Wettability alteration of organo-vermiculites induced by layer charge and tailored bis-N-heterocyclic quaternary ammonium salts

Wettability is an important surface property that deserves to further explore the factors on its alteration.Series of bis-N-heterocyclic quaternary ammonium salts with different spacer length and N-heterocyclic headgroups(morpholinium(BMMB,BMMD and BMMH),piperidinium(BPMH)and piperazinium(BMPMH))have been synthesized and employed for altering the wettability of vermiculite and its derivates(Vts)treated by Li^(+)-saturated heating method.The results of X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),thermogravimetric analysis(TG-DTG),scanning electron microscopy(SEM)and N_(2)adsorption/desorption isotherms indicate that all of the bis-N-heterocyclic quaternary ammonium salts have been successfully inserted into the vermiculite layers,leading to the organic monolayer.The results of capillary rise tests combined with Lipophilic to Hydrophilic Ratio(LHR)values unveil the wettability alteration of the organo-Vts.As the layer charge decreases,the hydrophilicity of the organo-Vts gradually increases,which is probably caused by the decline in binding sites.As the result of the change in spacer length of modifier,the wetting properties of morpholinium-based organo-Vts change in order of BMMD-Vts>BMMH-Vts>BMMB-Vts,and difference in N-heterocyclic headgroups leads to the sequence of wettability:BMPMH-Vts>BPMH-Vts>BMMH-Vts.Layer charge of Vt,spacer length and the type of the N-heterocyclic headgroup of modifier have the synergistic effect on the regulation of the wettability.

Effect of quaternary ammonium salts on flotation behavior of aluminosilicate minerals

The electrokinetic properties and flotation of diaspore, kaolinite, pyrophyllite and illite with quaternary ammonium salts collectors were studied. The results of flotation tests show that the collecting ability of quaternary ammonium salts for the four minerals is in the order（from strong to weak） ofoctadecyl dimethyl benzyl ammonium chloride（ODBA）, cetyl trimethyl ammonium bromide（CTAB）, dodecyl trimethyl ammonium chloride（DTAC）. Under the condition of alkalescence, it is possible to separate the diaspore from the silicate minerals such as kaolinite, illite and pyrophyllite using quaternary ammonium salts as collector. Isoelectric points （IEP） of diaspore, kaolinite, pyrophyllite and illite are pH=6.0, 3.4, 2.3 and 3.2, respectively. Quaternary ammonium salts can change ζ-potential of the aluminosilicate minerals obviously. The flotation mechanisms were explained by ζ-potential and Fourier transform infrared spectrum （FT-IR） measurements. The results demonstrate that only electrostatic interaction takes place between aluminosilicate minerals （diaspore, kaolinite, pyrophyllite and illite） and quaternary ammonium salts.

Flotation and adsorption of quaternary ammonium salts collectors on kaolinite of different particle size

The flotation behaviors of decyltrimethylammonium (103C), dodecyltrimethylammonium chloride (DTAC), tetradecyltrimethylammonium chloride (TTAC) and cetyltrimethylammonium chloride (CTAC) on kaolinite of different particle size fraction were studied. The adsorbed amount and adsorption isotherms of collectors on kaolinite were determined for painstaking investigation into the adsorption of quaternary amines at kaolinite-water interface by ultraviolet spectrophotometer methods. The flotation results show that the flotation recovery of kaolinite of different particle fraction increases with an increase in pH when 103C, DTAC, TTAC and CTAC are used as collectors. As the concentration of collectors increases, the flotation recovery increases. Particle size of kaolinite has a strong effect on flotation. The flotation recovery of fine kaolinite decreases with the carbon chain of quaternary ammonium salts collectors increasing, while coarse kaolinite is on the contrary. The adsorbed amount tests and adsorption isotherms show that adsorbed amount increases when the particle size of kaolinite increases or when the carbon chain length of quaternary ammonium salts increases. Within the range of flotation collector concentration, the longer the hydrocarbon chain, the more probable to be absolutely adsorbed by fine kaolinite particles and then the lower the collector concentration in the bulk, which leds to lower flotation recovery.

Aluminum-silicates flotation with quaternary ammonium salts

The zeta potential measurements show that the flotation separation of diaspore from kaolinite, illite and pyrophyllite could be achieved in the range of pH 46.5 with cationic collectors. A special quaternary ammonium salts(DTAL) shows better selectivity than that the dodecyl amine(DDA) does for the flotation of three silicates. The closed circuit flotation results show that the reverse flotation de silicate can be achieved with DTAL as collector, a new inorganic reagent(SFL) as depressant and MIBC as frother to obtain a bauxite concentrate m (Al 2O 3)/ m (SiO 2) >10, Al 2O 3 recovery>86%).

Synthesis of Chitosan Quaternary Ammonium Salts

A series of N-alkyl or N-aryl chitosan quaternary ammonium salts were prepared via Schiffs base intermediates. Quaternization of N-substituted chitosan derivatives was carried out using methyl iodide to produce water-soluble cationic chitosan quaternary ammonium salt. The products were characterized by IR, (HNMR)-H-1 and elemental analysis. The degree of substitution of chitosan quaternary ammonium salt was calculated by elemental analysis.

Biodegradable Quaternary Ammonium Salts for Processing Iron Ores

Two biodegradable quaternary ammonium salts were synthesized and used as cationic collectors in processing iron ores by froth flotation. The flotation behaviors of iron minerals with the new biodegradable quaternary ammonium collectors were investigated by micro-flotation tests of quartz (SiO2) and magnetite (Fe3O4). It was observed that the new biodegradable collectors were effective in separating quartz from magnetite by flotation. At the collector concentration of 1 × 10﹣4 mol/L, the recovery of quartz using the M301 and M302 collectors can reach its maximum of 67.97% and 91.18%, respectively. For a wide pH range, they also show good selectivity. By the measuring zeta potentials of the new quaternary ammonium salts, the results show that quaternary ammonium salt is preferred to adsorb on the surface of quartz. The two quaternary ammonium collectors are also determined as readily biodegradable collectors, according to the OECD301B evaluation standard.

Studies on a Cationically Modified Quaternary Ammonium Salt of Lignin

A new quaternary ammonium salt monomer was synthesized and a quaternary amination of lignin（ noted as QL）, with the monomer was carried out by grafting copolymerization. The products were characterized by Fourier Transform Infrared spectroscopy（ FTIR）. The experimental results indicate that the yield of the monomer was 99.06%, and the conversion of the monomer and the grafting yield of QL were 93.69% and 185.78%, respectively. The feasibility of QL as the flocculant to be applied in color removal of five artificial dyes, erioehrome black T（dye A）, gongo red（dye B ）, direct fast black G （dye C ）, cuprofix blue green B （dye D ）, and acid black ATT （dye E ） was examined. Results show that OL exhihits the favorable flocculation nerformance and high stability.

Superoxide Anion Radical Scavenging Ability of Quaternary Ammonium Salt of Chitosan

A series of N-alkyl or N-aryl chitosan quaternary ammonium salt were prepared using 96% deacetylated chitosan. Their scavenging activities against superoxide anion radical were investigated by chemiluminescence. The IC50 values of these compounds range from 280 to 880 μg/mL, which should be attributed to their different substitutes.

Dimethyl carbonate synthesis via transesterification catalyzed by quaternary ammonium salt functionalized chitosan

A quaternary ammonium salt covalently linked to chitosan was first used as a catalyst for dimethyl carbonate （DMC） synthesis by the transesterification of propylene carbonate （PC） with methanol. The effects of various reaction variables like reaction time, temperature and pressure on the catalytic performance were also investigated. 54% DMC yield and 71% PC conversion were obtained under the optimal reaction conditions. Notably, the catalyst was able to be reused with retention of high catalytic activity and selectivity. Consequently, the process presented here has great potential for industrial application due to its advantages such as stability, easy preparation from renewable biopolymer, and simple separation from products.

Preparation of spiro-type quaternary ammonium salt via economical and efficient synthetic route as electrolyte for electric double-layer capacitor

A spiro-type quaternary ammonium salt, spiro-(1,1′)-bipyrrolidinium tetrafluoroborate(SBP-BF4) was successfully prepared by an economical and efficient three-step process comprising the cyclization reaction of 1,4-dibromobutane and pyrrolidine, and subsequent ion exchange pathway with KOH followed by neutralization reaction via HBF4 in the system of ethanol solution. 1H NMR, 13 C NMR, FI-IR and XPS analyses showed the structure of SBP-BF4. The as-obtained SBP-BF4 was dissolved in AN and used as the electrolyte for supercapacitor. Electrochemical measurements demonstrate that, compared with commercial electrolyte TEMA-BF4/AN, SBP-BF4/AN exhibits high ionic conductivity, lower resistance and improved cycling performance, which is due to its smaller ion size and stable symmetry structure.

Preparation of Mesoporous ZSM-5 Zeolite under Double Ester Base Long Carbon Chains Organosilane Quaternary Ammonium Salt Template Agent

The pore sizes of traditional zeolites are in the range of0. 3-1. 5 nm,which strongly hinder the diffusion of large reactant and product molecules within the zeolite pores. To compensate for it,we tried to create mesopores in traditional microporous zeolites and retain all advantages of microporous zeolites. Mesoporous Zeolite Socony Mobile-Five( ZSM-5) zeolite was synthesized by a new double ester base long carbon chains organosilane quaternary ammonium salt as the soft template agent in hydrothermal method.The structure of the acquired zeolite crystals was confirmed by fieldemission scanning electron microscopy( FE-SEM), transmission electron microscopy( TEM), nitrogen adsorption-desorption measurements and X-ray diffraction( XRD),which indicated that their structure had the same characteristics as traditional ZSM-5 zeolites. Compared with traditional ZSM-5 zeolite,there were 4 nm and 15 nm mesopores in the crystal. The prepared hierarchical porous ZSM-5 zeolite was expected to be effective catalytic materials for chemical reactions involving large molecules.

POLYMER-SUPPORTED SINGLE AND MIXED AMMONIUM AND PHOSPHONIUM SALTS AS CATALYSTS FOR PHASE-TRANSFER REACTIONS

In this study was to investigate, by phase-transfer catalysis, the activity of single and mixed ammonium and phosphonium salts grafted on a 揼el-type?styrene-7% divinylbenzene copolymer in the oxidation of benzyl alcohol with hydrogen peroxide. A wide variety of catalysts with different quaternary groups and different quaternary chain length substituents were examined. The activity of single 搊nium?salts increases as a consequence of the association of ammonium and phosphonium salts grafted on the same polymeric support. The activity of polymer-supported ammonium and phosphonium salts increases with the number of carbon atoms contained in the alkyl radicals of the onium and of the functionalization degree with phosphonium groups.

ANTIBACTERIAL ACTIVITY OF SINGLE AND MIXED AMMONIUM AND PHOSPHONIUM SALTS GRAFTED ON "GEL-TYPE" STYRENE-DIVINYLBENZENE COPOLYMERS

A systematic study on the synthesis and antibacterial activity of the quaternary "onium" salts grafted on an insoluble "gel-type" styrene-7% divinylbenzene copolymer by polymer-analogous reactions is showed. Antibacterial activity of quaternary ammonium and/or phosphonium salts grafted on polymer-supports has been studied against Staphylococcus aureus and Escherichia coli. A wide variety of "onium" salts bound to macromolecular supports with different quaternary groups and different quaternary chain length substituents were examined. The antibacterial activity of mixed "onium" salts increases as a consequence of the association of ammonium and phosphonium salts grafted on the same polymeric support.

PREPARATION AND PHOTOSENSITIVITY OF WATER SOLUBLE PHENOLIC RESINS CONTAINING ACRYLOYL AND QUATERNARY AMMONIUM CHLORIDE GROUPS

New water soluble and photocrosslinkable prepolymers containing acrylate and quaternary ammonium salt groups were synthesized from epoxy phenolic resin via ring-opening reaction with acrylic acid and with aqueous solution of triethylamine hydrochloride successively. The second reaction needs no phase transfer catalyst to accelerate, since the product formed can act as a phase transfer catalyst. The prepolymer obtained contains both photocrosslinkable acrylate groups and hydrophilic quaternary ammonium salt groups. Optimum conditions for these reactions were studied. The photosensitivity of the prepolymer was also investigated. The effects of different photoinitiators, different crosslinkable diluent monomers and amine accelerator on the photosensitivity of the prepolymer were compared. The photoinitiator of hydrogen abstraction type is still effective without using amine or alcohol as accelerator, because the prepolymer contains a H beside the OH groups formed in the ring-opening reactions.

Facile fabrication of superior antibacterial cotton fabric based on ZnO nanoparticles/quaternary ammonium salts hybrid composites and mechanism study

In the research for the safe and efficiently antibacterial cotton fabrics to minimize risk for human health,an organic–inorganic hybrid material of ZnO nanoparticles(NPs)and quaternary ammonium salt(QAS)was employed to modify cotton fabrics by a dipping–padding–drying method.The synergistic effects of ZnO NPs and QAS on the structure and antibacterial properties of cotton fabrics were studied in detail.Results displayed that the QAS and ZnO NPs were immobilized firmly in cotton fabric by the formation of chemical covalent bonds and silica gel structure.ZnO/QAS/cotton had a good inhibitory effect on the growth of E.coli and S.aureus,with superior antibacterial efficiency of>99.99%.ZnO/QAS/cotton preserved good mechanical property,water absorbability,and limpness.We also provided a detailed analysis of antibacterial mechanism for the hybrid materials.The contact mechanism and the Zn2+release were considered as the main mechanisms for the ZnO/QAS/cotton,while the reactive oxygen species(ROS)generation only had a little contribution to the antibacterial activity.In short,the excellent integrated properties endowed the hybrid cotton fabrics as potential application in many fields,like healthcare,food packaging.

转向酸用缓蚀剂的制备及缓蚀机理

转向酸广泛应用于碳酸盐岩储层酸化酸压,由于黏弹性表面活性剂分子结构特殊,常规缓蚀剂配伍性较差,且缓蚀效率大幅降低。采用1-氯甲基萘、4-乙基吡啶、氯化苄和2,3-环戊烯并吡啶合成了2种吡啶季铵盐缓蚀剂SI-1和SI2。采用腐蚀仪、流变仪考察了SI-1和SI-2在转向酸中的缓蚀性能及其对转向酸黏度的影响;通过扫描电子显微镜、能谱仪、原子力显微镜和X射线光电子能谱等实验手段,从微观角度分析钢片腐蚀前后表面形貌和化学成分;采用分子动力学模拟方法对缓蚀剂SI-1和SI-2的缓蚀机理进行了探讨。结果表明:合成的2种吡啶季铵盐缓蚀剂在转向酸中的缓蚀性能良好,对转向酸黏度影响小,适用性强,成本低。其中缓蚀剂SI-2性能更优,1%加量下,90℃腐蚀速率为1.04 g/(m^(2)·h),120℃腐蚀速率为7.43 g/(m^(2)·h),VES残酸最终黏度可稳定在190 mPa·s以上,成本可降低20%。加入1%缓蚀剂后钢片表面均未出现明显腐蚀,Fe含量大幅上升,表面粗糙度大幅降低,其中添加缓蚀剂SI-2后,Fe含量从86%上升至94%,Ra从137 nm下降至84 nm。钢片表面均检测到C—N与Organic C=O(羰基),表明存在缓蚀剂吸附膜。分子动力学模拟显示缓蚀机理为:SI-2能隙小,吸附能大,缓蚀剂吸附到钢片表面后可形成致密吸附膜,隔绝腐蚀介质与钢片表面的接触,极大地抑制钢片腐蚀。SI-2在渤海油田和伊拉克米桑油田进行了现场应用,施工效果良好。

氯化胆碱改性聚酰胺纳滤膜的制备与分离性能

为了提高传统聚酰胺纳滤膜的分离性能,利用酰氯与羟基之间的酯化反应将带有正电荷的季铵盐氯化胆碱(CC)引入聚酰胺纳滤膜表面,制备在中性条件下具有近中性荷电性的氯化胆碱/聚酰胺纳滤膜,通过对无机盐的分离测试考察了CC质量分数对薄膜复合(TFC)膜性能的影响。结果表明,当CC质量分数达0.10%时,改性效果最佳,TFC膜对Na_(2)SO_(4)、MgSO_(4)和MgCl_(2)均具有较高的截留率,具有改善的Mg^(2+)/Li^(+)分离能力,渗透通量提升了315%。

改性蚕丝织物的胭脂虫红染色工艺探析

为使胭脂虫红上染蚕丝织物效果好,采用壳聚糖季铵盐(HACC)对蚕丝织物改性后,用胭脂虫红色素直接染色,探讨改性工艺。研究表明,最佳改性工艺条件为改性温度70℃,改性时间40 min,pH=5,HACC质量浓度4%。胭脂虫红对改性蚕丝织物进行直接染色,得出优化的染色工艺条件为染色温度80℃,染色时间40min,pH=7,染液质量浓度6%。在最佳的工艺条件下,对未改性及改性蚕丝织物进行直接染色和后媒染,用环保的氯化镧稀土为媒染剂,对染色织物的染色性能、色牢度进行测试。结果表明,HACC改性试样经过后媒染法染色,其染色性能、色牢度最好,对生态染整技术发展提供积极的意义。

新型高温酸化缓蚀剂的制备及性能评价

为了更好地减缓油气田高温酸化下金属的腐蚀,研究出一种耐高温且配方简单的复合酸化缓蚀剂。以喹啉和氯化苄为原料,采用“一锅法”制备得到了一种新型稠杂环季铵盐(BQD)缓蚀主剂。通过添加甲酸、乌洛托品等复配剂,经过单因素失重法优选,得到一种配方简单的新型高温酸化缓蚀剂GS-1,通过电化学测试、表面形貌分析研究其缓蚀性能,采用分子模拟的方法研究BQD的缓蚀机理。结果表明,GS-1缓蚀剂在添加量为3%时,在160℃下盐酸与土酸的酸化环境中,N80钢片的腐蚀速率分别降低至41.63g/(m^(2)·h)、31.94g/(m^(2)·h),均可达行业标准要求;GS-1缓蚀剂可在N80钢片表面形成一层吸附保护层,属于兼具抑制阳极和阴极反应的混合型缓蚀剂;量子化学计算及分子动力学模拟表明,BQD的缓蚀活性优于常见的苄基喹啉季铵盐缓蚀剂(BQC),同时BQD分子是以共轭平面为基准,与金属基底平行的角度被吸附于界面上,具有更加高效的缓蚀性能。

季铵盐阳离子改性剂的合成及其在栀子黄染色棉织物中的应用

为了提升天然植物染料栀子黄在纤维素纤维上的染色性能,设计合成了一系列以3-氯-2-羟丙基为反应基团、季铵盐为阳离子基团的阳离子改性剂,通过亲核加成反应在纤维素纤维上引入季铵基团,提升栀子黄染料对阳离子改性纤维素纤维的染色性能。借助电喷雾电离-串联质谱法(ESI-MS)、核磁共振氢谱(~1H NMR)对合成的不同烷基链长的季铵盐改性剂分子结构进行表征。通过红外光谱图和X射线光电子能谱图证实季铵盐化合物以醚键形式成功接枝在棉织物上。采用栀子黄染料对改性棉织物染色,比较不同烷基链长改性剂改性棉织物的染色K/S值发现,改性剂烷基链长为12时最佳,上染率为85.46%,K/S值为4.33。进一步研究染色工艺条件对染色织物K/S值、上染百分率以及色牢度的影响,结果表明,在染色温度为80℃,pH值为9,时间为60 min时,经3-氯-2-羟丙基二甲基辛烷氯化铵(CH-12)改性棉织物染色性能最佳,其上染率为88.07%,K/S值为4.71,耐皂洗牢度及耐摩擦色牢度均可达到3级以上。研究结果表明,CH-12改性棉织物可实现无盐染色,且改性织物的上染率、固色率、耐皂洗和耐摩擦牢度均优于未改性织物的传统有盐染色。