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。     

新型蓖麻油基季铵盐的合成及其抑菌性能研究

以蓖麻油酸甲酯为起始原料,与N,N-二甲基-1,3-丙二胺和溴化苄、溴乙烷通过酰胺化反应和季铵化反应生成了新型蓖麻油基季铵盐,其结构经FTIR、1HNMR、13CNMR及ESI-MS进行了确证。采用抑菌圈直径法对目标产物的抑菌性能进行了测试,结果表明,两种季铵盐均有一定的抑菌活性,N,N-二甲基-N-乙基-蓖麻油酸酰胺丙基溴化铵的抑菌活性略强于N,N-二甲基-N-苄基-蓖麻油酸酰胺丙基溴化铵。     

新型烷基酰胺丙基三甲基季铵盐表面活性剂的合成

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结构表征。利用得到的碳酸甲酯铵与有机酸反应,得到系列具有新型反离子X-〔X=HCOO,CH3COO,CH3CH(OH)COO〕的季铵盐。研究表明,该系列化合物随反离子亲水性的增强,最低表面张力变大,临界胶束浓度增大。     

Influence of the structure of the onium iodide salts on the properties of modified montmorillonite

Dialkyl imidazoline, alkyl pyridine and alkyl quinoline containing salts have been synthesized and used as new surfactants for cationic exchange of layered silicates, such as montmorillonite (MMT) in order to evaluate their role in the formation of intercalated MMT clays. The new salts have been characterized by FTIR, ¹H, ¹³C‐NMR spectra. These compounds have been intercalated into the layers of MMT via a solution dispersion technique and the extent of the interlayer space expansion was confirmed by using wide angle X‐ray diffraction and FTIR spectra. Thermogravimetry analysis shows that these salts can be used in place of ammonium salts to produce organophilic clays with higher thermal stability than commercial alkyl ammonium‐treated MMT. Moreover, the results also show that the imidazolium‐modified clays have a greater thermal stability compared to the quinolinium and the pyridinium‐modified clay. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of novel oligomeric poly(styrene‐co‐acrylonitrile)–clay complexes

Oligomeric poly(styrene‐co‐acrylonitrile) quaternary ammonium salts were prepared through reactions of trimethylamine with corresponding poly(styrene–acrylonitrile–vinyl benzyl chloride)s, which were synthesized by the free‐radical polymerization of a mixture of styrene, acrylonitrile, and vinyl benzyl chloride. Then, oligomeric poly(styrene‐co‐acrylonitrile)‐modified clays were prepared through the cation exchange of the sodium ions in the clay with the corresponding poly(styrene‐co‐acrylonitrile) quaternary ammonium salts. The poly(styrene–acrylonitrile–vinyl benzyl chloride)s, poly(styrene‐co‐acrylonitrile) quaternary ammonium salts, and their clay complexes were characterized with infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, proton nuclear magnetic resonance, X‐ray diffraction, and transmission electron microscopy. X‐ray diffraction and transmission electron microscopy studies showed that these novel clay complexes were well intercalated. Furthermore, thermogravimetric analysis data indicated that this series of polymerically modified clays had high enough thermal stability for nanocomposites by melt blending. The thermal treatment of one of these novel clays at 250°C under nitrogen was also conducted. Solubility and infrared studies of this thermally treated clay complex revealed that a novel polyimine/enamine structure clay complex had been formed in the gallery of the clay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

CO2‐derived latent nitrogen nucleophiles for controlled cross‐linking of brominated poly(isobutylene‐co‐isoprene)

New methods for preparing thermoset elastomer products from brominated poly(isobutylene‐co‐isoprene) (BIIR) are described, wherein control of cross‐linking dynamics is gained using latent forms of ammonia, primary amines, and cyclic amidines. BIIR cross‐linking by repeated alkylation of standard nitrogen nucleophiles is too rapid at standard polymer processing temperatures, whereas CO₂‐derived salts are shown to be sufficiently inactive under these conditions to support conventional BIIR compounding. Examples include the carbonate, bicarbonate and carbamate salts of ammonia; carbamate and carbamate esters of hexadecyl amine; and the bicarbonate salt of 1,8‐diazabicyclo[5.4.1]undec‐7‐ene. Thermal decomposition of these latent curatives releases CO₂ and the desired nucleophile to support high cross‐linking rates and yields at standard cure temperatures. Thermogravimetric analysis of salt decomposition, rheological measurements of cross‐link density, and spectroscopic analysis of polymer dehydrohalogenation products are used to define the relationship between latent nucleophile activation and BIIR cure dynamics. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

尼龙6/不同分子量的聚苯乙烯寡聚体修饰蒙脱土纳米复合材料的制备与性能测试

将分子量分别为1400、2500、5000的聚苯乙烯长链端基季铵盐改性的蒙脱土(OMMT),与尼龙6(PA6)母料熔融共混,注塑成型制备PA6/OMMT纳米复合材料,讨论不同分子量的聚苯乙烯长链季铵盐有机改性蒙脱土对纳米复合材料性能的影响。对所制得的复合材料通过TGA和热变形测试、弯曲、拉伸和冲击性能等力学性能测试。结果表明:分子量为2500,蒙脱土含量为3%时的复合材料的热稳定性和综合力学性能较好。     

Poly(ε-caprolactone)/clay nanocomposites prepared by melt intercalation: mechanical, thermal and rheological properties

(Nano)composites of poly(ε-caprolactone) (PCL) were prepared by melt blending the polymer with natural Na⁺ montmorillonite and montmorillonite modified by hydrogenated tallowalkyl (HTA)-based quaternary ammonium cations, such as dimethyl 2-ethylhexyl HTA ammonium and methyl bis(2-hydroxyethyl) HTA ammonium. Microcomposites or nanocomposites were prepared depending on whether neat or modified montmorillonites was used, as assessed by X-ray diffraction and transmission electron microscopy. Mechanical and thermal properties were studied as a function of the filler content by tensile testing, Izod impact testing, thermogravimetric analysis and differential scanning calorimetry. The rheological behaviour at 80 °C was also analysed in relation to the structure and content of the layered silicate. Effect of exfoliated silicates on the mechanical properties, thermal stability and flame resistance of PCL was considered. Stiffness and thermal stability improved with the filler loading until a content of 5 wt%. Further loading resulted in the levelling off and possibly in a decrease of these properties. A marked charring effect was observed upon exposure to a flame.     

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.     

Design and synthesis of ionic-conductive epoxy-based networked polymers

To develop ionic-conductive film-shaped electrolytes with high reliability, we designed and synthesized the following networked polymers with an epoxy/amine curing system using poly(ethylene glycol) as the main skeleton, and examined their fundamental properties such as ionic conductivity, thermal stability, and inflammability. (1) Networked polymers having quaternary ammonium salt structures. (2) Networked polymers having lithium sulfonate salt structures. (3) Networked polymers having lithium sulfonylimide salt structures. (4) Networked polymers swollen with ionic liquid solutions of lithium salts. Consequently, we found that networked polymers swollen with ionic liquid solutions containing lithium salts showed high ionic conductivity and high thermal stability with excellent non-flammability.     

New Takes on Nitrate Ester Chemistry: Salts with Oxygen‐Rich Ammonium Cations

Nitrate (anion) salts with nitroxy‐functionalized ammonium cations were synthesized. Several revealed surprising thermal and hydrolytic stability. Various physical properties were measured, and Gibbs free energy (ΔG_r(298)) differences between the salts and postulated products of their thermal decomposition were computed. The computed differences indicate that salts with cations that have more than one nitroxy group are endothermic at 298 K. Nevertheless, the stability observed for some salts with this property indicates that kinetic barriers are sufficient to prevent facile decomposition at this temperature. This is in contrast to the case observed for nitrate salts of nitroxy‐functionalized ammonium cations with acidic protons.     

季铵盐链长及用量对CnTA+/蒙脱石纳米复合物吸附PAEs的影响

用具有相同结构但不同烷基碳链长度的系列季铵盐制得C_nTA⁺/蒙脱石纳米复合物,并对水溶液中邻苯二甲酸酯进行吸附实验。探讨了季铵盐烷基碳链链长和用量对制得的C_nTA⁺/蒙脱石纳米复合物吸附水溶液中PAEs效果的影响。结果表明:C_nTA⁺/蒙脱石纳米复合物能有效地吸附溶液中的PAEs,季铵盐烷基碳链链长及用量均对C_nTA⁺/蒙脱石纳米复合物的吸附效果产生影响。当季铵盐用量较低时,随着季铵盐烷基链长的增加,PAEs的吸附去除率增加;增大季铵盐用量,随着季铵盐烷基链长的增加,PAEs的吸附去除率先增大后减小。     

山嵛酸双酯基有机硅季铵盐的微波合成工艺及性能

以山嵛酸、N-甲基二乙醇胺以及γ-氯丙基三甲氧基硅烷为主要原料,分别经过酯化和季铵化反应两步合成了一种超长碳链的双酯基有机硅季铵盐,并通过单因素、正交试验得到了微波法合成目标产物的最优工艺条件为：设置微波功率为800W,物料摩尔比为n（硅烷）∶n（酯胺）=1.2∶1,反应温度为170℃,溶剂用量为m（溶剂）∶m（原料）=0.8∶1,反应时间为12h,产品产率达96.60%。此方法克服了长链叔胺季铵化过程中普遍耗时过长的困难,提高了反应速率,而且实验重复性良好。实验中采用红外光谱、核磁共振氢谱对中间体及目标产物的结构进行了表征,与预期结果一致;建立了高效液相色谱-蒸发光散射检测器（HPLC-ELSD）测定季铵盐纯度的方法,基线稳定,峰型良好,产品纯度达98.77%,具有一定的参考价值。性能测试结果表明：对比DC-5700,目标产物具有良好的热稳定性,优异的乳化及增溶性能;其水溶液的临界胶束浓度为1.81mmol/L,表面张力（γ_CMC）为49.4mN/m。     

4,4′-(双3,4-二氰基苯氧基)联苯树脂复合材料研究

以二苯砜二胺为固化剂,钼酸铵为催化剂合成了4,4′-(双3,4-二氰基苯氧基)联苯(BPH)的预聚物树脂,采用溶液浸渍法制备了玻璃纤维布预浸料,热压方式制备了玻纤增强4,4′-(双3,4-二氰基苯氧基)联苯树脂复合材料。通过示差扫描量热仪(DSC)、旋转流变仪(Rheometer)、傅里叶变换红外光谱(FTIR)、热重分析仪(TGA)和扫描电子显微镜(SEM)对树脂的固化反应,化学结构,复合材料的热稳定性和断面形貌进行了研究与表征。结果表明,钼酸铵可以显著的促进单体的预聚反应,聚合物玻璃化转变温度为380℃,复合材料具有优良的热稳定性,在氮气和空气中的5%分解温度分别为542℃和482℃,375℃处理20 h后弯曲强度保持率为97%,沸水中处理24 h后吸水率为1.4%。     

季铵盐-季戊四醇低共熔混合物中合成磷酸铝分子筛

在4种季铵盐和季戊四醇的低共融混合物中合成了磷酸铝分子筛,并通过X射线衍射、扫描电子显微镜、热重分析以及核磁共振技术进行表征。结果表明,在氯化胆碱和四乙基氯化铵的低共熔混合物中分别合成了AlPO4-16和AlPO4-5分子筛,而在四丙基溴化铵和四丁基溴化铵低共熔混合物中仅得到方石英致密相。表明在实验条件下,季铵盐阳离子的电荷密度影响结构导向能力,电荷密度越小,结构导向能力越弱。     

桉木防腐的初步研究

以赤桉边材为试件,采用六种防腐剂,经加压浸注法对试件进行防腐处理,检验防腐剂的防腐效果,并且对用两种季铵盐防腐剂处理过的木材进行了抗流失实验。结果表明,当季铵盐-1、酸性铬酸铜(ACC)、铜铬硼(CCB)的药剂保持量为5,7.5,8.3 kg/m3时,经木腐菌腐朽后,试样的质量损失率分别为0.66%,0.59%和0.47%,有较好的耐腐效果。而且通过抗流失性实验发现,两种季铵盐与木材作用后,对水较为稳定,即两者的抗流失性能较好。     

Synthesis,Corrosion Inhibition Performance and Biodegradability of Novel Alkyl Hydroxyethyl Imidazoline Salts

New alkyl hydroxyethyl imidazoline salts were synthesized via a high pressure process with imidazoline and dimethyl carbonate, and their chemical structure were confirmed using mass spectral fragmentation and FTIR spectroscopic analysis. In addition, several quaternary ammonium salts with new counterions (formic acid, acetic acid and lactic acid) were also synthesized by ion exchange reaction of methyl carbonate quaternary ammoniums with the corresponding acids. These new compounds reduced the surface tension of water to a minimum value of approximately 27 mN m^?1 at a concentration of 8.72 × 10^?5 mol L^?1. They also show efficient corrosion inhibition performances and could significantly inhibit the corrosion of mild steel in acid solutions. It was also found that the biological degradation of these imidazoline surfactants was greater than 98 % after 7 days.     

特殊结构吉米奇(Gemini)季铵盐性能及其在油田中的应用

对几种特殊结构吉米奇(Gem in i)季铵盐的性能进行研究,其中包括含有聚氧乙烯基、超支化、不对称吉米奇季铵盐,并对其在油田三采驱油、油田防膨、油田杀菌方面的应用进行了综述。     

Keggin型磷钨钒杂多酸季铵盐的合成、表征及抑菌效果的研究

以不同钒原子数取代Keggin型磷钨杂多酸并与十六烷基三甲基溴化铵反应合成了3种杂多酸季铵盐.通过红外光谱(IR)、X-射线衍射(XRD)、紫外(UV)等表征手段确定了杂多酸以及杂多酸季铵盐的结构.结果表明,在红外光谱中,引入钒原子后阴离子负电荷增加,导致相应的特征峰出现红移现象;从X-射线衍射谱图中确定了杂多酸季铵盐的二级结构,最后通过热重分析(TG)得出杂多酸季铵盐所含结晶水的数目.通过杯碟法测试了目标产物对大肠杆菌、金黄色葡萄球菌、枯草芽孢杆菌、蜡样芽孢杆菌的抑菌性能,结果表明杂多酸季铵盐对枯草芽孢杆菌的抑菌能力最好,并且钒原子所占比例越高,抑菌效果越好.     

季铵盐改性蒙脱土的抗菌活性及抗菌机理

采用离子交换法将不同季钱盐插层到钠基蒙脱土中制备了改性蒙脱土.改性蒙脱土对革兰氏阳性菌(S.aereus)和革兰氏阴性菌(E coli)均有很强的抗菌作用,并且随着季铵盐在蒙脱土中的质量分数增加其抗菌活性增强.不同季铵盐改性蒙脱土的抗菌活性不同,其中双季铵盐改性蒙脱土的抗菌活性最好,对S.aereus和E coli的最小抑菌浓度分别为6.25 mg/L和12.5 mg/L.用扫描电镜对与细菌接触不同时间后的改性蒙脱土进行观察,结果表明:细菌先吸附到改性蒙脱土的表面,然后慢慢的变形死亡.同时,对在0.9%的生理盐水中浸泡不同时间后的改性蒙脱土进行X射线衍射和热重分析.结果表明:随着浸泡时间的增加,蒙脱土中的有机物质量分数及层间距均逐渐减少,说明季铵盐能从蒙脱土的层间解吸出来,并进入溶液中直接杀死细菌.因而,改性蒙脱土的抗菌活性是吸附与释放到溶液中的季铵盐离子协同作用的结果.