the surface morphology of the hydrogel composite. The swelling capacity of the hydrogel composite was evaluated in distilled water, and solutions with different pH values, and various salt solutions. It was found that the incorporation of 10 wt-% organo-mordenite enhanced the water absorbency by 144% (from 268 to 655 g·g⁻¹) and swelling was extremely sensitive to the pH values, the concentration of the salt solution and cation type. Swelling kinetics and water diffusion mechanism of the hydrogel composite in distilled water were also discussed. Moreover, the hydrogel composite showed excellent reversibility of water absorption even after five repetitive cycles and the hydrogel composite exhibited significant environmental-responsiveness by changing the swelling medium from distilled water to 0.1 mol·L⁻¹ NaCl solution. In addition, the loading and release of urea by the hydrogel composite were tested and the nutrient-slow-release capability of this material was found to be suitable for many potential applications.     

Hydrogel composites based on linear low‐density polyethylene‐g‐poly (acrylic acid)/Kaolin or halloysite nanotubes

Two series of superabsorbent hydrogel composites were prepared using waste linear low‐density polyethylene, acrylic acid, and two types of clays including kaolin and halloysite nanotube (HNT) through emulsion polymerization. The effects of the clay content on Water absorbency were investigated to obtain a high swelling capacity. The prepared samples were characterized using FTIR, SEM, thermogravimetric analysis, XRD, solid‐state ¹³C Nuclear Magnetic Resonance spectroscopy, and ²⁹Si NMR. SEM characterization of the samples showed that the hydrogel composites have more pores and a higher swelling ratio than the clay‐free hydrogels. The hydrogel composite containing kaolin had higher water absorbency compared to the hydrogel composites with HNT. The swelling behavior of the hydrogel composite was investigated in various saline solutions. The hydrogel composite containing 5 wt % kaolin had the highest water absorbency (760 g/g in distilled water). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40101.