Thermally stable organically modified layered silicates based on alkyl imidazolium salts

A series of imidazolium salts having various substituents and functional groups were synthesized and characterized by FTIR and NMR spectroscopy. Organic modification of natural and synthetic layered silicates involving montmorillonite (MMT), laponite (lap), and synthetic mica (mica) was carried out by ion-exchange reaction. The obtained organo-clays were characterized by FTIR and powder X-ray diffraction techniques. Results indicate that these organically modified clays have much higher thermal stabilities compared to their corresponding imidazolium halides. It was also observed from TGA analysis that thermal stability does not depend on the functional group present at the 3-position of the imidazolium salts. These studies strongly supports premise that the removal of halide is necessary to improve the thermal stability of the organo-clay produced.     

Exfoliation of smectite clays by branched polyamines consisting of multiple ionic sites

Exfoliation through an ionic exchange reaction of layered silicate clays, including synthetic fluorinated mica (Mica) and natural montmorillonite (MMT), were achieved by using polyvalent amine salts as the intercalating agents. The requisite polyamine was synthesized from the epoxy/amine coupling reaction, involving a trifunctional poly(oxypropylene)-triamine (ca. 440 g/mol M_w) and diglycidyl ether of bisphenol-A. The polyamine was a mixture of oligomeric adducts consisting of multiple amine functionalities and a branched backbone. Partial acidification by HCl addition generated a series of amine salts that affected the intercalation and the expansion of the silicate interlayer in the range of 15.2-60.0 Å XRD d spacing. At the specific acidified ratio (H⁺/amine = 1/3 equiv ratio), the polyamine salts rendered the clay’s layered structure into randomization. The result was confirmed by using XRD and transmission electronic microscopy (TEM). The hybrids of polyamines and Mica or MMT were blended into epoxy resins and cured into nanocomposites, which exhibited the improvements of thermal stability and hardness.     

季铵盐插层蒙脱土及其去除海洋卡盾藻的研究

利用插层法制备了5种季铵盐改性的蒙脱土,通过FTIR、XRD和DTG等表征表明5种季铵盐已成功插入蒙脱土中;随后以中国典型赤潮藻海洋卡盾藻(Chattonella marina)为研究对象,考察了5种季铵盐改性蒙脱土的除藻效果。发现以双溴化十四烷基二甲基乙基溴化铵改性的蒙脱土在用量为8mg·L-1时,24h内对海洋卡盾藻的去除率最高,可达100%,而未改性蒙脱土在相同条件下除藻率仅为5.64%;除藻效果与除藻剂的结构有密切关系,在官能团相同时,链长数为14的脂肪族季铵盐除藻率最高,24h可达67.03%;在链长数相同时,含吡啶官能团的季铵盐比脂肪族季铵盐除藻率高,24h为33.62%,且随时间延长明显提高。渗溢性评估实验显示,改性蒙脱土经72h浸泡后表观插层率从71.9%降低到69.6%,表明除藻剂在水体中基本不释放。     

Unusual Intercalation of Cationic Smectite Clays with Detergent‐Ranged Carboxylic Ions

Summary: The organic intercalation of cationic smectite clays is achieved by using alkali salts of alkyl carboxylic acids, instead of using conventional quaternary ammonium salts as ionic exchanging agents. Various organic acid salts, such as CH₃(CH₂)₁₆COO⁻Na⁺, can be incorporated into divalent montmorillonite (M²⁺‐MMT) with a 30–40 wt.‐% organic embedding and an X‐ray diffraction basal spacing of 43 Å from the pristine 10 Å. The intercalation is generalized for carboxylate salts of different alkyl lengths and for alkali metal ions, including sodium and potassium ions, but is specific for the divalent MMT clay. This new type of organic species for clay modification allows the preparation of organoclays in the absence of quaternary ammonium salts. It is proposed that the organic embedding is driven by the formation of a thermodynamically stable RCOO⁻/M²⁺/SiO⁻ complex.

Graphical illustration of the carboxylic acid salt complex with the divalent cations on silicate K10.     

Dispersibility of clay and crystallization kinetics for in situ polymerized PET/pristine and modified montmorillonite nanocomposites

Nanocomposite materials composed of poly (ethylene terephthalate) (PET) and montmorillonite (MMT) clays were prepared by in situ polymerization. Samples consisted of PET blended with various quantities of either pristine (Na⁺‐MMT) or organically modified MMT (A10‐MMT). The morphology and thermal and mechanical properties were evaluated for each sample. TEM micrographs, acquired at a 20 nm resolution, provide direct evidence of exfoliation of the clay particles into the PET matrix and show the effect of the alkyl‐modifier on clay dispersibility. The dispersion of PET/A10‐MMT was greater than that observed for the PET/Na⁺‐MMT nanocomposites. The greatest degree of exfoliation occurred for PET/A10‐MMT 0.5 wt %. However, PET/Na⁺‐MMT exhibited higher crystallization temperatures and rates suggesting that Na⁺‐MMT is a more efficient nucleating agent. Both mechanically and thermally, PET/A10‐MMT nanocomposites exhibited superior properties over pure PET. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1022–1035, 2008     

PMMA/MMT nanocomposites prepared by one-step in situ intercalative solution polymerization

Poly(methylmetacrylate)/montmorillonite (PMMA)/(MMT) nanocomposites were prepared by one-step in situ intercalative solution polymerization involving simultaneous modification of MMT with quaternary ammonium salts (QAS), polymerization and polymer intercalation. Polymerization proceeded at 70 °C in a mixture of ethanol and water, whereas the nanocomposite was precipitated with only water. Four QAS’s with different alkyl chain lengths, as well as a QAS with an additional acrylic group, were used to study the influence of the type of quaternary ammonium salt on intercalation. The largest extent of intercalation was achieved in nanocomposites with the QAS having one long alkyl (C16) chain. The obtained PMMA/MMT intercalated nanocomposites exhibited a higher glass transition temperature, better thermal stability, and improved solvent resistance than the pure PMMA.     

Study of individual Na-montmorillonite particles size, morphology, and apparent charge

Size, morphology, and apparent charge of individual Na-montmorillonite particles of natural MX-80 sodium montmorillonite were investigated in the present study by the use of three coupling methods. In the first part of this work, natural and synthetic montmorillonite clays were studied with atomic force microscopy (AFM) and photo-correlation spectroscopy (PCS). Both techniques exhibit the presence of two clay populations with a high dispersion of the length distribution. Microscopic analysis of the system revealed that clay particles could be reasonably approximated at low concentrations to ellipsoidal tactoids about 1.2 nm high. Average dimensions of the first population were typically 320-400 nm long/250 nm wide and 200-250 nm long/120 nm wide for natural and synthetic clays, respectively. The second population exhibits smaller sizes: 65 and 50 nm long and 35 and 25 nm wide for natural and synthetic clays, respectively. The statistics obtained for natural clay were then verified by PCS experiments on sodium montmorillonite suspensions. Both techniques reveal an important length dispersion. However, the relative proportions of the two kinds of particles could not be established properly because of both lack of statistics and limitations of the employed techniques. In the following part, conductivity measurements were performed on dilute montmorillonite clay suspensions. Raw data were then interpreted with the sizes and morphological information gained in the first part of the present work. The apparent charge of the clay sheets was found to be 8% of the structural charge.     

介孔硅层柱蒙脱石材料合成的新方法与表征

利用十六烷基三甲基溴化铵(CTAB)将天然钠基蒙脱石改性成有机蒙脱石,以十二烷胺为模板剂,正硅酸乙酯为层柱前驱体,在室温下合成了新型介孔硅层柱蒙脱石材料.用XRD,TG,FTIR以及N₂等温吸附-脱附等技术对产物进行了表征.结果表明,合成材料具有大通道(净层间距为2.75nm)、介孔孔径且孔分布窄(平均孔径为2.17nm)、比表面积高(SBET=821.6m²/g)、热稳定性高(大于800℃)等特征.同时,通过改变中性胺的链长,研究了孔结构的调变规律,分析了材料的成孔机理和热稳定性提高的原因.     

Synthesis and properties of polyimide-clay hybrid films

Polyimide-clay hybrid films with four different sizes of clay minerals have been synthesized to investigate the effect of the size of clay minerals to the properties of the hybrids. Hectrite, saponite, montmorillonite, and synthetic mica were used as clay minerals. Those clays consist of stacked silicate sheets about 460 Å (hectrite), 1650 Å (saponite), 2180 Å (montmorillonite), and 12300 Å (synthetic mica) in length, 10 Å in thickness. The longer the length of clay mineral was, the more effectively properties of polyimide were improved. In the case of polyimide-mica hybrid, only 2 wt % addition of synthetic mica brought permeability coefficients of water vapor to value less than one-tenth of that of ordinary unfilled polyimide, and thermal expansion coefficient was lowered at the level of 60% of the original one. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2289–2294, 1997     

Preparation of porous PMMA/Na–montmorillonite cation-exchange membranes for cationic dye adsorption

Porous PMMA/Na⁺–montmorillonite (MMT) cation-exchange membranes were successfully prepared by entrapment method in this study. One approach (simple mixing) was to mix commercial PMMA polymer with Na⁺–MMT clays in solvent for membrane preparation (Membrane A). The other approach (emulsion polymerization) was to synthesize the PMMA/Na⁺–MMT polymer composite via emulsion polymerization first, followed by membrane casting (Membrane B for Kunipia F clays and Membrane C for PK-802 clays). Membrane morphology and properties were characterized. The thermogravimetric analysis (TGA) verified the near complete incorporation of feed Na⁺–MMT clays in the PMMA/Na⁺–MMT composite membranes, while X-ray diffractograms (WXRD) exhibited the slightly enlarged interlayer spacing of Na⁺–MMT. The range of cation-exchange capacity (CEC) was 9–32 μequiv./47 mm disc. For batch cationic dye adsorption, the best performance was achieved by Membrane B with feed Na⁺–MMT/MMA (M/P) ratio (w/w) = 0.5 and Membrane C with feed M/P = 0.6, where about 95% Methyl violet adsorption was attained in 2 h. The optimal desorption solution was 1 M KSCN in 80% methanol and its related dye desorption efficiency was 92%. In the flow process using one piece of 47 mm disc of Membrane B (M/P = 0.5), dye solution was recirculated for 6 h and ≥85% dye could be removed. Higher than 94% of dye was desorbed at 1 or 4 mL/min, and the membrane regenerability was proved by successfully performing three consecutive cycles.     

Layered confinement of protein in synthetic fluorinated mica via stepwise polyamine exchange

We have developed a process to incorporate the model protein, bovine serum albumin (BSA), into the layered spacing of swelled mica. By a stepwise intercalation, the sodium form of synthetic fluorinated mica (Mica) was first exchanged with the poly(oxyalkylene)-diamine salts (POA-amine) through an ionic exchange reaction and then the BSA embedment. The first step of the Mica space expansion from the pristine 12 A to 18-93 A was affected by hydrophobic POP-amines (POP2000 of 2000 g/mol and POP4000 of 4000 g/mol M(w)) and the hydrophilic POE2000 that intercalated Na+-Mica to afford different basal spacing (39, 93, and 18 A, respectively). The POA modification was necessary for the BSA intercalation and resulted in an uncompressed form of protein conformation in the layered confinement (XRD d spacing = 60-71 A). For comparison, direct intercalation rendered only low d spacing (30 A), in which BSA was embedded in a compressed conformation. The BSA-mica complexes were characterized by X-ray, TGA, and solution analyses. The stepwise process provides a new method for embedding large protein molecules into the clay layered structure generating protein/layered silicate complexes.     

Styrene and Butyl Acrylate Polymerization in Nonionic Microemulsions in Presence of Layered Silicates

It was studied the polymerization of styrene (St) and of butyl acrylate (BuA) in nonionic microemulsions in the presence of a layered alumino silicates, montmorilonit (MMT) type. In time, the latexes separate in two distinct strata, MMT being distributed in the inferior strata where forms aggregates with on order of size bigger than the diameters of nanoparticles of latex. The solid products obtained are nanohybrids of intercalate type whose structural order increases direct proportional with the increase of hydrophobic character of the quaternary ammonium salts used for organophilization of MMT. The presence of nonionic surfactant, nonyl phenol with 25 mols of ethylene oxide, intercalated between the lamellar strata of MMT produces the decrease of thermal stability of hybrids and decreases the glass transition temperature of PSt which is more compatible than PBuA.     

The solid-phase Zincke reaction: preparation of omega-hydroxy pyridinium salts in the search for CFTR activation

A study of structural modifications of MPB-07 was undertaken as part of a synthetic program aimed at discovering small molecules with CFTR activation potential. Solid-phase synthesis techniques were used to prepare derivatives of MPB-07 employing the Zincke reaction for the construction of aromatic, quaternary ammonium salts such as those found in 2 or 3. In this transformation, primary amines react with highly electrophilic N-2,4-dinitrophenylpyridinium (DNP) salt 4 to afford pyridinium salt 8 with release of 2,4-dinitroaniline 6. Thus, the reaction of 1-(2,4-dinitrophenyl)pyridinium salts with various polymer-bound amino ethers, followed by cleavage from the resin, delivers the desired salts in good yield and high purity.     

Synthesis, antimicrobial and antifungal activity of double quaternary ammonium salts of biphenyls

The synthetic methods for new 2-, 2,2′-, and 3-substituted 4,4′-bis(chloromethyl)biphenyls were developed. Quaternization of them with various amines resulted in a series of new double quaternary ammonium salts containing the biphenyl moiety. The majority of the obtained compounds have a pronounced antifungal and antibacterial activity against the Gram-positive bacteria.     

Emulsion intercalation of smectite clays with comb-branched copolymers consisting of multiple quaternary amine salts and a poly(styrene-butadiene-styrene) backbone

Layered silicates were intercalated with comb-branched copolymers consisting of a hydrophobic polystyrene-b-poly(ethylene/butylene)-b-polystyrene (SEBS) backbone and multiple pendants of poly(oxyalkylene) (POA) quaternary ammonium salts. The requisite intercalating agents were synthesized by grafting POA amines on the maleated SEBS. The corresponding SEBS-POA amine salts were found to have two functions, the capability to emulsify toluene/water mixtures to fine particle sizes of 60-70 nm in diameter and to exchange ions with sodium montmorillonite. The resulting silicate hybrids were characterized by X-ray diffraction and transmission electron microscopy. Two types of intercalations with silicate d spacing of 18 and 50 A were obtained, in which the dissimilarity is attributed to disparate polymer incorporations, POA pendants only or the combination of both the SEBS backbone and POA in the gallery. Furthermore, the two conformations of polymer-intercalated silicates are reversibly transformable by varying emulsion conditions, micelle sizes, and solvents.     

Structural characteristics and moisture sorption behavior of nylon‐6/clay hybrid films

The structure of nylon‐6 hybrids with synthetic or natural clays was investigated for melt‐pressed films with Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, and differential scanning calorimetry in comparison with the nylon‐6 homopolymer. In contrast to the development of familiar α‐form crystals in plain nylon‐6 film, the hybrid films produced γ‐form crystals when nylon‐6 was conjugated with synthetic mica, whereas the hybridization with natural montmorillonite gave rise to both α‐ and γ‐crystalline modifications. The degree of crystallinity of the nylon‐6 hybrid with synthetic mica was the highest of the three series. Moisture sorption isotherms obtained for these nylon‐6‐based films were all typically sigmoid‐shaped, although the prevalence of a higher crystallinity in the hybrid samples lowered the degree of moisture regain. The sorption behavior was analyzed well in terms of the parameters of a Brunauer–Emmett–Teller multiplayer adsorption model and a Flory–Huggins treatment. It was also observed that the cluster formation of the water adsorbed into the nylon‐6 matrix tended to be restricted by the hybridization with clay. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 479–487, 2002; DOI 10.1002/polb.10106     

Hybrid materials: Magnetite-Polyethylenimine-Montmorillonite, as magnetic adsorbents for Cr(VI) water treatment

Hybrid materials formed by the combination of a sodium rich Montmorillonite (MMT), with magnetite nanoparticles (40nm, Fe(3)O(4) NPs) coated with Polyethylenimine polymer (PEI 800g/mol or PEI 25000g/mol) were prepared. The intercalation of the magnetite nanoparticles coated with PEI among MMT platelets was achieved by cationic exchange. The resulting materials presented a high degree of exfoliation of the MMT sheets and a good dispersion of Fe(3)O(4) NPs on both the surface and among the layers of MMT. The presence of amine groups in the PEI structure not only aids the exfoliation of the MMT layers, but also gives to the hybrid material the necessary functionality to interact with heavy metals. These hybrid materials were used as magnetic sorbent for the removal of hexavalent chromium from water. The effect that pH, Cr(VI) concentration, and adsorbent material composition have on the Cr(VI) removal efficiency was studied. A complete characterization of the materials was performed. The hybrid materials showed a slight dependence of the removal efficiency with the pH in a wide range (1-9). A maximum amount of adsorption capacity of 8.8mg/g was determined by the Langmuir isotherm. Results show that these hybrid materials can be considered as potential magnetic adsorbent for the Cr(VI) removal from water in a wide range of pH.     

Effects of organophilic clay on the solvent‐maintaining capability,dimensional stability,and electrochemical properties of gel poly(vinylidene fluoride) nanocomposite electrolytes

Four quaternary alkyl ammonium salts were used in an organophilic procedure, performed on montmorillonite clay, and resulted in intercalation in dimethylformamide (DMF) or ethylene carbonate (EC)/propylene carbonate (PC) as a cosolvent between poly(vinylidene fluoride) (PVdF) and the organophilic clay. An examination using X‐ray diffraction revealed that PVdF entered galleries of montmorillonite clay, and it exhibited exfoliation and intercalation phenomena when it was analyzed with transmission electron microscopy. Gel PVdF nanocomposite electrolyte materials were successfully prepared by the addition of the appropriate percentages of DMF or PC/EC as a cosolvent, organophilic clay, and lithium perchlorate to PVdF. The maximum ionic conductivity was 1.03 × 10^?2 S/cm, and the materials exhibited better film formation, solvent‐maintaining capability, and dimensional stability than electrolyte films without added organophilic clays. The results of cyclic voltammetry testing showed that the addition of the organophilic clays significantly enhanced the electrochemical stability of the polymer electrolyte system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3873–3882, 2002     

Ionic liquids based upon metal halide/substituted quaternary ammonium salt mixtures

The synthesis of ionic liquids based upon functionalized quaternary ammonium salts and metal salts of zinc, tin, or iron is demonstrated. The freezing point of these ionic liquids was studied as a function of the quaternary ammonium cation. The complex anions were identified and quantified using mass spectrometry and potentiometry. It is shown that the primary zinc anion is Zn(2)Cl(5)(-) with Zn(3)Cl(7)(-) becoming more abundant in more Lewis basic solutions. Similar results were observed for ionic liquids containing SnCl(2). The surface tension was also measured and was used to explain the high viscosity of the ionic liquids in terms of the large ion:hole size ratio and the small probability of finding a hole of suitable dimensions adjacent to a given ion to permit movement. The phase behavior of a variety of quaternary ammonium halides/ZnCl(2) mixtures is characterized and it is shown that the depression of freezing point is related to the increase in size of the component ions.     

聚N-甲基苯胺/蒙脱土纳米复合材料的合成及其协同电流变效应

用插层聚合法制备了聚N 甲基苯胺 蒙脱土纳米复合材料微粒 ,通过IR、XRD及TEM对其结构进行了表征 .观察发现聚N 甲基苯胺插入蒙脱土层间后 ,蒙脱土片层间距由 0 96nm扩大至 1 34nm .将其分散在甲基硅油中 (2 0wt% )配制成无水电流变液 ,该复合材料表现出显著的协同效应 ,具有较好的电流变行为 .实验表明在电场作用下聚N 甲基苯胺 蒙脱土纳米复合材料的电流变效应比聚苯胺、蒙脱土都有显著提高 ,在 3kV mm(DC ,74 5s- 1 )时 ,剪切强度达 6 0kPa ;同时抗沉降性极好 ,静置 6 0天沉淀率小于 3% .介电性能测试表明聚N 甲基苯胺 蒙脱土纳米颗粒的介电常数和介电损耗较蒙脱土和聚N 甲基苯胺明显提高 ,电导率也达到了最佳范围 .