含萘酰亚胺和烷基疏水基的新型表面活性剂合成及性能

为获得高效多功能表面活性剂,设计并合成了一系列萘酰亚胺和长链烷基为疏水基的新型季铵盐阳离子表面活性剂(C_nNDA,n=10,12,14,16代表长链烷基链长),并利用红外光谱(FT-IR)、核磁氢谱(¹H NMR)、核磁碳谱(¹³C NMR)和质谱(HRMS)对其结构进行了表征。研究了C_nNDA的表面活性、胶束性质、泡沫及抗菌性能。结果表明,C_nNDA具有优异的表面活性和泡沫性能。当疏水烷基链长碳数从10增加到16,其cmc值从1.01降至0.026 mmol/L;0.10 g/L的C₁₄NDA水溶液的泡沫半衰期可达16 h。同时C_nNDA具有良好的抗菌活性,C₁₆NDA对大肠杆菌和金黄色葡萄球菌的最低杀菌质量浓度分别为3.0和1.2μg/mL。另外,¹H NMR和荧光光谱研究表明,C_nNDA能够形成分子间氢键,且萘酰亚胺基团间形成了π-π堆积。C_n     

季铵盐-高岭石系列插层复合物的制备及结构表征

通过多次置换插层反应,以高岭石/甲醇插层复合物为中间体,将不同链长季铵盐分子插入高岭石层间,对其结构、形貌和插层机理进行了探讨。结果表明:季铵盐分子在高岭石层间主要以全反转式构形存在,季铵盐碳链长度对其插层复合体的结构和形貌具有明显控制作用。碳原子数小于8的季铵盐在高岭石层间以单层平卧形式存在,其形成的高岭石插层复合体晶形仍为片状;碳原子数大于等于8的季铵盐在高岭石层间呈石蜡型倾斜双层形式排列,且碳链与高岭石(001)晶面的夹角随碳原子数增大而减小。碳原子数大于等于8的季铵盐进入高岭石层间,将导致高岭石晶层的卷曲,形成纳米卷或管,且随季铵盐碳链长度增加,高岭石片层卷曲程度加深,纳米卷的数量增多。     

无机粘土的烷基铵盐改性及NBRCNs的结构与性能研究

采用长链脂肪族季铵盐改性有机粘土的方法,研究了烷基铵盐改性剂的碳链长度及配比对无机粘土(MMT)改性效果的影响。结果表明,同一改性剂配比下,由不同碳链长度的烷基铵盐改性剂改性MMT制备的丁腈橡胶/粘土纳米复合材料(NBRCNs)的微观结构、力学性能和分散相态不同,碳链长度适中的十二烷基三甲基溴化铵(CTAB)改性效果较好,碳链长度较长或较短都不利于MMT的改性。对于碳链长度较短的二十二烷基三甲基溴化铵(DTAB),当DTAB用量增加,粘土片层间距增大,力学性能提高。对于碳链长度较长的十八烷基三甲基溴化铵(STAB),STAB用量降低有助于扩大粘土片层间距和提高力学性能。     

芳基烷基磺酸盐链长对烷烃的油-水动态界面张力的影响

采用旋转滴法测定系列自制芳基烷基磺酸盐（C_nNPAS, n=8,10,12,14,16）水溶液对烷烃的油-水动态界面张力,考察了表面活性剂烷基链长、表面活性剂浓度、弱碱浓度、烷烃碳数等因素对油-水动态界面张力的影响。结果表明,增大C_nNPAS的烷基链长和碱含量均会使界面张力达到稳定值的时间增长;增加C_nNPAS浓度和烷烃碳数均会使界面张力动态变化加快,达到平衡所需时间减少。C_nNPAS表面活性剂可在低浓度范围较明显地降低界面张力,而随着浓度的增加界面张力回升明显。     

橡胶／改性膨润土纳米复合材料研究——不同改性剂的影响

用不同的烷基长碳链季铵盐对膨润土进行有机改性,并将改性膨润土与天然胶乳共沉制得插层型纳米复合材料,研究了结构性能的关系,筛选出一种实用的有机改性剂。     

多季铵盐表面活性剂的合成及流变性能研究

以二乙胺盐酸盐、环氧氯丙烷、长链烷基二甲基叔胺为原料,合成了3种多季铵盐表面活性剂CD3N-n(n=12,16,18,代表烷基链碳原子个数);测定了上述多季铵盐表面活性剂的表面活性,并研究了碳链长度、温度、浓度以及反离子对多季铵盐水溶液流变性的影响。结果表明,合成的多季铵盐水溶液的临界胶束浓度(cmc)分别为2.0×10-4,1.0×10-4和8.0×10-5mol/L,临界胶束浓度下的表面张力(γcmc)分别为39.05,37.45和34.12 m N/m,cmc和γcmc均随着烷基链长度的增加而减小;CD3N-18的增黏效果显著,溶液黏度随CD3N-18浓度的增大而增大,随温度升高和反离子的加入先增加后减小,反离子助剂氯化钾的增黏效果较好,而水杨酸钠有助于提升产品的耐温性。     

蒙脱石对OTMA的吸附研究及其复合物的结构分析

采用长碳链十八烷基三甲基氯化铵对提纯的钠基蒙脱石进行插层,研究了OTMA的吸附量随温度及时间的变化,利用XRD阐明了蒙脱石/OTMA复合物的结构特征。研究发现,温度较低有利于OTMA在蒙脱石层间及表面的吸附;80℃下,吸附反应在30~60 min内达到平衡。吸附量的增加并不一定引起层间距的增大,较高温度下OT-MA阳离子可能进入到更多的蒙脱石片层间。蒙脱石/OTMA复合物的层间距及衍射峰的相对强度随时间呈动态变化。     

高级脂肪胺/甲醛改性木质素季铵盐的制备及基本表面物化性能

采用温和的Mannich反应和O-烷基化反应,制得了高级脂肪胺/甲醛改性木质素季铵盐阳离子沥青乳化剂,对影响Mannich反应的一些因素进行了探讨.结果表明,Mannich反应在二氧六环水溶液均相介质中进行,可明显提高反应效率;反应温度为60℃;随十八胺用量增加,木质素胺的含氮量增加;甲醛与十八胺的摩尔比为1.5∶1时,改性产物的含氮量最高.基本表面物化性能测试表明,在不同链长的高级脂肪胺/甲醛改性木质素季铵盐中,以十二胺/甲醛改性产物的表面活性最好,表面张力为33.2 mN•m^-1,较木质素季铵盐的43.8 mN•m^-1明显降低.乳化能力也显著提高.沥青微粒表面的Zeta电位比木质素季铵盐上升得更快.     

烷基糖苷柠檬酸单酯盐水溶液表面张力研究

采用wilhelmy吊片法和最大气泡压力法分别测定了烷烃链碳原子数为8,10,12的三种烷基糖苷柠檬酸单酯盐水溶液的平衡表面张力及动态表面张力。考察了烷基糖苷柠檬酸单酯盐(AG-EC)的烷烃链长和浓度、温度、氯化钠对其动态表面张力的影响。结果表明,AG-EC12、AG-EC10及AG-EC08在25℃时的临界胶束浓度分别为0.226,1.038,5.104 mmol/L,三种烷基糖苷柠檬酸单酯盐在其各自的水溶液中均显示出表面活性。随着疏水碳链长由8增长至12,三种烷基糖苷柠檬酸单酯盐的动态表面活性升高。同一烷基糖苷柠檬酸单酯盐随着浓度增大,其动态表面张力参数n、t*减小,且R1/2增大,动态表面活性增大。随着实验温度的升高(25⁴5℃)或无机电解质Na Cl浓度增加至0.6 mol/L,动态表面活性均升高。     

有机MMT对高密度聚乙烯改性的研究

采用十二烷基三甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵和双十八烷基二甲基氯化铵4种阳离子表面活性剂对钠基蒙脱土(MMT)进行有机化处理,制备了有机MMT(OMMT)。将OMMT与高密度聚乙烯(HDPE)进行熔融插层制备了HDPE／OMMT纳米复合材料,研究了OMMT的层间距同季铵盐烷基链的关系。结果表明,OMMT的层间距随烷基链长度的增加而增大;随着OMMT含量的增加,HDPE／OMMT纳米复合材料的断裂伸长率和拉伸强度降低,弯曲弹性模量增加,弯曲强度出现极大值,使该纳米复合材料的力学性能得到了一定的改善。     

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.     

Covalent attachment of quaternary ammonium compounds to a polyethylene surface via a hydrolyzable ester linkage: Basis for a controlled‐release system of antiseptics from an inert surface

The colonization of medical devices such as catheters, topical wound dressings, and surgical implants by micro‐organisms is an ongoing problem, particularly as many strains of bacteria are becoming resistant to antibiotics. Such a problem may be addressed by a material surface that is able to provide a slow release of a disinfectant during its period of usage. To achieve this objective, a novel material was prepared in which a quaternary ammonium salt was covalently bound onto a polyethylene backbone via a hydrolyzable ester linkage, which provided a slow release of the disinfecting agent. A low‐density polyethylene film was treated with glow discharge followed by the graft polymerization of acrylic acid. A tertiary amine function was introduced onto the film by the esterification of the carboxylic acid groups, via an acid chloride intermediate, with 4‐hydroxy‐N‐methyl piperidine. The tertiary amine on the piperidine was then quaternized with a series of alkyl bromides of various chain lengths. The quaternary ammonium salt was released slowly by the hydrolysis of the ester bond over a 4‐h period. To test the efficacy of the quaternary ammonium function itself, soluble compounds were prepared as follows. 4‐Hydroxy‐N‐methyl piperidine was esterified with acetic anhydride and a corresponding series of quaternary ammonium salts prepared again by a reaction with alkyl bromides of various chain lengths. A preliminary microbiological survey of the materials included an investigation of the effect of the chain length as well as the efficacy of the soluble quaternary salts themselves. As expected, only the longer alkyl chains provided quaternary ammonium salts with bactericidal properties, chain lengths of less than 10 carbon atoms proving ineffective. Both the polymer‐bound and soluble long‐chain quaternary ammonium salts were effective against suspensions of Staphylococcus aureus and Escherichia coli. The results therefore indicate that such a system may well be useful in the development of biomedical materials such as surgical implants or dressings in which a slow release of a disinfectant or other physiologically active agent such as an anti‐inflammatory drug may be required. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 538–545, 2006     

长碳链烷基铵在蒙脱石层间的吸附热力学

采用十八烷基三甲基铵（octadecyltrimethyl ammonium,OTA）对钠基蒙脱石进行插层吸附,研究了OTA在蒙脱石层间的等温吸附规律,探讨了长碳链烷基铵在蒙脱石中的吸附热力学及吸附作用机理。结果表明：长碳链烷基铵在蒙脱石中的吸附符合Langmuir等温方程及ModifiedLangmuir等温方程,O...     

氧化铈-二氧化硅介孔材料制备及对铜离子的吸附性能

采用共沉淀法和沉淀浸渍法制备了纳米氧化铈-二氧化硅（CeO₂-SiO₂）介孔材料吸附剂,主要考察了其对水中铜离子（Cu²⁺）的吸附行为。通过X射线衍射（XRD）、扫描电镜（SEM）和氮吸附（BET）等手段对合成的介孔材料进行了性能表征,并通过静态吸附实验分析了溶液pH、溶液初始金属离子质量浓度、吸附剂用量、吸附时间等条件对介孔材料吸附Cu²⁺性能的影响。结果表明：共沉淀法制备的纳米CeO₂-SiO₂介孔材料对Cu²⁺的去除效果较沉淀浸渍法要好;当溶液pH=7.0时CeO₂-SiO₂介孔材料对Cu²⁺的吸附效果最好,20 min时基本达到吸附平衡;溶液初始Cu²⁺浓度增大Cu²⁺去除率降低,Cu²⁺累计吸附量增大;随着吸附剂用量增加Cu²⁺去除率增大,当CeO₂-SiO₂吸附剂用量为0.15 g/L时对Cu²⁺的去除率趋于稳定;CeO₂-SiO₂吸附剂对不同金属离子吸附性能由大到小的顺序为Cu²⁺、Fe²⁺、Mn²⁺,该吸附过程均符合准二级动力学模型。     

Functionalized activated carbon for the adsorptive removal of perchlorate from water solutions

Two types of activated carbon, namely, Filtrasorb 400 and Nuchar SA, were functionalized by quaternary ammonium salts (quats), as to enhance perchlorate adsorption. Results showed that the adsorption of quats on Nuchar SA increased with increase in chain length (hydrophobicity) of quats. Filtrasorb 400, however, had limited uptake of long-chain quats such as dodecyltrimethylammonium and hexadecyltrimethylammoium (HDTMA). Results indicated that perchlorate removal by the functionalized activated carbon was directly related to the chain length of the modifying quats. Perchlorate removal by functionalized activated carbon increased with increase in chain length of the modifying quats and became less pH-dependent. Modified Nuchar SA had higher overall perchlorate removal capacity than the modified Filtrasorb F400, but was more strongly affected by pH than Filtrasorb 400. Activated carbon treated with HDTMA exhibited the best perchlorate removal capacity among all quats studied. Results indicated that tailoring the activated carbon surface with HDTMA rendered the activated carbon surface positively charged, which resulted in substantial increase in perchlorate removal compared to unfunctionalized activated carbons.     

Adsorption of methyl orange from aqueous solution by composite magnetic microspheres of chitosan and quaternary ammonium chitosan derivative

Novel composite magnetic microspheres containing chitosan and quaternary ammonium chitosan derivative (CHMMs) were prepared by inverse suspension method, and used for the methyl orange (MO) removal from aqueous solutions. The CHMMs were characterized by a scanning electron microscope, a transmission electron microscope, and Fourier transform infrared spectroscopy, respectively. Compared with the chitosan beads, the incorporation of quaternary ammonium chitosan derivative significantly reduced the particle size. The MO adsorption by CHMMs was investigated by batch adsorption experiments. The adsorption kinetics was conformed to the pseudo second-order kinetics equation. The adsorption isotherm followed the Langmuir model better than the Freundlich model and the calculated maximum MO adsorption capacity was 266.6 mg·g^-1 at 293 K. Thermodynamic studies indicated that the MO adsorption was endothermic in nature with the enthalpy change (ΔH°) of 99.44 kJ·mol^-1. The CHMMs had a stable performance for MO adsorption in the pH range of 4-10, but high ionic strength deteriorated the MO removal due to the shielding of the ion exchange interaction. A 1 mol·L^-1 NaCl solution could be used to regenerate the exhausted CHMMs. The proposed CHMMs can be used as an effective adsorbent for dye removal or recovery from the dye wastewater.     

电解锰渣基沸石对锰离子的吸附性能研究

电解锰渣是电解锰行业露天堆存的大宗固体废弃物,在堆存过程中将产生毒性污染物锰离子。为有效利用电解锰渣的同时消除锰离子对环境的危害,以电解锰渣为原料采用微波碱熔活化法制备沸石,并用于吸附锰离子。考察了溶液初始锰离子质量浓度、溶液pH、吸附温度和吸附时间等因素对锰离子吸附效果的影响。结果表明:在溶液初始锰离子质量浓度为500 mg/L、溶液pH为6、吸附时间为2 h、吸附温度为50 ℃条件下,电解锰渣基沸石对锰离子具有较好的吸附能力,最大吸附量高达79.18 mg/g。探究了电解锰渣基沸石对锰离子的吸附行为。结果表明,锰离子在沸石表面的吸附符合准二级动力学模型,Langmuir等温吸附模型比Freundlich模型更适合于描述电解锰渣基沸石去除锰离子的等温吸附过程。电解锰渣基沸石循环使用性能良好,在重金属废水处理方面具有潜在的应用前景。     

PA6/蒙脱土纳米复合材料的力学性能研究

利用未改性蒙脱土和两种季胺盐改性蒙脱土与尼龙(PA)6混合,成功制备得到了不同结构的PA6/蒙脱土纳米复合材料.X射线衍射图谱和力学性能分析表明,季胺盐改性剂可以插入蒙脱土片层之间,使蒙脱土片层扩张,层间距增大.与PA6相比,制备得到的三种纳米复合材料的力学性能都有不同程度的提高.改性蒙脱土与PA6表现出良好的相容性,...     

Synthesis and antimicrobial activity of some cross‐linked copolymers with alkyl chains of various lengths

Amphoteric polymer hydrogels were prepared by the copolymerization of three kinds of N,N′‐dimethyl‐N‐alkylmethacryloxylethyl ammoniumbromide (DMAEA) with different lengths of alkyl chains (DMAEA‐RB) (R‐ehtyl/hexyl/dodecyl), acrylic acid (AA), and acrylamide (AM). The water content of the AA‐AM‐(DMAEA‐RB) terpolymers decreased with the increasing length of alkyl chains in quaternary ammonium group in the terpolymers and increased with the increasing molar ratio of DMAEA‐RB to 2 mol % and then decreased. Their antibacterial activities against Escherichia coli and Staphylococcus hyicus were investigated by a colony count method. It was found that the copolymer exhibited higher antibacterial activity with increasing chain length of alkyl groups in ammonium groups. For P[AA‐AM‐(DMAEA‐DB)], the DMAEA‐DB content is higher and contact time is longer, its antibacterial activity is better. However, when the contact time and quaternary ammonium content were above 30 min and 2%, respectively, the amount of live cells N(t) in a cell suspension increased in the presence of P[AA‐AM‐(DMAEA‐EB)] or P[AA‐AM‐(DMAEA‐HB)]. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and Surface Active Properties of tri[(N‐alkyl‐N‐ethyl‐N‐Sodium carboxymethyl)‐2‐Ammonium bromide ethylene] Amines

Trimeric betaine surfactants tri[(N‐alkyl‐N‐ethyl‐N‐sodium carboxymethyl)‐2‐ammonium bromide ethylene] amines were prepared with raw materials containing tris(2‐aminoethyl) amine, alkyloyl chloride, lithium aluminium hydride, sodium chloroacetate, and bromoethane by alkylation, Hoffman degradation reaction, carboxymethylation and quaternary amination reaction. The chemical structures of the prepared compounds were confirmed by FTIR, ¹H NMR, MS and elemental analysis. With the increasing length of the carbon chain, the values of their critical micelle concentration initially decreased. Surface active properties of these compounds were superior to general carboxylate surfactants C₁₀H₂₁CHN⁺(CH₃)₂COONa. The minimum cross‐sectional area per surfactant molecule (A_min), standard Gibbs free energy adsorption (ΔG_ads) and standard Gibbs free energy micellization (ΔG_mic) are notably influenced by the chain length n, and the trimeric betaine surfactants have greater ability to adsorb at the air/water interface than form micelles in solution. The efficiency of adsorption at the water/air interface (pC₂₀) of these surfactants increased with the increasing length of the alkyl chain. Their foaming properties, wetting ability of a felt chip, and lime‐soap dispersing ability were also investigated.