WO2024037067A1 - 一种含多季铵头基阳离子低聚表面活性剂及其制备方法 - Google Patents

一种含多季铵头基阳离子低聚表面活性剂及其制备方法 Download PDF

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WO2024037067A1
WO2024037067A1 PCT/CN2023/093862 CN2023093862W WO2024037067A1 WO 2024037067 A1 WO2024037067 A1 WO 2024037067A1 CN 2023093862 W CN2023093862 W CN 2023093862W WO 2024037067 A1 WO2024037067 A1 WO 2024037067A1
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head groups
quaternary ammonium
ammonium head
cationic oligomeric
containing multiple
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PCT/CN2023/093862
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French (fr)
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姜亚洁
侯仕达
王亚魁
耿涛
李俊
鞠洪斌
王志飞
张璐
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中国日用化学研究院有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
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    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/18—Quaternary ammonium compounds

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  • the invention relates to the technical field of surfactants, and in particular to a cationic oligomeric surfactant containing multiple quaternary ammonium head groups and a preparation method thereof.
  • Quaternary ammonium surfactants are a type of cationic surfactants that have experienced great development in recent years and have been widely used in industry and daily necessities. With the continuous development of the surfactant industry and the changing needs of production and life, quaternary ammonium salt surfactants continue to develop new uses and are used in many industries such as light industry, disinfection and sterilization, textile auxiliaries, petrochemicals, and sanitary product additives. field played an important role.
  • oligomeric quaternary ammonium salts are gemini quaternary ammonium salts containing two quaternary ammonium head groups and oligomeric quaternary ammonium salt surfactants containing three quaternary ammonium head groups; oligomeric quaternary ammonium salts are formed by connecting groups. It is a new type of surfactant that connects several monomer quaternary ammonium salts at or near the hydrophilic head group. This connection weakens the electrostatic repulsion between ionic head groups, enhances the hydrophobic binding force between hydrophobic chains, and makes the surfactant molecules more closely arranged at the surface/interface.
  • the test results show that the product has a CMC of 8.2 ⁇ 10 -5 mol ⁇ L -1 and a ⁇ CMC of 38.57mN ⁇ m -1 . It has excellent surface activity, and the presence of multiple quaternary ammonium head groups makes the product significantly bactericidal. promote.
  • the product obtained by this method contains three quaternary ammonium salt structures and has excellent structural properties. However, the reaction time of the three-step reaction is more than 48 hours, and the synthesis efficiency is low. The obtained product is a light yellow oily liquid, which is difficult to purify. Improving the synthesis method and process conditions is the main problem that needs to be solved urgently in this type of synthesis research.
  • the object of the present invention is to provide a cationic oligomeric surfactant containing multiple quaternary ammonium head groups, and to solve the problems of complex synthesis processes, long time, and difficulty in product purification of existing cationic surfactants containing multiple quaternary ammonium head groups. question.
  • the invention provides a cationic oligomeric surfactant containing multiple quaternary ammonium head groups, which has the following general structural formula:
  • R is a C 1 to C 18 alkyl group; n is a positive integer between 2 and 10; X is one of Cl, Br or I.
  • the invention also provides a preparation method of a cationic oligomeric surfactant containing multiple quaternary ammonium head groups, which includes the following steps:
  • the solvent in S1 is a low-carbon alcohol solvent; the acid is a monovalent inorganic acid.
  • the C 1 to C 18 alkyl tertiary amine (2), acid, and quaternization reagent (3) described in S1 The molar ratio of 20 ⁇ 50%.
  • the reaction time described in S1 is 2 to 6 hours, and the reaction temperature is 60 to 100°C.
  • the molar ratio of the intermediate compound (4) described in S2 to the alkyldiamine compound (5) is 1: 0.5 ⁇ 0.55.
  • the reaction time described in S2 is 4 to 12 hours, and the reaction temperature is 80 to 120°C.
  • the cationic oligomeric surfactant containing multiple quaternary ammonium head groups provided by the present invention is an organic compound with a stable structure.
  • the structure contains 2 hydroxyl groups and 4 quaternary ammonium head groups.
  • the product has good water solubility and excellent surface properties. /interface activity.
  • the cationic oligomeric surfactant containing polyquaternary ammonium head groups provided by the present invention has not been reported before. It has a simple preparation process, easy access to reaction raw materials, mild reaction conditions, and the entire reaction process does not produce toxic and harmful by-products. It belongs to the atom economy. type reaction.
  • Figure 1 is the hydrogen nuclear magnetic resonance spectrum and signal attribution diagram of the cationic oligomeric surfactant containing multiple quaternary ammonium head groups prepared in Example 1;
  • Figure 2 is the Fourier transform infrared spectrum of the cationic oligomeric surfactant containing multiple quaternary ammonium head groups prepared in Example 1;
  • Figure 3 is a surface tension curve diagram of the cationic oligomeric surfactant aqueous solution containing multiple quaternary ammonium head groups prepared in Example 1;
  • Figure 4 is a graph of the oil-water interfacial tension-time change curve of the cationic oligomeric surfactant containing multiple quaternary ammonium head groups prepared in Example 1.
  • the invention provides a cationic oligomeric surfactant containing multiple quaternary ammonium head groups, which has the following general structural formula:
  • R is a C 1 to C 18 alkyl group; n is a positive integer between 2 and 10; X is one of Cl, Br or I.
  • the general structural formula of the cationic oligomeric surfactant containing multiple quaternary ammonium head groups is preferably:
  • R is a C 1 to C 18 alkyl group
  • X is one of Cl, Br or I
  • R is a C 1 to C 18 alkyl group
  • the invention also provides a preparation method of a cationic oligomeric surfactant containing multiple quaternary ammonium head groups, which includes the following steps:
  • the specific process of mixing the C 1 to C 18 alkyl tertiary amine (2), quaternizing reagent (3), acid, and solvent is: stirring the C 1 to C 18 alkyl tertiary amine (2 ), add the acid solution diluted with the solvent dropwise, add the quaternization reagent (3) after the acid mist disappears, and obtain the intermediate compound (4) through a quaternization reaction under the action of acid.
  • the solvent mentioned in S1 is preferably a low-carbon alcohol solvent, and further preferably is any one or a combination of ethanol, isopropanol, n-propanol, and n-butanol.
  • the acid mentioned in S1 is preferably a monobasic inorganic acid, and further preferably is one of HCl, HBr or HI.
  • the molar ratio of the C 1 to C 18 alkyl tertiary amine (2), acid, and quaternization reagent (3) mentioned in S1 is preferably 1:1 to 1.1:1 to 1.1, and more preferably 1 : 1.02 ⁇ 1.0.8: 1.02 ⁇ 1.0.8, more preferably 1:1.05:1.05;
  • the quality of the solvent is the C 1 to C 18 alkyl tertiary amine (2) described in S1, the quaternization reagent ( 3), 20 to 50% of the total mass of acid and solvent, more preferably 25 to 40%, more preferably 30%.
  • the reaction time in S1 is preferably 2 to 6 hours, more preferably 3 to 5 hours, and more preferably 4 hours; the reaction temperature is preferably 60 to 100°C, further preferably 70 to 90°C. More preferably, it is 80°C.
  • the molar ratio of the intermediate compound (4) described in S2 to the alkyldiamine compound (5) is preferably 1:0.5-0.55, more preferably 1:0.51-0.53, and more preferably 1: 0.52.
  • the reaction time in S2 is preferably 4 to 12 hours, more preferably 6 to 10 hours, and more preferably 8 hours; the reaction temperature is preferably 80 to 120°C, and further preferably 90 to 110°C. More preferably, it is 100°C.
  • the alkyl diamine compound (5) is added to the intermediate compound (4) as described in S2. After the reaction, the solvent is removed by distillation under reduced pressure, and recrystallization is performed to obtain the target product containing polyquaternary ammonium heads.
  • the recrystallization solvent is preferably a mixed solvent of ethyl acetate and ethanol, and the volume ratio of ethyl acetate and ethanol in the mixed solvent is preferably 10 to 20:1, and further preferably 12 ⁇ 18:1, more preferably 15:1.
  • the invention provides a preparation method of a cationic oligomeric surfactant containing multiple quaternary ammonium head groups, which includes the following steps:
  • the intermediate product prepared above and the target product contain polyquaternary ammonium head groups cationic oligomerization surface
  • the Fourier transform infrared spectrum of the active agent is shown in Figure 2. As can be seen from Figure 2, the profiles of the intermediate product and the target product are basically similar.
  • the absorption peak at 3386cm -1 is the stretching vibration of the OH bond, and the absorption peaks at 2920, 2850 and 1467cm -1 It is the stretching vibration of the CH bond in the methyl or methylene group, the absorption peak at 1103cm -1 is the stretching vibration of the CO bond, and the absorption peak at 719cm -1 is the stretching vibration of the methylene group; in the infrared spectrum of the target product , the absorption peak at 3431cm -1 is the stretching vibration of the OH bond, the absorption peaks at 2920, 2850 and 1467cm -1 are the stretching vibration of the CH bond in the methyl or methylene group, and the absorption peak at 1109cm -1 is the CO bond The stretching vibration of methylene group is the absorption peak at 719cm -1 .
  • the infrared spectrum of the target product shows absorption vibration peaks at 1257 and 1058 cm -1 , while the intermediate product has no or weak absorption vibration peaks there.
  • This peak is the characteristic absorption peak of CN, from which the target can be inferred.
  • the product contains more CN bonds.
  • the OH bond absorption peak of the target product at 3431 cm -1 is blue-shifted compared to the OH bond absorption peak of the intermediate product at 3386 cm -1 . This is due to the influence of two adjacent quaternary ammonium head groups. And because the presence of short carbon chain linking groups in the target product molecule weakens the hydrogen bond association, the OH bond absorption peak formed by the target product is sharper.
  • the product synthesized in the present invention is basically consistent with the cationic oligomeric surfactant containing multiple quaternary ammonium head groups.
  • the surface tension-concentration diagram of the cationic oligomeric surfactant aqueous solution containing polyquaternary ammonium head groups prepared above is shown in Figure 3. It can be seen from Figure 3 that the surface tension of the product solution changes with concentration: the surface tension first decreases with the increase in concentration, and then reaches equilibrium after reaching the CMC, which has the properties of a typical surfactant. Analysis of the data in Figure 3 shows that the synthesized cationic oligomeric surfactant containing polyquaternary ammonium head groups has good ability and efficiency in reducing the surface tension of aqueous solutions.
  • the ⁇ CMC can reach 33.08mN ⁇ m -1 and the CMC can reach 0.23mmol. ⁇ L -1 , at the level typical of cationic oligomeric surfactants.
  • the oil-water interfacial tension-time change curve of the cationic oligomeric surfactant containing multiple quaternary ammonium head groups prepared above is shown in Figure 4. It can be seen from Figure 4 that the changing trend of the oil-water interfacial tension of the sample solution between different concentrations is: the oil-water interfacial tension first decreases with the increase of concentration, and can reach the lowest level of 0.0013mN ⁇ when the concentration is 5 ⁇ 10 -5 mol ⁇ L -1 m -1 , and then increases with further increase in concentration; the oil-water interfacial tension of the same concentration sample solution changes with time: the oil-water interfacial tension first decreases with time, and then increases after reaching the lowest point and gradually approaches equilibrium. . It can be seen that the synthesized cationic oligomeric surfactant containing multiple quaternary ammonium head groups has good ability to reduce the oil-water interfacial tension.
  • the invention provides a preparation method of a cationic oligomeric surfactant containing multiple quaternary ammonium head groups, which includes the following steps:
  • the invention provides a preparation method of a cationic oligomeric surfactant containing multiple quaternary ammonium head groups, which includes the following steps:

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Abstract

含多季铵头基阳离子低聚表面活性剂及其制备方法，向酸化后的C1～C18烷基叔胺中滴加季铵化试剂进行季铵化反应得到中间产物，再向反应液中滴加定量的烷基二胺类化合物进行第二步季铵化反应，所得产物为一种含多季铵头基阳离子低聚表面活性剂。该表面活性剂含有四个季铵头基和两个羟基，具有优异的表面和界面活性，合成工艺温和，不产生有毒有害的副产物。

Description

一种含多季铵头基阳离子低聚表面活性剂及其制备方法 技术领域
本发明涉及表面活性剂技术领域，尤其涉及一种含多季铵头基阳离子低聚表面活性剂及其制备方法。
背景技术
季铵盐型表面活性剂是一类阳离子表面活性剂，近年来经历了较大发展，已经广泛应用于工业和日用品中。随着表面活性剂工业的不断发展、生产生活需求不断更迭，季铵盐型表面活性剂不断开发出新的用途，在轻工、消毒杀菌、纺织助剂、石油化工、卫生用品添加剂等诸多行业领域发挥了重要的作用。
目前对低聚季铵盐研究较多是含两个季铵头基的双子季铵盐和含三个季铵头基的低聚季铵盐表面活性剂；低聚季铵盐是通过连接基团将几个单体季铵盐在亲水头基或靠近亲水头基的地方连接起来的一类新型表面活性剂。这种连接作用削弱了离子头基间的静电斥力，增强了疏水链间的疏水结合力，使表面活性剂分子在表/界面处排列得更加紧密，因此相比于单链表面活性剂，具有临界胶束浓度低、降低表面张力能力强、复配协同效应优良等性能，常用于护理用品、催化化学反应、杀菌消毒、三次采油等领域。如文献“双子表面活性剂的合成及性能研究”(日用化学工业，2015，vol.48No.8)以二乙胺盐酸盐、N-十二烷基-N，N-二甲基叔胺、环氧氯丙烷和丙磺酸内酯等为主要原料，经过三步反应合成了一种含三个季铵头基的两性表面活性剂。测试结果表明，产物的CMC为8.2×10-5mol·L-1，γCMC为38.57mN·m-1，具有优异的表面活性，且多个季铵头基的存在使产物的杀菌性显著提升。该方法所得物含有三个季铵盐结构，具有优良的结构特性，但三步反应的反应时间均大于48h，合成效率较低。所得产物为淡黄色油状液体，提纯较难，改善合成方法和工艺条件是目前此类合成研究亟待解决的主要问题。
因此，亟需设计一种新的含多个季铵头基的阳离子低聚表面活性剂，既能够保证结构新颖，具有高电荷密度的亲水头基，又能够保证表面活性剂的 合成方法简单，工艺条件温和，且制备过程中不产生有毒有害的副产物，满足经济环保的需要。
发明内容
本发明的目的在于提供一种含多季铵头基阳离子低聚表面活性剂，解决现有含多个季铵头基的阳离子表面活性剂存在的合成工艺复杂、时间长、产物提纯难等技术问题。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种含多季铵头基阳离子低聚表面活性剂，具有以下结构通式：
其中，R为C1～C18的烷基；n为2～10之间的正整数；X为Cl、Br或I中的一种。
本发明还提供了一种含多季铵头基阳离子低聚表面活性剂的制备方法，包括以下步骤：
S1、C1～C18烷基叔胺(2)、季铵化试剂(3)、酸、溶剂混合，反应得到中间体化合物(4)；
S2、向中间体化合物(4)中加入烷基二胺类化合物(5)，反应得到含多季铵头基阳离子低聚表面活性剂(1)。
优选的，在上述一种含多季铵头基阳离子低聚表面活性剂的制备方法中，S1中所述溶剂为低碳醇溶剂；所述酸为一元无机酸。
优选的，在上述一种含多季铵头基阳离子低聚表面活性剂的制备方法中，S1中所述C1～C18烷基叔胺(2)、酸、季铵化试剂(3)的摩尔比为1：1～1.1：1～1.1，所述溶剂的质量为S1中所述C1～C18烷基叔胺(2)、季铵化试剂(3)、酸、溶剂总质量的20～50％。
优选的，在上述一种含多季铵头基阳离子低聚表面活性剂的制备方法 中，S1中所述反应的时间为2～6h，反应的温度为60～100℃。
优选的，在上述一种含多季铵头基阳离子低聚表面活性剂的制备方法中，S2中所述中间体化合物(4)与烷基二胺类化合物(5)的摩尔比为1:0.5～0.55。
优选的，在上述一种含多季铵头基阳离子低聚表面活性剂的制备方法中，S2中所述反应的时间为4～12h，反应的温度为80～120℃。
经由上述的技术方案可知，与现有技术相比，本发明具有如下有益效果：
1、本发明提供的含多季铵头基阳离子低聚表面活性剂是一种结构稳定的有机化合物，结构中包含2个羟基和4个季铵头基，产物水溶性好，具有优异的表/界面活性。
2、本发明提供的含多季铵头基阳离子低聚表面活性剂未经报道，制备过程简易，反应原料易得，反应条件温和，且整个反应过程不产生有毒有害的副产物，属于原子经济型反应。
3、本发明提供的含多季铵头基阳离子低聚表面活性剂具有较好的降低水表面张力和油水界面张力的能力，可以将水的表面张力降低到33.08mN·m-1(γCMC＝33.08mN·m-1)，且CMC为0.23mmol·L-1，可以将油/水界面张力降低到超低界面张力0.0013mN·m-1(油相为煤油)。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，以下将对实施例或现有技术描述中所需要使用的附图作简单地介绍。
图1为实施例1制备的含多季铵头基阳离子低聚表面活性剂的核磁共振氢谱及信号归属图；
图2为实施例1制备的含多季铵头基阳离子低聚表面活性剂的傅里叶变换红外光谱图；
图3是实施例1制备的含多季铵头基阳离子低聚表面活性剂水溶液的表面张力曲线图；
图4为实施例1制备的含多季铵头基阳离子低聚表面活性剂的油水界面张力-时间变化曲线图。
具体实施方式
本发明提供了一种含多季铵头基阳离子低聚表面活性剂，具有以下结构通式：
其中，R为C1～C18的烷基；n为2～10之间的正整数；X为Cl、Br或I中的一种。
在本发明中，所述含多季铵头基阳离子低聚表面活性剂，结构通式优选为：
其中，R为C1～C18的烷基；X为Cl、Br或I中的一种；
或优选为：
其中，R为C1～C18的烷基；
更优选为：
本发明还提供了一种含多季铵头基阳离子低聚表面活性剂的制备方法，包括以下步骤：
S1、C1～C18烷基叔胺(2)、季铵化试剂(3)、酸、溶剂混合，反应得到中间体化合物(4)；
S2、向中间体化合物(4)中加入烷基二胺类化合物(5)，反应得到含多季铵头基阳离子低聚表面活性剂(1)。
在本发明中，所述C1～C18烷基叔胺(2)、季铵化试剂(3)、酸、溶剂混合的具体过程为：边搅拌C1～C18烷基叔胺(2)边滴加入经溶剂稀释后的酸溶液，待酸雾消失后加入季铵化试剂(3)，在酸的作用下通过季铵化反应获得中间体化合物(4)。
在本发明中，S1中所述溶剂优选为低碳醇溶剂，进一步优选为乙醇、异丙醇、正丙醇、正丁醇中的任意一种或多种组合。
在本发明中，S1中所述酸优选为一元无机酸，进一步优选为HCl、HBr或HI中的一种。
在本发明中，S1中所述C1～C18烷基叔胺(2)、酸、季铵化试剂(3)的摩尔比优选为1：1～1.1：1～1.1，进一步优选为1：1.02～1.0.8：1.02～1.0.8，更优选为1：1.05：1.05；所述溶剂的质量为S1中所述C1～C18烷基叔胺(2)、季铵化试剂(3)、酸、溶剂总质量的20～50％，进一步优选为25～40％，更优选为30％。
在本发明中，S1中所述反应的时间优选为2～6h，进一步优选为3～5h，更优选为4h；所述反应的温度优选为60～100℃，进一步优选为70～90℃，更优选为80℃。
在本发明中，S2中所述中间体化合物(4)与烷基二胺类化合物(5)的摩尔比优选为1：0.5～0.55，进一步优选为1：0.51～0.53，更优选为1：0.52。
在本发明中，S2中所述反应的时间优选为4～12h，进一步优选为6～10h，更优选为8h；所述反应的温度优选为80～120℃，进一步优选为90～110℃，更优选为100℃。
在本发明中，S2中所述向中间体化合物(4)中加入烷基二胺类化合物(5)，反应后还包括：通过减压蒸馏除去溶剂，重结晶得到目标产物含多季铵头基阳离子低聚表面活性剂；所述重结晶的溶剂优选为乙酸乙酯和乙醇的混合溶剂，所述混合溶剂中乙酸乙酯和乙醇的体积比优选为10～20:1，进一步优选为12～18：1，更优选为15：1。
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本发明提供一种含多季铵头基阳离子低聚表面活性剂的制备方法，包括以下步骤：
S1、取32.109g(0.139mol)十二/十四烷基叔胺(R为C12/14)于四口烧瓶中，边搅拌边滴加入用41.37g正丙醇稀释13.7g(0.139mol HCl)盐酸溶液，滴加过程中会放热并产生酸雾，待酸雾消失后加入12.86g(0.139mol)环氧氯丙烷，在搅拌条件下于80℃下反应4h，得到淡黄色澄清透明的中间产物，经测定产率为98.72％；
S2、向S1中所述中间产物中加入11.95g(0.0695mol)1,6-四甲基己二胺，在搅拌条件下于94℃下反应8h，得到黄色澄清透明的产物；将所述产物经减压蒸馏去除溶剂，再用乙酸乙酯/乙醇溶液(乙酸乙酯/乙醇溶液中乙酸乙酯和乙醇的体积比为10:1)重结晶，干燥后得到目标产物含多季铵头基阳离子低聚表面活性剂，经测定活性剂含量为98.1％。
上述制备得到的含多季铵头基阳离子低聚表面活性剂的核磁共振氢谱图如图1所示。由图1可知，核磁中的峰出现的位置与目标产物分子中的H的种类相对应。1HNMR(300MHz，CDCl3)：0.813(6H，a)，0.943-1.545(40H，b)，1.562-1.994(8H，c)，3.058-3.490(12H，e)，3.498-3.721(8H，d)，3.4824-4.063(8H，f)，4.835-5.177(2H，h)，6.540-6.905(2H，g)，溶剂的峰出现在7.289ppm。
上述制备得到的中间产物以及目标产物含多季铵头基阳离子低聚表面 活性剂的傅里叶变换红外光谱图如图2所示。由图2可知，中间产物与目标产物二者的轮廓基本相似，中间产物的红外谱图中，3386cm-1处的吸收峰为O-H键的伸缩振动，2920、2850和1467cm-1处的吸收峰为甲基或亚甲基中C-H键的伸缩振动，1103cm-1处的吸收峰为C-O键的伸缩振动，719cm-1处的吸收峰为亚甲基的伸缩振动；目标产物的红外谱图中，3431cm-1处的吸收峰为O-H键的伸缩振动，2920、2850和1467cm-1处的吸收峰为甲基或亚甲基中C-H键的伸缩振动，1109cm-1处的吸收峰为C-O键的伸缩振动，719cm-1处的吸收峰为亚甲基的伸缩振动。其中，目标产物的红外图谱显示在1257和1058cm-1处有吸收振动峰，而中间产物在该处没有或具有较弱的吸收振动峰，该峰是C-N的特征吸收峰，由此可以推断目标产物中含有较多C-N键存在。此外，目标产物在3431cm-1处的O-H键吸收峰相比于中间产物在3386cm-1处的O-H键吸收峰位置发生了蓝移，这是由于受到相邻两个季铵头基的影响，又因为目标产物分子中短碳链连接基的存在削弱了氢键缔合作用，所以目标产物形成的O-H键吸收峰更加尖锐。通过以上的分析，本发明合成的产物与含多季铵头基阳离子低聚表面活性剂基本相符。
上述制备得到的含多季铵头基阳离子低聚表面活性剂水溶液的表面张力-浓度图如图3所示。由图3可知，产物溶液的表面张力随浓度的变化趋势为：表面张力先随浓度的提高而降低，待达到CMC后趋于平衡，具有典型表面活性剂的性质。分析图三数据可知，所合成的含多季铵头基阳离子低聚表面活性剂具有较好的降低水溶液表面张力的能力和效率，γCMC能达到33.08mN·m-1，CMC能达到0.23mmol·L-1，处于典型的阳离子低聚表面活性剂的水平。
上述制备得到的含多季铵头基阳离子低聚表面活性剂的油水界面张力-时间变化曲线如图4所示。由图4可知，不同浓度间样品溶液的油水界面张力的变化趋势为：油水界面张力先随浓度的提高而降低，在浓度为5×10-5mol·L-1时最低能达到0.0013mN·m-1，而后随浓度的进一步提高而增大；同一浓度样品溶液的油水界面张力随时间的变化趋势为：油水界面张力随时间变化先降低，待达到最低点后升高并逐渐趋于平衡。可知，所合成的含多季铵头基阳离子低聚表面活性剂具有较好的降低油水界面张力的能力。
实施例2
本发明提供一种含多季铵头基阳离子低聚表面活性剂的制备方法，包括以下步骤：
S1、取31.95g(0.15mol)十二烷基叔胺(R为C12)于四口烧瓶中，边搅拌边滴加入用41.37g乙醇稀释25.2g(0.15mol HBr)溴化氢溶液，滴加过程中会放热并产生酸雾，待酸雾消失后加入20.55g(0.15mol)环氧溴丙烷，在搅拌条件下于100℃下反应2h，得到淡黄色澄清透明的中间产物，经测定产率为97.99％；
S2、向S1中所述中间产物中加入11.85g(0.075mol)1,5-四甲基戊二胺，在搅拌条件下于80℃下反应10h，得到黄色澄清透明的产物；将所述产物经减压蒸馏去除溶剂，再用乙酸乙酯/乙醇溶液(乙酸乙酯/乙醇溶液中乙酸乙酯和乙醇的体积比为5:1)重结晶，干燥后得到目标产物含多季铵头基阳离子低聚表面活性剂，经测定活性剂含量为97.5％。
实施例3
本发明提供一种含多季铵头基阳离子低聚表面活性剂的制备方法，包括以下步骤：
S1、取28.92g(0.12mol)十四烷基叔胺(R为C14)于三口烧瓶中，边搅拌边滴加入用42.50g正丙醇稀释11.8g(0.12mol HCl)盐酸溶液，滴加过程中会放热并产生酸雾，待酸雾消失后加入11.1g(0.12mol)环氧氯丙烷，在搅拌条件下于60℃下反应4h，得到淡黄色澄清透明的中间产物，经测定产率为98.50％；
S2、向S1中所述中间产物中加入13.68g(0.06mol)1,10-四甲基癸二胺，在搅拌条件下于100℃下反应6h，得到黄色澄清透明的产物；将所述产物经减压蒸馏去除溶剂，再用乙酸乙酯/乙醇溶液(乙酸乙酯/乙醇溶液中乙酸乙酯和乙醇的体积比为15:1)重结晶，干燥后得到目标产物含多季铵头基阳离子低聚表面活性剂，经测定活性剂含量为97.9％。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (7)

  1. 一种含多季铵头基阳离子低聚表面活性剂，其特征在于，具有以下结构通式：
    其中，R为C1～C18的烷基；n为2～10之间的正整数；X为Cl、Br或I中的一种。
  2. 权利要求1所述的含多季铵头基阳离子低聚表面活性剂的制备方法，其特征在于，包括以下步骤：
    S1、C1～C18烷基叔胺(2)、季铵化试剂(3)、酸、溶剂混合，反应得到中间体化合物(4)；
    S2、向中间体化合物(4)中加入烷基二胺类化合物(5)，反应得到含多季铵头基阳离子低聚表面活性剂(1)。
  3. 根据权利要求2所述的含多季铵头基阳离子低聚表面活性剂的制备方法，其特征在于，S1中所述溶剂为低碳醇溶剂；所述酸为一元无机酸。
  4. 根据权利要求3所述的含多季铵头基阳离子低聚表面活性剂的制备方法，其特征在于，S1中所述C1～C18烷基叔胺(2)、酸、季铵化试剂(3)的摩尔比为1：1～1.1：1～1.1，所述溶剂的质量为S1中所述C1～C18烷基叔胺(2)、季铵化试剂(3)、酸、溶剂总质量的20～50％。
  5. 根据权利要求4所述的含多季铵头基阳离子低聚表面活性剂的制备方法，其特征在于，S1中所述反应的时间为2～6h，反应的温度为60～100℃。
  6. 根据权利要求5所述的含多季铵头基阳离子低聚表面活性剂的制备方法，其特征在于，S2中所述中间体化合物(4)与烷基二胺类化合物(5)的摩尔比为1:0.5～0.55。
  7. 根据权利要求2～6中任一项所述的含多季铵头基阳离子低聚表面活性剂的制备方法，其特征在于，S2中所述反应的时间为4～12h，反应的温度为80～120℃。
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