Preparation of alginate/poly(N‐isopropylacrylamide) semi‐interpenetrating and fully interpenetrating polymer network hydrogels with γ‐ray irradiation and their swelling behaviors

Semi‐interpenetrating polymer network (semi‐IPN) and fully interpenetrating polymer network (full‐IPN) hydrogels composed of alginate and poly(N‐isopropylacrylamide) were prepared with γ‐ray irradiation. The semi‐IPN hydrogels were prepared through the irradiation of a mixed solution composed of alginate and N‐isopropylacrylamide (NIPAAm) monomer to simultaneously achieve the polymerization and self‐crosslinking of NIPAAm. The full‐IPN hydrogels were formed through the immersion of the semi‐IPN film in a calcium‐ion solution. The results for the swelling and deswelling behaviors showed that the swelling ratio of semi‐IPN hydrogels was higher than that of full‐IPN hydrogels. A semi‐IPN hydrogel containing more alginate exhibited relatively rapid swelling and deswelling rates, whereas a full‐IPN hydrogel showed an adverse tendency. All the hydrogels with NIPAAm exhibited a change in the swelling ratio around 30–40°C, and full‐IPN hydrogels showed more sensitive and reversible behavior than semi‐IPN hydrogels under a stepwise stimulus. In addition, the swelling ratio of the hydrogels continuously increased with the pH values, and the swelling processes were proven to be repeatable with pH changes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4439–4446, 2006     

通过RAFT聚合方法合成具有高强度和高溶胀率的纳米水凝胶

为了得到具有高强度和高溶胀率的纳米水凝胶(NCgels),N-异丙基丙烯酰胺通过可逆加成断裂链转移(RAFT)聚合的方法,插层在含有质量分数为0.25%～15%的可扩展的有机化的蒙脱土(Clay-S)层间并交联。结果表明,与传统水凝胶相比,该水凝胶的强度和溶胀性能得到了很大提高,并且对温度的变化具有较快的响应速率。以质量分数为5%的蒙脱土,链转移剂的质量分数为0.5%制备的纳米水凝胶为例,该水凝胶在20℃的溶胀率为450,而传统水凝胶在相同温度时的溶胀率仅为20;该水凝胶在1min内失去75%的水,在4min内失去约90%的水,而传统水凝胶在15min内仅失去66%左右的水。     

Arrays of polyacrylamide hydrogels using a carbodiimide‐mediated crosslinking reaction

This study introduces a radical‐free approach for generating polyacrylamide (PAM) hydrogels with no toxic residues remaining in the networks. Acrylamide and bisacrylamide, which are neurotoxins, are not used during the hydrogel synthesis and only nontoxic side products are generated. This is achieved using a gentle carbodiimide‐mediated crosslinking (CMCL) reaction that does not require complex initiation systems and is effective in the presence of oxygen. This overcomes some of the key limitations related to PAM hydrogel synthesis using free‐radical routes and maintains the advantages of synthetic hydrogels over biopolymers. In addition, the CMCL reaction allows for accurate placement of functional groups, which controls hydrogel structure and performance including mechanical strength, swelling capacity, and hydrophobic balance. This flexibility is demonstrated through the synthesis and rheological characterization of a library of structurally diverse hydrogels as well as spherical hydrogels. PAM‐based hydrogels are used extensively in a broad number of applications, and this study demonstrates the applicability of this method as a nontoxic and radical‐free complementary alternative route that can generate structures analogous to those prepared using free‐radical routes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40416.     

纳米CaO2激发餐厨垃圾碳组分合成水凝胶及溶胀性能分析

为了实现餐厨垃圾中含碳组分的回收与增值化利用，以自制纳米CaO₂作为氧化剂激发餐厨垃圾中的碳组分释放，尿素作为改性剂，丙烯酰胺作为单体，N,N′-亚甲基双丙烯酰胺作为交联剂，过硫酸钠作为引发剂，通过自由基聚合交联反应合成水凝胶，并对制得的水凝胶进行了溶胀性能的分析。研究通过单因素实验考察了水凝胶制备的影响因素，结果表明在氧化剂用量为0.70g、改性剂用量为4.60g、单体用量为2.80g、交联剂用量为0.14g、引发剂用量为0.38g时，水凝胶的溶胀率可以达到1429.78%。水凝胶在去离子水中0~12h的溶胀行为符合Fickian的Case I扩散模型，12~84h的溶胀行为符合Schott溶胀动力学的二级模型，微观表征结果证明溶胀性与水凝胶的网状结构有关，热重分析证明餐厨垃圾制备得到的水凝胶具有良好的热稳定性。     

A promising porous polymer-nanoclay hydrogel nanocomposite as water reservoir material: synthesis and kinetic study

A porous hydrogel nanocopmposite based on biodegradable salep and montmorillonite (MMT) was synthesized by in-situ free radical graft polymerization of salep chains with acrylic acid (AA) monomers. The chemical structure and morphological properties of the prepared hydrogels was evaluated by FTIR spectroscopy, X-ray diffraction and SEM techniques. The effect of reaction variables such as crosslinker, initiator, monomer and clay contents on equilibrium water absorption capacity and swelling kinetic of hydrogel were investigated and optimized. Swelling behavior of the hydrogels in various pH and saline solutions was also studied. Incorporation of MMT into hydrogel matrix caused the formation of porous hydrogel network. These porous structures resulted in higher water uptake capacity and swelling rate in hydrogel nanocomposite in comparison to neat hydrogel sample. Moreover, hydrogel nanocomposite sample exhibited proper salt and pH-sensitive behavior. High swelling capacity and rate, porosity, salt and pH sensitivity make hydrogel nanocomposite a profitable candidate in agricultural and horticultural applications, such as water reservoir system.     

Swelling properties of CMC‐g‐poly (AAm‐co‐AMPS) superabsorbent hydrogel

A series of biopolymer‐based superabsorbent hydrogels based on carboxymethyl cellulose has been prepared by free‐radical graft copolymerization of acrylamide and 2‐acrylamido‐2‐methylpropan sulfonic acid (AMPS) in aqueous solution using methylenebisacrylamide as a crosslinking agent and ammonium persulfate as an initiator. The effect of variables on the swelling capacity such as: acrylamide/AMPS weight ratio, reaction temperature, and concentration of the initiator and crosslinker were systematically optimized. The results indicated that with increasing the amount of AMPS, the swelling capacity is increased. FT‐IR spectroscopy and scanning electron microscope analysis were used to confirm the hydrogel structure. Swelling measurements of the synthesized hydrogels in different salt solutions indicated considerable swelling capacity. The absorbency under load of the superabsorbent hydrogels was determined by using an absorbency under load tester at various applied pressures. A preliminary swelling and deswelling behaviors of the hydrogels were also studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Reentrant phase transition and fast responsive behaviors of poly{N‐[3‐(dimethylaminopropyl)] methacrylamide} hydrogels prepared in poly(ethylene glycol) solutions

Macroporous temperature‐sensitive poly {N‐[3‐(dimethylaminopropyl)] methacrylamide} hydrogels were synthesized by free‐radical crosslinking polymerization of the monomer N‐[3‐(dimethylaminopropyl)] methacrylamide and the crosslinker N,N′‐methylenebisacrylamide in aqueous solutions at 22°C. Poly(ethylene glycol) (PEG) with a molecular weight of 1000 g/mol was used as the pore‐forming agent during the polymerization reaction. The concentration of PEG in the polymerization solutions was varied between 0 and 18 wt %, whereas the crosslinker (N,N′‐methylenebisacrylamide) concentration was fixed at 2 wt % (with respect to the monomer). The effects of the PEG concentration on the thermo‐induced phase‐transition behavior and the chemical structure, interior morphology, and swelling/deswelling kinetics were investigated. Normal‐type hydrogels were also prepared under the same conditions without PEG. An interesting feature of the swelling behavior of both the normal‐type and macroporous hydrogels was the reentrant phase transition, in which the hydrogels collapsed once and reswelled as the temperature was continuously increased. Scanning electron micrographs revealed that the interior network structure of the hydrogels prepared in PEG solutions became more porous with an increase in the PEG concentration in the polymerization solution. This more porous matrix provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved responsive rate to external temperature changes during the deswelling and swelling processes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and evaluation of swelling kinetics of electric field responsive poly(vinyl alcohol)‐g‐polyacrylic acid/OMNT nanocomposite hydrogels

Novel electro‐responsive nanocomposite hydrogels were prepared by the radical graft polymerization reaction of partially neutralized acrylic acid on poly(vinyl alcohol) and organically modified MMT nanoclay (OMMT) using glutaraldehyde as a crosslinker and potassium initiator. The structures of the hydrogels were confirmed by using Fourier transform infrared, X‐ray diffraction, and scanning electron microscopy study. The nanocomposite hydrogels were characterized by evaluating such molecular weight between crosslinks, (Mc) crosslinking density (ρ), and mesh size (ξ). The effects of various parameters on the swelling behavior of the hydrogels were studied. The thermogravimetric analysis indicated that introduction of clay resulted in an increase in thermal stability. Finally, the electric stimuli responsive measurement indicates the bending of hydrogel toward the cathode in an aqueous solution of NaCl. POLYM. COMPOS., 36:34–41, 2015. © 2014 Society of Plastics Engineers     

pH sensitivity and swelling behavior of partially hydrolyzed formaldehyde-crosslinked poly(acrylamide) superabsorbent hydrogels

Poly(acrylamide) superabsorbent hydrogel was synthesized through crosslinking method. Formaldehyde was used as a crosslinking agent. To achieve a hydrogel with high swelling capacity, the resulted hydrogels were saponified using NaOH solution at high temperature. During saponification, ammonia gas is produced from hydrolysis reaction of amide groups. The arising of ammonia produces porous structure in hydrogels, which is confirmed using scanning electron microscopy. The conversion of amide groups to carboxylate groups was identified by FTIR spectroscopy. The reaction variables in both crosslinking and hydrolysis reactions that affect the swelling of hydrogels were optimized. The swelling of the hydrogels in various salt solutions with various valencies and radii was studied. Also, the absorbency under load was measured. The hydrogels exhibited pH-sensitivity characteristics. A sharp swelling change was observed in lieu of pH variations in a wide range (1–13). The swelling variations were explained according to the swelling theory based on the hydrogel chemical structure. The pH-reversibility and on–off switching behavior makes the intelligent hydrogels as good candidates for considering as potential drug carries. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and superswelling behavior of carboxymethylcellulose–poly(sodium acrylate‐co‐acrylamide) hydrogel

In this paper, attention is paid to synthesis and swelling behavior of a superabsorbent hydrogel based carboxymethylcellulose (CMC) and polyacrylonitrile (PAN). The physical mixture of CMC and PAN was hydrolyzed in NaOH solution to yield hydrogel, CMC–poly(NaAA‐co‐AAm). During alkaline hydrolysis, the nitrile groups of PAN were completely converted to a mixture of hydrophilic carboxamide and carboxylate groups followed by in situ crosslinking of the grafted PAN chains. A proposed mechanism for hydrogel formation was suggested and the structure of the product was established using FTIR spectroscopy. The reaction variables affecting the swelling capacity of the hydrogel were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. Swelling measurements of the synthesized hydrogels in various chloride salt solutions indicated a swelling‐loss with increase in the ionic strength of the salt solutions. The pH of the various solutions also affected the swelling of the superabsorbent. Furthermore, the present hydrogels showed a pH‐reversible property. Finally, the swelling kinetics of synthesized hydrogels with various absorbent particle sizes was briefly examined. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

亲水-疏水PVP-semi-IPN-PCL水凝胶的制备与溶胀性能

N-乙烯基吡咯烷酮（NVP）在聚己内酯（PCL）的乙酸乙酯溶液中进行自由基聚合,制备了亲水-疏水性聚乙烯吡咯烷酮（PVP）/聚己内酯（PCL）半互穿网络水凝胶（PVP-semi-IPN-PCL）。凝胶中PCL的熔融温度T_m无明显变化,而T_m吸热峰形状随PVP含量变化。凝胶平衡溶胀率（ESR）随PVP含量的升高而增大,结合水量的增大尤其显著。由于“笼蔽效应”,低浓度引发剂时,偶氮二异丁睛（AIBN）引发制备的凝胶ESR低于过氧化苯甲酰（BPO）引发剂。交联剂浓度较低时,以戊二醛交联形成凝胶的ESR较N,N-亚甲基双丙烯酰胺（NMBA）交联形成的凝胶大。浓度较高时,戊二醛交联凝胶ESR较NMBA低。PVP含量（质量）分别为20%、40%、60%、80%时,凝胶溶胀动力学Fick模型中的n值分别为0.854、0.471、0.466、0.253,说明在合适的PVP含量时,凝胶的溶胀动力学符合Fick模型。     

pH-温度双重敏感性水凝胶的制备及溶胀性能研究

制备具有pH及温度双重敏感性水凝胶。通过自由基聚合反应制备出NIPAM-co-PMAA水凝胶材料。考察不同单体甲基丙烯酸(MAA)和N-异丙基丙烯酰胺(NIPA)配比对pH和温度的响应能力,探究其溶胀性能。结果表明,不同配比的水凝胶具有双重敏感性。NIPA含量不同时,对于LSCT温度有影响,MAA含量不同时,在酸性条件下溶胀率较大。结论,NIPAM-co-PMAA水凝胶有望成为药物载体。     

Gelatin based pH‐sensitive hydrogels for colon‐specific oral drug delivery: Synthesis,characterization, and in vitro release study

Based on gelatin (Gltn) and acrylic acid (AAc), biodegradable pH‐sensitive hydrogel was prepared using gamma radiation as super clean source for polymerization and crosslinking. Incorporation of PAAc in the prepared hydrogel was confirmed by Fourier transform infrared spectroscopy (FTIR). The effect of PAAc content on the morphological structure of the prepared hydrogel swollen at pH 1, 5, and 7 was examined using scanning electron microscopy (SEM). The results showed the dependence of the porous structure of the prepared hydrogels on AAc content and the pH of the swelling medium. Swelling properties of gelatin/acrylic acid copolymer hydrogels with different AAc contents were investigated at different pH values. Swelling data showed that the prepared hydrogels possessed pronounced pH sensitivity. In vitro release studies were performed to evaluate the hydrogel potential as drug carrier using ketoprofen as a model drug. Experimental data showed that the release profile depends on both hydrogel composition and pH of the releasing medium. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymer Nanocomposite Hydrogels with Improved Metal Adsorption Capacity and Swelling Behavior: Influence of Spirulina Immobilization onto Montmorillonite Clay

Polacrylamide nanocomposite hydrogels were prepared by in situ free radical polymerization reaction in presence of Spirulina microalgae, which is immobilized in montmorillonite clay (Sp-MMT). The nanocomposite hydrogel having 1 wt.% Sp-MMT clay was found to have desired exfoliated structure, maximum swelling and improved thermal stability. It also showed maximum metal adsorption capacity, which is about 312% higher than that of neat PAAm hydrogel at the highest metal concentration. The presence of Spirulina's porous network structure where all potential binding sites are under receptive position was found to be responsible for the dramatic increase in the metal adsorption and swelling behavior.     

Additive-free photosynthesis of acrylamide hydrogels initiated with CdS and TiO<Subscript>2</Subscript> as light visible nano-photocatalysts

Hydrogels are three-dimensional polymer networks which can be synthesized by different techniques, such as free-radical addition reaction which is the most well-known technique in functional vinyl monomer polymerization. Photopolymerization, as an attractive technique, has been used in radical polymerization of monomers and has revitalized interest in the idea that it congregates a wide range of economic and ecological expectations. Due to the spatial–temporal control and a mild curing process of polymerization, photoinitiator semiconductor nano-particles offer great advantages, such as effective and quantitative reaction. Cadmium sulfide nanowire, titanium dioxide (TiO₂) nanotube, and TiO₂ nanowire were used as visible photocatalysts for photopolymerization of acrylamide hydrogel without using any additive under the sunlight and purple LED irradiations. The effects of different synthetic parameters, including initiator type and concentration and type of light sources, were investigated to achieve hydrogels with maximum swelling capacity. The results showed that the swelling of hydrogel reached 80 g water/g hydrogel when the TiO₂ nanowire was used as the photoinitiator. The synthesized semiconductors and hydrogels were characterized by X-ray diffractometry, adsorption isotherm, infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy. According to the results, the new initiators led to semiconductor-based hydrogels, achieved with high swelling property through a high-speed high-efficient photopolymerization reaction in a safe manner.     

Preparation and characterization of polyacrylic acid‐poly(vinyl alcohol)‐based interpenetrating hydrogels

Some structural features of hydrogels from poly(acrylic acid) (PAAc) of various crosslinking degrees have been investigated through mechanical and swelling measurements. Interpenetrating polymer hydrogels (IPHs) of poly(vinyl alcohol) (PVA) and PAAc have been prepared by a sequential method: crosslinked PAAc chains were formed in aqueous solution by crosslinking copolymerization of acrylic acid and N,N‐methylenebisacrylamide in the presence of PVA. The application of freeze–thaw (F–T) cycles leads to the formation of a PVA hydrogel within the synthesized PAAc hydrogel. The swelling and viscoelastic properties of the IPHs were evaluated as a function of the content of crosslinker and the application of one F–T cycle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5789–5794, 2006     

Hybrid double‐network hydrogel based on poly(aspartic acid) and poly(acryl amide) with improved mechanical properties

Hydrogels usually have a smaller mechanical strength and toughness than generic polymeric materials. Therefore, many studies report improvements for mechanical properties of hydrogels by preparing double‐network hydrogels, nanocomposite hydrogels, and nanostructured hydrogels. In this study, interpenetrating‐type dually‐crosslinked hydrogels were prepared via free radical crosslinking polymerization of acrylamide monomers in the presence of poly(aspartic acid) and subsequent immersion in a metal ion containing aqueous solution to induce extra physical crosslinking through ionic or coordination bonding. Using this approach, the mechanical properties of inherently weak and brittle homopolymer gels could be improved via interpenetrating the double network formed by both covalent bonding and metal coordination‐assisted reversible physical crosslinks. The preparation, swelling behavior, morphology, and mechanical properties of these hydrogels are presented. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45925.     

Synthesis and characterization of poly(N‐vinyl imidazole) hydrogels crosslinked by gamma irradiation

Crosslinked poly(N‐vinyl imidazole) (PVIm) hydrogels in the form of rods have been prepared by ⁶⁰Co γ‐radiation initiated simultaneous polymerization and crosslinking of N‐vinyl imidazole in bulk and water. In binary aqueous systems, the percentage gelation decreased with increasing water content. The PVIm hydrogels synthesized were further protonated in HCl solutions of different concentration. PVIm and protonated PVIm (H‐PVIm) hydrogels have been characterized using spectroscopic and thermal methods, and the swelling behaviour of these two types of hydrogel has been investigated. PVIm hydrogels originally swelled to 600% (by volume) but in their protonated form at pH 7.0 reached 4000% swelling. © 2002 Society of Chemical Industry     

Influence of MEOBiPA content on the properties of novel photoluminescent thermosensitive hydrogels

In order to establish a dual functional hydrogel, a special monomer, methacryloyloxy‐ethylene‐oxy‐carbonyl bis[4‐(phenyl‐isopropyl)phenyl]amine (MEOBiPA), was prepared from bis[4‐(phenyl‐isopropyl)phenyl]‐4‐cyanophenyl amine and 2‐hydroxyethyl methacrylate. Subsequently, a series of thermosensitive hydrogels was obtained through copolymerization of N‐isopropyl acrylamide (NIPAAm) with MEOBiPA by UV irradiation (named the NM series). The effect of MEOBiPA content on the swelling behavior, mechanical properties and drug release behavior of the hydrogels was further investigated. Results showed that the swelling ratios of the NM copolymeric hydrogels decreased from 4.73 to 1.74 g g^?1 when the MEOBiPA content in the hydrogel increased from 0.1 to 0.9 mol%. Both gel strength and crosslinking density of the NM hydrogels increased with increasing MEOBiPA. Conversely, the thermosensitive behavior of NM hydrogels significantly decreased upon increase of MEOBiPA content. Likewise, the caffeine release ratio also decreased from 70% to 25%. Notably, the intensity of photoluminescence increased with increasing MEOBiPA content in the hydrogels. Further, the corresponding copolymers of the hydrogels were prepared using free radical polymerization. The UV absorbance and photoluminescent behavior of the MEOBiPA, NIPAAm/MEOBiPA copolymeric hydrogels and their corresponding copolymers in different polar solvents were also investigated. © 2015 Society of Chemical Industry     

Dynamic and equilibrium swelling studies: crosslinked pH sensitive methyl methacrylate-co-itaconic acid (MMA-co-IA) hydrogels

In the present work crosslinked methyl methacrylate-co-itaconic acid (MMA-co-IA) hydrogels were prepared by free radical copolymerization of methyl methacrylate (MMA) with itaconic acid (IA) using ethylene glycol dimethacrylate (EGDMA) and N, N methylene bisacrylamide (MBAAm) as crosslinkers and benzoyl peroxide as initiator. Prepared hydrogels were investigated for dynamic and equilibrium swelling studies. For swelling behaviour, effect of pH, monomeric compositions, degree of crosslinking and type of crosslinking agent were investigated. Swelling studies were performed in the USP phosphate buffer solutions of varying pH 1.2, 4.5, 5.5, 6.5 and 7.0. Results showed that swelling increased by increasing IA content in hydrogels structure. This may be due to the presence of more carboxylic groups available for ionization. Swelling was decreased with increase in crosslinking ratio owing to tighter hydrogel structure. Hydrogels were characterized by Fourier transform infrared (FTIR), and scanning electron microscope (SEM). Polymer-solvent interaction parameters (χ) of hydrogels were determined by using Flory–Rehner theory of equilibrium swelling values. The analysis of diffusion mechanism from gels using Peppas model showed that all monomeric compositions and degrees of crosslinking followed Fickian diffusion.