WO2020198899A1 - 一种多功能、高活性阳离子双子表面活性剂及生产方法 - Google Patents

一种多功能、高活性阳离子双子表面活性剂及生产方法 Download PDF

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WO2020198899A1
WO2020198899A1 PCT/CN2019/000148 CN2019000148W WO2020198899A1 WO 2020198899 A1 WO2020198899 A1 WO 2020198899A1 CN 2019000148 W CN2019000148 W CN 2019000148W WO 2020198899 A1 WO2020198899 A1 WO 2020198899A1
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organic amine
protic acid
highly active
cationic gemini
epichlorohydrin
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PCT/CN2019/000148
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French (fr)
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朱年德
张银广
曾岩
马驰
朱天宇
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山东天成化工有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
    • 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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  • the invention belongs to the technical field of surfactants, and specifically relates to a multifunctional and highly active cationic gemini surfactant and a production method.
  • Surfactants are a class of substances that can significantly reduce the surface tension even at very low concentrations. Its molecular structure is composed of two parts. One end of the molecule is a very lipophilic hydrophobic group, and the other end of the molecule is a polar hydrophilic hydrophilic group. The two types of molecular fragments or groups with completely opposite structures and properties are in the same The two ends of the molecule are connected by chemical bonds to form an asymmetric and polar structure, which gives this kind of special molecules the characteristics of being both hydrophilic and lipophilic, but not integrally water or lipophilic. This unique structure It is usually called "amphipathic structure". Due to its amphipathic nature, it indicates that the application of active agents covers almost all fields of fine chemical industry.
  • Surfactant consists of a polar hydrophilic group and a non-polar lipophilic group, and the two parts are divided into two ends. Therefore, surfactants have both hydrophilic and lipophilic amphiphilic properties, and can therefore occur on the surface or phase interface (liquid/liquid, liquid/solid) adsorption and enrichment, as well as self-assembly within the solution to form various This kind of orderly combination structure can reduce the surface/interface tension and change the interface energy and solution properties.
  • Gemini surfactants determines that it has better performance than traditional surfactants. It has two hydrophilic groups and hydrophobic groups. The two parts are connected by a linking group.
  • the linking group has a chemical bond function, which reduces the electrostatic repulsion between the two polarities and the force between the hydration layers, making the gemini surface active
  • the agent has low CMC characteristics.
  • gemini surfactants Compared with ordinary surfactants composed of monoalkane chains and single ion head groups, gemini surfactants have the following characteristics: (1) It is easy to adsorb on the gas/liquid surface, effectively reducing the surface tension of water; (2) Easy Aggregate to form micelles, with a lower critical micelle concentration; (3) It has a very low Kraff point; (4) The combination with common surfactants can produce greater synergistic effects; (5) It has a good Calcium soap dispersion performance; (6) Excellent wetting performance.
  • gemini surfactants have been favored by scientists from all over the world, and a new wave of research has been set off. Therefore, in application, a very small amount of cationic gemini surfactants will bring great results. Gemini surfactants are significantly different from traditional surfactants due to the formation of various ordered combinations in solution, so they can endow the system with unique properties such as special rheological properties.
  • the raw materials used are long-chain branched tertiary amines, and the resulting products are solid, which must be dissolved before use; organic solvents are used in the reaction process, and the products need to be desolventized, causing a certain waste of resources .
  • the present invention provides a multifunctional, highly active cationic gemini surfactant and a production method to solve the above technical problems.
  • the invention provides a method for preparing a series of multifunctional and highly active cationic gemini surfactants by using protic acid, epichlorohydrin and organic amine as main raw materials.
  • the cationic gemini surfactant product prepared by this method has the characteristics of high product content and high reaction efficiency, overcomes the defect that a large excess of one material must be used in the prior art to increase the reaction yield, short reaction period, and water-based reaction Green environmental protection, three wastes less, high production safety, in line with the development trend of green chemistry, suitable for industrial-scale production.
  • a multifunctional and highly active cationic gemini surfactant its structural formula is as follows:
  • Another object of the present invention is to provide the above-mentioned multifunctional and highly active cationic gemini surfactant production method, which uses epichlorohydrin and organic amine as raw materials.
  • the specific method is as follows: The first step is to use a mass concentration of 10% -40% protic acid reacts with organic amine to obtain an organic amine protic acid salt solution; in the second step, add epichlorohydrin to the organic amine protic acid salt solution through a dropping funnel, and heat to react for 0.5-5 hours before adding The catalyst continues to react to obtain a quaternary ammonium salt cationic gemini surfactant solution.
  • the first step preparing an organic amine protic acid salt, specifically, adding the protic acid solution in a reactor equipped with a stirring device and a reflux device under stirring at room temperature
  • the organic amine protic acid salt aqueous solution is obtained by reaction; wherein the mass ratio of deionized water to organic amine is 0 ⁇ 1.5:1, and the mass concentration of protic acid in the protic acid solution is: 10% ⁇ 40%; the addition rate of the protic acid solution is such that the reaction system does not bump; the molar ratio of the organic amine to the protic acid is 0.5-3:1; the stirring reaction time is 0.5-5 hours.
  • the first step in the preparation of organic amine protic acid salt, the protic acid solution is added to the mixture of organic amine and deionized water through a dropping funnel, wherein the mass ratio of deionized water to organic amine is 0.5 to 1.5:1 ; The mass concentration of the protic acid in the protic acid solution is 15% to 40%.
  • the second step nucleophilic substitution reaction to generate cationic gemini surfactants, specifically, adding epichlorohydrin to the organic amine in a reactor with a stirring device and a reflux device
  • the reaction is carried out by heating in the proton acid aqueous solution, the reaction temperature is 30 ⁇ 90°C, after 0.5 ⁇ 5h, the catalyst is added, and the reaction is continued for 2 ⁇ 12h to obtain the quaternary ammonium cationic gemini surfactant solution; epichlorohydrin and organic
  • the molar ratio of the amine proton acid salt is 0.95-2.5:1; the molar ratio of the catalyst to the epichlorohydrin is 0.08-0.2:1.
  • epichlorohydrin is added to the aqueous solution of organic amine protic acid salt through a dropping funnel, wherein the molar ratio of epichlorohydrin to the organic amine protic acid salt is 0.95 to 1.5:1; the reaction temperature 70 ⁇ 90°C; the molar ratio of catalyst to epichlorohydrin is 0.08 ⁇ 0.1:1.
  • the catalyst used in the second step is sodium sulfate, potassium sulfate, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, sodium persulfate, persulfuric acid
  • the use of the catalyst can promote the reaction of epichlorohydrin and organic amine protonate.
  • the catalyst used in the second step is one or more of sodium bisulfite, sodium sulfite, and triethanolamine.
  • the protic acid mentioned in the first step includes one or more of sulfuric acid, nitric acid, hydrochloric acid, formic acid, and acetic acid.
  • the organic amines described in the first step include N,N-dimethylmethanediamine, N,N-dimethylethylenediamine, N,N-dimethylpropylenediamine, N-methyl Ethylenediamine, N-methyl-1,3-propanediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetra Methyl-1,3-butanediamine, N,N,N,N-tetramethylmethylenediamine, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetra One or more of methylpropanediamine and N,N,N,N-tetramethylbutanediamine.
  • the production method of the present invention adopts a two-step reaction, using epichlorohydrin as a raw material, the first step is to prepare organic amine protonate; the second step is to prepare cationic gemini surfactant; the process of the present invention uses short-chain organic Amine is used as a raw material, and the product is liquid at room temperature, which is convenient to use; no organic solvent is added in the reaction process, which reduces the use of organic solvents and the preparation process is more environmentally friendly.
  • water is used as a solvent when preparing the organic amine protic acid salt, and a protic acid solution is used to reduce the severity of the acid-base neutralization reaction, so that the reaction process is gentle and easy to control.
  • a protic acid solution is used to reduce the severity of the acid-base neutralization reaction, so that the reaction process is gentle and easy to control.
  • the reaction started as a heterogeneous reaction, with the addition of protic acid, the organic amine was converted into water-soluble protic acid salt.
  • a catalyst is used to increase the conversion rate of the reaction.
  • the solvent in this product is deionized water, which can be directly used in high-tech fields such as materials science, energy science, environmental science, life science and information science.
  • the production method of the present invention adopts a two-step reaction, using epichlorohydrin as a raw material, the first step is to prepare the organic amine protonate; the second step is to prepare the cationic gemini surfactant; the cationic gemini surface prepared by this method
  • the active agent product has the characteristics of high product content and high reaction efficiency. It overcomes the defects in the prior art that a large excess of one material must be used to increase the reaction yield.
  • the reaction cycle is short, the water-based reaction is green and environmentally friendly, and the three wastes are less. High safety, in line with the development trend of green chemistry, suitable for industrial-scale production.
  • Step 1 Add 144g (about 1mol) N,N,N',N'-tetramethyl-1,4-butanediamine and a 1000ml three-necked flask equipped with a mechanical stirring device and a reflux tube. 80g deionized water, at room temperature, under stirring, add 223g sulfuric acid solution with a mass concentration of 20% into the flask through a dropping funnel, adding time 20min, after adding all the sulfuric acid solution, continue to stir for 1h to obtain N, N, N ',N'-Tetramethyl-1,4-butanediamine sulfate (I) aqueous solution.
  • I N, N, N ',N'-Tetramethyl-1,4-butanediamine sulfate
  • the solution is cooled to room temperature to obtain a colorless to light yellow transparent solution-like product with a solid content of 52-60%.
  • Step 1 Add 111g (about 1.5mol) N,N-dimethylmethanediamine and 65g water in a 1000ml three-necked flask equipped with a mechanical stirring device and a reflux tube. At room temperature, under stirring Add 220g of formic acid solution with a mass concentration of 15% into the flask through a dropping funnel. Adding time is 20 minutes. After all the formic acid solution is added, continue to stir for 1 hour to obtain an aqueous solution of N,N-dimethylmethanediamine formate (I) .
  • Example 3 Preparation of multifunctional and highly active cationic gemini surfactant bis 3-chloro-2-hydroxypropyl N, N-dimethylamine chloride:
  • Step 1 Add 176g (about 2mol) N,N-dimethylethylenediamine and 100g water into a 1000ml three-necked flask equipped with a mechanical stirring device and a reflux tube. 115 g of a hydrochloric acid solution with a mass concentration of 35% was added to the flask through a dropping funnel for 30 minutes. After all the hydrochloric acid solution was added, stirring was continued for 1 hour to obtain an aqueous solution of N,N-dimethylethylenediamine hydrochloride (I).
  • Table 1 shows the surface activity of Gemini cationic surfactant products prepared in each embodiment (measured at 25.0°C)
  • Table 1 The number of product surface activity of the products obtained in Examples 1-3
  • water is used as a solvent when preparing the organic amine protic acid salt, and a protic acid solution is used to reduce the severity of the acid-base neutralization reaction, so that the reaction process is gentle and easy to control.
  • a protic acid solution is used to reduce the severity of the acid-base neutralization reaction, so that the reaction process is gentle and easy to control.
  • the reaction was a heterogeneous reaction at the beginning, with the addition of protic acid, the organic amine was converted to water-soluble hydrochloride.
  • a catalyst is used to increase the conversion rate of the reaction.
  • the solvent in this product is deionized water, which can be directly used in high-tech fields such as materials science, energy science, environmental science, life science and information science.

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Abstract

一种多功能、高活性阳离子双子表面活性剂及生产方法，采用质子酸、环氧氯丙烷和有机胺为主要原料，制备一系列多功能、高活性阳离子双子表面活性剂。

Description

一种多功能、高活性阳离子双子表面活性剂及生产方法 技术领域
本发明属于表面活性剂的技术领域，具体涉及一种多功能、高活性阳离子双子表面活性剂及生产方法。
背景技术
表面活性剂是一类即使在很低浓度时也能显著降低表(界)面张力的物质。其分子结构均由两部分构成，分子的一端为极亲油的疏水基，分子的另一端为极性亲水的亲水基，两类结构与性能截然相反的分子碎片或基团分处于同一分子的两端并以化学键相连接，形成了一种不对称的、极性的结构，赋予了该类特殊分子既亲水又亲油，又不是整体水或亲油的特性，这种特有结构通常称之为“双亲结构”，由于其双亲性质，表明活性剂的应用几乎涵盖了精细化工的所有领域。
表面活性剂由具有极性的亲水基和非极性的亲油基组成，而且两部分分处两端。因此，表面活性剂具有既亲水又亲油的两亲性质，并可因此发生在表面或相界面(液/液、液/固)的吸附和富集，以及在溶液内部发生自组装形成各种有序组合结构，从而可以降低表/界面张力，改变界面能和溶液性质。
与传统表面活性剂不同，双子表面活性剂特殊的结构决定它比传统表面活性剂具有更优良的性能。它具有两个亲水基和疏水基，通过联接基团将两部分连接，联接基团有化学键作用，降低了两极性间的静电排斥力及其水化层间的作用力，使得双子表面活性剂具有低CMC特性。与单烷烃链和单离子头基组成的普通表面活性剂相比，双子表面活性剂具有如下特征性质：(1)易吸附在气/液表面，有效地降低水的表面张力；(2)易聚集生成胶团，有更低的临界胶束浓度；(3)具有很低的Kraff点；(4)与普通表面活性剂间的复配能产生更大的协同效应；(5)具有良好的钙皂分散性能；(6)优良的润湿性能。
目前，双子表面活性剂已经受到世界各国科学家的青睐，并掀起了一股新的研究热潮因此在应用中，极少量的阳离子双子表面活性剂就会带来极大的使用效果。双子表面活性剂由于在溶液中形成各种有序组合体的性质与传统表面活性剂有显著差异，因而可以赋予体系特殊的流变学性质等独特性能。
常用表面活性剂的制备方法，其使用的原材料为长支链叔胺，所生成的产物为固体，必须溶解后使用；反应过程中使用有机溶剂，产物需进行脱溶剂处理，造成一定的资源浪费。
发明内容
针对现有技术的上述不足，本发明提供一种多功能、高活性阳离子双子表面活性剂及生产方法，以解决上述技术问题。本发明提供了一种采用质子酸、环氧氯丙烷和有机胺为主要原料，制备一系列多功能、高活性阳离子双子表面活性剂的方法。该方法制备的阳离子双子表面活性剂产品，具有产品含量高、反应效率高的特点，克服现有技术中必须以一种物料极大过量来提高反应收率的缺陷，反应周期短，水基反应绿色环保、三废少、生产安全性高，符合绿色化学发展趋势，适合工业规模生产。
本发明的技术方案为：
一种多功能、高活性阳离子双子表面活性剂，其结构式如下：
Figure PCTCN2019000148-appb-000001
其中：n＝1，2，3，4；a＝0，1，2；b＝0，1，2；a，b，n可以相同，也可以不相同。
本发明的另一目的，提供上述一种多功能、高活性阳离子双子表面活性剂的生产方法，采用环氧氯丙烷和有机胺为原料，具体方法如下：第一步，采用质量浓度为10％-40％质子酸和有机胺反应，得到有机胺质子酸盐溶液；第二步，将环氧氯丙烷通过滴液漏斗加入到有机胺质子酸盐溶液中，加热进行反应0.5-5小时后加入催化剂继续反应，得到季铵盐类阳离子双子表面活性剂溶液。
本发明的生产方法特点还有：
本发明的生产方法，所述的第一步：制备有机胺质子酸盐，具体为，在带有搅拌装置、冷凝回流装置的反应器中，室温下，在搅拌状态下，将质子酸溶液加入有机胺与去离子水的混合物中，反应得到有机胺质子酸盐水溶液；其中去离子水与有机胺的质量比为0～1.5∶1，质子酸溶液中质子酸的质量浓度为：10％～40％；质子酸溶液加入速度以反应体系不爆沸即可；有机胺与质子酸的摩尔比为0.5-3∶1；搅拌反应时间0.5～5小时。
进一步的，第一步：制备有机胺质子酸盐中，将质子酸溶液通过滴液漏斗加入有机胺与去离子水的混合物中，其中去离子水与有机胺的质量比为0.5～1.5∶1；质子酸溶液中质子酸的质量浓度为15％～40％。
本发明的生产方法，所述的第二步：亲核取代反应，生成阳离子双子表面活性剂，具体为，在带有搅拌装置、冷凝回流装置的反应器中，将环氧氯丙烷加入有机胺质子酸盐水溶液中，加热进行反应，反应温度30～90℃，反应0.5～5h后，加入催化剂，继续反应2～12h，得到季铵盐类阳离子双子表面活性剂溶液；环氧氯丙烷与有机胺质子酸盐的摩尔比为0.95～2.5∶1；催化剂与环氧氯丙烷摩尔比为0.08～0.2∶1。
进一步的，第二步中，将环氧氯丙烷通过滴液漏斗加入到有机胺质子酸盐水溶液中，其中环氧氯丙烷与有机胺质子酸盐的摩尔比为0.95～1.5∶1；反应温度70～90℃；催化剂与环 氧氯丙烷摩尔比为0.08～0.1∶1。
进一步的，第二步中的所使用催化剂为硫酸钠、硫酸钾、亚硫酸钠、亚硫酸钾、亚硫酸氢钠、亚硫酸氢钾、硫代硫酸钠、硫代硫酸钾、过硫酸钠、过硫酸钾、过硫酸铵、硫化钠、硫化钾、硫氢化钠、硫氢化钾、硫氰酸钠、硫氰酸钾、胺基硫脲、乙酰硫脲、三乙醇胺、硫代乙酸的一种或两种以上。该催化剂的使用可促进环氧氯丙烷与有机胺质子酸盐的反应。
进一步的，第二步中的所使用催化剂为亚硫酸氢钠、亚硫酸钠、三乙醇胺、中的一种或两种以上。
进一步的，第一步中所述的质子酸包括硫酸、硝酸、盐酸、甲酸、乙酸中的一种或者多种。
进一步的，第一步中所述的有机胺包括N，N-二甲基甲二胺、N，N-二甲基乙二胺、N，N-二甲基丙二胺，N-甲基乙二胺，N-甲基-1，3-丙二胺，N，N，N’，N’-四甲基-1，4-丁二胺，N，N，N’，N’-四甲基-1，3-丁二胺，N，N，N，N-四甲基甲二胺、N，N，N，N-四甲基乙二胺、N，N，N，N-四甲基丙二胺、N，N，N，N-四甲基丁二胺中的一种或者多种。
本发明的有益效果在于，
本发明的生产方法是采用两步反应，以环氧氯丙烷为原料，第一步，制备有机胺质子酸盐；第二步，制备阳离子双子表面活性剂；本发明的工艺中使用短链有机胺做原材料，产物常温下为液态，方便使用；反应过程中未加入有机溶剂，减少有机溶剂的使用，制备工艺更为环保。
本发明在制备有机胺质子酸盐时采用水作为溶剂，使用质子酸溶液，降低酸碱中和反应剧烈程度，使反应过程缓和，易于控制。虽然反应开始时为非均相反应，但随着质子酸的加入，有机胺转化为水溶性的质子酸盐。在亲核取代反应时，采用催化剂，提高反应转化率。该产品中溶剂为去离子水，可直接应用于材料科学、能源科学、环境科学、生命科学和信息科学等高新技术领域。
用本发明方法制备得到的多功能、高活性阳离子双子表面活性剂固形物含量不低于50％(测定方法参照中华人民共和国国家标准《GB/T 5174-2004表面活性剂阳离子活性物含量的测定中7.2节阳离子活性物含量测定方法)，质量百分比10％的水溶液pH＝3-6(测定方法参照中华人民共和国国家标准GB/T6368-2008《表面活性剂水溶液pH值的测定电位法》)。
总之，本发明的生产方法是采用两步反应，以环氧氯丙烷为原料，第一步，制备有机胺质子酸盐；第二步，制备阳离子双子表面活性剂；该方法制备的阳离子双子表面活性剂产品，具有产品含量高、反应效率高的特点，克服现有技术中必须以一种物料极大过量来提高反应收率的缺陷，反应周期短，水基反应绿色环保、三废少、生产安全性高，符合绿色化学 发展趋势，适合工业规模生产。
具体实施方式
为了使本技术领域的人员更好地理解本发明中的技术方案，下面将结合本发明实施例，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，都应当属于本发明保护的范围。
实施例1制备多功能、高活性阳离子双子表面活性剂，双3-氯2-羟丙基二乙基N，N二甲基硫酸二胺
第一步：在带有机械搅拌装置、装有冷凝回流管的1000ml三口瓶中，加入144g(约1mol)N，N，N’，N’-四甲基-1，4-丁二胺和80g去离子水，室温下，在搅拌状态下将223g质量浓度为20％的硫酸溶液通过滴液漏斗加入烧瓶中，加入时间20min，硫酸溶液全部加入后，继续搅拌1h，得到N，N，N’，N’-四甲基-1，4-丁二胺硫酸盐(I)水溶液。
第二步，将90g(约0.97mol)环氧氯丙烷加入上述I水溶液中，升温至80-85℃，反应3h后，加入10g的亚硫酸钠，继续反应12h得到阳离子双子表面活性剂双3-氯2-羟丙基二乙基N，N-二甲基硫酸二胺溶液。
溶液冷却到室温，得到无色到淡黄色透明溶液状产品，产品固含量52-60％。
实施例2：制备多功能、高活性阳离子双子表面活性剂双3-氯2-羟丙基N-甲基甲酸胺
第一步：在带有机械搅拌装置、装有冷凝回流管的1000ml三口瓶中，加入111g(约1.5mol)N，N-二甲基甲二胺和65g水，室温下，在搅拌状态下将220g质量浓度为15％的甲酸溶液通过滴液漏斗加入烧瓶中，加入时间20min，甲酸溶液全部加入后，继续搅拌1h，得到N，N-二甲基甲二胺甲酸盐(I)水溶液。
第二步，将203.5g(约2.2mol)环氧氯丙烷加入上述I水溶液中，升温至70-80℃，反应1h后，加入30g的三乙醇胺，继续反应12h，溶液冷却到室温，得到无色到淡黄色透明溶液状双3-氯2-羟丙基N-甲基甲酸胺产品，产品固含量约51-58％。
实施例3：制备多功能、高活性阳离子双子表面活性剂双3-氯2-羟丙基N，N-二甲基氯化胺：
第一步：在带有机械搅拌装置、装有冷凝回流管的1000ml三口瓶中，加入176g(约2mol)N，N-二甲基乙二胺和100g水，室温下，在搅拌状态下将115g质量浓度为35％的盐酸溶液通过滴液漏斗加入烧瓶中，加入时间30min，盐酸溶液全部加入后，继续搅拌1h，得到N，N-二甲基乙二胺盐酸盐(I)水溶液。
第二步，将277g(约3mol)环氧氯丙烷加入上述I水溶液中，升温至70-90℃，反应1h后，加入30g的亚硫酸氢钠，继续反应12h，溶液冷却到室温，得到无色到淡黄色透明溶液状双3-氯2-羟丙基N，N-二甲基氯化胺产品，产品固含量约52-53％。
下表1为各实施例制备的双子阳离子表面活性剂产品表面活性数(25.0℃测量)
表1实施例1-3得到的产品的产品表面活性数
Figure PCTCN2019000148-appb-000002
本发明在制备有机胺质子酸盐时采用水作为溶剂，使用质子酸溶液，降低酸碱中和反应剧烈程度，使反应过程缓和，易于控制。虽然反应开始时为非均相反应，但随着质子酸的加入，有机胺转化为水溶性的盐酸盐。在亲核取代反应时，采用催化剂，提高反应转化率。该产品中溶剂为去离子水，可直接应用于材料科学、能源科学、环境科学、生命科学和信息科学等高新技术领域。
尽管通过结合优选实施例的方式对本发明进行了详细描述，但本发明并不限于此。在不脱离本发明的精神和实质的前提下，本领域普通技术人员可以对本发明的实施例进行各种等效的修改或替换，而这些修改或替换都应在本发明的涵盖范围内/任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应所述以权利要求的保护范围为准。

Claims (10)

  1. 一种多功能、高活性阳离子双子表面活性剂，其特征在于，其结构式如下：
    Figure PCTCN2019000148-appb-100001
    其中：n＝1，2，3，4；a＝0，1，2；b＝0，1，2；a，b，n可以相同，也可以不相同。
  2. 如权利要求1所述的多功能、高活性阳离子双子表面活性剂的生产方法，其特征在于，采用环氧氯丙烷和有机胺为原料，具体方法如下：第一步，采用质量浓度为10％-40％质子酸和有机胺反应，得到有机胺质子酸盐溶液；第二步，将环氧氯丙烷通过滴液漏斗加入到有机胺质子酸盐溶液中，加热进行反应0.5-5小时后加入催化剂继续反应，得到季铵盐类阳离子双子表面活性剂溶液。
  3. 根据权利要求2所述的多功能、高活性阳离子双子表面活性剂的生产方法，其特征在于，所述的第一步：制备有机胺质子酸盐，具体为，在带有搅拌装置、冷凝回流装置的反应器中，室温下，在搅拌状态下，将质子酸溶液加入有机胺与去离子水的混合物中，反应得到有机胺质子酸盐水溶液；其中去离子水与有机胺的质量比为0～1.5∶1，质子酸溶液中质子酸的质量浓度为：10％～40％；质子酸溶液加入速度以反应体系不爆沸即可；有机胺与质子酸的摩尔比为0.5-3∶1；搅拌反应时间0.5～5小时。
  4. 根据权利要求3所述的多功能、高活性阳离子双子表面活性剂的生产方法，其特征在于，第一步：制备有机胺质子酸盐中，将质子酸溶液通过滴液漏斗加入有机胺与去离子水的混合物中，其中去离子水与有机胺的质量比为0.5～1.5∶1；质子酸溶液中质子酸的质量浓度为15％～40％。
  5. 根据权利要求2所述的多功能、高活性阳离子双子表面活性剂的生产方法，其特征在于，所述的第二步：亲核取代反应，生成阳离子双子表面活性剂，具体为，在带有搅拌装置、冷凝回流装置的反应器中，将环氧氯丙烷加入有机胺质子酸盐水溶液中，加热进行反应，反应温度30～90℃，反应0.5～5h后，加入催化剂，继续反应2～12h，得到季铵盐类阳离子双子表面活性剂溶液；环氧氯丙烷与有机胺质子酸盐的摩尔比为0.95～2.5∶1；催化剂与环氧氯丙烷摩尔比为0.08～0.2∶1。
  6. 根据权利要求5所述的多功能、高活性阳离子双子表面活性剂的生产方法，其特征在于，第二步中，将环氧氯丙烷通过滴液漏斗加入到有机胺质子酸盐水溶液中，其中环氧氯丙烷与有机胺质子酸盐的摩尔比为0.95～1.5∶1；反应温度70～90℃；催化剂与环氧氯丙烷摩尔比为0.08～0.1∶1。
  7. 根据权利要求2所述的多功能、高活性阳离子双子表面活性剂的生产方法，其特征在于，第二步中的所使用催化剂为硫酸钠、硫酸钾、亚硫酸钠、亚硫酸钾、亚硫酸氢钠、亚硫酸氢钾、硫代硫酸钠、硫代硫酸钾、过硫酸钠、过硫酸钾、过硫酸铵、硫化钠、硫化钾、硫氢化钠、硫氢化钾、硫氰酸钠、硫氰酸钾、胺基硫脲、乙酰硫脲、三乙醇胺、硫代乙酸的一种或两种以上。该催化剂的使用可促进环氧氯丙烷与有机胺质子酸盐的反应。
  8. 根据权利要求7所述的多功能、高活性阳离子双子表面活性剂的生产方法，其特征在于，第二步中的所使用催化剂为亚硫酸氢钠、亚硫酸钠、三乙醇胺、中的一种或两种以上。
  9. 根据权利要求2所述的多功能、高活性阳离子双子表面活性剂的生产方法，其特征在于，第一步中所述的质子酸包括硫酸、硝酸、盐酸、甲酸、乙酸中的一种或者多种。
  10. 根据权利要求2所述的多功能、高活性阳离子双子表面活性剂的生产方法，其特征在于，第一步中所述的有机胺包括N，N-二甲基甲二胺、N，N-二甲基乙二胺、N，N-二甲基丙二胺，N-甲基乙二胺，N-甲基-1，3-丙二胺，N，N，N’，N’-四甲基-1，4-丁二胺，N，N，N’，N’-四甲基-1，3-丁二胺，N，N，N，N-四甲基甲二胺、N，N，N，N-四甲基乙二胺、N，N，N，N-四甲基丙二胺、N，N，N，N-四甲基丁二胺中的一种或者多种。
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