新型双亲性水基钻井液页岩抑制剂的合成及应用

针对河南油田泌阳泥页岩井段钻井施工过程中,因频繁出现水化膨胀而导致井壁失稳、剥落掉块等问题,本文以月桂酰氯改性超支化聚乙烯亚胺(HPEI)为原料,于室内合成了一种新型的双亲性页岩抑制剂(HPEI-C₁₂),并对其合成条件和页岩水化抑制性能进行了评价。结果表明：在引发剂N,N-二乙基乙胺加量(质量分数,下同)为8%、月桂酰氯加量为30%、反应时间为24 h和反应温度为25℃条件下合成的HPEI-C₁₂性能最佳;通过线性膨胀实验和岩屑滚动回收实验对HPEI-C₁₂抑制性能进行评价。结果表明：HPEI-C₁₂具备优异的抑制性能和耐温性能,在120℃条件下,岩屑滚动回收率为65.0%;此外,HPEI-C₁₂与现场钻井液体系具备良好的适配性,对体系流变性能影响极小,加入体系后岩屑滚动回收率提升至82.0%,能够满足目标井段对钻井液性能的要求。     

一种超支化阳离子聚合物的制备及其防膨性能

以顺丁烯二酸酐及二乙醇胺为原料，采用“一步熔融法”合成了端羟基超支化聚酯酰胺（HBP-OH）；以环氧氯丙烷改性HBP-OH制得端基为氯甲基的超支化聚酯酰胺（HBP-ECH）；以三乙胺改性HBP-ECH制得端基为季铵基的超支化聚酯酰胺（HBP-L），其结构经IR表征。研究了HBP-L的静态防膨率、耐水洗能力及对岩心的渗透伤害率。结果表明：HBP-L加量为1 wt%时，粘土防膨率为90.36%；经10次水洗后，其防膨率仍超过85%；模拟地层温度为45 ℃时，HBP-L对岩心的渗透伤害率仅3.86%。采用XRD和Zeta电位法分析了HBP-L对粘土水化膨胀及运移分散的抑制机理。结果表明：经1 wt%HBP-L处理的粘土，其晶层间距为6.91 nm，较去离子水处理层间距（4.71 nm）小；粘土表面的zeta电位由-39.2 mV升高至-19.6 mV。     

两亲性全季铵盐超支化聚合物的设计与合成及主-客体超分子着色应用研究

采用高效的巯基-炔点击化学与Menschutkin季铵化反应,合成了一种带有1个叠氮基、2个炔基和2个季铵盐基团的AB2型季铵盐单体,通过核磁共振、红外光谱、质谱等方法对单体结构进行了确认.将所得单体进行点击聚合,得到全季铵盐超支化聚合物,并用端叠氮基的长链烷烃封端,得到核亲水-壳憎水的两亲性超支化聚季铵盐.研究所得两亲性超支化聚合物对染料的装载性能,结果表明所合成的带正电荷两亲性聚合物对多种带负电荷的水性染料装载效果好,平均相转移率高达95%.进一步将装载染料的主-客体超分子复合物用于聚合物制品着色,发现其对SBS及PMMA等聚合物有很好的着色效果,着色均匀且不掉色,着色的膜色泽鲜艳透明.     

新型载药壳聚糖季铵盐的合成、结构与性能

通过羧甲基壳聚糖接枝二甲基十八烷基环氧丙基氯化铵, 制备了一系列不同取代度和分子量的羧甲基壳聚糖十八烷基季铵盐(QACMC). 用傅立叶变换红外(FTIR)光谱、核磁共振谱(1H-NMR)、X射线衍射(XRD)谱、差式扫描量热法(DSC)等对其分子结构、结晶和热性能进行研究, 同时研究QACMC的吸湿保湿性能, 并与透明质酸(HA)、壳聚糖(chitosan)和羧甲基壳聚糖(CMC)进行比较. 结果表明, QACMC具有较好的结晶性和热稳定性, 结晶度可达72.3%; 其吸湿保湿性低于透明质酸(HA)和羧甲基壳聚糖, 而受季铵基团取代度和QACMC分子量的影响, 羧酸盐和季铵盐两种亲水基团对QACMC吸湿性的影响不具有协同作用; QACMC对亲脂性药物盐酸米诺环素的载药率可达10.9%(质量分数), 远高于壳聚糖和羧甲基壳聚糖.     

季铵盐催化合成端烯丙基聚氧化烯大单体

用季铵盐作催化剂，由聚氧　化乙烯－氧化丙烯嵌段共聚物和烯丙基氯合成了端烯丙基聚氧化烯大单体，考察了催化剂及其用量，溶剂及反应温度，反应时间对反应封端率的影响，确定了最佳反应条件；与Ｗｉｌｌｉａｍｓｏｎ醚合成法比较，季铵盐催化法操作简便安全，并且可以制得封端率高的端烯丙基聚氧化烯大单体。     

辛可宁季铵盐的合成及催化不对称烷基化研究

探索了辛可宁季铵盐的通用合成方法, 确定辛可宁与取代苄溴在四氢呋喃中回流为最优反应途径, 合成了11个羟基保留的辛可宁季铵盐, 收率57%~88%, 并合成了4种羟基保护季铵盐, 羟基成醚过程在生成季铵盐前后均可进行, 总收率62%~71%; 羟基酯化只能在生成季铵盐之后进行, 总收率78%. 本文共合成了15个季铵盐(Cn-1~Cn-15), 其中5个为新化合物, 另有4个的合成方法未见文献报道. 选用该类季铵盐催化剂催化二苯亚甲基甘氨酸叔丁酯的不对称苄基化反应, 结果发现, 催化剂苄基具有4-Br取代或羟基成醚均有助于提高反应产物的对映选择性. Cn-9可得到最优的反应结果, 产率93%, e.e.值91%.     

壳聚糖季铵盐/滤纸复合膜对胆红素的吸附研究

用2,3-环氧丙基三甲基氯化铵对壳聚糖进行化学修饰,在壳聚糖的分子结构中引入季胺盐基团,提高其阳离子含量。将壳聚糖季铵盐涂在滤纸上,用戊二醛交联,制得壳聚糖季铵盐/滤纸复合膜,考察该复合膜的强度以及对胆红素的吸附性能。实验结果表明,壳聚糖季铵盐/滤纸复合膜具有良好的力学性能;对胆红素的吸附在3h基本达到平衡,其吸附量远大于壳聚糖/滤纸复合膜;适当取代度及高交联度的复合膜吸附效果较好。复合膜对胆红素的吸附量随离子强度的增加而降低;血清白蛋白的加入使吸附量下降。     

新型咪唑啉缓蚀剂的合成与应用

采用苯甲酸、月桂酸、二乙烯三胺和三乙烯四胺为原料,合成了4种咪唑啉季铵盐缓蚀剂,研究了在50℃、体积分数为5%的HCl介质中,咪唑啉季铵盐与阴离子表面活性剂和无机阴离子的协同作用.结果表明,以月桂酸和三乙烯四胺为原料合成的咪唑啉季铵盐与I-质量比为1:1时,缓蚀效果最佳.在不同时间和不同温度下对复合型缓蚀剂的缓蚀率的研究结果表明,缓蚀剂在静态条件下对A3钢的缓蚀率可达99.4%.较之单独使用咪唑啉季铵盐提高了1.1%左右.     

大黄素衍生物的合成及抗癌活性

通过对大黄素的C6位进行化学修饰, 设计合成了7个含氮杂环的大黄素衍生物和3个含季铵盐基团的大黄素衍生物. 通过红外光谱、 ¹H NMR和质谱表征了所制备化合物的结构, 并测试了它们对白血病细胞Molt-4和淋巴瘤细胞CA46的体外抑制活性. 其中化合物8, 9a+9b, 20a, 20b和20c均显示出比大黄素更高的抗癌活性, 表明苯并咪唑基团和季铵盐基团是大黄素提高抗癌活性的有效药效团.     

GABAA受体萜类抑制剂构效关系研究

采用DISCOtech方法建立了大鼠和家蝇GABAA受体萜类抑制剂的药效团模型, 根据药效团模型叠加规则建立了大鼠和家蝇GABAA受体萜类抑制剂CoMFA模型, 模型的交叉验证相关系数分别为0.713和0.738. 构效关系研究显示， 家蝇和大鼠受体抑制剂结合部位之间存在一个主要差别: 与受体作用的抑制剂的负电荷基团取代有利于保持其对哺乳动物的高抑制活性, 而保持对昆虫的高抑制活性是不需要的, 从而为寻找先导化合物和设计高选择性杀虫剂提供了理论指导.     

Preparation and application of a glucose graft copolyammonium as shale inhibitor

In the paper, a shale inhibitor, glucose graft copolyammonium (GGPA), was prepared and evaluated by bentonite linear expansion test, anti-swelling experiments, mud ball experiments. The drilling fluid properties were evaluated. Anti-swelling results shows that anti-swelling rate of 0.8% GGPA reaches up to 94.5%. Mud ball experiment and drilling fluid evaluation showed that GGPA has strong inhibitive capability to bentonite hydration swelling. GGPA can control the particle size of bentonite. The inhibition mechanism of the polyamine salt was analyzed by thermogravimetric analysis and scanning electron microscope. The results demonstrate that the GGPA can be adsorbed on clay surface through electrostatic interaction and hydrogen bonds by an anchoring effect and a hydrophobic effect.     

季铵盐在油田化学品中的研究进展

介绍了季铵盐分子的特性(安全低毒、性能稳定、水溶性强)以及合成工艺,综述了季铵盐分子近年来在缓蚀剂、杀菌剂、页岩抑制剂以及有机改性剂方面的研究进展,以及作用机理.对于同一类处理剂的优缺点,季铵盐分子易生物降解、作用效果强使其使其广泛地应用于油田化学品中并符合钻井、完井、采油环保以及抗高温要求.结合上述四种油田化学处理剂...     

疏水改性低分子量阳离子聚丙烯酰胺抑制剂的制备及性能评价

针对现有阳离子类抑制剂与钻井液配伍性、抑制性较差的不足,本文以丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵、丙烯酸十八酯为原料,以乙醇和乙酸丁酯的混合物作溶剂,采用沉淀聚合法,制备出了疏水改性低分子量阳离子聚丙烯酰胺BJX-1页岩抑制剂。通过研究不同反应条件对BJX-1分子量的影响规律,得出溶剂组成对BJX-1分子量影响最大,可通过调节溶剂组成实现BJX-1分子量的控制。当分子量为1.45×10~5g/mol~1.87×10~5g/mol时,BJX-1的抑制性最好,页岩岩屑120℃热滚回收率约为78%;增加BJX-1中疏水结构单元含量至2%~4%时,可进一步提高BJX-1抑制性,使页岩岩屑120℃热滚回收率高于90%;此时的最佳反应条件为:以乙醇和乙酸丁酯按体积比90∶10~100∶0组成的混合物作为溶剂,引发剂质量分数为0.1%,单体质量分数为3%,在80℃下反应7h。通过对比研究发现,当加量为1%时,BJX-1所对应的页岩岩屑120℃热滚回收率分别比常用小分子阳离子化合物JA-1和高分子量阳离子聚合物DY-1高27.85%和50.06%。BJX-1更能提高钻井液的综合流变性能,使钻井液流变性更加稳定,而且具有优良的高温高压降滤失性。     

Mild pre-heating of organic cation-exchanged clays enhances their interactions with nitrobenzene in aqueous environment

Aqueous sorption kinetics and equilibrium isotherms of nitrobenzene were studied on two series of sorbents that were prepared by (i) replacing inorganic exchangeable cations in Wyoming bentonite with tetraethylammonium (TEA) and benzyltrimethylammonium (BTMA) and (ii) heating synthesized complexes in air at different temperatures (between 150 and 420°C). The aim of this work was to examine recently observed enhancement of aqueous sorption of a probe organic sorbate on organoclays after mild thermal pre-treatment of sorbents. Thermal pre-treatment of TEA- and BTMA-clays at 150°C results in the maximal enhancement of nitrobenzene–sorbent interactions as compared with treatment of original bentonite and its exchange complexes formed with long-chain quaternary ammonium (n-hexadecyltrimethylammonium, HDTMA). Based on C, N content data and FTIR spectra of TEA- and BTMA-clay complexes, no indications of decomposition of organic matter were found in organoclays heated at 250°C (and below this temperature). Suppressed hydration of pre-heated sorbents resulting in a lessening of water–organic sorbate competition for sorption sites is considered to be responsible for thermally induced enhancement of nitrobenzene–sorbent interactions. In the HDTMA-based organoclays, the long-chain aliphatic groups of the quaternary ammonium can additionally interact with clay surface thus competing with organic sorbate–sorbent surface interactions and, in this way, mitigating the enhancement of nitrobenzene sorption on thermally treated sorbents.     

Experimental Investigation of the Rheological Behavior of an Oil-Based Drilling Fluid with Rheology Modifier and Oil Wetter Additives

Drilling issues such as shale hydration, high-temperature tolerance, torque and drag are often resolved by applying an appropriate drilling fluid formulation. Oil-based drilling fluid (OBDF) formulations are usually composed of emulsifiers, lime, brine, viscosifier, fluid loss controller and weighting agent. These additives sometimes outperform in extended exposure to high pressure high temperature (HPHT) conditions encountered in deep wells, resulting in weighting material segregation, high fluid loss, poor rheology and poor emulsion stability. In this study, two additives, oil wetter and rheology modifier were incorporated into the OBDF and their performance was investigated by conducting rheology, fluid loss, zeta potential and emulsion stability tests before and after hot rolling at 16 h and 32 h. Extending the hot rolling period beyond what is commonly used in this type of experiment is necessary to ensure the fluid’s stability. It was found that HPHT hot rolling affected the properties of drilling fluids by decreasing the rheology parameters and emulsion stability with the increase in the hot rolling time to 32 h. Also, the fluid loss additive’s performance degraded as rolling temperature and time increased. Adding oil wetter and rheology modifier additives resulted in a slight loss of rheological profile after 32 h and maintained flat rheology profile. The emulsion stability was slightly decreased and stayed close to the recommended value (400 V). The fluid loss was controlled by optimizing the concentration of fluid loss additive and oil wetter. The presence of oil wetter improved the carrying capacity of drilling fluids and prevented the barite sag problem. The zeta potential test confirmed that the oil wetter converted the surface of barite from water to oil and improved its dispersion in the oil.     

Flammability and morphology of HDPE/clay nanocomposites

High-density polyethylene/modified bentonite clay/polar compatibilizer nanocomposites were prepared through the melt intercalation process. The clay was organophilizated using different percentages of quaternary ammonium salt 100, 125, and 150 % based cation exchange capacity of the clay. The nanocomposites were prepared in a counter-rotating twin-screw extruder and then specimens were injection molded. For the evaluation of flammability of the test system was used for burning in the horizontal position according to the norm (Underwriters Laboratories, UL94HB) and to the method of cone calorimeter. The thermal behavior of nanocomposites was evaluated by thermogravimetry and X-ray diffraction techniques, and transmission electron microscopy were used to characterize the morphology and analyze the degree of expansion of the clays prepared and the degree of exfoliation of nanocomposites. It was observed that the percentage of ammonium salt and the compatibilizer polar influence on the final properties of the systems and consequently improving the thermal stability and reducing the flammability of the matrix.     

Binol quinone methides as bisalkylating and DNA cross-linking agents

The photogeneration and detection of new binol quinone methides undergoing mono- and bisalkylation of free nucleophiles was investigated by product distribution analysis and laser flash photolysis in water solution using binol quaternary ammonium derivatives 2 and 12 as photoactivated precursors. The alkylation processes of N and S nucleophiles are strongly competitive with the hydration reaction. DNA cross-linking potency of the water-soluble binol quaternary ammonium salt 2 was investigated as a pH function and compared to that of other quaternary ammonium salts capable of benzo-QM (QM = quinone methide) photogeneration by gel electrophoresis. DFT calculations in the gas phase and in water bulk on the binol and benzo quaternary ammonium salts 2 and 4 evidence structural and electrostatic features of the binol derivative which might offer a rationalization of its promising high photo-cross-linking efficiency.     

Modified bentonite by polyhedral oligomeric silsesquioxane and quaternary ammonium salt and adsorption characteristics for dye

To remove methylene blue dye from water by adsorption, bentonites were modified by polyhedral oligomeric silsesquioxane (POSS) and three kind of quaternary ammonium surfactants (dodecyl trimethyl ammonium bromide, tetrabutyl ammonium bromide, cetyl trimethylammonium bromide) in aqueous solution. Systematic adsorption experiments were carried out, the adsorption mechanism was studied, and the factors governing the adsorption of methylene blue on modified bentonite were discussed. The adsorption capacity of methylene blue on all three modified bentonites in 1000 mg·L⁻¹ solutions quickly reached equilibrium within 2000 s, and the removal rate was basically 100%; however, the removal rate in raw bentonite samples was only 60%. The pseudo second-order kinetic model can provide satisfactory kinetic data fitting. The obtained adsorption isotherms fit well with the Dubinin-Radushkevich isotherm model. The thermodynamic results showed that the adsorption process was a spontaneous endothermic physical adsorption process. With increasing pH and KCl concentration, the removal of methylene blue increased significantly. The results of this study confirmed that the modified bentonite is a candidate material as a cationic dye adsorbent.     

有机改性膨润土对己唑醇水悬浮体系物理稳定性的影响

利用4种季铵盐阳离子表面活性剂（十二烷基二甲基苄基氯化铵(1227)、十四烷基二甲基苄基氯化铵(1427)、十六烷基三甲基氯化铵(1631)和十八烷基三甲基氯化铵(1831)）分别对钠基膨润土（Na-Ben）进行有机改性,制得4种有机膨润土（1227-Ben、1427-Ben、1631-Ben和1831-Ben）并进行了红外光谱及X射线分析,考察了4种有机膨润土在水中的悬浮性能及对5%己唑醇水悬体系物理稳定性能的影响。 FT-IR及XRD分析结果表明,供试季铵盐阳离子的有机碳链均进入到膨润土的片层间。 水中悬浮性能测定实验表明,1831-Ben在水中悬浮性能相对较好,而其它3种均不理想,特别是1227-Ben和1427-Ben表现出强烈的斥水现象。 沉降试验表明,有机膨润土的使用有助于5%己唑醇水悬浮剂物理稳定性的提高,其中用1831-Ben制备出的水悬浮体系的物理稳定性明显优于其它3种,制剂析水率最低,屈服值与粘度最大,体系悬浮率最高,可见1831-Ben可以用作5%己唑醇水悬浮剂的抗沉降剂。     

Characterization of pristine and purified organobentonites

Pristine and purified Argel sodium bentonites were organically modified with quaternary ammonium and phosphonium surfactants by ion exchange reaction in order to investigate the effect of the chemical identity of the surfactant and of the clay purification procedure in the intercalation process, final structure and thermal stability of organobentonites. The bentonites were characterized by X-ray diffraction analysis, thermogravimetric analysis and Fourier transform infrared spectroscopy. The bentonite purification treatment and, especially, the chemical structure of surfactant affected the thermal behavior of the organobentonites. The phosphonium modified bentonites were thermally more stable than those modified with ammonium, particularly the purified bentonite. These results seem to be promising regarding to the potential application of phosphonium modified Argel bentonites for the melt processing preparation of nanocomposites with polymeric matrices requiring high processing temperatures.