季膦化聚砜和季胺化聚砜共混阴离子交换膜的制备与表征

以聚砜为基材制备阴离子导电膜材料。将季膦化聚砜筑膜液与已证实成膜性能良好的季铵化聚砜共混,制备阴离子交换共混膜QAPSFOH/QPPSFOH,以改善季膦化聚砜成膜困难问题。通过改变两种成分比例,可以得到不同性能的阴离子交换膜。在QAPSF:QPPSF摩尔比为1:2时,共混膜电导率达0.0309 S/cm,拉伸强度达775 MPa,热分解温度达160℃,满足理论对阴离子交换膜的需要。     

Physical and electrochemical properties of room-temperature dicyanamide ionic liquids based on quaternary phosphonium cations

The physicochemical and electrochemical properties of room temperature ionic liquids based on quaternary phosphonium cations together with a dicyanamide anion are presented in this report. The most dicyanamide-based phosphonium ionic liquids prepared were hydrophilic, except ionic liquids containing a long alkyl chain in the phosohonium cation. It was found that asymmetric phosphonium cations gave low-melting salts in combination with a dicyanamide anion. The dicyanamide-based phosphonium ionic liquids exhibited relatively low viscosities and high conductivities when compared to those of the corresponding ammonium ionic liquids. Particularly, the ionic liquids containing a methoxy group in the phosphonium cations indicated very low viscosities. Comparatively good electrochemical stability of the dicyanamide-based phosphonium ionic liquids was confirmed by voltammetric measurements. The thermogravimetric analysis suggested that the dicyanamide-based phosphonium ionic liquids showed higher thermal stability than those of the corresponding ammonium ionic liquids, indicating an improving effect of the phosphonium cations on the thermal stability.     

季铵化改性氨基聚硅氧烷的合成及应用性能

采用氯乙酸乙酯对N,N-二甲基-γ-氨丙基-γ-氨丙基聚二甲基硅氧烷(ASO-121)进行季铵化改性,合成了一种季铵化改性氨基聚硅氧烷(QASO-121)。利用红外光谱(IR)、核磁共振氢谱(1HNMR)、扫描电镜(SEM)、纳米粒度仪等仪器对QASO-121及其乳液进行了表征和纤维表面的成膜性分析,并讨论了氨值、黏度及硅乳用量对所整理织物应用性能的影响。结果表明,QASO-121乳液平均粒径为75.3 nm,电位为+21.2mV,且其在织物纤维表面具有良好的成膜性。经氨值为0.6 mmol/g、黏度为2.600 Pa·s、硅乳用量为4 g/L的QASO-121整理的布样,织物柔软性提高,亲水性增强,白度基本不变。将QASO-121与未季铵化ASO-121进行应用性能对比,发现两者整理织物的柔软性相近,但经QASO-121所整理织物具有良好的亲水性且富有弹性,其抗黄变性能也得到了改善。     

Chirality-antimicrobial relationship of quaternary ammonium cationics

Optically active and racemic quaternary ammonium cationics containing a chiral alkyl group, such as N,N-dimethyl-N-(1-phenylethyl)alkylammonium bromides were prepared and showed excellent antimicrobial properties against Gram positive and negative bacteria, with some exceptions, and against fungi. The influence of optical isomerism on their antimicrobial properties showed that the antimicrobial properties between racemic and optically active cationics were obscure. The order of activity of substituted alkyl groups was tetradecyl > dodecyl ° hexadecyl.     

Modification of montmorillonite with cationic surfactants. Thermal and chemical analysis including CEC determination

The thermal stability of synthesized and commercial organically modified montmorillonites has been investigated using thermogravimetric analysis (TGA). Four organo-montmorillonites have been prepared by replacing the inorganic cations of a commercial montmorillonite with aliphatic and aromatic ammonium bromide or chloride salts. The modification has been carried out by cation exchange to obtain a high level of intercalation in the montmorillonite. Conformations of the intercalated surfactants have been characterized using Fourier transform infrared spectroscopy (FTIR). Besides fixed organic surfactant, some surfactant in excess still remained in the montmorillonite after repeated washing with water or ethanol/water. The use of a suitable eluent for the surfactants in the washing step was the key issue as shown by the changes of the first degradation peak of Cloisite-Na⁺-hexadecyl benzyl dimethylammonium (CLO-BDHA), Cloisite-Na⁺-benzyl triethylammonium (CLO-BTA) and Cloisite-Na⁺-hexadecyl trimethylammonium (CLO-HTA). Hexadecyl trimethylammonium (HTA) was more sensitive to water and ethanol/water as eluents. Sonication and the use of a polar activator during the modification of montmorillonite increased the amount of surfactant adsorbed by cation exchange. Ammonium acetate method has been revealed as an adequate chemical method to measure the cation exchange capacity (CEC) of inorganic and organic montmorillonites. This method has the advantage with respect to TGA that it does not measure the unfixed surfactant.     

HPLC analysis of quaternary ammonium surfactants with the evaporative light scattering detector

A normal-phase high-pressure liquid chromatography technique has been elaborated for the separation of quaternary ammonium surfactants. The separation was achieved on a bonded polyphenol silica gel column with gradient elution and evaporative light-scattering (ELS) detection. The proposed method has been applied to the quantitative determination of low levels of monoalkyltrimethylammonium and trialkylmethylammonium chlorides in dialkyldimethylammonium chloride.     

m-n-m型Gemini季铵盐表面活性剂的合成及性能研究

以N,N-二甲基十四胺和1,8-二溴辛烷反应生成了14-8-14型Gemini季铵盐表面活性剂,通过单因素试验优化了反应条件,确定较佳合成条件为:N,N-二甲基胺的用量为5 mmol,N,N-二甲基胺与二溴烷烃的摩尔比为2.2:1,溶剂乙腈用量为10 mL,反应温度为80℃,反应时间为24 h,在此条件下合成了24种m-n-m型Gemini季铵盐表面活性剂,大部分反应的收率大于80%。采用吊环法对产物的表面张力进行了测定,分别研究了疏水烷基链、连接基对Gemini季铵盐表面活性剂表面活性的影响,研究发现,当连接基n相同时,随着疏水烷基链的增长(m10时),Gemini季铵盐表面活性剂的表面张力呈现先减小后增大的趋势,14-n-14型Gemini季铵盐表面活性剂呈现出最好的表面活性;当疏水烷基链m=14时,随着连接基n的增大,Gemini季铵盐表面活性剂的表面张力呈现先增大后减小的趋势。     

Synthesis of an active quaternary phosphonium salt and its application to the Wittig reaction: Kinetic study

The synthesis of liquid crystal methyl [4-(nonyloxy) styryl] benzoate was achieved in four stages. First, toluic acid [1] was brominated with N-bromosuccinimide in refluxing CCl₄ to form 4-bromotoluic acid [2] (BTA); second, BTA was esterified with methanol in SOCl₂/CH₂Cl₂ to afford methyl (4-bromomethyl) benzoate [3] (BME); third, BME was condensed with triphenylphosphine (PPh₃) in CH₂Cl₂ to produce the active Wittig reagent methyl (4-methylbenzoate) triphenylphosphonium bromide [4] (MBPB) and fourth, MBPB reacted with 4-nonyloxybenzaldehyde to produce MNSB in high yield. Each of these four reactions was carried out in a separate homogeneous organic solution and the effects of the reaction conditions in each reaction as well as a kinetic model for each individual reaction were studied. Furthermore, the active reagent was applied to the reaction of 4-nonyloxybenzaldehyde (n-C₉H₁₉O(C₆H₄)CHO) to synthesise cis-(E) and trans-(Z)methyl[4-(nonyloxy)styryl]benzoate (n-C₉H₁₉(C₆H₄)CHCH(C₆H₄)COOCH₃) from a two-phase medium alkaline solution of NaOH/organic solvent. High conversion and high selectivity were obtained via this reaction.     

葡萄糖酰胺季铵盐表面活性剂的合成与性能

以葡萄糖酸内酯、N, N-二丁基-1, 3-丙二胺和溴代烷为原料，采用先胺酯反应、后季铵化两步法合成了系列葡萄糖酰胺季铵盐表面活性剂（CnDGMAPB，n=8、10、12、14、16)。采用FTIR、1HNMR和13CNMR对中间体和产物结构进行了鉴定，并对其表面活性、润湿性能、乳化性能、泡沫性能和产品毒性等性能进行研究。结果显示，CnDGMAPB具有较好的表面活性，随着碳链的增长，临界胶束浓度（cmc）和分子截面积（Amin）逐渐减小，表面活性效率（pC20）和饱和吸附量（Гmax）逐渐增大，表面张力（γcmc）在28~32 mN/m之间。在考察浓度（0.01-5 mmol/L）范围内，C12DGMAPB和C16DGMAPB溶液与聚四氟乙烯膜（PTFE）的接触角降低到47o，此类糖基酰胺季铵盐具有较好的润湿和乳化性能。5 min时泡沫体积都很小，属于典型的低泡型产品。细胞毒性和急性经口毒性实验均显示，此类葡萄糖酰胺季铵盐表面活性剂为低毒产品。当C12DGMAPB质量浓度在0.2 g/L时，对大肠杆菌和金黄色葡萄球菌的抑菌率都能达到100%，对皮肤无刺激，具有较好的抗静电性能。     

利用荧光素异硫氰酸酯检测季铵盐阳离子表面活性剂的方法

使用荧光素异硫氰酸酯（FITC）实现了对季铵盐阳离子表面活性剂（QAS）在水溶液中临界胶束浓度（CMC）的准确测量及其在CMC以下的浓度定量。用该法测得十二烷基三甲基溴化铵（DTAB）和十六烷基三甲基溴化铵（CTAB）在水中的CMC分别为12～13 mmol·L^-1和0.70～096 mmol·L^-1,与电导率法、表面张力法和芘荧光法的检测值相近。对DTAB和CTAB的检测下限分别是011 mmol·L^-1和1.7 μmol·L^-1,定量范围分别为0.11～9.73 mmol·L^-1（0.034～3.0 g·L^-1）和1.7 μmol·L^-1～0.27 mmol·L^-1（6.2×10^-4～0.1 g·L^-1）。结果表明,使用FITC荧光探针检测QAS具有安全、简便、灵敏度和准确度高的优点。     

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.     

Physical and electrochemical characterization of ionic liquids based on quaternary phosphonium cations containing a carbon–carbon double bond

Physical and electrochemical characterizations of novel two ionic liquids based on quaternary phosphonium cations containing an unsaturated carbon–carbon bond (triethyl(4-pentenyl)phosphonium and allyltributylphosphonium cations) are presented in this report. It was found that both unsaturated phosphonium cations gave low-melting salts in combination with a bis(trifluoromethylsulfonyl)amide anion. The thermogravimetric analysis suggested that the unsaturated phosphonium ionic liquids showed higher thermal stability than those of the corresponding saturated phosphonium ILs. The unsaturated phosphonium ionic liquids also exhibited relatively low viscosity and high conductivities when compared to those of the corresponding saturated phosphonium ionic liquids. These results indicate an improving effect of introducing a carbon–carbon double bond into the phosphonium cations on both the thermal stability and the transport property. The voltammetric measurements suggested that the triethyl(4-pentenyl)phosphonium-based ionic liquid showed a high cathodic stability, enabling the deposition and dissolution of metallic lithium in the phosphonium ionic liquid system.     

酯基Gemini季铵盐阳离子表面活性剂的研究进展

含酯基季铵盐表面活性剂具有良好的表面活性及生物降解性能而广受国内外学者关注。本文回顾了近几年来国内外对可降解的含酯基双子季铵盐（对称型、非对称型及含杂环型）的研究概况,并简要介绍产物作为消毒杀菌剂、金属腐蚀抑制剂、乳化剂、泡沫剂、基因载体等在工业上的应用。最后,指出通过分子设计开发性价比优异的新型表面活性剂、优化合成工艺、提高与传统表面活性剂的配伍性能等是当前的研究热点。     

季铵盐型水性环氧树脂乳化剂的制备及特性研究

以二乙醇胺、环氧E-44树脂等为原料,合成叔胺结构中间体,与溴乙烷反应制得季铵盐型水性环氧树脂乳化剂,以相反转技术乳化环氧树脂E-44.研究了乳化剂合成过程中反应温度、反应时间和环氧基转化率的关系;探讨了乳化剂用量对水性环氧树脂水分散性,稳定性及固化性能的影响.利用红外光谱对产物的结构进行了表征.结果表明:二乙醇胺与环氧E-44树脂在80 ℃反应3 h,环氧基转化率可达98%以上;乳化剂用量为ω=22%时其乳化效果及所制得乳液的稳定性最好.DSC和TG分析结果表明,水性环氧树脂乳液和工业环氧树脂E-44比较,固化后热性能基本一样,分解温度约在350 ℃,但其玻璃化转变温度有所降低,说明其韧性有一定提高.     

恶唑基季鏻盐的合成及杀菌性初步探讨

利用二乙醇胺、苯甲醛、环氧氯丙烷、三苯基膦为原料，经过脱水缩合环化、烷氧基化和季锚化等反应制得一种带有嗯唑环的新型季铹盐杀菌剂。介绍了该新型水处理剂的合成方法及杀菌性能。通过电导率仪和红外光谱仪分析确证了其结构，并由抑菌圈实验评定该季镌盐对大肠杆菌、葡萄球菌的杀菌作用。结果表明其杀菌性能优于单一季镌盐或单-恶唑烷的杀菌性能。     

Comparison of antimicrobial activities of polyacrylonitrile fibers modified with quaternary phosphonium salts having different alkyl chain lengths

A series of polyacrylonitrile fibers (PANF) modified with quaternary phosphonium salts having various alkyl chain lengths (C₁, C₂, C₆, C₈, C₁₂) were synthesized and compared for their antimicrobial activities by the improved shake flask method. The as‐prepared fibers were named MTPB‐PANF, ETPB‐PANF, HTPB‐PANF, OTPB‐PANF, and DTPB‐PANF, respectively. The representative microorganisms employed were Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), Pseudomonas aeruginosa (P. aeruginosa), and Candida albicans (C. albicans). Results from the current study showed that the alkyl chain length of quaternary phosphonium salts not only affected the synthesis of the fibers, but also impacted their antimicrobial activities. There was a rule that the longer the alkyl chain length, the more easily the quaternary phosphonium salts modify the fibers and the better the antimicrobial activities of the modified fibers. All the modified fibers exhibited good broad‐spectrum antimicrobial activities. Specifically, DTPB‐PANF exhibited an outstandingly high antimicrobial activity, which was nearly unaffected by the environmental pH (3–10). It can kill all the four pathogens in 15 min and had an excellent wash‐resistant property. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43689.     

非对称双子季铵盐阳离子表面活性剂的合成及性能

以十二烷基二甲基叔胺、盐酸、环氧氯丙烷为原料,合成了中间体N-(3-氯-2-羟丙基)-N,N-二甲基十二烷基氯化铵,后与3种不同烷基链长的长链烷基叔胺反应,得到3种非对称Gemini季铵盐阳离子表面活性剂(Ⅰ～Ⅲ)。通过IR光谱,1HNMR确证了中间体及目的产物的结构。测定了产物的临界胶束浓度cmc及γcmc。cmc分别为1 07×10-3mol·dm-3、1 99×10-3mol·dm-3和9 55×10-3mol·dm-3,γcmc分别为40 9mN·m-1、48 0mN·m-1和50 9mN·m-1。结果表明:所合成的非对称Gemini季铵盐阳离子表面活性剂具有较高的表面活性。     

几种常见非离子表面活性剂与季铵盐复合对致病菌的杀菌性能研究

以阳离子表面活性剂十二烷基二甲基苄基氯化铵(1227)、聚六亚甲基双胍盐酸盐(IB)、双癸基二甲基氯化铵为主的双8-10(D8-10)和双癸基甲基羟乙基氯化铵(DEQ)以及非离子表面活性剂脂肪醇聚氧乙烯(9)醚(BAN)、格尔伯特醇聚氧乙烯(5⁶)醚(BAE)、异辛醇聚氧乙烯(56)醚(BAE)、异辛醇聚氧乙烯(5⁶)醚(HYT)、烷基多苷(FCET)为研究对象,研究了复合组分的季铵盐、非离子表面活性剂与复合组分的季铵盐对大肠杆菌、金黄色葡萄菌以及白色念珠菌作用20 min后的杀菌活性。结果表明,60 mg/L 1227、IB、D8-10和DEQ复合溶液,杀菌作用20 min,即可对大肠杆菌、金黄色葡萄菌和白色念珠菌的KL>1;1227、IB、D8-10和DEQ对3种人体致病菌的杀灭效果除了与组合方式有关以外,还可能与之复合非离子表面活性剂的结构及浓度密切相关。     

Preparation and antimicrobial activity of Konjac Glucomannan modified with quaternary ammonium compound

Seven kind of graft copolymerization Konjac Glucomannan with quaternary ammonium group have been prepared, using Konjac Glucomannan (KGM) and methacryloxylethyl alkyl dimethyl ammonium bromide with c₈–c₁₈ alkyl and benzyl in water, ceric ammonium nitrate as initiator, the reaction temperature of 348 K, and the reaction period of 3 h. The structures were confirmed by FTIR. The 15 min inhibitory rates of all the graft copolymerization KGM against Escherichia coli and Staphylococcus aureus reached 99.99%, against Candida albicans somewhat lower, but 30 min inhibitory rate still reached 99.02% for graft copolymerization KGM with quaternary ammonium group having 14 alkyl. The antibacterial mechanism of the graft copolymerization KGM has been investigated by adsorption ability to E. coli, measure of 260 nm absorbing materials and SEM micrographs. Firstly, the bacteria were fastly adsorbed by graft copolymerization KGM. Interactions between bacterial membranes and antibacterial product cause fundamental changes in both membrane structure and function, induced leakage of cytoplasmic contents is a classic indication of damage to the bacterial cytoplasmic membrane. The loss of the connection between the outer membrane and the underlying peptidoglycan induces the abnormality of nodular structures and bleb formation of the cell envelope of E. coli. The antibacterial mechanism is in accordance with microbiologic findings identifying surface blebbing as the first morphologic change occurring in the permeability barrier of gram‐negative bacteria under mild heat stress and laser irradiation, etc. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

季盐型抗菌纤维素纤维的制备及性能研究

利用γ-胺丙基-三甲氧基硅烷将卤代烷基三苯基溴化物固载到纤维素纤维上,制得具有抗菌性能的季盐水不溶性高分子杀菌材料。杀菌性能测试结果表明,该杀菌材料对水中的异养菌有很强的吸附杀灭作用。使用后的纤维经次氯酸钠溶液清洗后仍具有很强的杀菌效果,说明该杀菌材料有较好的可再生性。