Preparation ofbis-quaternary ammonium salts from epichlorohydrin

A novelbis-quaternary ammonium salt was prepared conveniently and almost quantitatively fromN,N-dimethyldodecylamine, its hydrochloride, and epichlorohydrin. Reaction ofN,N-dimethyldodecylamine with epichlorohydrin (in the presence of the amine hydrochloride) or various dichloro compounds was investigated by using¹H nuclear magnetic resonance. The reaction route was studied by examining the reactivity of reagents with the amine and the effect of reaction temperature. The ease of the reaction with epichlorohydrin was found to be due to the assistance of amine hydrochloride in opening the epoxide ring and to neighboring-group participation by the hydroxyl group of the intermediatemono-ammonium salt in the quaternization step. Neighboring-group participation by the hydroxyl group in these quaternization reactions is also discussed.     

Preparation, surface-active and antielectrostatic properties of multiple quaternary ammonium salts

A series of new cationic surfactants, bis-quaternary ammonium salts and tris-ammonium salts, were prepared from N,N-dimethyldodecylamine and a product of the reaction of epichlorohydrin with ethyl-, propyl-, butyl-, pentyl-, hexyl-, and octylamine (in the xase of bis-ammonium salts) or the hydrochloride of diethyl-, dipropyl-, dibutyl-, or dihexylamine (in the case of tris-ammonium salts). The obtained multiple salts were examined with respect to their surface-active properties: Critical micelle concentrations (CMC), effectiveness of surface tension reductions (γ_CMC), and adsorption efficiencies (pC₂₀) were measured. All these surfactants showed good water solubility and low CMC of more than one order of magnitude lower than those of corresponding monoalkylammonium salts. They also showed good foaming properties, but worse wetting capability. The obtained multiple salts showed excellent antielectrostatic properties.     

Preparation of Novel Cationic Surfactants from Epichlorohydrin: their Surface Properties and Biological Activities

A novel series of mono-quaternary ammonium salts was prepared by the reaction of fatty esters of methyldiethanolamine with epichlorohydrin in the presence of amine hydrochloride. The ease of the reaction with epichlorohydrin was found to be due to the assistance of amine hydrochloride in opening the epoxide ring and to neighboring-group participation by the hydroxyl group of the mono-ammonium salt in the quaternization step. The surface properties of the prepared compounds and their biological activities were measured. The prepared compounds had good water solubility and showed characteristic surface active properties.     

Preparation,Surface-Active Properties and Antimicrobial Activities of Bis(Ester Quaternary Ammonium) Salts

New cationic surfactants, bis-quaternary ammonium salts, were prepared from N,N-dimethylaminoalkyl esters of saturated fatty acids and products of the reactions of epichlorohydrin with primary amines: pentyl-, hexyl- and octylamine. The bis (ester–ammonium) salts obtained were examined in respect to their surface-active properties: critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), and adsorption efficiency (pC₂₀). All these surfactants showed good water solubility and low critical micelle concentrations of more than two orders of magnitude lower than these of corresponding mono-alkylammonium salts. They also showed good wetting capability, but worse foaming properties. All the surfactants tested were nontoxic to gram-negative bacteria, but some of them inhibited the growth of gram-positive bacteria and yeast.

Synthesis, characterization and biocidal properties of epoxy resins containing quaternary ammonium salts

Summary Quaternary ammonium salts (QAS) were covalently-bound to epoxy resins of different DP in two steps: addition of a N,N-dialkylaminoethanethiol followed by the quaternization of the tertiary amine by an alkylbromide (C₈H₁₇Br to C₁₄H₂₉Br). The products were characterized by ¹H NMR spectroscopy. The QAS-containing oligomers were used as polyols to prepare polyurethane (PU) films by reaction with a triisocyanate. The films show a good bactericidal activity against Escherichia coli, which is preserved after 6 months of immersion in water. Received: 30 December 1999/Revised version: 23 March 2000/Accepted: 23 March 2000     

Synthesis and Properties of Three N-Alkyl Bis-Quaternary Ammonium Salt Surfactants

Three N-alkyl bis-quaternary ammonium salt surfactants were synthesized by using epichlorohydrin, trimethylamine hydrochloride, and N,N-dimethylalkyl amine as raw materials in a two-step manner. The products were characterized by ¹H NMR and MS, confirming the successful synthesis of 2-Hydroxy-N¹,N¹,N³,N³-tetramethyl-N³-dodecylpropane-1,3-diammonium chloride (HPDDC), 2-Hydroxy-N¹,N¹,N³,N³-tetramethyl-N³-tetradecylpropane-1,3-diammonium chloride (HPTDC), and 2-Hydroxy-N¹, N¹, N³, N³-tetramethyl-N³-hexadecylpropane-1,3-diammonium chloride (HPHDC). Moreover, the influence of carbon chain length on surface-active properties, foaming properties, and paraffin liquid emulsion stability was investigated. Results indicated that critical micelle concentrations (cmc) decreased with increasing carbon chain length from 12 to 16, and the cmc and γ_cmc were lower than those of Dodecyl trimethyl ammonium chloride (DTAC). The products exhibited better foam properties and worse emulsifying performance than those of DTAC. The Krafft points of all products were determined to be below 0 °C. Moreover, the products also demonstrated outstanding antibacterial properties.     

Preparation,surface-active properties,and antimicrobial activities of bis-quaternary ammonium salts from amines and epichlorohydrin

A series of new cationic surfactants, bis-quaternary ammonium salts, were prepared from tert-alkylamine and a product of the reaction of epichlorohydrin with decyl- and dodecylamine, and their surface-active properties were measured. Specifically, the critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), surface excess concentration (Γ), area per molecule at the interface (A), and standard free energies of adsorption (ΔG _ads ^o) and of micellization (ΔG _mic ^o) were determined. All these surfactants showed good water solubility and low CMC, more than one order of magnitude lower than those of corresponding mono-alkylammonium salts. They also showed good foaming properties but worse wetting capabilities. Many of these compounds had antimicrobial activities against gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis) and yeast (Candida albicans), but they were not active against molds.     

Influence of Nature of Spacer and Hydrocarbon Chain Length on Micellar Encapsulation of Polynuclear Aromatic Hydrocarbons by Carbohydrate Derived Non-Ionic Gemini Surfactants in Aqueous Ethanol Medium

Gemini surfactants with rigid aromatic spacer -CH₂-Ar-CH₂-: 6,6′-(N,N′-di(alkyl)-1,4-phenylenedimethylamino)bis(6-deoxy-1,2-O-isopropylidene-α-D-glucofuranose) and Gemini surfactants with flexible aliphatic spacer -(CH₂)₆-: 6,6′-(N,N′-di(2-hydroxyalkyl)-1,6-hexanediamino)bis(6-deoxy-1,2-O-isopropylidene-α-D-glucofuranose) have been synthesized, and their micellar properties for encapsulation of polynuclear aromatic hydrocarbons (PAH) viz. fluorene, anthracene, triptycene, and pyrene in aqueous ethanol medium have been studied by means of electronic spectroscopy. The micellar study reveals that nature of spacer and length of hydrocarbon chain of the surfactant has profound effect on micellar encapsulation of PAH. The surfactants with rigid aromatic spacer show greater encapsulation as compared to surfactants with flexible aliphatic spacer. Moreover, the more hydrophobic surfactant, i.e. the surfactant with a longer hydrocarbon chain, shows greater encapsulation toward PAH which are encapsulated in the order of their smaller size.     

A method of obtention of N substituted quaternary ammonium salts supported by a polymeric chain

Summary Starting from tertiary amine polymers the reaction can be written in two steps 1) quaternization of the amine group by acid halide 2) addition of an electrophylic ethylenic reagent on the quaternary ammonium salt : X^– is Cl^– or is the tertiary amine supported by the polymers. Tertiary amine group tested are : pyridine, pyrazine, quinoleine, quinoxaline and N dimethyl phenyl. Z is an attracting group as :     

Controlled radical polymerization of poly(methyl methacrylate‐g‐epichlorohydrin) using N,N‐dithiocarbamate‐mediated iniferters

Poly(epichlorohydrin) (PECH) with pendent N,N‐diethyl dithiocarbamate groups (PECH‐DDC) was prepared by reaction of PECH with sodium N,N‐diethyl dithiocarbamate (DDC) in anhydrous ethanol, before being used as a macrophotoinitiator for the graft polymerization of methyl methacrylate. Photopolymerization was carried out in a photochemical reactor at a wavelength greater than 300 nm. Controlled radical polymerization was confirmed by the linear increase of the molecular weight of polymers with conversion. The polydispersity remained at 1.4–1.6 during polymerization. The formation of PMMA‐g‐PECH copolymer was characterized by GPC, ¹H‐NMR, FTIR spectroscopy, and DSC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

甲基碳酸酯季铵盐的合成与表征

研究了碳酸二甲酯与长链烷基叔胺的季铵化反应。考察了反应温度、反应时间、物料摩尔比和溶剂用量等反应条件对十二烷基二甲基叔胺季铵化反应的影响,确定了优化条件:反应温度130℃、反应时间5h、n(碳酸二甲酯)/n(烷基叔胺)=5、甲醇质量分数(相对于反应原料的质量)10%。在该条件下,不同碳链长度的单烷基叔胺的季铵化率均达到98%以上,而双碳十和双碳十八叔胺的转化率较低,分别为88.09%和68.77%。说明空间位阻是影响季铵化反应进程的重要因素,与分子空间结构模拟的结果一致。通过增加反应时间,双碳十叔胺反应7h季铵化率为98.85%,双十八烷基甲基叔胺反应12h季铵化率为95.68%。采用1HNMR与IR对合成季铵盐的结构进行了表征,结果表明,成功合成了甲基碳酸酯季铵盐。     

Change in the aggregational character of the cationic surfactant cetyl trimethyl ammonium bromide in the presence of <Emphasis Type="Italic">o</Emphasis>- and <Emphasis Type="Italic">p</Emphasis>-itrophenolates

The effect of the addition of sodium salts of p-nitrophenol and o-nitrophenol on the structural transition of aqueous micellar solutions of the cationic surfactant cetyl trimethyl ammonium bromide (CTAB) was studied by viscosity, ¹H nuclear magnetic resonance, and dynamic light scattering measurements. The rapid increase in the relative viscosity of CTAB solutions on the addition of sodium salts of o-nitrophenol and p-nitrophenol was due to the transition in micellar shape from spheres to rods. Dynamic light scattering studies indicated a decrease in the diffusion coefficient of the micelles with the addition of p-nitrophenol. The adsorption and orientation of the salts on the micellar surface and subsequent growth of the micelles was studied by nuclear magnetic resonance.     

2-环氧基丙基三烷基季铵盐的合成

以高级叔胺和环氧氯丙烷为原料合成了几种阳离子季铵盐，该类季铵盐可以作为一些反应的催化剂，也可以作为一些化合物的中间体。对该类季铵盐的合成条件做了优化，得到反应的最佳条件，并应用红外光谱和元素分析对合成的化合物结构作了表证。     

Separation and Determination of Some Amines by Ion-Exchange Chromatography

Abstract

Papers impregnated with stannic molybdate have been used to chromatograph various amine hydrochlorides in varying concentrations of aqueous sodium nitrate and hydrochloric acid solutions. Various important separations are listed. The theoretical behavior of the movement of amine hydrochlorides on these papers is discussed with the help of plots of pH vs R_M .     

含咪唑啉环不对称双季铵盐的合成及其缓蚀性能

以长链烷基叔胺、长链烷基叔胺盐酸盐、环氧氯丙烷为原料合成了N-(3-氯-2-羟丙基)-N,N-二甲基长链烷基季铵盐,利用其与长链烷基咪唑啉季铵化合成了含咪唑啉环的不对称双季铵盐。通过FTIR,1HNMR验证了中间体和目标产物结构,考察了其合成工艺。合成含咪唑啉环不对称双季铵盐的最佳反应条件为:n[N-(3-氯-2-羟丙基)-N,N-二甲基长链烷基季铵盐]∶n(长链烷基咪唑啉)=1∶1.1,反应溶剂采用异丙醇,反应温度80℃。用失重法测定了25℃时含咪唑啉环不对称双季铵盐在1.0mol/L盐酸溶液中的缓蚀性能,结果表明,仅添加50mg/L,对Q235钢缓蚀率达98.89%。     

Crosslinked anion exchange membrane with improved membrane stability and conductivity for alkaline fuel cells

As a core component of anion exchange membrane (AEM) fuel cells, it has practical significance to improve the performance of AEMs. However, it is difficult to obtain AEM with both good stability and high conductivity. In this study, a series of AEMs were prepared by chloromethylation, quaternization, and crosslinking reactions. The quaternization reaction was carried out first to ensure that there are abundant quaternary ammonium groups on AEM and enhance the conductivity of membrane. N,N,N′,N′-tetramethylethylenediamine was used as a crosslinker to improve membrane stability and mechanical property. A simple, mild, and cost-effective AEM synthetic route was developed. This strategy achieves a certain balance of electrochemical and physical properties. The effect of the crosslinking reactions on the property of membrane was evaluated. Crosslinked membranes have better dimensional stability (water uptake: 20.2% and swelling ratio: 2.1%), mechanical properties (55.84 MPa), and alkaline stability because crosslinked structures result in large steric hindrance. The mutually independent quaternization and crosslinking reaction do not affect the electrochemical performance of membranes; in the crosslinking reaction stage, crosslinker also reacted as quaternization agent and increased the number of reactive groups in AEM. Thus, the resulting crosslinked AEM exhibits higher ion exchange capacity and ionic conductivities (46.4 mS cm⁻¹). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48169.     

山嵛酸双酯基有机硅季铵盐的微波合成工艺及性能

以山嵛酸、N-甲基二乙醇胺以及γ-氯丙基三甲氧基硅烷为主要原料,分别经过酯化和季铵化反应两步合成了一种超长碳链的双酯基有机硅季铵盐,并通过单因素、正交试验得到了微波法合成目标产物的最优工艺条件为：设置微波功率为800W,物料摩尔比为n（硅烷）∶n（酯胺）=1.2∶1,反应温度为170℃,溶剂用量为m（溶剂）∶m（原料）=0.8∶1,反应时间为12h,产品产率达96.60%。此方法克服了长链叔胺季铵化过程中普遍耗时过长的困难,提高了反应速率,而且实验重复性良好。实验中采用红外光谱、核磁共振氢谱对中间体及目标产物的结构进行了表征,与预期结果一致;建立了高效液相色谱-蒸发光散射检测器（HPLC-ELSD）测定季铵盐纯度的方法,基线稳定,峰型良好,产品纯度达98.77%,具有一定的参考价值。性能测试结果表明：对比DC-5700,目标产物具有良好的热稳定性,优异的乳化及增溶性能;其水溶液的临界胶束浓度为1.81mmol/L,表面张力（γ_CMC）为49.4mN/m。     

Preparation of iodine containing quaternary amine methacrylate copolymers and their contact killing antimicrobial properties

A novel quaternary amine methacrylate monomer (QAMA) was synthesized by amination of dimethacrylate with piperazine followed by its quaternization using an alkyl iodide. Copolymerization of QAMA with 2‐hydroxyethyl methacrylate was carried out by free radical bulk polymerization technique at room temperature using ammonium persulfate and N,N,N′,N′‐tetramethyl ethylenediamine as a redox initiator. The monomer as well as copolymers was characterized by FTIR and ¹H NMR spectral studies. Thermal and physical characteristics of copolymers of varying compositions of QAMA were evaluated by thermogravimetric analysis, differential calorimetry, contact angle and scanning electron microscopy. The antibacterial activity of the synthesized quaternary amine dimethacrylate copolymers against Escherichia coli and Staphylococcus aureus was studied by zone of inhibition and colony count method. QAMA copolymers showed broad‐spectrum contact killing antibacterial properties without releasing any active agent as checked by iodide‐selective ion meter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1038–1044, 2006     

Poly(sulfobetaine)s and corresponding cationic polymers. VIII. Synthesis and aqueous solution properties of a cationic poly(methyl iodide quaternized styrene–n,n‐dimethylaminopropyl maleamidic acid) copolymer

A cationic poly(methyl iodide quaternized styrene–N,N‐dimethylaminopropylmaleamidic acid) copolymer was synthesized through amidoacidification reaction of styrene‐maleic anhydride copolymer with N,N‐dimethylaminopropylamine (ring‐opening reaction). Its properties in various aqueous salt solutions and pH solutions were studied by measurements of reduced viscosity and intrinsic viscosity. The results indicated that the reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the type and concentration of the added salts and the results also showed a contrary tendency in some salts with monovalent acid groups to polyelectrolyte. At the same time, some salt ions were observed to strongly attract the quaternary ammonium group of the cationic polymeric side chain and resulted in agglomeration of the polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1619–1626, 2001     

Synthesis and Application of Perfluoroalkyl Quaternary Ammonium Salts in Protein-Based Fire-Fighting Foam Concentrates

Nine perfluoroalkyl quaternary ammonium salts containing a perfluorinated tail were synthesized in order to evaluate their properties as additives in protein-based fire-fighting foam concentrates. They were obtained in high yield starting from (perfluoro-n-octyl)methyl oxirane via a two-step reaction scheme. Their structures were identified by Fourier-transform infrared spectroscopy and elemental analysis. Surface tension, interfacial tension, critical micellar concentration, and spreading coefficient of aqueous solutions of the synthesized compounds were first determined. Synthetic perfluoroalkyl quaternary ammonium salts were then added at reduced concentration (0.5 wt.%) to a commercial protein-based fire-fighting foam concentrate and their effects on foam spreading properties were further investigated via five specific laboratory tests: sealing time test, burn back time test, foam expansion test, drain time test, and foam flowing test. Results showed that the perfluoroalkyl quaternary ammonium salts strongly influence surface and extinguishing properties of protein-based fire-fighting foam concentrates, producing stable foams able to spread spontaneously over hydrocarbons and forming aqueous films with enhanced organic-vapor sealing properties.