Ethanol‐assisted dispersion of attapulgite and its effect on improving properties of alginate‐based superabsorbent nanocomposite

The dispersion of attapulgite (APT) as nanorod‐like single crystals is crucial to fully develop its functionality of one‐dimensional nanometer material as a filler of composite materials. In this study, APT was dispersed by the assistance of ethanol during the high‐pressure homogenization process to form individual nanorod‐like crystals. The dispersed APT was used to prepare new sodium alginate‐g‐poly(sodium acrylate‐co‐styrene)/attapulgite (NaAlg‐g‐P(NaA‐co‐St)/APT) superabsorbent nanocomposites. The effect of ethanol/water ratio on the dispersion of crystal bundles of APT was investigated by field emission scanning electron microscopy, and the results indicate that APT crystal bundles were effectively disaggregated in ν(CH₃CH₂OH) : ν(H₂O) ? 5 : 5 solution after homogenized at 50 MPa. The better dispersion of APT in NaAlg‐g‐P(NaA‐co‐St) matrix has clearly improved the gel strength (from 1300 Pa to 1410 Pa, ω = 100 rad/s), swelling capacity (442–521 g/g), swelling rate (3.3303–4.5736 g/g/s), and reswelling ability of the superabsorbent nanocomposite. Moreover, the nanocomposites showed fast swelling–deswelling responsive behavior in different saline solutions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhanced swelling and responsive properties of an alginate-based superabsorbent hydrogel by sodium p-styrenesulfonate and attapulgite nanorods

In this work, a series of sodium alginate-g-poly(sodium acrylate-co-sodium p-styrenesulfonate)/attapulgite (NaAlg-g-poly(NaA-co-NaSS)/APT) superabsorbent composites were prepared by graft copolymerization using N,N’-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate as an initiator. Fourier transform infrared spectroscopy revealed that NaA and NaSS had been grafted onto NaAlg, and APT participated in polymerization reaction through reactive –OH groups. The introduction of proper amount of NaSS and APT induced the improved surface morphology, swelling capacity, and swelling rate. Moreover, the swelling behaviors of the superabsorbent composites were remarkably influenced by various salt medium, pH buffer solutions and organic solvents, and especially an intriguing swelling–deswelling behavior was observed with altering water/organic solvent ratio.     

Preparation and swelling properties of superabsorbent nanocomposites based on natural guar gum and organo-vermiculite

Vermiculite (VMT) was modified with cetyl trimethylammonium bromide (CTAB). Superabsorbent nanocomposites were prepared by solution polymerization of natural guar gum (GG), partially neutralized acrylic acid (NaA) and organo-vermiculite (CTA⁺-VMT), ammonium persulfate (APS) as initiator and N,N′-methylene-bis-acrylamide (MBA) as crosslinking agent. FTIR spectra confirmed that NaA had been grafted onto GG and the OH groups of CTA⁺-VMT participated in the polymerization reaction. The intercalated-VMT was exfoliated during polymerization and uniformly dispersed in the GG-g-PNaA matrix. Swelling tests show that CTA⁺-VMT improved swelling and swelling rate more remarkably than VMT, and the nanocomposite exhibited distinct kinetic swelling behavior in NaCl and CaCl₂ solution. Organo-VMT improved the gel strength of the nanocomposite compared to VMT, and the maximum storage modulus of the nanocomposite reached 658 Pa (γ = 0.5%, ω = 100 rad/s).     

Preparation,Characterization, and Drug-Release Behaviors of a pH-Sensitive Composite Hydrogel Bead Based on Guar Gum,Attapulgite, and Sodium Alginate

A novel guar gum-g-poly (acrylic acid)/attapulgite/sodium alginate (GG-g-PAA/APT/SA) composite hydrogel bead with excellent pH sensitivity was prepared via a facile ionic gelation approach and characterized by FTIR and SEM techniques. The effect of APT content on the encapsulation efficiency (EE), swelling ratio, and drug release behaviors of the beads was investigated and the in-vitro release kinetics were also evaluated using diclofenac sodium (DS) as the model drug. The results indicate that the burst release effect of DS drug was eliminated due to the incorporation of APT, and the DS cumulative release was clearly decreased with increasing the APT content.     

Preparation and swelling characteristics of a superabsorbent nanocomposite based on natural guar gum and cation‐modified vermiculite

A series of novel superabsorbent nanocomposites were prepared by the solution radical polymerization of natural guar gum (GG), partially neutralized acrylic acid [sodium acrylate (NaA)], and cation‐exchanged vermiculite (Mⁿ⁺‐VMT) with ammonium persulfate as the initiator in the presence of the crosslinking agent N,N′‐methylene‐bis‐acrylamide. Fourier transform infrared analysis revealed that NaA was grafted onto the GG chains and that Mⁿ⁺‐VMT participated in the polymerization. X‐ray diffraction results showed that the occurrence of the cation‐exchange process changed the interlayer gap of vermiculite (VMT) and that Mⁿ⁺‐VMT was exfoliated during polymerization to form a nanocomposite. The exfoliated VMT led to better dispersion in the GG‐g‐poly(sodium acrylate) matrix, as shown by scanning electron microscopy and transmission electron microscopy analysis. Mⁿ⁺‐VMT improved the water absorption of the nanocomposite more remarkably than raw VMT, and Al³⁺‐VMT enhanced the water absorption to the highest degree. The nanocomposite exhibited intriguing overshooting swelling characteristics in a multivalent saline solution and acidic pH solution and showed switching pH‐responsive behaviors in buffer solutions between pH 2 and pH 7.2. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

瓜尔胶-g-聚(丙烯酸钠-co-苯乙烯)/海泡石复合高吸水性树脂的制备及溶胀行为

以瓜尔胶(GG)、部分中和丙烯酸(NaA)、苯乙烯(St)和海泡石(ST)为原料, 过硫酸铵(APS)为引发剂, N,N′-亚甲基双丙烯酰胺(MBA)为交联剂, 在水溶液中通过接枝共聚反应合成了瓜尔胶-g-聚(丙烯酸钠-co-相似文献   

Synthesis and swelling characteristics of a pH‐responsive guar gum‐g‐poly(sodium acrylate)/medicinal stone superabsorbent composite

A series of pH‐responsive superabsorbent composites were synthesized by the free‐radical grafting copolymerization of natural guar gum (GG), partially neutralized acrylic acid (NaA), and medicinal stone (MS) using ammonium persulfate (APS) as the initiator and N,N′‐methylene‐bis‐acrylamide (MBA) as the crosslinker. The structure, surface morphologies, and thermal stability of the developed composites were characterized by FTIR spectra, SEM, and TGA techniques, respectively. The effects of various saline, surfactant, and dye solutions on swelling properties were investigated, and the pH‐responsivity was also evaluated. Results indicated that NaA had been grafted onto GG macromolecular chains and MS participated in the polymerization reaction. The incorporation of MS obviously improved the surface structure, thermal stability, water absorption capacity, and rate. Multivalent saline, cationic surfactant, and dye showed more remarkable effect on the water absorption than did monovalent or anionic ones. The composites showed excellent responsive properties and reversible On–Off switching characteristics in various pH buffer solutions, which provided great possibility to extend the application domain of the superabsorbent composites. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Preparation and Swelling Behavior of a pH-Responsive Psyllium-g-Poly(acrylic acid)/Attapulgite Superabsorbent Nanocomposite

In this study, a series of psyllium-g-poly(acrylic acid)/attapulgite (PSY-g-PAA/APT) superabsorbent nanocomposites were prepared. The effects of the content of APT on equilibrium water absorption, swelling rate, and the swelling behaviors of the nanocomposites in various cationic saline solutions and different pH solutions were also systematically investigated. The nanocomposite containing 10 wt% APT gives the best water absorption of 568 g/g in distilled water and 64 g/g in 0.9 wt% NaCl solution. The excellent responsive properties and reversible On-Off switching characteristics can be observed in various pH buffer solutions.     

Superabsorbent composite. XIII. Effects of Al3+‐attapulgite on hydrogel strength and swelling behaviors of poly(acrylic acid)/Al3+‐attapulgite superabsorbent composites

Al³⁺‐attapulgite (Al³⁺‐APT) was prepared by treating attapulgite (APT) with AlCl₃ aqueous solution of various concentrations. The poly(acrylic acid)/Al³⁺‐attapulgite (PAA/Al³⁺‐APT) superabsorbent composite was prepared by reaction of partly neutralized acrylic acid, and Al³⁺‐APT in aqueous solution using N, N′‐methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator. The surface morphology of the composite was investigated by SEM, and the Al³⁺‐APT composite generated a relatively planar surface comparing the nature APT. The effects of Al³⁺‐APT on hydrogel strength and swelling behaviors, such as equilibrium water absorbency, swelling rate, and reswelling capability, of the superabsorbent composites were also studied. The hydrogel strength and reswelling capability were improved, however, the equilibrium water absorbency and swelling rate decreased with increasing AlCl₃ solution concentration. The equilibrium water absorbency firstly increased, and then decreased with increasing Al³⁺‐APT content. The results indicate that Al³⁺‐APT acts as an assistant crosslinker in the polymeric network, which has great influences on hydrogel strength and swelling behaviors of the PAA/Al³⁺‐APT superabsorbent composites. POLYM. ENG. SCI., 47:619–624, 2007. © 2007 Society of Plastics Engineers.     

Synthesis,characterization and swelling behaviors of hydroxyethyl cellulose‐g‐poly(acrylic acid)/attapulgite superabsorbent composite

In this work, a series of novel hydroxyethyl cellulose‐ g‐poly(acrylic acid)/attapulgite (HEC‐g‐PAA/APT) superabsorbent composites were prepared through the graft polymerization of hydroxyethyl cellulose (HEC), partially neutralized acrylic acid (AA), and attapulgite (APT) in aqueous solution, and the composites were characterized by means of Fourier‐transform spectroscopy, scanning electron microscopy, and transmission electronmicroscopy. The effects of polymerization variables including concentrations of the initiator and crosslinker and APT content on water absorbency were studied, and the swelling properties in various pH solutions as well as the swelling kinetics in various saline solutions were also systematically evaluated. Results showed that the introduction of 5 wt% APT into HEC‐g‐PAA polymeric network could improve both water absorbency and water absorption rate of the superabsorbent composites. In addition, the superabsorbent composites retained high water absorbency over a wide pH range of 4–10, and the swelling kinetics of the superabsorbent composites in CaCl₂ and FeCl₃ solutions exhibited a remarkable overshooting phenomenon. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Stabilized electrospinning of heat stimuli/in situ crosslinkable nanofibers and their self‐same nanocomposites

We present a strategy for stabilizing the morphological integrity of electrospun polymeric nanofibers by heat stimuli in situ crosslinking. Amorphous polymer nanofibers, such as polystyrene (PS) and its co‐polymers tend to lose their fiber morphology during processing at temperatures above their glass transition temperature (T_g) typically bound to happen in nanocomposite/structural composite applications. As an answer to this problem, incorporation of the crosslinking agents, phthalic anhydride (PA) and tributylamine (TBA), into the electrospinning polymer solution functionalized by glycidylmethacrylate (GMA) copolymerization, namely P(St‐co‐GMA), is demonstrated. Despite the presence of the crosslinker molecules, the electrospinning polymer solution is stable and its viscosity remains unaffected below 60 °C. Crosslinking reaction stands‐by and can be thermally stimulated during post‐processing of the electrospun P(St‐co‐GMA)/PA‐TBA fiber mat at intermediate temperatures (below the T_g). This strategy enables the preservation of the nanofiber morphology during subsequent high temperature processing. The crosslinking event leads to an increase in T_g of the base polymer by 30 °C depending on degree of crosslinking. Crosslinked nanofibers are able to maintain their nanofibrous morphology above the T_g and upon exposure to organic solvents. In situ crosslinking in epoxy matrix is also reported as an example of high temperature demanding application/processing. Finally, a self‐same fibrous nanocomposite is demonstrated by dual electrospinning of P(St‐co‐GMA) and stabilized P(St‐co‐GMA)/PA‐TBA, forming an intermingled nanofibrous mat, followed by a heating cycle. The product is a composite of crosslinked P(St‐co‐GMA)/PA‐TBA fibers fused by P(St‐co‐GMA) matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44090.     

CMC-g-PAMPS/APT复合高吸水树脂的溶胀行为及热稳定性能

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为单体,凹凸棒黏土(APT)和羧甲基纤维素钠(CMC)为复合组分,采用微波辐射方法制备了CMC-g-PAMPS/APT环境友好复合高吸水性树脂。考察了APT用量对树脂吸水速率、保水性能和反复吸水性能的影响,利用XRD和TG等方法分析了该树脂的结构及其热稳定性能。结果表明,APT和CMC参与了接枝共聚反应,其反应仅在APT的表面进行,单体并没有插入到APT的层间。在APT质量分数为7.5%时,树脂的分解温度主要在250℃以上,具有良好的热稳定性。经过5次反复溶胀后,树脂的吸水倍率较不含APT的树脂提高了近42%。在体系中引入APT能显著提高树脂的吸水速率和保水性能。     

聚乙烯醇/凹凸棒黏土纳米复合膜的制备及其性能

以聚乙烯醇(PVA)和提纯凹凸棒黏土(APT)为原料,采用溶液流延成膜法,制备了系列不同APT含量的PVA/APT纳米复合膜。采用XRD、FTIR和SEM对复合膜的结构进行了表征,测试了复合膜的热性能、力学性能和耐水性能。结果表明,APT可均匀分散在PVA基体中,APT的加入使得PVA的结晶度有所下降但并未改变其晶型。APT与PVA通过氢键作用,改善了复合膜的热稳定性、力学性能和耐水性。当APT含量为4%时,纳米复合膜有最优的性能。     

冷冻处理凹凸棒黏土对PVA/APT纳米复合膜性能的影响

以聚乙烯醇(PVA)和经过不同时间冷冻处理的凹凸棒黏土(APT)为原料,采用溶液-流延成膜法,制备了PVA/APT纳米复合膜,通过红外光谱、XRD和SEM对纳米复合膜的结构和形貌进行了表征,并对复合膜的力学性能及耐水性能进行了测试.结果表明,与未冷冻处理APT相比,经冷冻处理后APT的棒晶可以更好的分散在PVA基体中,纳米复合膜的力学性能和耐水性有明显提高.其中,以冷冻处理16 h APT制备的纳米复合膜性能最优,其拉伸强度、断裂延伸率和耐水性分别提高了17.4％、25.4％和19.2％.     

Synthesis of allyl ether and benzyl methacrylate functionalized silane monomers for application in acrylate/montmorillonite nanocomposite emulsion

Abstract

Allyl trimethylsiloxybutyl ether (ATE) and 3-(trimethylsiloxy) benzylmethacrylate (TBM), tow novel silane involving monomers were successfully synthesized. Then, by in situ intercalative emulsion polymerization of styrene (St), butyl acrylate (BA), ATE and TBM, poly (silane-co-styrene-co-butylacrylate)/montmorillonite, P (Si-co-St-co-BA)/OMMT nanocomposite emulsions were prepared. The structures of monomers were clarified by the FT-IR, ¹H-NMR, and ¹³?C-NMR spectroscopic techniques and nanocomposites by FT-IR. The results indicated that addition of OMMT improved the thermal and morphological properties of emulsions and among the samples tested, the modified nanocomposites which were prepared by intercalating 1?wt% OMMT showed the most desirable effect. It was also demonstrated by TEM that OMMT addition causes some clusters or agglomerated particles into the polymer matrix and the most OMMT layers are dispersed homogeneously.     

酸处理凹凸棒黏土对PVA/APT纳米复合膜理化性能的影响

在固体与液体质量比(简称固液比,下同)为1∶10时,将凹凸棒黏土(APT)分别采用体积分数1%盐酸、H2 SO4、H3 PO4、HClO4和H4 P2 O7溶液进行处理。以聚乙烯醇(PVA)和各种酸处理APT为原料,采用溶液-流延成膜法,制备了系列PVA/APT纳米复合膜。采用FTIR、SEM和XRD对PVA/APT纳米复合膜的结构进行了表征,测试了PVA/APT纳米复合膜的力学性能和耐水性能。结果表明,酸处理能溶出APT孔道中的杂质和碳酸盐,提高棒晶束的分散程度,因而APT可均匀分散在PVA基体中。与APT原土相比,酸处理APT明显改善了纳米复合膜的力学性能和耐水性能。其中,以HClO4处理APT时纳米复合膜的性能最优,拉伸强度及断裂延伸率分别提高了29.3%和74.9%,耐水性提高了32.2%。     

Effect of attapulgite contents on release behaviors of a pH sensitive carboxymethyl cellulose‐g‐poly(acrylic acid)/attapulgite/sodium alginate composite hydrogel bead containing diclofenac

A series of pH‐sensitive composite hydrogel beads, carboxymethyl cellulose‐g‐poly(acrylic acid)/attapulgite/sodium alginate (CMC‐g‐PAA/APT/SA), were prepared by combining CMC‐g‐PAA/APT composite and SA, using Ca²⁺ as the ionic crosslinking agent and diclofenac sodium (DS) as the model drug. The effects of APT content and external pH on the swelling properties and release behaviors of DS from the composite hydrogel beads were investigated. The results showed that the composite hydrogel beads exhibited good pH‐sensitivity. Introducing 20% APT into CMC‐g‐PAA hydrogel could change the surface structure of the composite hydrogel beads, decrease the swelling ability, and relieve the burst release effect of DS. The drug cumulative release ratio of DS from the hydrogel beads in simulated gastric fluid was only 3.71% within 3 hour, but in simulated intestinal fluid about 50% for 3 hour, 85% for 12 hour, up to 90% after 24 hour. The obtained results indicated that the CMC‐g‐PAA/APT/SA hydrogel beads could be applied to the drug delivery system as drug carriers in the intestinal tract. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)]/silica nanocomposite latex prepared using an acidic silica sol

BACKGROUND: Polyacrylate/silica nanocomposite latexes have been fabricated using blending methods with silica nanopowder, in situ polymerization with surface‐functionalized silica nanoparticles or sol–gel processes with silica precursors. But these approaches have the disadvantages of limited silica load, poor emulsion stability or poor film‐forming ability. RESULTS: In this work, poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)] [P(St‐BA‐AA)]/silica nanocomposite latexes and their dried films were prepared by adding an acidic silica sol to the emulsion polymerization stage. Morphological and rheological characterization shows that the silica nanoparticles are not encapsulated within polymer latex particles, but interact partially with polymer latex particles via hydrogen bonds between the silanol groups and the ? COOH groups at the surface of the polymer particles. The dried nanocomposite films have a better UV‐blocking ability than the pure polymer film, and retain their transparency even with a silica content up to 9.1 wt%. More interestingly, the hardness of the nanocomposite films increases markedly with increasing silica content, and the toughness of the films is not reduced at silica contents up to 33.3 wt%. An unexpected improvement of the solvent resistance of the nanocomposite films is also observed. CONCLUSION: Highly stable P(St‐BA‐AA)/silica nanocomposite latexes can be prepared with a wide range of silica content using an acidic silica sol. The dried nanocomposite films of these latexes exhibit simultaneous improvement of hardness and toughness even at high silica load, and enhanced solvent resistance, presumably resulting from hydrogen bond interactions between polymer chains and silica particles as well as silica aggregate/particle networks. Copyright © 2009 Society of Chemical Industry     

Graft copolymerization of thiophene onto polystyrene synthesized via nitroxide‐mediated polymerization and its polymer − clay nanocomposite

A new strategy for graft copolymerization of thiophene onto a polystyrene (PSt) backbone by a multi‐step process is suggested and the effects of an organoclay on the final properties of the graft copolymer sample are described. For this purpose, first poly(styrene‐co‐4‐chloromethyl styrene) [P(St‐co‐CMSt)] was synthesized via nitroxide‐mediated polymerization. Afterwards, the chlorine groups of P(St‐co‐CMSt) were converted to thiophene groups using the Kumada cross‐coupling reaction and thiophene‐functionalized PSt multicenter macromonomer (ThPStM) was synthesized. The graft copolymerization of thiophene monomers onto PSt was initiated by oxidized thiophene groups in the PSt chains after addition of ferric chloride (FeCl₃), an oxidative catalyst for polythiophene synthesis, and FeCl₃‐doped polythiophene was chemically grafted onto PSt chains via oxidation polymerization. The graft copolymer obtained was characterized by ¹H NMR and Fourier transform infrared spectroscopy, and its electroactivity behavior was verified under cyclic voltammetric conditions. Finally, PSt‐g‐PTh/montmorillonite nanocomposite was prepared by a solution intercalation method. The level of dispersion of organoclay and the microstructure of the resulting nanocomposite were probed by means of XRD and transmission electron microscopy. It was found that the addition of only a small amount of organoclay (5 wt%) was enough to improve the thermal stabilities of the nanocomposite.© 2013 Society of Chemical Industry     

Synthesis and characterization of a novel silicone containing vinylic macromonomer and its uses in the preparation of poly (silicone‐co‐styrene‐co‐butylacrylate) with montmorillonite nanocomposite emulsion

A new silicone containing macromonomer, 4‐(methacrylamido) phenoxy polymethylhydrosiloxane (4‐MPMHS) with a vinyl group, was successfully synthesized. Then poly (silicone‐co‐styrene‐co‐butylacrylate) with montmorillonite, P (Si‐co‐St‐co‐BA) with MMT nanocomposite emulsion was prepared by in situ intercalative emulsion polymerization of styrene (St), butyl acrylate (BA), and 4‐MPMHS, in the presence of organic modified montmorillonite (OMMT) with different OMMT contents (0, 0.5, 1.0, 1.5, and 2 wt %). Potassium persulphate (KPS) was used as an initiator and sodium lauryl sulfoacetate (SLSA) and nonyl phenol ethylene oxide—40 U (NP‐40) were used as anionic and nonionic emulsifiers, respectively. The resulting macromonomer was characterized by elemental analysis, Fourier transformer infrared (FT‐IR), proton (¹H NMR), and carbon (¹³C NMR) nuclear magnetic resonance spectroscopes. The OMMT was characterized by FT‐IR and X‐ray diffraction (XRD). The nanocomposite emulsions were characterized by using Fourier Transform infrared spectroscopy (FT‐IR), laser light scattering, and surface tension method. Thermal properties of the copolymers were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and then the effects of OMMT percent on the water absorption ratio and drying speed were examined. Results showed that OMMT could improve the properties of emulsion. In other words, the properties of nanocomposite emulsions were better when compared with those of the silicone‐acrylate emulsion. The property of nanocomposite emulsion containing 1 wt % OMMT was the best one, and the following advantages were obtained: smaller particle size, faster drying speed, smaller surface tension, and improved water resistance by the incorporation of OMMT. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011