The influence of a quaternary ammonium salt and MMT on the in situ intercalative polymerization of PMMA

Poly(methylmetacrylate)/montmorillonite (PMMA)/(MMT) nanocomposites were prepared by a one-step in situ intercalative solution polymerization involving the simultaneous modification of the MMT with a quaternary ammonium salt (cetyl-trimethylammonium bromide (CTMAB)), polymerization and polymer intercalation. Using benzoyl peroxide as an initiator, intercalated nanocomposites were formed and characterized by NMR, DSC, TGA, XRD, TEM and SEC. It was observed that it was not the MMT, but rather the CTMAB, that influences the polymerization reaction, especially the reaction yield, the molar mass averages and the molar mass distribution of the PMMA. The thermal stability of the PMMA was improved by the addition of both the MMT and/or the CTMAB.     

Synthesis and characterization of polymer/clay nanocomposites by intercalated chain transfer agent

In situ synthesis of poly(methyl methacrylate) (PMMA) and polystyrene (PS) nanocomposites by free radical polymerization using intercalated chain transfer agent (I-CTA) in the layers of montmorillonite (MMT) clay is reported. MMT clay was ion-exchanged with diethyl octyl ammonium ethylmercaptan bromide, which acts both as suitable intercalant and as chain transfer agent. These modified clays were then dispersed in methyl methacrylate (MMA) or styrene (St) monomers in different loading degrees to carry out the in situ free radical polymerization. The intercalation ability of the chain transfer agent and exfoliated nanocomposite structure were evidenced by both X-ray diffraction spectroscopy (XRD) and transmission electron microscopy (TEM). Thermal properties and morphologies of the resultant nanocomposites were also studied.     

Structure and thermal stability of PMMA/MMT nanocomposites as denture base material

Poly(methyl methacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were prepared by in situ suspension polymerization. MMT was previously organically modified by three different intercalating agents: methacrylatoethyl trimethyl ammonium chloride (DMC), dodecylamine (12CNH), and hexadecyl allyl ammonium chloride (HADC). The structures of the nanocomposites were investigated by X-ray diffraction and transmission electron microscopy, while the interaction between PMMA and MMT was characterized by Fourier transform infrared spectroscopy. The molecular mass of the extracted PMMA was measured by gel permeation chromatography. The thermal stability of PMMA/MMT nanocomposites was evaluated by thermogravimetric and differential scanning calorimetry. The results indicated that PMMA/MMT nanocomposites were successfully prepared and the interaction between PMMA and MMT of PMMA/MMT–HADC nanocomposites was the strongest. The thermal stability of the nanocomposites was improved and found to be optimal for PMMA/MMT–HADC with T ₁₀ increasing to 304 °C, 52 °C higher than that of neat PMMA.     

Effective preparation of montmorillonite/polyurethane nanocomposites by introducing cationic groups into the polyurethane main chain

In this study, the effect of introducing a small amount of cationic groups into the polymer main chain on the exfoliation of montmorillonite (MMT) and the physical properties of the subsequent MMT/polymer nanocomposites were investigated. As a matrix polymer, a polyurethane cationomer (PUC) containing 3 mol% of quaternary ammonium groups was synthesized and MMT/PUC nanocomposites containing various amounts of MMT were prepared by the solution intercalation method. From the WAXS and TEM analyses, it was found that the MMT layers were completely exfoliated and dispersed in the PUC matrix. The Young’s modulus of the MMT/PUC nanocomposites significantly increased with increasing MMT content, but their elongation at break and maximum stress were maintained at a level close to that of the PU only at an MMT content of 1 wt% and decreased as the content of MMT increased above this level. The phase separation of the MMT/PUC nanocomposites was retarded with increasing content of MMT, due to the strong interactions between the PUC chains and the exfoliated MMT layers. It was found that the presence of small amounts of cationic groups in the main chain of the matrix polymer was very effective in facilitating the preparation of the MMT/polymer nanocomposites.     

Effect of tetraalkylammonium salts on the tacticity of poly(methyl methacrylate), 2.. Initiation by potassium tert-butoxide

The anionic polymerization of methyl methacrylate was carried out in the presence of potassium tert-butoxide (t-BuOK)/quaternary ammonium salts (QAS) in toluene and tetrahydrofuran at −60°C. It was found that in toluene some QAS additives substantially increase the syndiotacticity of poly(methyl methacrylate). Two types of QAS were distinguished, quite different in their action. The addition of QAS with one or two longchain alkyl groups (>C₁₂), does not change significantly the mode of the monomer addition, whereas the polymerization in the presence of tetraalkylammonium salts with four equal substituents and dimethyldidodecylammonium bromide yields predominantly a syndiotactic polymer with high conversion and comparatively low polydispersity (M̄_w/M̄_w = 1.3−1.5). In some cases QAS additives are more effective modifiers than cryptand [2.2.2].     

Effect of tetraalkylammonium salts on the tacticity of poly(methyl methacrylate), 1. Initiation by ethyl α-lithioisobutyrate

The anionic polymerization of methyl methacrylate (MMA) was carried out in the presence of ethyl α-lithioisobutyrate (α-LiEtIB)/quaternary ammonium salts (QAS) in toluene and tetrahydrofuran/toluene (vol. ratio 75/25) at −60°C. It was found that the tacticity of PMMA strongly depends on size and shape of QAS. A highly isotactic polymerization in toluene was observed, when using the system α-LiEtIB/trimethylhexadecylammonium bromide. The initiator system α-LiEtIB/tetrahexylammonium chloride produces polymers with a high (>50%) syndiotactic content and relatively low polydispersity. The influence of QAS on the mode of polymerization is due to specific salt effect resulting from the cation exchange reaction, from the participation of the bulky substituent in the primary solvation shell, and ionic aggregation between the growing anion, Q⁺ and LiX.     

Tetraalkylammonium salts as additives in anionic polymerization of methyl methacrylate

The anionic polymerization of methyl methacrylate was carried out in the presence of t-BuOK/Quaternary ammonium salt (QAS) and α-lithio-ethylisobutyrate/QAS in toluene and THF. Seven QAS and one quaternary phosphonium salt of different size and shape were used as modifiers. With the aid of the model system alkali picrate/QAS, it was found that the interaction between the picrate salt and QAS in toluene does not proceed as a pure cation exchange reaction. Two types of adducts were distinguished: Initiator/QAS with a very long hydrocarbon chain (>C₁₂) promote isotactic placement, while the adducts t-BuOK/QAS with two or more bulky substituents produce a highly syndiotactic polymer with high conversion and comparatively low polydispersity in pure toluene.     

Effects of melt‐processing conditions on the quality of poly(ethylene terephthalate) montmorillonite clay nanocomposites

Organically modified montmorillonite was synthesized with a novel 1,2‐dimethyl‐3‐N‐alkyl imidazolium salt or a typical quaternary ammonium salt as a control. Poly(ethylene terephthalate) montmorillonite clay nanocomposites were compounded via melt‐blending in a corotating mini twin‐screw extruder operating at 285 °C. The nanocomposites were characterized with thermal analysis, X‐ray diffraction, and transmission electron microscopy to determine the extent of intercalation and/or exfoliation present in the system. Nanocomposites produced with N,N‐dimethyl‐N,N‐dioctadecylammonium treated montmorillonite (DMDODA‐MMT), which has a decomposition temperature of 250 °C, were black, brittle, and tarlike resulting from DMDODA degradation under the processing conditions. Nanocomposites compounded with 1,2‐dimethyl‐3‐N‐hexadecyl imidazolium treated MMT, which has a decomposition temperature of 350 °C, showed high levels of dispersion and delamination. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2661–2666, 2002     

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。     

Preparation and properties of PU/MCMMT nanocomposites

The cetyltrimethyl ammonium bromide (CTAB) was used as a swelling agent to be intercalated into the galleries of the montmorillonite (MMT) platelets to get the organic MMT (CMMT). Then 4,4′‐diphenylmethane diisocyanate (MDI) were grafted on CMMT by the reaction between hydroxyls in organic MMT platelets and MDI to synthesize the MDI modified CMMT (MCMMT). Polyurethane (PU)/MCMMT composites were prepared by situ polymerization. The MCMMT platelets dispersed in a PU matrix in nanometer scale. The dispersion and intercalation degree of the MCMMT platelets decreased with increase in the content of MCMMT. Under the same content of fillers, the tensile strength and tear strength of PU/MCMMT nanocomposites were higher than those of PU/organic MMT nanocomposites. The reinforcing effect of the MCMMT platelets to the PU was better than that of the organic MMT platelets. With increase in the content of MCMMT, the tensile strength and tear strength of the PU/MCMMT nanocomposites were increased, while the extent of the increase slowed down. Compared with those of PU, the thermal stability of PU/MCMMT nanocomposites was increased. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation of poly(propylene)/clay layered nanocomposites by melt intercalation from pristine montmorillonite (MMT)

Poly(propylene)/clay nanocomposites were prepared by melt intercalation, using pristine montmorillonite (MMT), hexadecyl trimethyl ammonium bromide (C16), poly(propylene) (PP) and maleic acid (MA) modified PP (MAPP), The nanocomposites structure is demonstrated using X‐ray diffraction (XRD) and high resolution electronic microscopy (HREM). Our purpose is to provide a general concept for manufacturing polymer nanocomposites by melt intercalation starting from the pristine MMT. We found different kneaders (twin‐screw extruder or twin‐roll mill) have influence on the morphology of the PP/clay nanocomposites. Thermogravimetric analysis (TGA) shows that the thermal stability of PP/clay nanocomposites has been improved compared with that of pure PP. Copyright © 2003 John Wiley & Sons, Ltd.     

Structure Characterization and Thermal Properties of PMMA／Montmorillonite Nanocomposites via Emulsion Polymerization

Montmorillonite(MMT) modified with sodium silicate can change the arrangement of its layers fromedge-face and edge-edge to face-face. With the fine dispersion of the modified MMT in water, the cation-ex-change reaction was carried out with cetyltrimethyl ammonium bromide (CTAB) to obtain organo-montmoril-lonite (OMMT). As OMMT was uniformly dispersed in methyl methacrylate (MMA) monomer, PMMA/OMMT nanocomposites were formed via a common emulsion polymerization. The products were extractedwith hot acetone and characterized by FTIR, molecular weight, X-ray diffraction(XRD), transmission elec-tron microscopy(TEM), DSC and TGA. These results show that most of the OMMT layers have been exfo-liated, while the thermal stability is increased obviously. By means of FTIR spectral analysis, the ratios ofthe macromolecular radicals‘ termination of disproportionation patterns to combination are increased with theaddition of OMMT. This result further confirms the increase of the thermal degradation temperatures andglass transition temperatures of the PMMA/OMMT nanocomposites.     

First colorimetric sensor array for the identification of quaternary ammonium salts

A colorimetric sensor array based on supramolecular host-guest complexes has been developed for the identification and quantification of quaternary ammonium salts (QAS). QAS are ubiquitous undesirable compounds for which the identification of the individual compounds is not trivial and needs instrumental techniques. The sensor array developed by us is constituted by host-guest complexes formed by the inclusion of tricyclic basic dyes such as proflavine, acridine orange, thionin, and methylene blue inside the hollow space defined by cucurbit[n]urils with n = 7 and 8. The operation of the sensor array has been demonstrated by differentiating 14 quaternary ammonium salts, some of them differing by a single carbon atom in the alkyl group. The detection limit concentration was 10⁻⁵ M and the system can also be used to quantify the concentration of the quaternary ammonium ion.     

Novel Anion Exchangers for Electrodes with Improved Selectivity to Divalent Anions

It has been found that replacing of several long‐chain alkyl substituents at the nitrogen atom of lipophilic quaternary ammonium salts (QAS) by methyls results in a dramatic increase of the potentiometric selectivity of ion‐selective electrodes (ISE) with QAS‐based plasticized PVC membranes to some divalent anions against the monovalent ones. The discussed effect of QAS cation nature on the potentiometric selectivity is also partly retained for ISE with neutral carrier‐based membranes doped with QAS to provide anion permselectivity. This opens up new possibilities to control the potentiometric selectivity of ISE for divalent anions by the appropriate selection of the anion exchanger.     

Homoionic inorganic montmorillonites as fillers for polyamide 6 nanocomposites

The homoionic montmorillonites Ca-MMT, Mg-MMT, Ba-MMT and Ca-MMT intercalated with ε-caprolactam - Ca-MMT·CL were prepared from commercial Na-MMT and characterized by WAXS and TGA. They were used as fillers for nanocomposites of polyamide 6 synthesized either by anionic polymerization of ε-caprolactam (monomer casting) or by melt blending. WAXS analysis showed that the intercalation of MMT by the polyamide was complete for all nanocomposites, with only a very small fraction of exfoliated platelets being detected by TEM. The decrease in the number of layers in the MMT tactoids suggests that tactoid splitting was lower for the blended nanocomposites than for the polymerized ones. Both the rate of polymerization and the polyamide yield in the nanocomposites were comparable to those of an unfilled system. The MMT fillers, the density of which was more than twice that of the ε-caprolactam in which they were suspended, sedimented during the first stage of polymerization. TGA was used to determine the degree of sedimentation at various levels of the resulting mold. In line with the coordination of polyamide chains to the surface cations of MMT particles, the sedimentation level increased in the following sequence: Mg-MMT < Ba-MMT < Ca-MMT·CL << Na-MMT. Ca-MMT was found to be the only non-sedimenting filler suitable for use in the synthesis of polyamide nanocomposites by either monomer casting or the use of reactive injection molding (RIM) technologies.     

原位插层聚合制备聚丁二烯/蒙脱土纳米复合材料的结构与性能研究

聚合物 /粘土纳米复合材料由于具有常规复合材料所没有的结构、形态及更优异的力学、热学、阻燃、阻隔等性能 ,自 1 987由日本丰田公司首次报道了制备尼龙 6 粘土纳米复合材料以来 ,立刻引起人们的普遍关注[1～ 17] .目前报道的聚合物 /粘土纳米复合材料主要集中在以树脂为基体 ,例如 ,聚酰胺[1～ 4] 、聚苯乙烯[5～ 8] 、聚甲基丙烯酸甲酯[9,10 ] 、聚丙烯[11,12 ] 等 .制备以橡胶为基体的橡胶/粘土纳米复合材料研究较少 ,采用的方法多为通过橡胶大分子插层 ,如熔融插层法[1 3] 、溶液插层法[14 ] 、乳液法[15,16] 等 ,这些方法均存在插层…     

Synthesis of poly(methyl methacrylate) nanocomposites via emulsion polymerization using a zwitterionic surfactant

The synthesis of nanocomposites via emulsion polymerization was investigated using methyl methacrylate (MMA) monomer, 10 wt % montmorillonite (MMT) clay, and a zwitterionic surfactant octadecyl dimethyl betaine (C18DMB). The particle size of the diluted polymer emulsion was about 550 nm, as determined by light scattering, while the sample without clay had a diameter of about 350 nm. The increase in the droplet size suggests that clay was present in the emulsion droplets. X-ray diffraction indicated no peak in the nanocomposites. Transmission electron microscopy showed that emulsion polymerization of MMA in the presence of C18DMB and MMT formed partially exfoliated nanocomposites. Differential scanning calorimetry showed an increase of 18 degrees C in the glass transition temperature (Tg) of the nanocomposites. A dynamic mechanical thermal analyzer also verified a similar Tg increase, 16 degrees C, for the partially exfoliated nanocomposites over poly(methyl methacrylate) (PMMA). Thermogravimetric analysis indicated a 37 degrees C increase in the decomposition temperature for a 20 wt % loss. A PMMA nanocomposite with 10 wt % C18DMB-MMT was also synthesized via in situ polymerization. This nanocomposite was intercalated and had a Tg 10 degrees lower than the emulsion nanocomposite. The storage modulus of the partially exfoliated emulsion nanocomposite was superior to the intercalated structure at higher temperatures and to the pure polymer. The rubbery plateau modulus was over 30 times higher for the emulsion product versus pure PMMA. The emulsion technique produced nanocomposites of the highest molecular weight with a bimodal distribution. This reinstates that exfoliated structures have enhanced thermal and mechanical properties over intercalated hybrids.     

Influence of Fe‐MMT on crosslinking and thermal degradation in silicone rubber/clay nanocomposites

In this article, silicone rubber (SR)/clay nanocomposites were synthesized by a melt‐intercalation process using synthetic Fe‐montmorillonite (Fe‐MMT) and natural Na‐MMT which were modified by cetyltrimethyl ammonium bromide (CTAB). This study has been designed to determine if the presence of structural iron in the matrix can result in radical trapping and then enhance thermal stability, affect the crosslinking degree and elongation. The SR/clay nanocomposites were characterized by X‐ray diffraction (XRD) patterns and transmission electron microscopy (TEM). Exfoliated and intercalated nanocomposites were obtained. Thermo gravimetric analysis (TGA) and mechanical performance were applied to test the properties of the SR/clay nanocomposites. The presence of iron significantly increased the onset temperature of thermal degradation in SR/Fe‐MMT nanocomposites. The thermal stability, gel fraction and mechanical property of SR/Fe‐MMT were different from the SR/Na‐MMT nanocomposites. So the iron not only in thermal degradation but in the vulcanization process acted as an antioxidant and radicals trap. Copyright © 2006 John Wiley & Sons, Ltd.     

Phase Transfer Catalysis without Solvent. Use of Alkyl Iodides

The Phase Transfer Catalysis (PTC) without solvent method allows the use of quaternary ammonium salts (QAS) when alkyl iodides are used.     

A new sulfate-selective electrode and its use in analysis

The improvement of the steric accessibility of exchange centers of higher quaternary ammonium salts (QAS) by replacing several long-chain alkyl substituents at the nitrogen atom with methyl groups enhanced the selectivity of ion-selective electrodes (ISEs) based on the specified ion exchangers for the SO ₄ ^2? ion up to six orders of magnitude in the presence of singly charged anions. This can be qualitatively explained by the specific features of ion pair formation between quaternary ammonium cations and singly and doubly charged anions. The effect of the steric accessibility of the QAS exchange center on the selectivity of ISEs is partially retained in the presence of a neutral anion carrier, hexyl p-trifluoroacetylbenzoate (HTFAB), which is used for enhancing the selectivity for the sulfate ion in the presence of singly charged anions. A sulfate-selective electrode with a reasonable selectivity for practical purposes was proposed. It is based on the HTFAB-higher QAS ion pair bearing three methyl substituents at the nitrogen atom. The ISE was used in the analysis of natural water.