Swelling and mechanical properties of pH‐sensitive hydrogel filled with polystyrene nanoparticles

We investigated the effect of organic filler and the degree of crosslinking on the performance of a hydrogel/filler system to control its diffusion and mechanical properties. A series of poly(acrylic acid) gels filled with polystyrene (PS) nanoparticles at well‐controlled filler loading levels was synthesized by free radical polymerization in the presence of a crosslinking agent. Three different concentrations of the crosslinking agent (methylene bis‐acrylamide), that is, 5 mg/(g of AAc), 10 mg/(g of AAc), and 20 mg/(g of AAc), were used. The hydrogel crosslinked to the least extent that included a high amount of PS showed fast swelling rates, high equilibrium swelling ratios, and the highest pH sensitivity. Three gel/filler combinations including the gel without filler, gel/filler mixture, and gel/filler copolymerization were considered. The PS particles of ～40 nm in diameter, which were used as the fillers, were prepared by microemulsion polymerization. Copolymerization of styrene and AAc having different reactivities ratios was achieved by a seed‐microemulsion polymerization with the crosslinking agent. The gel/filler mixture showed the highest swelling rate and the gel/filler copolymer resulted in highly enforced mechanical properties and the highest pH sensitivity. The incorporation of filler by copolymerization to mechanically enforce the equilibrium swelling hydrogel was more efficient than the increase of crosslinking degree. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3574–3587, 2013     

制备CS-Ca2+-SAL中空凝胶球及其对碳纳米的缓释行为

将海藻酸钠溶液(SAL)滴入壳聚糖-钙(CS-Ca2+)分散溶液中，海藻酸钠与壳聚糖分子链之间发生物理交联的同时，也与钙离子进行同步交联，可一步制备毫米级壳聚糖-钙-海藻酸钠(CS-Ca2+-SAL) 水凝胶球。通过调控原料用量比例、滴加速度和方式，成功制备内部中空，球壁均匀，表面致密的凝胶球。以荧光性碳纳米点为标记物，考察凝胶球的溶胀性能和缓释性能。结果表明，凝胶球在中性水溶液中12h溶胀率可达26.09%，并能保持完整球形结构。溶胀性能受到pH的影响显著，处于pH=1.2的溶液体系中溶胀率最小，处于pH =6.8溶液环境中溶胀率最大。荧光凝胶球在pH=7.1的Tris-HCl缓冲液中的释放率实验结果表明，对碳纳米的释放模型最符合Hixon-crowell溶蚀方程，说明凝胶球的缓释机制以溶蚀为主，扩散为辅。     

Effect of gelatin on the swelling behavior of organic hybrid gels based on N‐isopropylacrylamide and gelatin

Organic hybrid gels based on poly(N‐isopropylacrylamide) and a natural polymer, gelatin, were prepared through two‐step crosslinking with genipin or glutaraldehyde. The effects of the gelatin content on the swelling behaviors and physical properties of these hybrid gels were investigated. The results indicated that the swelling ratio decreased with an increase in the content of gelatin in these hybrid gels. The swelling ratio for the gel crosslinked by genipin was significantly smaller than that for the gel crosslinked by glutaraldehyde. The results also showed that the gel crosslinked with genipin had a higher crosslinking density and a higher gel strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1092–1099, 2005     

Characterization of hydrogels based on chitosan and copolymer of poly(dimethylsiloxane) and poly(vinyl alcohol)

Copolymers composed of poly(vinyl alcohol) (PVA) and poly(dimethylsiloxane) (PDMS) were crosslinked with chitosan to prepare semi‐interpenetrating polymer network (IPN) hydrogels by an ultraviolet (UV) irradiation method for application as potential biomedical materials. PVA/PDMS copolymer and chitosan was cast to prepare hydrogel films, followed by a subsequent crosslinking with 2,2‐dimethoxy‐2‐phenylacetophenone as a nontoxic photoinitiator by UV irradiation. Various semi‐interpenetrating polymer networks (semi‐IPNs) were prepared from different weight ratios of chitosan and the copolymer of PVA/PDMS. Photocrosslinked hydrogels exhibited an equilibrium water content (EWC) in the range of 65–95%. Swelling behaviors of these hydrogels were studied by immersion of the gels in various buffer solutions. Particularly, the PCN13 as the highest chitosan weight ratio in semi‐IPN hydrogels showed the highest EWC in time‐dependent and pH‐dependent swelling. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2591–2596, 2002     

Mechanical and swelling properties of polyacrylamide gel spheres

Spheres of crosslinked acrylamide-methylene bisacrylamide copolymer were produced by suspension polymerization. By introducing a vibrating stream of aqueous solution into an organic matrix, particle sizes of 0.33 ± 0.06 to 0.99 ± 0.41 mm in diameter resulted. The swelling of gel spheres in water was compared to that of larger ‘bulk’ gels, and a significant amount of hydrolysis occurred in the spheres due to the presence of tetramethylethylenediamine (TEMED), used as an initiator. The dependence of the elastic modulus of the gel spheres upon the crosslinker concentration was non-linear, even in the regime where linearity is observed for bulk gels; this appears to be due to the varying amounts of TEMED that diffuses in the spheres and is known to affect the modulus of bulk gels.     

Crosslinked PVC polymerization: Study on process dependencies

A systematic study of how different processes and crosslinking agents affect the crosslinked polymerization of poly(vinyl chloride) (PVC) to be used for plastisol application was carried out. Two processes, microsuspension (MS) and seeded polymerization (SP), and two crosslinking agents, diallyl phthalate (DAP) and 1,3‐butanediol dimethacrylate (BDMA), were considered. Variations in degree of polymerization and gel content as functions of conversion, as well as the amount of crosslinking agent, was experimentally investigated for both processes and the results were precisely analyzed. We found that the microsuspension process is much better for crosslinked polymerization of PVC to be used for plastisol application; the seeded polymerization process was restricted by the transfer of crosslinking agents to the polymerization sites. Diallyl phthalate was proven to be a good crosslinking agent as generally known until now. Consequently, to perform crosslinked PVC polymerization in industry, the type of process should be taken into account and proper materials and steps should be set up. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1947–1954, 2002     

Insolubilization of sodium chondroitin sulfate by forming a semi‐interpenetrating polymer network with acrylic acid: A potential carrier for colon‐specific drug delivery

To reduce the highly hydrophilic property of chondroitin sulfate (ChS), a semi‐interpenetrating polymer network (semi‐IPN) of chondroitin sulfate/polyacrylic acid (PAA) was prepared as a drug carrier by crosslinking acrylic acid with diethyleneglycol diacrylate. The swelling properties of the semi‐IPNs with different concentrations of crosslinking agent were correlated. The moisture sorption profiles were evaluated using differential thermal analysis. Ketoprofen was used as a drug probe to evaluate the performance of the drug released from the semi‐IPN matrices. The prepared semi‐IPNs demonstrated significant swelling reduction properties with both gastric and intestinal fluids compared with those of both the pure ChS and the ChSAA blend without the crosslinking agent. The amount of accumulated drug released from the semi‐IPNs was less than 30 wt % at pH 1.2 and up to 80 wt % at pH 7.4. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 114–122, 2002     

Poly(vinyl alcohol)‐controlled synthesis of monodispersed crosslinked poly(methyl methacrylate) microparticles with significantly improved mechanical properties

A facile synthesis concept focusing on the poly(vinyl alcohol) (PVA) concentration induced interfacial energy effects in seed swelling polymerization was realized for the successful fabrication of a series of monodispersed poly(methyl methacrylate) (PMMA) microparticles with four crosslinking agents, 2,2‐bis[(methacryloyloxy)methyl]butyl methacrylate, 1,2‐ethanediyl bis(2‐methylacrylate), 1,3‐divinylbenzene and 1,2‐ethanediyl diacetate. We revealed a special role of PVA in regulating the diffusion of crosslinking agents as well as the swelling degree of latex seeds and, more noticeably, the consequent improved mechanical properties of the crosslinked PMMA microparticles formed. The highest recovery rate obtained from the PMMA microparticles with 0.6 wt% PVA approached 67%, which is higher than or comparable to reported values. This work not only developed a new facile synthesis approach for producing highly uniform tough crosslinked PMMA microparticles for more potential applications but also provided valuable insights into fundamental aspects of seed swelling polymerization. © 2019 Society of Chemical Industry     

两步法制备交联聚苯乙烯微球研究

采用两步法制备出了粒径均一,球形度好的3μm交联聚苯乙烯微球。通过对两种条件下溶胀所得微球进行比较可知加入溶胀剂时制备出的微球球形度更好,表面更光滑,粒径分布范围更窄。较佳的制备条件为:聚苯乙烯单体的用量为种子微球的2.5~3.5倍,溶胀剂用量为种子微球的1~2倍,交联剂的用量为苯乙烯用量的5%~12%。     

Mechanical characteristics of poly(2‐hydroxyethyl methacrylate) hydrogels crosslinked with various difunctional compounds

Poly(2‐hydroxyethyl methacrylate) hydrogels were prepared in the presence of 30 wt% water using two series of crosslinking agents including divinylic (ethyleneglycol dimethacrylate, 1,4‐butanediol dimethacrylate, 2,3‐dihydroxybutanediol 1,4‐dimethacrylate) and diallylic (1,5‐hexadiene‐3,4‐diol and 1,5‐hexadiene) compounds, over a concentration range between 0.1 and 5 mol%. The resulting polymers were swollen in water to yield homogeneous transparent hydrogels. These hydrogels were characterised in terms of equilibrium swelling in water, tensile properties and compression stress–strain measurements. The influences of the nature and the concentration of crosslinking agent on the swelling behaviour and the mechanical properties of these hydrogels were investigated. The crosslinking efficiency of two representative agents (ethyleneglycol dimethacrylate and 1,5‐hexadiene‐3,4‐diol) was quantified by compression experiments. A much lower crosslinking efficiency (0.013) was observed for 1,5‐hexadiene‐3,4‐diol than for ethyleneglycol dimethacrylate (0.336). It is suggested that the low crosslinking efficiency of diallylic agents is responsible for a trend in properties different from that displayed by the gels crosslinked with dimethacrylates. A comparison was made to the similar effect observed previously in heterogeneous PHEMA hydrogels. © 2001 Society of Chemical Industry     

Studies on synthesis and physicochemical properties of new bis[4‐(2‐hydroxy‐3‐methacryloyloxypropoxy)phenyl]sulfide terpolymers

Synthesis and physicochemical properties of the new glycidyl methacrylate, styrene, and bis[4(2‐hydroxy‐3‐methacryloyloxypropoxy)phenyl]sulfide terpolymers of different crosslinking degrees are presented. The terpolymers were obtained in the form of regular microspheres by suspension polymerization. The epoxy group content, thermal properties (DSC, thermogravimetric analysis), and swelling characteristic of the functional microspheres were examined. In addition, a selected terpolymer was modified in the epoxide ring opening reaction with diethylenetriamine. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Equilibrium swelling and solvation studies on crosslinked polyacrylamides

Polyacrylamide (PA) crosslinked with four different crosslinking agents, triethyleneglycol dimethacrylate (TEGDMA), N,N′‐methylene bisacrylamide (NNMBA), hexanediol dimethacrylate (HDDMA) and divinylbenzene (DVB), with mole percents ranging from 5 to 20, was prepared by solution polymerization and subjected to swelling and solvation studies. Solubility parameters and cohesive energy density were determined from swelling studies. Molecular weight between crosslinks for these systems were determined by Flory–Rehner analysis. There is a discontinuous volume change for 10% NNMBA and HDDMA crosslinked PA, 15% TEGDMA crosslinked PA and 10 and 15% DVB crosslinked PA in solvent mixtures of acetic acid and water due to phase change occurring at this stage. The hydrogels exhibit inhomogeneous crosslink distribution due to multiple crosslinking, cyclization and network irregularity owing from arising from entanglements. As the percentage of crosslinking increases, crosslinks become more homogeneous due to a decrease in entanglements. Copyright © 2004 Society of Chemical Industry     

均匀设计在交联淀粉微球合成中的应用

以N,N′-亚甲基双丙烯酰胺为交联剂,用反相悬浮法合成了新型交联淀粉微球CSM。采用均匀设计实验法,考察了影响产率、溶胀度、平均粒径的因素,对实验结果进行了回归分析和多目标综合寻优。结果表明,影响产率和溶胀度的主要因素是交联剂质量分数、反应温度和引发剂浓度,而平均粒径则更多地取决于搅拌速度和分散剂质量分数。调节这些因素,可以在一定程度上实现微球结构与形态的控制。在最佳工艺条件下合成CSM的产率是77.5%,溶胀度是246%,平均粒径是16.5μm。     

Investigation of mechanical and thermodynamic properties of pH‐sensitive poly(N,N‐dimethylaminoethyl methacrylate) hydrogels prepared with different crosslinking agents

pH‐sensitive poly(N,N‐dimethylaminoethyl methacrylate) hydrogels were synthesized by free‐radical crosslinking polymerization using two different crosslinking agents; tetraethylene glycol dimethacrylate (TEGMA) and N,N′‐methylenebis(acrylamide) (BAAm). The influence of the polymerization factors such as the type of the crosslinking agent and the gel preparation concentration on the swelling behavior, the gel strength, the effective crosslinking density and the average chain length between the crosslink points for the resulting hydrogels was investigated. The results of the equilibrium swelling measurements in water showed that the linear swelling ratio of the resulting hydrogels increases with increasing gel preparation concentration. The swelling ratio of PDMAEMA hydrogels crosslinked with BAAm is larger than those for hydrogels crosslinked with TEGMA over the entire range of the polymer network concentration. The hydrogels exhibit very sharp pH‐sensitive phase transition in a very narrow range of pH between 7.7 and 8.0. From the mechanical measurements, it was also found that the linear swelling ratio of resulting hydrogels depends on the crosslinking density and also the type of the crosslinker used in the preparation. The resulting hydrogels are thought to be good candidates for pH‐sensitive drug delivery systems. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Gelation and crosslinking characteristics of photopolymerized poly(ethylene glycol) hydrogels

The gelation and crosslinking features of poly(ethylene glycol) (PEG) hydrogels were scrutinized through the UV polymerization processes of poly(ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) mixtures. The real‐time evolutions of the elastic moduli of the prepolymerized mixtures with different crosslinking ratios of PEGMA and PEGDMA and the photoinitiator concentrations were measured during photopolymerization. The rheological properties were compared with other properties of the PEG hydrogels, including the relative changes in the C?C amounts in the mixtures before and after UV irradiation, water swelling ratio, gel fraction, mesh size, and mechanical hardness. As the portion of PEGDMA as a crosslinker increased, the final elastic modulus and gel fraction increased, whereas the swelling ratio and scratch penetration depth at the hydrogel film surface decreased because of the formation of compact networks inside the hydrogels. These results indicate that there was a good correlation between the rheological analysis for predicting the crosslinking transition during photopolymerization and the macroscopic properties of the crosslinked hydrogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41939.     

Multi‐responsive hydrogels based on N‐isopropylacrylamide and sodium alginate

Hydrogels consisting of sodium alginate and N‐isopropylacrylamide covalently crosslinked with N,N′‐methylenebisacrylamide were prepared. The mixed‐interpenetrated networks obtained were characterized using elemental analysis, Fourier transform infrared and Raman spectroscopy, swelling measurements and environmental scanning electron microscopy. The thermo‐ and pH‐responsive properties of these hydrogels were evidenced by their swelling behaviour, which depended also on the amount of crosslinking agent and hydrogel composition. Copyright © 2010 Society of Chemical Industry     

聚丙烯酸水凝胶的制备研究

以丙烯酸为单体,N,N＇-亚甲基双丙烯酰胺为交联剂,过硫酸铵为引发剂,通过自由基聚合制备了聚丙烯酸水凝胶.考察了交联剂、引发剂、单体中和度、聚合温度以及盐溶液对水凝胶溶胀性能的影响.结果表明,引发剂为单体质量的0.6％,交联剂为0.8％,单体的中和度为70％时,凝胶的溶胀性能最佳,吸水率达到了3 000％以上,聚丙烯酸水凝胶的溶胀性能随着盐溶液浓度的增大而降低.     

Novel degradable superabsorbent materials of silicate/acrylic‐based polymer hybrids

Novel superabsorbent materials, inorganic–organic hybrids, were synthesized by polymerizing acrylic acid or acrylamide with sodium silicate without any other crosslinking agent. The crosslinking bonds of Si? O? C form through the reaction of carboxyl groups with silanol groups (Si? OH) existing in reaction system. Results of FTIR, swelling, and degrading experiments show that the crosslinking degree increased as the mol ratio of silicate increased in a certain range. The hybrids possess the properties of high absorbency and high absorption rate in both distilled water and normal saline solution. Because of the hydrolysis of Si? O? C bonds in aqueous solution, the hybrid hydrogels can degrade in days, and maybe beneficial to environment protection. This property is quite different from those superabsorbent polymer crosslinked with organic crosslinking agent. By monitoring the temperature of the reaction system, sodium silicate was also found to facilitate the trommsdorff effect in polymerization process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 936–940, 2004     

Facile fabrication of double‐walled polymeric hollow spheres with independent temperature and pH dual‐responsiveness for synergetic drug delivery

A dual‐responsive double‐walled polymeric hollow sphere (PHS) serving as a candidate for synergetic drug delivery platform is prepared by a simple and green template polymerization in aqueous medium. The PHS, comprised of thermo‐responsive crosslinked poly(N‐isopropylacrylamide) (PNIPAM) as the inner shell and pH‐responsive crosslinked poly(methacrylic acid) (PMAAc) as the outer shell, is assembled through self‐removal of the thermo‐responsive template from a core‐triple shell structure by free radical polymerization with sequential addition of reactants. The discrete double‐shell structure renders the PHS independent temperature and pH‐controlled swelling/shrinking capability. Taking the advantage of two compartmentalized internal spaces (the core and the interlayer spaces) with independent temperature‐ and pH‐dependent behaviors, two model drugs representing the small molecule and the macromolecule are loaded in selective locations of the PHS. Two drugs show dramatically different release profiles according to environmental temperature and pH, due to the localization of drugs and the stimuli‐dependent property of its protective shells. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44335.     

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.