高分子季铵盐型抗菌材料的制备

通过γ-氯丙基三甲氧基硅烷的偶联,将水溶性聚乙烯亚胺(PEI)接枝在纳米SiO2表面,随后分别用1-溴己烷和碘甲烷对接枝的PEI进行N-烷基化修饰,使PEI中的部分氨基转变成季铵盐,得到水不溶性QPEI/SiO2微粒。通过测定PEI/SiO2上PEI的接枝量,考察了各种反应条件对QPEI/SiO2微粒制备的影响规律。研究结果表明,纳米SiO2表面接枝PEI的适宜条件为:反应溶剂为DMF,反应温度90~100℃,反应时间8 h,氯丙基化SiO2与PEI质量比为4∶1,在此条件下制备的QPEI/SiO2微粒中PEI接枝量为14.8%。QPEI/SiO2微粒经甲基化修饰后,季铵盐含量由0.96%增加到3.37%,其抗菌性能显著增强。     

Surfactant studies of quaternary ammonium compounds: Critical surfactant concentration

Quaternary ammonium salts (otherwise known as “quats”) commonly form the foundation of formulations in the antimicrobial industry. Although many studies have been conducted on the surfactant and biological aspects of single-component systems, there are few studies concerning the surfactant or biological efficacy of these compounds in multiple-component formulations. Preliminary data using simple emulsion studies with decane were determined to be inadequate. Several inexpensive ways to determine critical surfactant concentrations were developed with limited resources.     

两种抗菌型水性聚氨酯——季铵盐型与三丹油型的比较

对两种不同类型的抗菌型聚氨酯(PU)——季铵盐型PU和三丹油(TNO)型PU进行了研究(包括其抗菌机理、合成方法、结构以及抗菌效果等),通过抑菌圈法定性分析了两者的抗菌效果。实验结果表明,随着TNO和季铵盐用量的增加,两种抗菌型PU的抗菌效果均显著增加;季铵盐型PU的抗菌效果优于TNO型PU。     

Development and evaluation of self-polishing urethane coatings with tethered quaternary ammonium biocides

The synthesis and characterization of hydrolysable, antimicrobial cross-linked polyurethanes are described. Cross-linking of isocyanate-terminated urethane oligomers with glycol-modified silanes was used as a novel method for imparting enhanced mechanical integrity and hydrolytic potential to polyurethane coating systems. By combining these cross-linkers with a variety of biocidal quaternary ammonium salts and polyisocyanates, a library of hydrolysable polyurethanes were developed with controllable mechanical, thermal, hydrolytic, and antimicrobial properties. Up to a 3-log reduction of viable microbes was observed and correlated with the surface content of side chain quaternary ammonium salt moieties. Diminished antibacterial characteristics of completely amorphous systems are attributed to the segregation of low surface energy constituents at the material:air interface and relegation of biocidal species to within the bulk material.     

Oxidative desulfurization of diesel fuel using amphiphilic quaternary ammonium phosphomolybdate catalysts

Phosphomolybdic acid (HPMo) modified respectively with tetramethyl ammonium chloride (TMAC), dodecyl trimethyl ammonium chloride (DTAC) and hexadecyl trimethyl ammonium chloride (HTAC) as the catalysts were prepared and characterized by FT-IR, XRD and SEM. The catalysts were evaluated for the oxidative desulfurization of benzothiophene (BT), dibenzothiophene (DBT) and straight-run diesel using hydrogen peroxide as an oxidant. Results show that all of the catalysts keep the Keggin structures and are finely dispersed with mixing of quaternary ammonium salts. Hexadecyl chains are more favorable to wrap up DBT to the catalytic center and form stable emulsion system with higher conversion rates of DBT. The shorter dodecyl chains can wrap up BT more suitably and bring smaller steric hindrance, which display higher conversion rates of BT. The oxidative reactions fit apparent first-order kinetics, and the apparent activation energies of DBT are much lower than those of BT. The desulfurization rate of straight-run diesel can be up to 84.4% with the recovery rate of 98.1% catalyzed by [HPMo][HTAC]₂ in 2 h. When increasing the extraction times, the desulfurization rates increase, but the recovery rates of diesel decrease significantly.     

壳聚糖季铵盐的制备及性能测试

以壳聚糖(CTS)作为季铵盐化改性原料,以环氧丙基三甲基氯化铵(GTA)作为改性剂,在CTS的C-2位氨基上定位接上季铵盐基团得到壳聚糖季铵盐(CTS-QTS)。采用FTIR、13C NMR、H1NMR、热分析(TG)表征产物CTS-QTS的结构,采用莫尔滴定法研究CTS-QTS的DS,采用凝胶渗透色谱法测定CTS和CTS-QTS的分子量,采用琼脂平板法测定CTS和CTS-QTS对金黄色葡萄球菌(S.aureus)和大肠杆菌(E.coli)的最小抑菌浓度和杀菌率,通过测试CTS-QTS对雄性小鼠和雌性小鼠急性经口毒性试验来验证CTS-QTS是否毒性类材料。研究结果表明:在p H值为7的条件下,CTS和GTA可发生温和的取代反应生成CTS-QTS,其最优反应条件为反应时间8 h、反应温度80℃、CTS与GTA的摩尔比为3。CTS改性生成CTS-QTS后分子链发生了降解,分子量下降。CTS-QTS在低于200℃时分子链几乎不发生降解,具有优良的高温稳定性。CTS-QTS对S.aureus和E.coli均有抑菌和杀菌作用,对S.aureus的抑菌和杀菌作用强于对E.coli。由CTS-QTS和CTS对S.aureus和E.coli的最低抑菌浓度可知,CTSQTS对S.aureus和E.coli的抑菌活性大于CTS。CTS-QTS对雄性小鼠和雌性小鼠急性经口毒性试验结果显示,CTS-QTS属于无毒性类材料。     

有机硅季铵盐抗菌剂的研究进展

综述了有机硅季铵盐抗菌剂的抗菌机理、合成方法及应用性能,并对其今后的发展作了展望。有机硅季铵盐主要通过季铵化、硅氢化加成和平衡或缩聚等反应制得。由于该产品具有抗菌、抗静电、柔软及滑爽等特点,因此可厂泛用作织物抗菌整理剂、柔软整理剂、防腐剂及头发调理剂等。由于其与被处理材料的表面以化学键结合,因而不易脱落,是一种安全高效的新型阳离子表面活性剂,具有广阔的应用前景。     

有机硅季铵盐的制备及其抗菌性能研究

利用三甲氧基硅烷(WD-930)与二甲基十八烷基烯丙基氯化铵(DAOAAC)进行反应,合成了阳离子抗菌剂[N,N-二甲基-N-十八烷基氨丙基三甲氧基硅烷氯化铵(DOATAC)]。以溴酚蓝为指示剂、二氯乙烷为分相溶剂,采用两相化学滴定法测定DOATAC的含量;用红外光谱(FT-IR)、元素分析和熔点测定仪等对DOATAC产物进行了理化分析;利用薄层色谱法,对所制备的阳离子抗菌剂的合成路线及其纯化过程进行跟踪;最后对产物的抗菌性能和耐洗性能进行测定。研究结果表明,当抗菌整理液中w(DOATAC)=0.06%时,经该整理液整理的棉布,对金黄色葡萄球菌和大肠杆菌的抑菌率均超过90%,并具有优良的抗菌耐洗性,洗涤50次后其抑菌率仍超过70%。     

羧甲基壳聚糖季铵盐的制备及其抑菌性能研究

以不同分子量的壳聚糖为原料合成了一种新型水溶性O-羧甲基-N-三甲基壳聚糖季铵盐(CMTMC),用FTIR表征了其结构,同时进行了抑菌实验.结果表明在水介质中CMTMC对大肠杆菌、金黄色葡萄球菌和枯草芽孢杆菌的最低抑菌浓度分别为1 μg·mL-1、1 μg·mL-1和2 μg·mL-1,在0.5%醋酸溶液介质中的抑菌效果比在水介质中更好.     

Effect of small cation addition on the conductivity of quaternary ammonium ionic liquids

Several quaternary ammonium or lithium bis(trifluoromethane sulfone) imide (TFSI) salts were dissolved into N,N,N,N-hexyltrimethyl ammonium TFSI ionic liquid, and the conductivities of the resulting solutions were measured. Some asymmetric quaternary ammonium salts contributed to increase the conductivity of the solution, while cyano-containing quaternary ammonium and lithium salts decreased the conductivity. Based on the results of differential scanning calorimetry (DSC) measurements, such conductivity behaviors appeared to be related to the intrinsic miscibility of the ionic liquid solutions.     

Catalytic performance of quaternary ammonium salts in the reaction of butyl glycidyl ether and carbon dioxide

The synthesis of cyclic carbonate from butyl glycidyl ether (BGE) and carbon dioxide was performed in the presence of quaternary ammonium salt catalysts. Quaternary ammonium salts of different alkyl group (C₃, C₄, C₆ and C₈) and anions (Cl⁻, Br⁻ and I⁻) were used for this reaction carried out in a batch autoclave reactor at 60–120 °C. The catalytic activity increased with increasing alkyl chain length in the order of C₃ < C₄ < C₆. But, the quaternary ammonium salt with longer alkyl chain length (C₈) decreased the conversion of BGE because it is too bulky to form an intermediate with BGE. For the counter anion of the tetrabutyl ammonium salt catalysts, the BGE conversion decreased in the order Cl⁻ > Br⁻ > I⁻. The effects of carbon dioxide pressure and reaction temperature on this reaction were also studied to better understand the reaction mechanism.     

Improvement of the deflocculating power of polyacrylates in ceramic slips by small additions of quaternary ammonium salts

In this work, we examine the effect of small additions of cationic quaternary ammonium salts (QAS) of different molecular weight on the rheology of an industrial ceramic suspension deflocculated with sodium polyacrylate and sodium metasilicate. The observed shear thinning behaviors obey the typical power law of fluid rheology. In order to characterize the rheological behavior of these slurries, three new parameters are introduced: a low shear rate consistency index and two transient viscosities, distant from the equilibrium, after increasing and decreasing the shear rates. These parameters vary with polyacrylate molecular weight and on additions of small quantities of QAS, which we found to be useful for decreasing the slurry viscosity.     

Polymer electrolytes from PEO and novel quaternary ammonium iodides for dye-sensitized solar cells

Polymer electrolytes were prepared by blending high molecular weight poly(ethylene oxide) (PEO) and a series of novel quaternary ammonium iodides, the polysiloxanes with oligo(oxyethylene) side chains and quaternary ammonium groups. X-ray diffraction (XRD) measurements ensured relatively low crystallinity when the quaternary ammonium iodides were incorporated into the PEO host. The ionic conductivity of these complexes was improved with the addition of plasticizers. The improvement in the ionic conductivity was determined by the polarity, viscosity and amounts of plasticizers. A plasticized electrolyte containing the novel quaternary ammonium iodide was successfully used in fabricating a quasi-solid-state dye-sensitized solar cell for the first time. The fill factor and energy conversion efficiency of the cell were calculated to be 0.68 and 1.39%, respectively.     

Comparative studies on the performance of immobilized quaternary ammonium salt catalysts for the addition of carbon dioxide to glycidyl methacrylate

The addition of carbon dioxide to glycidyl methacrylate (GMA) was investigated in a semi-batch reactor using immobilized quaternary ammonium chloride catalysts. Five different catalysts were prepared with the following supports: (1) soluble poly(ST-co-VBC)[C1], (2) insoluble poly(ST-DVB-VBC)[C2], (3) macroporous poly(ST-DVB-VBC)[C3], (4) poly(ST-co-VBC)-MMT[C4], (5) modified MCM-41[C5]. The addition of carbon dioxide to GMA can be considered as pseudo first-order with the concentration of GMA. The soluble poly(ST-co-VBC)-supported catalyst containing benzyltributylammonium chloride group showed the highest reaction rate. The order of the pseudo first-order rate constant for the catalysts was C1 > C3 > C2 > C4 > C5. The activation energy for the C1–C5 catalysts was 11.5, 28.1, 20.8, 36.6 and 39.3 kJ/mol, respectively. The immobilized catalysts can be reused for at least four successive runs without any considerable loss of their initial reactivities.     

聚苯胺季铵盐的合成及其性能研究

以邻氨基苯甲酸为原料,与氯乙醇反应生成2-氨基苯甲酸氯乙酯,然后用三乙胺季铵化合成了苯胺季铵盐,并将其聚合,通过红外光谱、紫外-可见光谱、X-射线衍射、循环伏安法和热重分析等对其结构与性能进行了研究。     

Quaternary ammonium elastomeric ionomers by melt-state conversion

Quaternizations of benzyl bromide units in brominated poly(isobutylene-co-p-methylstyrene), or BIMS, elastomers with tertiary amines can be readily accomplished either by solution techniques or by melt reactive mixing. At temperatures of 130 °C and above, the nucleophilic substitution of benzyl bromide with ammonium bromide occurs instantaneously in an internal mixer. The conversion is around 95% for both dimethyl alkyl and dialkyl methyl amines. Suppressions in loss tangent measured in dimethyl alkyl amine melt quaternized BIMS indicate that molecular weight amplifications as a result of ionic association in these ionomers are in line with that obtained from solution quaternized BIMS. These melt quaternized BIMS ionomers become gels when their molecular weight amplification factors are greater than 1.5. Viscosity of BIMS can be raised significantly through quaternization to facilitate its mixing with thermoplastics. BIMS ionomers can also be added into bromobutyl innerliner compounds to enhance their green strengths. The efficiency in promoting ionic associations during melt mixing of BIMS with only 0.1 mol equiv. of dimethyl alkyl amines allows residual benzyl bromide units for subsequent curing.     

乙氧基化三酯基季铵盐的性能研究

考察了不同平均EO数的乙氧基化二酯基季铵盐的柔软性、再润湿性、去污力和对织物白度的影响等性能,并分别与单、双、三和混合酯基季铵盐进行了对比。结果表明,3EQDMS-6EO是一种性能良好的新型柔软剂,其柔软性与MEQDMS相近,再润湿性优于MEQDMS、EQDMS和2EQDMS,多次处理后对织物白度影响不大,具有酯基季铵盐所不具备的去污力。     

Tuning of activity, induction period and polymer properties of double metal cyanide catalyzed ring-opening polymerizations of propylene oxide by using quaternary ammonium salts

Polymerizations of propylene oxide (PO) have been carried out by using double metal cyanide (DMC) catalyst prepared by reacting ZnCl₂ and K₃[Co(CN)₆] in the presence of tert-butyl alcohol (^tBuOH) as a complexing agent. The catalytic activity and the induction period for PO polymerizations catalyzed by DMC are tunable by using various quaternary ammonium salts (QAS) as external additives. The DMC/QAS binary catalyst improves polymer properties as well such as molecular weight, molecular weight distribution, viscosity, and unsaturation level.     

壳聚糖季铵盐研究进展

壳聚糖是应用广泛的天然多糖,资源丰富,壳聚糖化学改性后得到的衍生物改善了壳聚糖的功能,并保留了壳聚糖本身的可生物降解性、生物相容性等优点.其中壳聚糖的季铵盐改性明显提高了其抑菌、抗氧化等活性,并增强了壳聚糖的水溶性,近年来研究较多,介绍了壳聚糖季铵盐的化学改性及应用研究进展,这些化学改性方式均在一定程度上提高了壳聚糖的...     

Synthesis of a quaternary ammonium derivative of chito‐oligosaccharide as antimicrobial agent for cellulosic fibers

A derivative of chito‐oligosaccharide (COS), N‐(2‐hydroxyl)propyl‐3‐trimethyl ammonium chito‐oligosaccharide chloride (HTACC), was synthesized using a reaction of glycidyltrimethylammonium chloride (GTMAC) and COS prepared by depolymerization of a fully deacetylated chitosan. COS and HTACC were applied to the cotton fabrics with a pad‐dry‐cure process using the reaction between the hydroxyl group of cellulose and terminal aldehyde group in COS and HTACC. Their minimum inhibition concentration (MIC) was evaluated, and the antimicrobial activity and durability to laundering of cotton fabrics treated with them were compared. The complete substitution of NH₂ groups in COS with GTMAC was obtained at a 4 : 1 mol ratio of GTMAC to NH₂ in 18 h at 80°C under the presence of acetic acid. MIC values of the 1.04 DS of HTACC and COS were 50 and 400 μg/mL, respectively. A cotton fabric treated with 0.2% of HTACC and 1.8% of COS exhibited 100% reduction of bacteria. At the 50th laundering cycle, 0.3% of HTACC and 2.4% of COS indicated 100% bacterial reduction. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2009–2015, 2000