Synthesis, Characterization and Properties of New Lauryl Amidopropyl Trimethyl Ammoniums

A new lauryl amidopropyl trimethyl ammonium methyl carbonate with the formula CH₃(CH₂)₁₀CONH(CH₂)₃N⁺(CH₃)₃CH₃CO₃ ^? was synthesized via a high pressure process with tertiary amines and dimethyl carbonate, and its chemical structure was confirmed using ¹H-NMR spectra, mass spectral fragmentation, and FTIR spectroscopic analysis. In addition, several quaternary ammonium salts with new counterions X^? (X^?=HCO₃ ^?, HCOO^?, CH₃COO^?, CH₃CH(OH)COO^?) were also synthesized by the ion exchange reaction of methyl carbonate quaternary ammoniums with corresponding acids. The surface activities of these compounds were measured, including surface tension (??), critical micelle concentration and minimum surface area (A _min) at 25?°C. Adsorption and micellization free energies of these quaternary ammonium salts in their solutions showed a good tendency towards adsorption at interfaces. The antimicrobial activities are reported for the first time against representative bacteria and fungi for lauryl amidopropyl trimethyl ammoniums. It was found that the antimicrobial potency was Gram-positive bacteria?>?fungi?>?Gram-negative bacteria.     

两种高效低成本咪唑啉类缓蚀剂的研制

为了缓解油田设备因腐蚀引起的问题,实验通过有机合成方法,用苯甲酸(油酸)和三乙烯四胺及氯化苄合成得到咪唑啉季铵盐缓蚀剂,经过油酸咪唑啉季铵盐缓蚀剂与苯甲酸咪唑啉季铵盐缓蚀剂的复配后,通过静态失重法进行评价。结果表明这类缓蚀剂的最佳加药浓度为30 mg·L-1,此时两种酸类咪唑啉季铵盐含量比为2∶3时的缓蚀效率可以达到97.4%;主剂(苯甲酸∶油酸=2∶3)与硫脲、乌洛托品、乙酰苯胺按比例10∶5∶2∶1复配缓蚀效率可以达到98.4%,符合油田生产需求。     

Synthesis and Characterization of Lauryl Trimethyl Ammonium Surfactants with New Counteranion Types

A new family of lauryl trimethyl ammonium surfactants of the general formula CH₃(CH₂)₁₁ N⁺(CH₃)₃X^? (X = CH₃OCOO, HCOO, CH₃COO, CH₃CHOHCOO) were prepared and characterized both structurally and as aqueous surfactants. Lauryl trimethyl ammonium mono-methyl carbonate was synthesized by using dimethyl carbonate (DMC) as the alkylating agent and lauryl dimethyl amine as the starting material. The latter compound was reacted with formic acid, acetic acid, and lactic acid, respectively, to give the corresponding quaternary ammonium salts with other counteranions. They were structurally characterized by IR, ¹H NMR, MS. Members of this family reduced the surface tension of water to 32–38 mN/m at concentration levels of 10^?2 mol/L.     

盐类浓度对油酸咪唑啉季铵盐缓蚀率的影响

针对油田污水富含钙、镁、钠等盐类的现状,合成了油酸咪唑啉季铵盐,采用电化学极化法和静态失重法测试了其缓蚀性能,并采用电化学极化法考察了强酸腐蚀介质中氯化钙、氯化镁及氯化钠3种盐的浓度对该缓蚀剂缓蚀率的影响。结果表明:该缓蚀剂是一种以阳极抑制为主的混合型缓蚀剂;在1mol·L-1 HCl溶液中,当缓蚀剂浓度为5mg·L-1时,N80钢片的腐蚀速率和缓蚀剂的缓蚀率趋于稳定;随着介质中盐类浓度的增大,缓蚀剂的缓蚀率逐渐减小。分析认为,缓蚀率减小的原因可能是由于介质的电导率增大,导致腐蚀速率加快。     

油田注水缓蚀剂SW-638的研制及应用

以长链脂肪酸、多乙烯多胺等为原料,以磷酸酯为季胺化试剂,合成了含膦咪唑啉季胺盐,与缓蚀增效剂H和缓蚀增效剂T复配,研制出油田注水缓蚀剂SW-638,其最优组成为：咪唑啉季胺盐60％、缓蚀增效剂H10％和缓蚀增效剂T4％;在延长油田-污水处理站进行了应用试验,SW-638投加量为50mg/L,经过连续30d的监测,结果试片表面光亮,无点蚀,平均腐蚀速率为0．0326mm／a,满足〈0．076mm／a的油田注水要求。     

咪唑啉季铵盐缓蚀剂的合成与复配研究

以油酸、二乙烯三胺及硫酸二甲酯为主要原料,二甲苯为携水剂,合成咪唑啉季铵盐。结果表明,咪唑啉季铵盐的最佳合成条件为:二乙烯三胺与油酸摩尔比为1.2∶1,二甲苯10 mL,酰胺化温度160℃,反应时间2 h,环化温度200℃,环化时间6 h,季铵化试剂为硫酸二甲酯,季铵化反应温度50℃,季铵化反应时间2.5 h。4 mg/L加量的咪唑啉缓蚀剂在模拟盐水介质中的缓蚀率可达到90.1%。当其与丙炔醇、碘化钾、十二烷基硫酸钠(SDS)单独复配时,在合适的复配比例下,均具有良好的协同效应。     

一种新型固体缓蚀剂的合成及性能

以二聚油酸和二乙烯三胺为原料,氯乙酸为反应介质,经酰胺化、环化和季铵化反应合成了新型咪唑啉。通过正交实验研究,确定最优合成条件为:n(二乙烯三胺)∶n(二聚油酸)=1∶2.1;酰胺化时间3.5 h,季铵化时间3 h。通过红外光谱分析表明,产物为咪唑啉季铵盐,经测定其季铵盐质量分数为理论值的80%左右;通过ρ(C l-)=157 305 mg/L、CO2分压为3.5 MPa、在120℃和20 MPa条件下的油田模拟工况实验,证明该咪唑啉季铵盐对N80套管钢缓蚀率在85%以上,符合西部油田苛刻的腐蚀环境要求。     

咪唑啉季铵盐缓蚀剂改性蒙脱土/水性环氧纳米复合涂料

以油酸、二乙烯三胺和氯化苄为原料,合成了油酸基咪唑啉季铵盐缓蚀剂。通过FTIR、¹HNMR对其结构进行了表征,并离子交换至钠基蒙脱土(DK0)层间,制备了缓蚀剂改性蒙脱土(QACDK0)。通过XRD、TGA和UV-Vis对其结构、组成及层间缓蚀剂释放性能进行了表征。结果表明,咪唑啉季铵盐缓蚀剂约占QACDK0质量的38.96%,并将蒙脱土层间距由1.28 nm(DK0)扩大至3.98 nm(QACDK0)。利用DLS及Zeta电位对添加有QACDK0的水性环氧树脂进行了稳定性测试,其Zeta电位为–27.8 m V,具有较高的稳定性。电化学阻抗谱(EIS)测试表明,在腐蚀介质中浸泡30 d后,基于QACDK0制备的清漆漆膜仍具有2.29×10⁸?·cm²的高阻抗,表明涂层具有较好的耐腐蚀性。并且在耐中性盐雾测试中,QACDK0对应的防腐色漆耐盐雾时间最长,验证了该涂层具有良好的耐盐雾性能。     

水溶性咪唑啉缓蚀剂的合成及缓蚀性能评

采用硬脂酸、壬酸、二乙烯三胺和羟乙基乙二胺为原料,合成了四种咪唑啉母体,以丙烯酸甲酯为烷基化试剂、氯乙酸钠为季胺化试剂分别合成新型的咪唑啉缓蚀剂。采用红外光谱对产物进行分析表征,考察咪唑啉缓蚀剂的溶解度及水溶液的稳定性,用静态失重法和电化学法研究了缓蚀剂与有机胺类复配后在HCl腐蚀介质中的缓蚀性能。结果表明,合成的咪唑啉季铵盐水溶性良好,复配后在HCl体系中缓蚀率达到85%以上,且是以阴极型为主的复合型缓蚀剂。     

Synthesis of Quaternary Ammonium Salts with Novel Counterions

The preparations of quaternary ammonium compounds from various tertiary amines and the (environmentally friendly) alkylation agent dimethyl carbonate were carried out. The effects of reaction temperature, reaction time, material mol ratio and solvent dosage on quaternization were examined, and the optimum reaction conditions were determined. Under the optimum conditions, the conversions of mono-alkyl tertiary amines could attain over 99%, while the conversions of di-alkyl tertiary amines reached over 95%. Moreover, a series of quaternary ammonium salts with new counterions (HCO₃, CH₃COO, CH₃CH₂COO, CH₃CH(OH)COO) were synthesized by the hydrolysis of methyl carbonate quaternary ammonium salts or by ion exchange reaction of methyl carbonate quaternary ammonium salts with corresponding acids.     

Properties of the Quaternary Ammonium Salts with Novel Counterions

The Krafft temperatures, surface tensions and bacteriostatic efficacies of a series of dodecyl/tetradecyltrimethylammonium salts with new type counterions based on the general formula RN⁺(CH₃)₃?A^? were measured. The results revealed that the Krafft temperatures of the studied products were below 0?°C and the surface tensions of water were decreased to 22?C42?mN?m^?1 when applying these surfactants at a concentration range from 10^?2 to 10^?4?mol?L^?1. Moreover, the physicochemical parameters such as the saturation adsorption value, the minimum area per surfactant molecule and the standard thermodynamic parameters of adsorption and micellization varied with different counterions for these prepared quaternary ammonium salts. In addition, the bacteriostatic tests showed that the counterions with shorter carbon chain lengths were associated with greater efficacy for the novel quaternary ammonium salts studied here.     

咪唑啉缓蚀剂合成工艺优化及吸附性能

以油酸、二乙烯三胺为原料,氧化钙为脱水剂,氯化苄为季铵化试剂,经酰胺化-环化、季铵化合成了新型咪唑啉季铵盐缓蚀剂,并对其吸附过程进行了研究.响应面法优化了油酸与二乙烯三胺摩尔比、环化时间和环化温度等合成关键工艺条件,采用红外光谱和可见光吸收光谱法分析产品结构,以动电位扫描极化曲线法评价缓蚀效果.以0.05mol油酸为基准,氧化钙0.10mol,氯化苄0.06mol,季铵化时间2.5h,季铵化温度55℃条件下,优化结果为:n(油酸):n(二乙烯三胺)为1:1.18,环化温度162.8℃,环化时间5.55h;在50℃缓蚀剂浓度200mg/L、15%盐酸溶液中缓蚀率可达94%;该缓蚀剂的吸附行为符合Langmuir 吸附等温式,为自发放热过程,50℃下吸附平衡常数为1.0277′10⁵L/mol,吉布斯自由能为-41.75kJ/mol,吸附热能为-54.07kJ/mol,熵值为-38.11J/(K·mol),属于以化学吸附为主的过程.与同类合成工艺相比较,环化温度明显降低,产物具有优异的缓蚀性能.     

咪唑啉衍生物在含有饱和CO2的10%NaCl溶液中对Q235钢的缓蚀性能研究

合成了三种不同结构的咪唑啉季铵盐YZS、ZLS和YS,采用线性极化和动电位扫描研究了三种缓蚀剂对Q235钢在90℃下CO2饱和的10%NaCl体系中的缓蚀效率。结果表明,三种缓蚀剂的作用类型为以阳极抑制为主的混合型缓蚀剂,其中YZS的缓蚀效率最高,ZLS的缓蚀效率最低,且YZS和YS缓蚀剂存在一个吸附饱和浓度。     

新型烷基酰胺丙基三甲基季铵盐表面活性剂的绿色合成

在高压条件下,以叔胺和碳酸二甲酯为原料,合成了新型季铵盐表面活性剂-C16/C18烷基酰胺丙基三甲基碳酸甲酯铵,通过质谱和红外光谱对其进行表征。利用得到的碳酸甲酯铵分别与相应的酸进行反离子转化反应,得到系列具有新型反离子X- (X=HCOO, CH3COO, CH3CH(OH)COO)的季铵盐。初步研究了此系列化合物的表面张力,结果表明反离子对季铵盐的表面性能有影响。     

Synthesis,Characterization and Surface-Activity of Hydroxyethyl Group-Containing Quaternary Ammonium Surfactants

A novel series of hydroxyethyl group-containing quaternary ammonium salts were synthesized from mono-, di-, tri-alkyl tertiary amines, hydrochloric acid and ethylene oxide by a two-step process with mild reaction conditions. The structures of the quaternary ammonium salts were characterized by infrared spectroscopy and ¹H-nuclear magnetic resonance spectroscopy. The surface tensions at the critical micelle concentrations were measured to investigate the surface activities of the prepared compounds. The results showed that the hydroxyethyl group quaternary ammonium salts exhibit high surface activities.     

一种油田注水缓蚀剂的合成及性能评价

合成缓蚀剂的最佳工艺条件为：油酸与二乙烯三胺的摩尔比为1：1．2,咪唑啉中间体的合成时间8h,环化温度为220℃,中间体与季铵化试剂DMS的摩尔比为1：1。采用静态失重法,对在最佳工艺条件下合成的咪唑啉季铵盐进行缓蚀性能评价。结果表明,当咪唑啉季铵盐缓蚀剂加量为1000mg／L时,就能达到很好的缓蚀性能;并且缓蚀剂的用量为500mg／L时,24h腐蚀速率为0．019mm／a,80℃时腐蚀速度为0．0214mm／a,将咪唑啉季铵盐以500mg／L与十二烷基硫酸钠（SDS）300mg／L、碘化钾（KI）1500mg／L、十二烷基苯磺酸钠（SDBS）200mg／L复配。其缓蚀率最高可达77．16％。     

硫脲基松香咪唑啉季铵盐 对A3碳钢的缓蚀性能研究

合成了硫脲基松香咪唑啉季铵盐,对其结构进行了红外和核磁表征。采用失重法、动电位极化曲线、交流阻抗以及接触角测试分析了目标产物在质量分数为15%HCl溶液中对A3碳钢的缓蚀性能。采用AFM以及XPS测试对产物的吸附膜进行了表征。结果表明：目标产物的缓蚀效率随添加质量分数的增加先增大后减小,当目标产物质量分数增加到占盐酸质量的0.4%时,缓蚀效率最高达到90.78%;此物质是一种阴极控制为主的混合型缓蚀剂;AFM以及XPS结果证实目标产物确实可以在碳钢表面形成缓蚀剂吸附膜。     

新咪唑啉缓蚀剂的合成及性能表征

以菜籽油,二乙烯三胺为原料合成咪唑啉中间体,以丙烯酸甲酯为烷基化试剂、氯乙酸钠为季胺盐化试剂合成新型的咪唑啉缓蚀剂,并以不同浓度的硫酸溶液为介质研究其对钢样的缓释效率。实验结果表明:当硫酸的浓度为20%,缓蚀剂量为0.5%(v/v),浸泡时间为4h时,其缓释效率最好,达到了93.9%。     

新型咪唑啉季铵盐缓蚀剂合成工艺研究与性能评价

以油酸和二乙烯三胺为原料,氧化钙为脱水剂,氯化苄为季铵化试剂,合成了新型咪唑啉季铵盐缓蚀剂。合成工艺条件为：油酸0．05mol,二乙烯三胺0．06mol,氧化钙0．1mol,在80℃下酰胺化2h,升温至160℃环化反应6h,加入氯化苄0．06mol,在55℃季铵化反应2．5h。结果表明,与现有甲苯为挟水剂工艺比较,该工艺酰胺化及环化反应温度低,咪唑啉成环性能及缓蚀效果好;N80钢片在25℃下HCl浓度0．5mol／L,缓蚀剂浓度200mg／L的溶液中,缓蚀率高达85．6％。     

咪唑啉缓蚀剂对J55钢的缓蚀性能研究

以油酸、二乙烯三胺、氯化苄为原料合成反应得到咪唑啉季铵盐缓蚀剂。通过失重法和极化曲线法研究了这种咪唑啉化合物在模拟油田地层水中对J55钢的缓蚀性能,并通过金相显微镜观察了J55钢表面的腐蚀形貌。结果表明,咪唑啉季铵盐缓蚀剂在酸性油田地层水中对J55钢有较好的缓蚀效果。