WO2021196777A1 - 一种具有还原性的可聚合表面活性剂及其制备方法 - Google Patents

一种具有还原性的可聚合表面活性剂及其制备方法 Download PDF

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WO2021196777A1
WO2021196777A1 PCT/CN2020/140467 CN2020140467W WO2021196777A1 WO 2021196777 A1 WO2021196777 A1 WO 2021196777A1 CN 2020140467 W CN2020140467 W CN 2020140467W WO 2021196777 A1 WO2021196777 A1 WO 2021196777A1
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polymerizable surfactant
reducing
acid anhydride
preparing
solution
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PCT/CN2020/140467
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French (fr)
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黄文艳
孙邱杰
蒋必彪
薛小强
杨宏军
江力
蒋其民
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常州大学
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Publication of WO2021196777A1 publication Critical patent/WO2021196777A1/zh
Priority to US17/936,932 priority Critical patent/US11674108B2/en
Priority to US18/333,514 priority patent/US20230340362A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
    • 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
    • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
    • 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
    • C07C213/10—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene

Definitions

  • the invention belongs to the technical field of fine chemicals, and specifically relates to a reducing polymerizable surfactant and a preparation method thereof.
  • polymerizable surfactants also include a reactive functional group.
  • This reactive functional group can participate in the emulsion polymerization reaction. While acting as a conventional emulsifier, it can also covalently bond It is bonded to the surface of polymer particles and becomes part of the polymer to prevent the emulsifier from desorbing from the polymer particles or migrating in the latex film, thereby improving the stability of the emulsion and improving the performance of the latex film.
  • the existing polymerizable surfactants are a series of polymerizable surfactants including different reactive groups (acrylate, styrene, maleic anhydride, etc.) and different ionic characteristics (cationic, anionic, nonionic, etc.). Since the soap-free emulsion system does not contain emulsifiers, it has many excellent properties. However, due to the lack of the protective effect of the emulsifier, the stability of the emulsion is reduced, and the solid content is relatively low. Therefore, the development of new reactive surfactants is the primary problem faced by soap-free emulsion polymerization.
  • the redox initiation system forms free radical active species through inner electron transfer (ISET), thereby initiating the polymerization of vinyl monomers.
  • ISET inner electron transfer
  • the redox system not only shortens the induction period, but also increases the rate of polymerization.
  • the chain initiation activation energy of the redox system is about 40-60 kJ/mol lower, so that the polymerization temperature can be lowered, and it can even be polymerized at or below room temperature.
  • the redox initiation system initiates the polymerization fast and can initiate the polymerization at a lower temperature.
  • the polymer obtained has a high molecular weight, but as a kind of emulsion polymerization, it also has insufficient film-forming properties and mechanical properties of the emulsion due to the addition of a large amount of emulsifiers Shortcomings.
  • the purpose of the present invention is to introduce a reducing tertiary amine group into one end of the acid anhydride. Because the tertiary amine has certain hydrophilic properties as the hydrophilic end of the polymerizable surfactant, the other end of the acid anhydride is connected with a long carbon chain as the lipophilic end. . In this way, a polymerizable surfactant with one end hydrophilic and one end lipophilic and with reducing properties is obtained.
  • the surfactant provided by the present invention uses acid anhydride, long-chain fatty alcohol and dimethylamino haloalkane hydrochloride as main raw materials, and the prepared polymerizable surfactant has excellent emulsifying properties and can also be used as a reducing agent. Redox initiates the reaction.
  • One-step emulsion polymerization can be carried out at room temperature or low temperature to obtain an environmentally friendly emulsion with a branched structure, thereby obtaining a coating with excellent water resistance, weather resistance and impact resistance.
  • the long-chain alkyl R 1 is -C 12 H 25 , -C 14 H 29 or -C 16 H 33
  • R 2 is -C 2 H 4 -, -C 3 H 6 -or -C(CH 3 ) CH 2 -.
  • the present invention also provides a method for preparing a reducing polymerizable surfactant: the acid anhydride is reacted with a long-chain fatty alcohol to obtain the monoester product of the intermediate acid anhydride, and then the obtained intermediate is continued with the dimethylamino haloalkane The hydrochloride is reacted, and finally a reductive polymerizable surfactant is obtained through post-treatment.
  • the acid anhydride is maleic anhydride or itaconic anhydride
  • the long-chain fatty alcohol is dodecanol, myristyl alcohol or cetyl alcohol, etc.
  • the hydrochloride of the dimethylamino haloalkane is: 2-dimethylaminochloroethane hydrochloride, 3-(N,N-dimethyl)amino-1-chloropropane hydrochloride or 3-
  • the amount ratio of the added dimethylamino haloalkane and the intermediate monoester is 1-1.1:1.
  • the reaction solution obtained from the reaction in step (2) is cooled to room temperature, the layers are separated, and the separated chloroform solution is added to anhydrous sodium sulfate and dried overnight. Pass the chloroform solution over an alkaline alumina column, use a rotary evaporator to remove the chloroform at 30-40°C, and then vacuum dry overnight at 30°C with a vacuum of 2-3kPa.
  • the resulting product has a reducing polymerizable surface activity. Agent.
  • the present invention uses a synthetic method to prepare a reducing polymerizable surfactant, and the prepared surfactant has excellent emulsifying properties.
  • the synthesized surfactant can form a redox initiation system with an oxidizing agent, and soap-free emulsion polymerization can be carried out at room temperature or even low temperature without adding additional reducing agent, which can greatly reduce the energy consumption of production.
  • the surfactant of the present invention has the properties of a reducing monomer, and an emulsion with a branched structure can be obtained, thereby obtaining a coating with excellent water resistance, weather resistance and impact resistance.
  • Figure 1 is a nuclear magnetic map of 2-(dimethylamino)ethyl dodecyl maleate in Example 1.
  • Fig. 2 is a NMR chart of 2-(dimethylamino)ethyl lauryl itaconic acid in Example 2.
  • FIG. 3 is a molecular weight distribution curve of the branched polymer obtained in Example 7.
  • FIG. 3 is a molecular weight distribution curve of the branched polymer obtained in Example 7.
  • step (3) Product post-treatment: the reaction solution obtained in step (2) is cooled to room temperature, the layers are separated, and the separated chloroform solution is added to anhydrous sodium sulfate and dried overnight. Pass the chloroform solution over an alkaline alumina column, use a rotary evaporator to remove the chloroform at 30-40°C, and then vacuum dry overnight at 30°C with a vacuum of 2-3kPa. The resulting product has a reducing polymerizable surface activity. Agent.
  • step (3) Product post-treatment: the reaction solution obtained in step (2) is cooled to room temperature, the layers are separated, and the separated chloroform solution is added to anhydrous sodium sulfate and dried overnight. Pass the chloroform solution over an alkaline alumina column, use a rotary evaporator to remove the chloroform at 30-40°C, and then vacuum dry overnight at 30°C with a vacuum of 2-3kPa. The resulting product has a reducing polymerizable surface activity. Agent.
  • step (3) Product post-treatment: the reaction solution obtained in step (2) is cooled to room temperature, the layers are separated, and the separated chloroform solution is added to anhydrous sodium sulfate and dried overnight. Pass the chloroform solution over an alkaline alumina column, use a rotary evaporator to remove the chloroform at 30-40°C, and then vacuum dry overnight at 30°C with a vacuum of 2-3kPa. The resulting product has a reducing polymerizable surface activity. Agent.
  • step (3) Product post-treatment: the reaction solution obtained in step (2) is cooled to room temperature, the layers are separated, and the separated chloroform solution is added to anhydrous sodium sulfate and dried overnight. Pass the chloroform solution over an alkaline alumina column, use a rotary evaporator to remove the chloroform at 30-40°C, and then vacuum dry overnight at 30°C with a vacuum of 2-3kPa. The resulting product has a reducing polymerizable surface activity. Agent.
  • step (3) Product post-treatment: the reaction solution obtained in step (2) is cooled to room temperature, the layers are separated, and the separated chloroform solution is added to anhydrous sodium sulfate and dried overnight. Pass the chloroform solution over an alkaline alumina column, use a rotary evaporator to remove the chloroform at 30-40°C, and then vacuum dry overnight at 30°C with a vacuum of 2-3kPa. The resulting product has a reducing polymerizable surface activity. Agent.
  • step (3) Product post-treatment: the reaction solution obtained in step (2) is cooled to room temperature, the layers are separated, and the separated chloroform solution is added to anhydrous sodium sulfate and dried overnight. Pass the chloroform solution over an alkaline alumina column, use a rotary evaporator to remove the chloroform at 30-40°C, and then vacuum dry overnight at 30°C with a vacuum of 2-3kPa. The resulting product has a reducing polymerizable surface activity. Agent.
  • Styrene (5.01g, 0.0480mol) was added to the dissolved 2-(dimethylamino) ethyl dodecyl maleate (0.3550g, 0.0010mol), sodium bicarbonate (0.15g, 3wt% styrene ), potassium persulfate (0.1344g, 0.0005mol) and water (20.07g, 400wt% styrene), stir evenly, vacuum and exhaust oxygen, and react at 25°C for 8 hours to obtain a stable emulsion .
  • the measured styrene conversion rate was 91.07%.
  • Styrene (5.0005g, 0.0480mol) was added to the dissolved itaconic acid 2-(dimethylamino) ethyl lauryl ester (0.3552g, 0.0010mol), sodium bicarbonate (0.15g, 3wt% styrene ), potassium persulfate (0.1340g, 0.0005mol) and water (20.07g, 400wt% styrene), stir evenly, vacuum and exhaust oxygen, and react at 25°C for 8 hours to obtain a stable emulsion .
  • the measured styrene conversion rate was 98.05%.
  • Styrene (5.00g, 0.0480mol) was added to the dissolved maleic acid 3-(dimethylamino)propyl dodecyl ester (0.3555g, 0.0010mol), sodium bicarbonate (0.15g, 3wt% styrene ), potassium persulfate (0.2619g, 0.0010mol) and water (20.07g, 400wt% styrene), stir evenly, vacuum and exhaust oxygen, and react at 25°C for 8 hours to obtain a stable emulsion .
  • the measured styrene conversion rate was 90.25%.
  • Styrene 5.0006g, 0.0480mol
  • N,N-dimethylaminoethyl methacrylate 0.1510g, 0.0010mol
  • sodium bicarbonate 0.1500g, 3wt% styrene
  • persulfuric acid 0.1500g, 3wt% styrene

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Abstract

本发明属于精细化工技术领域，具体涉及一种具有还原性的可聚合表面活性剂及其制备方法。取酸酐与长链脂肪醇反应，得到中间体酸酐的单酯产物，然后将所得中间体继续与二甲氨基卤代烷烃的盐酸盐反应，最后通过后处理得到具有还原性的可聚合表面活性剂。所得可聚合表面活性剂，不仅可以作为反应型乳化剂起到乳化作用并且与单体进行共聚得到无皂乳液，还可以与过氧化物构成氧化还原引发体系，常温下进行氧化还原乳液聚合。本发明合成的可聚合表面活性剂合成的无皂乳液可以大大减少生产中的能量消耗，并且可以在常温或低温下进行一步法乳液聚合得到具有支化结构的环境友好乳液，进而获得耐水性，耐候性及抗冲击性能优异的涂层。

Description

一种具有还原性的可聚合表面活性剂及其制备方法 技术领域
本发明属于精细化工技术领域，具体涉及一种具有还原性的可聚合表面活性剂及其制备方法。
背景技术
可聚合表面活性剂除了亲水，亲油基团外，还包括一个反应性官能团，这种反应性官能团能参与乳液聚合反应，在起到常规乳化剂的作用的同时，还可以以共价键的方式键合到聚合物粒子表面，成为聚合物的一部分，避免乳化剂从聚合物粒子上解吸或在乳胶膜中迁移，从而提高乳液稳定性并改进乳胶膜的性能。
自从1956年Bistline等人应用可聚合乳化剂进行聚合反应以来，大量可聚合乳化剂被合成并应用到各个方面，得到了性能优良的各种材料。现有的可聚合表面活性剂为一系列包括不同反应基团(丙烯酸酯、苯乙烯、马来酸酐等)和不同离子特性(阳离子、阴离子、非离子等)的可聚合表面活性剂。由于无皂乳液体系中不含乳化剂，所以具有许多优异的性能。但也正由于缺少乳化剂的保护作用，从而使的乳液的稳定性下降，固含量相对较低。因此，开发新型的反应性表面活性剂是无皂乳液聚合面临的首要问题。
氧化还原引发体系通过内层电子转移(ISET)形成自由基活性种，从而引发乙烯基单体的聚合。上世纪30～40年代，德、美、英等国科学家先后发现，氧化还原体系不仅能缩短诱导期，而且能提高聚合速率。与一般热分解的单一引发剂相比，氧化还原体系的链引发活化能要低约40～60kJ/mol，从而可使聚合温度降低，甚至可在或低于室温聚合。
氧化还原引发体系引发聚合速度快，可以在较低温度下引发聚合，得到的聚合物分子量高，但是作为乳液聚合的一种同样具有因为加入大量乳化剂而导致乳液的成膜性能和力学性能不足的缺点。
目前绿色环保型涂料的分子量和固体含量低，无法满足日益严格的法规和施工要求，乳液型涂料制备需要大量乳化剂来维持体系的稳定性，乳液成膜后的涂层耐水性和力学性能差，限制了绿色环保涂料的发展及应用。
发明内容
本发明的目的在于将具有还原性的叔胺基团引入酸酐一端，由于叔胺具有一定的亲水性能作为可聚合表面活性剂的亲水端，酸酐另一端接上长碳链作为亲油端。从而得到一端亲水一端亲油，并且具有还原性的可聚合表面活性剂。本发明提供的表面活性剂，其以酸酐，长链脂肪醇和二甲氨基卤代烷烃的盐酸盐为主要原料，制备得到的可聚合表面活性剂既有优良的乳化性能，还能作为还原剂参与氧化还原引发反应。可以在常温或低温下进行一步法乳液聚合得到具有支化结构的环境友好乳液，进而获得耐水性，耐候性及抗冲击性能优异的涂层。
本发明提供的具有还原性的可聚合表面活性剂的结构通式为以下两种：
Figure PCTCN2020140467-appb-000001
式中，长链烷基R 1为-C 12H 25，-C 14H 29或-C 16H 33，R 2为-C 2H 4-,-C 3H 6-或-C(CH 3)CH 2-。
本发明还提供了一种具有还原性的可聚合表面活性剂的制备方法：将酸酐 与长链脂肪醇反应，得到中间体酸酐的单酯产物，然后将所得中间体继续与二甲氨基卤代烷烃的盐酸盐反应，最后通过后处理得到具有还原性的可聚合表面活性剂。
可聚合表面活性剂的制备方法，具体步骤如下：
(1)中间体的制备：将酸酐与长链脂肪醇按物质的量比1:1～1.1混合，在80℃下加热至熔融状态，搅拌1h。然后将庚烷添加到熔融反应混合物中，搅拌形成均匀溶液。将该溶液搅拌冷却至室温，放置3h，继续搅拌冷却至15℃，放置2h。收集形成的沉淀物，用庚烷重结晶2～3次，抽滤固体并用水洗2～3次，最后冷冻干燥，得到中间体酸酐单酯。
其中，所述酸酐为马来酸酐或衣康酸酐；所述长链脂肪醇为十二醇，十四醇或十六醇等。
(2)具有还原性可聚合表面活性剂的制备：将中间体酸酐单酯溶解于氯仿中，在室温下，将碳酸钾(中间体单酯物质的量的2倍)和18-crown-6(中间体单酯物质的量的1/10)的水溶液逐滴加入到上述中间体酸酐单酯氯仿溶液中，在50～60℃搅拌0.4h。将二甲氨基卤代烷烃的盐酸盐逐滴加入到上述溶液中，于50℃下反应15-20h后结束反应，得到反应液。
其中，所述二甲氨基卤代烷烃的盐酸盐为：2-二甲氨基氯乙烷盐酸盐，3-(N,N-二甲基)氨基-1-氯丙烷盐酸盐或3-二甲氨基-2-甲基-1-氯丙烷盐酸盐等，加入的二甲氨基卤代烷烃和中间体单酯的物质的量比为1～1.1:1。
(3)产物后处理：将步骤(2)反应所得到的反应液冷却至室温，分离各层，将分离出来的氯仿溶液加入无水硫酸钠干燥过夜。将氯仿溶液过碱性氧化铝柱子，用旋转蒸发仪在30～40℃下除去氯仿，然后于30℃下真空干燥过夜，真空度为2～3kPa，所得产品为具有还原性的可聚合表面活性剂。
本发明具有如下优点：
1.本发明用合成的方法制备了一种具有还原性的可聚合表面活性剂，所制备的表面活性剂具有优秀的乳化性能。
2.合成的表面活性剂能与氧化剂构成氧化还原引发体系，可以常温甚至低温下进行无皂乳液聚合，而不需要额外加入还原剂，能大大减少生产的能源消耗。
3.本发明的表面活性剂具有还原性单体的性质，可以得到具有支化结构的乳液，进而获得耐水性，耐候性及抗冲击性能优异的涂层。
附图说明
图1为实施例1中马来酸2-(二甲氨基)乙酯十二烷基酯的核磁图。
图2为实施例2中衣康酸2-(二甲氨基)乙酯十二烷基酯的核磁图。
图3为实施例7中所得支化聚合物的分子量分布曲线。
具体实施方式
本发明用下列实施例来进一步说明本发明的技术特征，但本发明的保护范围并非限于下列实施例。
实施例1
(1)中间体的制备：取4.90g(0.05mol)马来酸酐与10.25g(0.055mol)十二醇在熔融状态下于80℃搅拌1h。然后将15ml庚烷添加到反应混合物中，搅拌直到形成均匀溶液。将该溶液于室温下放置3h，然后在15℃下放置2h，并保持搅拌。收集形成的沉淀物，用庚烷重结晶2～3次，抽滤固体并用水洗2～3次，最后冷冻干燥过夜，得到中间体酸酐单酯。计算产率，产率可达92.8％。
(2)还原性可聚合表面活性剂的制备：将11.36g(0.04mol)马来酸单十二醇酯溶解于100ml氯仿中。在室温下，将11.06g(0.08mol)碳酸钾和 1.05g(0.004mol)18-crown-6的水溶液逐滴加入到氯仿溶液中，然后将混合物在60℃搅拌0.4h。将5.76g(0.04mol)2-二甲氨基氯乙烷盐酸盐(阿拉丁，CAS：4584-46-7)的水溶液逐滴加入到上述水-氯仿溶液中，50℃反应20h后结束反应。
(3)产品后处理：将步骤(2)反应所得到的反应液冷却至室温，分离各层，将分离出来的氯仿溶液加入无水硫酸钠干燥过夜。将氯仿溶液过碱性氧化铝柱子，用旋转蒸发仪在30～40℃下除去氯仿，然后于30℃下真空干燥过夜，真空度为2～3kPa，所得产品为具有还原性的可聚合表面活性剂。
(4)产品核磁分析：取少量产物进行核磁分析，溶剂为氘代氯仿。化学位移δ＝6.26处的峰为双键上的2个H，化学位移δ＝4.29，δ＝4.15两个三重峰为与酯键相连的-CH 2-，δ＝2.60为与N相连的-CH 2-，δ＝2.29为与N相连的两个-CH 3，δ＝1.2-1.7为长烷基上的-CH 2-，δ＝0.88为长烷基末端的-CH 3。图1为马来酸2-(二甲氨基)乙酯十二烷基酯的核磁图。
实施例2
(1)中间体的制备：取5.61g(0.05mol)衣康酸酐与9.32g(0.05mol)十二醇在熔融状态下于80℃搅拌1h。然后将15ml庚烷添加到反应混合物中，搅拌直到形成均匀溶液。将该溶液于室温下放置3h，然后在15℃下放置2h，并保持搅拌。收集形成的沉淀物，用庚烷重结晶2～3次，抽滤固体并用水洗2～3次，最后冷冻干燥过夜，得到中间体酸酐单酯。计算产率，产率可达93.5％。
(2)还原性可聚合表面活性剂的制备：将11.92g(0.04mol)衣康酸单十二醇酯溶解于100ml氯仿中。在室温下，将11.06g(0.08mol)碳酸钾和1.05g(0.004mol)18-crown-6的水溶液逐滴加入到氯仿溶液中，然后将混合物在50℃搅拌0.4h。将5.76g(0.04mol)2-二甲氨基氯乙烷盐酸盐(阿拉 丁，CAS：4584-46-7)的水溶液逐滴加入到上述水-氯仿溶液中，50℃反应20h后结束反应。
(3)产品后处理：将步骤(2)反应所得到的反应液冷却至室温，分离各层，将分离出来的氯仿溶液加入无水硫酸钠干燥过夜。将氯仿溶液过碱性氧化铝柱子，用旋转蒸发仪在30～40℃下除去氯仿，然后于30℃下真空干燥过夜，真空度为2～3kPa，所得产品为具有还原性的可聚合表面活性剂。
(4)产品核磁分析：取少量产物进行核磁分析，溶剂为氘代氯仿。化学位移δ＝6.34，δ＝5.72处的峰为双键上的2个H，δ＝3.34为与羰基相连的-CH 2-，化学位移δ＝4.27，δ＝4.08两个三重峰为与酯键相连的-CH 2-，δ＝2.60为与N相连的-CH 2-，δ＝2.29为与N相连的两个-CH 3，δ＝1.2-1.7为长烷基上的-CH 2-，δ＝0.88为长烷基末端的-CH 3。图2为衣康酸2-(二甲氨基)乙酯十二烷基酯的核磁图。
实施例3
(1)中间体的制备：取4.90g(0.05mol)马来酸酐与11.79g(0.055mol)十四醇在熔融状态下于80℃搅拌1h。然后将15ml庚烷添加到反应混合物中，搅拌直到形成均匀溶液。将该溶液于室温下放置3h，然后在15℃下放置2h，并保持搅拌。收集形成的沉淀物，用庚烷重结晶2～3次，抽滤固体并用水洗2～3次，最后冷冻干燥过夜，得到中间体酸酐单酯。计算产率，产率可达91.5％。
(2)还原性可聚合表面活性剂的制备：将12.48g(0.04mol)马来酸单十四醇酯溶解于100ml氯仿中。在室温下，将11.06g(0.08mol)碳酸钾和1.05g(0.004mol)18-crown-6的水溶液逐滴加入到氯仿溶液中，然后将混合物在60℃搅拌0.4h。将5.76g(0.04mol)2-二甲氨基氯乙烷盐酸盐(阿拉丁，CAS：4584-46-7)逐滴加入到上述水-氯仿溶液中，50℃反应20h后结束 反应。
(3)产品后处理：将步骤(2)反应所得到的反应液冷却至室温，分离各层，将分离出来的氯仿溶液加入无水硫酸钠干燥过夜。将氯仿溶液过碱性氧化铝柱子，用旋转蒸发仪在30～40℃下除去氯仿，然后于30℃下真空干燥过夜，真空度为2～3kPa，所得产品为具有还原性的可聚合表面活性剂。
实施例4
(1)中间体的制备：取5.61g(0.05mol)衣康酸酐与10.72g(0.05mol)十四醇在熔融状态下于80℃搅拌1h。然后将15ml庚烷添加到反应混合物中，搅拌直到形成均匀溶液。将该溶液于室温下放置3h，然后在15℃下放置2h，并保持搅拌。收集形成的沉淀物，用庚烷重结晶2～3次，抽滤固体并用水洗2～3次，最后冷冻干燥过夜，得到中间体酸酐单酯。计算产率，产率可达92.5％。
(2)还原性可聚合表面活性剂的制备：将13.04g(0.04mol)衣康酸单十四醇酯溶解于100ml氯仿中。在室温下，将11.06g(0.08mol)碳酸钾和1.05g(0.004mol)18-crown-6的水溶液逐滴加入到氯仿溶液中，然后将混合物在50℃搅拌0.4h。将5.76g(0.04mol)2-二甲氨基氯乙烷盐酸盐(阿拉丁，CAS：4584-46-7)逐滴加入到上述水-氯仿溶液中，50℃反应20h后结束反应。
(3)产品后处理：将步骤(2)反应所得到的反应液冷却至室温，分离各层，将分离出来的氯仿溶液加入无水硫酸钠干燥过夜。将氯仿溶液过碱性氧化铝柱子，用旋转蒸发仪在30～40℃下除去氯仿，然后于30℃下真空干燥过夜，真空度为2～3kPa，所得产品为具有还原性的可聚合表面活性剂。
实施例5
(1)中间体的制备：取4.90g(0.05mol)马来酸酐与10.25g(0.055mol) 十二醇在熔融状态下于80℃搅拌1h。然后将15ml庚烷添加到反应混合物中，搅拌直到形成均匀溶液。将该溶液于室温下放置3h，然后在15℃下放置2h，并保持搅拌。收集形成的沉淀物，用庚烷重结晶2～3次，抽滤固体并用水洗2～3次，最后冷冻干燥过夜，得到中间体酸酐单酯。计算产率，产率可达91.3％。
(2)还原性可聚合表面活性剂的制备：将11.36g(0.04mol)马来酸单十二醇酯溶解于100ml氯仿中。在室温下，将11.06g(0.08mol)碳酸钾和1.05g(0.004mol)18-crown-6的水溶液逐滴加入到氯仿溶液中，然后将混合物在60℃搅拌0.4h。将6.32g(0.04mol)3-(N,N-二甲基)氨基-1-氯丙烷盐酸盐(阿拉丁，CAS：5407-04-5)的水溶液逐滴加入到上述水-氯仿溶液中，50℃反应20h后结束反应。
(3)产品后处理：将步骤(2)反应所得到的反应液冷却至室温，分离各层，将分离出来的氯仿溶液加入无水硫酸钠干燥过夜。将氯仿溶液过碱性氧化铝柱子，用旋转蒸发仪在30～40℃下除去氯仿，然后于30℃下真空干燥过夜，真空度为2～3kPa，所得产品为具有还原性的可聚合表面活性剂。
实施例6
(1)中间体的制备：取4.90g(0.05mol)马来酸酐与10.25g(0.055mol)十二醇在熔融状态下于80℃搅拌1h。然后将15ml庚烷添加到反应混合物中，搅拌直到形成均匀溶液。将该溶液于室温下放置3h，然后在15℃下放置2h，并保持搅拌。收集形成的沉淀物，用庚烷重结晶2～3次，抽滤固体并用水洗2～3次，最后冷冻干燥过夜，得到中间体酸酐单酯。计算产率，产率可达92.8％。
(2)还原性可聚合表面活性剂的制备：将11.36g(0.04mol)马来酸单十二醇酯溶解于100ml氯仿中。在室温下，将11.06g(0.08mol)碳酸钾和1.05g(0.004mol)18-crown-6的水溶液逐滴加入到氯仿溶液中，然后将混合 物在60℃搅拌0.4h。将6.88g(0.04mol)3-二甲氨基-2-甲基-1-氯丙烷盐酸盐(阿拉丁，CAS：4261-67-0)的水溶液逐滴加入到上述水-氯仿溶液中，50℃反应20h后结束反应。
(3)产品后处理：将步骤(2)反应所得到的反应液冷却至室温，分离各层，将分离出来的氯仿溶液加入无水硫酸钠干燥过夜。将氯仿溶液过碱性氧化铝柱子，用旋转蒸发仪在30～40℃下除去氯仿，然后于30℃下真空干燥过夜，真空度为2～3kPa，所得产品为具有还原性的可聚合表面活性剂。
实施例7
将苯乙烯(5.01g，0.0480mol)加入到溶有马来酸2-(二甲氨基)乙酯十二烷基酯(0.3550g，0.0010mol)、碳酸氢钠(0.15g，3wt％苯乙烯)、过硫酸钾(0.1344g，0.0005mol)和水(20.07g，400wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于25℃下反应8小时，得到稳定的乳液。测得苯乙烯转化率为91.07％。采用三检测凝胶渗透色谱对聚合物进行分析，结果如下：M n.SEC＝418000g/mol，M w.SEC＝2560000g/mol，PDI＝6.1.Mark-Houwink指数α＝0.6756，平均支化因子g'＝0.66。所得聚合物的分子量分布曲线见附图3。
实施例8
将苯乙烯(5.0005g，0.0480mol)加入到溶有衣康酸2-(二甲氨基)乙酯十二烷基酯(0.3552g，0.0010mol)、碳酸氢钠(0.15g，3wt％苯乙烯)、过硫酸钾(0.1340g，0.0005mol)和水(20.07g，400wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于25℃下反应8小时，得到稳定的乳液。测得苯乙烯转化率为98.05％。采用三检测凝胶渗透色谱对聚合物进行分析，结果如下：M n.SEC＝263000g/mol，M w.SEC＝2970000g/mol，PDI＝11.3.Mark-Houwink指数α＝0.5992，平均支化因子g'＝0.52。
实施例9
将苯乙烯(5.00g，0.0480mol)加入到溶有马来酸3-(二甲氨基)丙酯十二烷基酯(0.3555g，0.0010mol)、碳酸氢钠(0.15g，3wt％苯乙烯)、过硫酸钾(0.2619g，0.0010mol)和水(20.07g，400wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于25℃下反应8小时，得到稳定的乳液。测得苯乙烯转化率为90.25％。采用三检测凝胶渗透色谱对聚合物进行分析，结果如下：M n.SEC＝530000g/mol，M w.SEC＝6520000g/mol，PDI＝12.3.Mark-Houwink指数α＝0.5889，平均支化因子g'＝0.50。
对照例1
将苯乙烯(5.0006g，0.0480mol)和甲基丙烯酸N,N-二甲氨基乙酯(0.1510g，0.0010mol)依次加入到溶有碳酸氢钠(0.1500g，3wt％苯乙烯)、过硫酸钾(0.2596g，0.0010mol)和水(20.0020g，400wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于25℃下，体系不反应。

Claims (9)

  1. 一种具有还原性的可聚合表面活性剂，其特征在于，所述表面活性剂的结构通式为以下两种：
    Figure PCTCN2020140467-appb-100001
    式中，长链烷基R 1为-C 12H 25，-C 14H 29或-C 16H 33,R 2为-C 2H 4-,-C 3H 6-或-C(CH 3)CH 2-。
  2. 一种具有还原性的可聚合表面活性剂的制备方法，其特征在于，所述制备方法为：将酸酐与长链脂肪醇反应，得到中间体酸酐的单酯产物，然后将所得中间体继续与二甲氨基卤代烷烃的盐酸盐反应，最后通过后处理得到具有还原性的可聚合表面活性剂。
  3. 根据权利要求2所述的具有还原性的可聚合表面活性剂的制备方法，其特征在于，所述可聚合表面活性剂的制备方法步骤如下：
    (1)中间体的制备：将酸酐与长链脂肪醇混合，在80℃下加热至熔融状态，搅拌1h，然后将庚烷添加到熔融反应混合物中，搅拌形成均匀溶液，再将该溶液搅拌冷却至室温，放置3h，继续搅拌冷却至15℃，放置2h，收集形成的沉淀物，用庚烷重结晶2～3次，抽滤固体并用水洗2～3次，最后冷冻干燥，得到中间体酸酐单酯；
    (2)具有还原性可聚合表面活性剂的制备：将步骤(1)的中间体酸酐单酯溶解于氯仿中，在室温下，将碳酸钾和18-crown-6的水溶液逐滴加入到中间体酸酐单酯氯仿溶液中，在50～60℃搅拌0.4h，将二甲氨基卤代烷烃的盐酸盐水溶液逐滴加入到上述溶液中，于50℃下反应15～20h后结束反应，得到反应液；
    (3)产物后处理：将步骤(2)反应所得到的反应液冷却至室温，分离各层，将分离出来的氯仿溶液加入无水硫酸钠干燥过夜，将氯仿溶液过碱性氧化铝柱子，用旋转蒸发仪在30～40℃下除去氯仿，然后于30℃下真空干燥过夜，真空度为2～3kPa，所得产品为具有还原性的可聚合表面活性剂。
  4. 根据权利要求2或3所述的具有还原性的可聚合表面活性剂的制备方法，其特征在于，所述酸酐为马来酸酐或衣康酸酐。
  5. 根据权利要求2或3所述的具有还原性的可聚合表面活性剂的制备方法，其特征在于，所述长链脂肪醇为十二醇，十四醇或十六醇。
  6. 根据权利要求2或3所述的具有还原性的可聚合表面活性剂的制备方法，其特征在于，所述二甲氨基卤代烷烃的盐酸盐为2-二甲氨基氯乙烷盐酸盐，3-(N,N-二甲基)氨基-1-氯丙烷盐酸盐或3-二甲氨基-2-甲基-1-氯丙烷盐酸盐。
  7. 根据权利要求3所述的具有还原性的可聚合表面活性剂的制备方法，其特征在于，步骤(1)所述酸酐与长链脂肪醇的物质的量比为1:1～1.1。
  8. 根据权利要求3所述的具有还原性的可聚合表面活性剂的制备方法，其特征在于，步骤(2)所述碳酸钾和18-crown-6与中间体单酯的物质的量的比为2：0.1：1。
  9. 根据权利要求3所述的具有还原性的可聚合表面活性剂的制备方法，其特征在于，步骤(2)所述二甲氨基卤代烷烃和中间体单酯的物质的量比为1～1.1:1。
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