CN112138604A - Double-carboxyl surfactant with anion-cation reversal capability and preparation method thereof - Google Patents
Double-carboxyl surfactant with anion-cation reversal capability and preparation method thereof Download PDFInfo
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 150000001450 anions Chemical class 0.000 claims abstract description 22
- 150000001768 cations Chemical class 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 22
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003949 imides Chemical class 0.000 claims abstract description 16
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910010082 LiAlH Inorganic materials 0.000 claims abstract description 15
- HAUDLKKUHAFHRO-UHFFFAOYSA-N 2-oxaspiro[3.3]hept-6-ene-1,3-dione Chemical compound O=C1OC(=O)C11C=CC1 HAUDLKKUHAFHRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012467 final product Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 7
- 238000003379 elimination reaction Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 6
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 6
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000012280 lithium aluminium hydride Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000005909 Kieselgur Substances 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000010791 quenching Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000004809 thin layer chromatography Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
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- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
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- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LNVWRBNPXCUYJI-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazol-4-amine Chemical compound CC1=NNC(C)=C1N LNVWRBNPXCUYJI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
本发明公开了一种具有阴阳离子反转能力的双羧基表面活性剂及其制备方法,制备方法包括:1)在三口烧瓶中加入十二胺和环丁‑3‑烯二甲酸酐,通氮气,进行亲核加成‑消除反应生成酰亚胺;随后以LiAlH4为还原剂还原羰基。2)将上述产物稀释,缓慢加入高锰酸钾,升温进行氧化反应生成羧基,反应完成后加入亚硫酸钠除去过量的高锰酸钾,采用硅藻土过滤及乙酸乙酯萃出杂质,收集水相,将pH调至为2~4将产品析出,经过滤干燥至恒重得到最终产物。该表面活性剂具有优异的阴阳离子反转特性,可根据外界环境改变表面活性剂类型。在外界环境为碱性条件下为阴离子表面活性剂,外界环境为酸性条件下为阳离子表面活性剂。The invention discloses a double carboxyl surfactant with anion and cation reversal ability and a preparation method thereof. The preparation method comprises: 1) adding dodecylamine and cyclobutane-3-enedicarboxylic acid anhydride into a three-necked flask, passing nitrogen gas through , carry out a nucleophilic addition-elimination reaction to generate an imide; then use LiAlH 4 as a reducing agent to reduce the carbonyl group. 2) above-mentioned product is diluted, slowly add potassium permanganate, heat up and carry out oxidation reaction to generate carboxyl group, add sodium sulfite after the reaction is completed to remove excess potassium permanganate, use diatomaceous earth filtration and ethyl acetate to extract impurities, and collect the water phase. , adjust the pH to 2-4 to separate out the product, filter and dry to constant weight to obtain the final product. The surfactant has excellent anion and cation reversal properties, and the surfactant type can be changed according to the external environment. When the external environment is alkaline, it is an anionic surfactant, and when the external environment is acidic, it is a cationic surfactant.
Description
技术领域technical field
本发明属于功能性表面活性剂领域,特别涉及一种具有阴阳离子反转能力的双羧基表面活性剂及其制备方法。The invention belongs to the field of functional surfactants, and particularly relates to a dicarboxylate surfactant with anion and cation inversion ability and a preparation method thereof.
背景技术Background technique
表面活性剂是指分子结构中含有非极性亲油基团和极性亲水基团的两亲性化合物,能够在气液、固液界面形成定向排列,溶液中加入少量即可显著降低溶液表面张力,有效改变界面物理化学性质。因此广泛应用于日常生活、工农业及高新技术等领域,已成为化学工艺的重要产业之一。表面活性剂产业由于长久以来的薄弱基础,导致表面活性剂仍存有品种单一、结构简单、工艺落后等缺陷,特别是高端表面活性剂产品和技术,与国外仍有很大差距。Surfactants refer to amphiphilic compounds containing non-polar lipophilic groups and polar hydrophilic groups in the molecular structure, which can form directional arrangements at the gas-liquid and solid-liquid interfaces. Surface tension can effectively change the physical and chemical properties of the interface. Therefore, it is widely used in daily life, industry and agriculture and high-tech fields, and has become one of the important industries of chemical technology. Due to the weak foundation of the surfactant industry for a long time, the surfactants still have defects such as single variety, simple structure and backward technology, especially the high-end surfactant products and technologies, which still have a big gap with foreign countries.
发明内容SUMMARY OF THE INVENTION
为了丰富表面活性剂类型,赋予表面活性剂功能化,本发明设计和制备了一种具有阴阳离子反转能力的双羧基表面活性剂及其制备方法。In order to enrich the types of surfactants and endow the surfactants with functionalization, the present invention designs and prepares a dicarboxylate surfactant with anion and cation inversion ability and a preparation method thereof.
为达到上述目的,本发明采用以下技术方案:To achieve the above object, the present invention adopts the following technical solutions:
一种具有阴阳离子反转能力的双羧基表面活性剂,该化合物结构式为:A double carboxyl surfactant with anion and cation inversion ability, the compound structural formula is:
作为本发明进一步改进,该表面活性剂根据外界环境pH的变化,阴阳离子性质进行反转。As a further improvement of the present invention, the anion and cation properties of the surfactant are reversed according to the pH change of the external environment.
作为本发明进一步改进,所述双羧基表面活性剂在外界环境为碱性条件下为阴离子表面活性剂,外界环境为酸性条件下为阳离子表面活性剂。该表面活性剂具有优异的阴阳离子反转特性,可根据外界环境改变表面活性剂类型。在外界环境为碱性条件下为阴离子表面活性剂,外界环境为酸性条件下为阳离子表面活性剂。As a further improvement of the present invention, the dicarboxyl surfactant is an anionic surfactant when the external environment is an alkaline condition, and a cationic surfactant when the external environment is an acidic condition. The surfactant has excellent anion and cation reversal properties, and the surfactant type can be changed according to the external environment. When the external environment is alkaline, it is an anionic surfactant, and when the external environment is acidic, it is a cationic surfactant.
一种具有阴阳离子反转能力的双羧基表面活性剂的制备方法,包括以下步骤:A kind of preparation method of the double carboxyl surfactant with anion and cation inversion ability, comprises the following steps:
将十二胺和环丁-3-烯二甲酸酐混合,通氮气,在150~200℃进行亲核加成-消除反应生成酰亚胺;Mix dodecylamine and cyclobut-3-enedicarboxylic acid anhydride, pass nitrogen, and carry out nucleophilic addition-elimination reaction at 150-200°C to generate imide;
向酰亚胺中加入还原剂LiAlH4,在0~35℃下还原羰基;Adding reducing agent LiAlH 4 to the imide, reducing the carbonyl group at 0~35°C;
再加入氧化剂高锰酸钾,升温90~100℃进行氧化反应生成羧基,经后处理,得到最终产物。The oxidant potassium permanganate is then added, and the temperature is increased to 90-100° C. to carry out oxidation reaction to generate carboxyl groups, and after post-treatment, the final product is obtained.
作为本发明进一步改进,所述亲核加成-消除反应中,十二胺和环丁-3-烯二甲酸酐的摩尔比为1:2。As a further improvement of the present invention, in the nucleophilic addition-elimination reaction, the molar ratio of dodecylamine and cyclobut-3-enedicarboxylic anhydride is 1:2.
作为本发明进一步改进,所述还原羰基中,LiAlH4与十二胺的摩尔比为1~1.2:1;As a further improvement of the present invention, in the reduced carbonyl group, the molar ratio of LiAlH 4 to dodecylamine is 1-1.2:1;
作为本发明进一步改进,所述高锰酸钾的物质的量是十二胺的物质的量的1~2倍。As a further improvement of the present invention, the amount of potassium permanganate is 1-2 times that of dodecylamine.
作为本发明进一步改进,所述氧化反应中,将还原羰基后的产物稀释后,在0℃下缓慢加入高锰酸钾,然后升温反应。As a further improvement of the present invention, in the oxidation reaction, after the product after reducing the carbonyl group is diluted, potassium permanganate is slowly added at 0° C., and then the temperature is raised for the reaction.
作为本发明进一步改进,所述后处理包括:As a further improvement of the present invention, the post-processing includes:
反应结束后加入亚硫酸钠除去过量的高锰酸钾,采用硅藻土过滤及乙酸乙酯萃出杂质,收集水相,将pH调至为2~4将产品析出,经过滤干燥至恒重得到最终产物。After the reaction, sodium sulfite was added to remove excess potassium permanganate, diatomaceous earth was used to filter and ethyl acetate was used to extract impurities, the aqueous phase was collected, the pH was adjusted to 2 to 4 to separate out the product, and the final product was obtained by filtration and drying to constant weight. product.
本发明具有以下优点:The present invention has the following advantages:
本发明制备方法通过十二胺和环丁-3-烯二甲酸酐亲核加成-消除反应生成酰亚胺,以LiAlH4为还原剂还原酰亚胺;再通过还原剂高锰酸钾,得最终产物。整个制备方法简单,便捷,制备得到具有阴阳离子反转能力的双羧基表面活性剂。The preparation method of the invention generates imide through nucleophilic addition-elimination reaction of dodecylamine and cyclobut-3-enedicarboxylic anhydride, uses LiAlH 4 as reducing agent to reduce imide; get the final product. The whole preparation method is simple and convenient, and the double carboxyl surfactant with anion and cation inversion ability is prepared.
本发明制备的具有阴阳离子反转能力的双羧基表面活性剂可应用于石油开采,原油回收,土壤修复等领域。该表面活性剂具有优异的阴阳离子反转特性,可根据外界环境改变表面活性剂类型。在外界环境为碱性条件下为阴离子表面活性剂,外界环境为酸性条件下为阳离子表面活性剂。The dicarboxyl surfactant with anion and cation reversal ability prepared by the invention can be applied to the fields of oil exploitation, crude oil recovery, soil restoration and the like. The surfactant has excellent anion and cation reversal properties, and the surfactant type can be changed according to the external environment. When the external environment is alkaline, it is an anionic surfactant, and when the external environment is acidic, it is a cationic surfactant.
附图说明Description of drawings
图1为实施例4所得具有阴阳离子反转能力的双羧基表面活性剂的合成路线图。Fig. 1 is the synthetic route diagram of the dicarboxyl surfactant with anion and cation inversion ability obtained in Example 4.
图2为实施例4中所得具有阴阳离子反转能力的双羧基表面活性剂的表面张力随pH的变化图。FIG. 2 is a graph showing the change of the surface tension with pH of the dicarboxylated surfactant with anion and cation inversion ability obtained in Example 4. FIG.
具体实施方式Detailed ways
本发明一种具有阴阳离子反转能力的双羧基表面活性剂,其制备过程的反应方程式为:A kind of double carboxyl surfactant with anion and cation inversion ability of the present invention, the reaction equation of its preparation process is:
根据上述反应机理,本发明采用如下技术方案:According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
一种具有阴阳离子反转能力的双羧基表面活性剂,该表面活性剂的结构式为:A double carboxyl surfactant with anion and cation inversion ability, the structural formula of the surfactant is:
制备上述的具有阴阳离子反转能力的双羧基表面活性剂的方法,该方法的步骤为:The method for preparing the above-mentioned dicarboxyl surfactant with anion and cation inversion ability, the steps of the method are:
1)在装有回流冷凝管的三口烧瓶中依次滴加十二胺和环丁-3-烯二甲酸酐,通氮气,在150~200℃反应2~5h,进行第一步亲核加成-消除反应生成酰亚胺,其中十二胺和环丁-3-烯二甲酸酐的摩尔比为1:2;随后以LiAlH4为还原剂还原酰亚胺,其中LiAlH4与十二胺的摩尔比为1~1.2:1,还原温度为0~35℃,优选20~35℃,还原时间为4~6h。1) Add dodecylamine and cyclobut-3-ene dicarboxylic anhydride dropwise in turn in a three-necked flask equipped with a reflux condenser, pass nitrogen, and react at 150-200° C. for 2-5 hours to carry out the first step of nucleophilic addition -elimination reaction generates imide, wherein the molar ratio of dodecylamine and cyclobut-3-enedicarboxylic acid anhydride is 1:2; then imide is reduced with LiAlH 4 as reducing agent, wherein the molar ratio of LiAlH 4 and dodecylamine is The molar ratio is 1-1.2:1, the reduction temperature is 0-35°C, preferably 20-35°C, and the reduction time is 4-6h.
2)将上述产物稀释后,在0℃下缓慢加入高锰酸钾,升温反应10~12h,其中高锰酸钾的物质的量是十二胺的1~2倍;采用亚硫酸钠还原过量高锰酸钾,滴加稀盐酸至反应液pH为2~4将产品析出,经过滤干燥至恒重得到最终产物。2) After diluting the above product, slowly add potassium permanganate at 0°C, and the temperature rises for 10 to 12 h, wherein the amount of potassium permanganate is 1 to 2 times that of dodecylamine; sodium sulfite is used to reduce excess permanganate potassium acid, dilute hydrochloric acid was added dropwise until the pH of the reaction solution was 2-4, the product was precipitated, and the final product was obtained by filtration and drying to constant weight.
该表面活性剂可根据外界环境pH的变化,实现阴阳离子性质的反转。The surfactant can realize the reversal of the properties of anions and cations according to the change of the pH of the external environment.
具有阴阳离子反转能力的双羧基表面活性剂的反转原理通过以下反应实现:The inversion principle of biscarboxyl surfactants with anion and cation inversion ability is realized by the following reaction:
具有阴阳离子反转能力的双羧基表面活性剂在外界环境为碱性条件下为阴离子表面活性剂,外界环境为酸性条件下为阳离子表面活性剂。The dicarboxyl surfactant with anion and cation inversion ability is an anionic surfactant when the external environment is an alkaline condition, and a cationic surfactant when the external environment is an acidic condition.
下面将对本发明实施例中的技术方案进行清楚、完整的描述。显然,所描述的实施例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。The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
(1)在装有回流冷凝管的250mL三口烧瓶中依次滴加十二胺(18.5g,0.1mol)和环丁-3-烯二甲酸酐(24.8g,0.2mol),通氮气3次,然后加热至180℃反应3h,TLC(Thin LayerChromatography,薄层色谱)监测反应完成。待反应完成后冷却至室温,加入50mL蒸馏水,采用80mL乙酸乙酯萃取3次,经无水硫酸镁干燥,过滤,减压浓缩得到粗产品,最后经柱分离得到无色油状酰亚胺。(1) Dodecylamine (18.5g, 0.1mol) and cyclobut-3-ene dicarboxylic anhydride (24.8g, 0.2mol) were successively added dropwise in a 250mL three-necked flask equipped with a reflux condenser, and nitrogen was passed 3 times, Then, it was heated to 180° C. to react for 3 h, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction was completed, it was cooled to room temperature, 50 mL of distilled water was added, extracted three times with 80 mL of ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which was finally separated by column to obtain a colorless oily imide.
(2)将80mL用金属钠干燥过的四氢呋喃加入到250mL三口烧瓶中,采用冰盐浴冷却至0℃,分批缓慢加入3.8gLiAlH4,搅拌3min后再将溶解在四氢呋喃中的酰亚胺缓慢滴加至三口烧瓶中,待加完后升至25℃反应4h。TLC(ThinLayerChromatography,薄层色谱)监测反应完成。待反应完成后冷却至0℃,冰盐浴下,依次加入3.8mLH2O,3.8mL15%NaOH水溶液及11.4mLH2O淬灭过量的LiAlH4,过滤,滤饼用20ml乙酸乙酯充分洗涤,滤液经无水硫酸镁干燥,减压浓缩得到粗产品,最后经柱分离得到产物。(2) 80 mL of tetrahydrofuran dried with metallic sodium was added to a 250 mL three-necked flask, cooled to 0° C. using an ice-salt bath, 3.8 g of LiAlH 4 was slowly added in batches, and the imide dissolved in tetrahydrofuran was slowly added after stirring for 3 min. It was added dropwise to the three-necked flask, and after the addition was completed, it was raised to 25° C. for reaction for 4 hours. The completion of the reaction was monitored by TLC (ThinLayerChromatography). After the reaction was completed, it was cooled to 0°C, and under an ice-salt bath, 3.8 mL of H 2 O, 3.8 mL of 15% NaOH aqueous solution and 11.4 mL of H 2 O were sequentially added to quench the excess LiAlH 4 , filtered, and the filter cake was washed with 20 mL of ethyl acetate. The filtrate was dried over anhydrous magnesium sulfate, concentrated under reduced pressure to obtain the crude product, and finally the product was obtained by column separation.
(3)将上述产物及40mL蒸馏水加入到250mL三口烧瓶中,置于冰盐浴冷却至0℃,缓慢加入高锰酸钾KMnO4(20g,添加时间为40min),待全部加完后缓慢升温至90℃下反应12h。向三口烧瓶中加入80mL饱和亚硫酸钠水溶液淬灭过量的KMnO4;待紫色褪去后,缓慢降温并趁热用硅藻土过滤掉反应中生成的MnO2,得到澄清滤液;然后用乙酸乙酯将滤液萃取3次除去杂质,收集水相,采用稀盐酸将水相pH调至2析出固体,过滤干燥得到纯净的最终产物。(3) above-mentioned product and 40mL distilled water are added in 250mL there-necked flask, be placed in ice-salt bath and be cooled to 0 ℃, slowly add potassium permanganate KMnO 4 (20g, adding time is 40min), slowly heat up after adding all Reaction at 90°C for 12h. Add 80 mL of saturated aqueous sodium sulfite solution to the three-necked flask to quench the excess KMnO 4 ; after the purple color fades, slowly lower the temperature and filter out the MnO 2 generated in the reaction with diatomaceous earth while hot to obtain a clear filtrate; then the filtrate is washed with ethyl acetate. Extracting 3 times to remove impurities, collecting the aqueous phase, using dilute hydrochloric acid to adjust the pH of the aqueous phase to 2 to precipitate solids, filtering and drying to obtain the pure final product.
实施例1所得产物的产率为58%。The yield of the product obtained in Example 1 was 58%.
实施例2Example 2
(1)在装有回流冷凝管的250mL三口烧瓶中依次滴加十二胺(18.5g,0.1mol)和环丁-3-烯二甲酸酐(24.8g,0.2mol),通氮气3次,然后加热至150℃反应2h,TLC(Thin LayerChromatography,薄层色谱)监测反应完成。待反应完成后冷却至室温,加入50mL蒸馏水,采用80mL乙酸乙酯萃取3次,经无水硫酸镁干燥,过滤,减压浓缩得到粗产品,最后经柱分离得到无色油状酰亚胺。(1) Dodecylamine (18.5g, 0.1mol) and cyclobut-3-ene dicarboxylic anhydride (24.8g, 0.2mol) were successively added dropwise in a 250mL three-necked flask equipped with a reflux condenser, and nitrogen was passed 3 times, Then, it was heated to 150° C. for 2 h, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction was completed, it was cooled to room temperature, 50 mL of distilled water was added, extracted three times with 80 mL of ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which was finally separated by column to obtain a colorless oily imide.
(2)将90mL用金属钠干燥过的四氢呋喃加入到250mL三口烧瓶中,采用冰盐浴冷却至0℃,分批缓慢加入4.18gLiAlH4,搅拌3min后再将溶解在四氢呋喃中的酰亚胺缓慢滴加至三口烧瓶中,待加完后升至30℃反应5h。TLC(ThinLayerChromatography,薄层色谱)监测反应完成。待反应完成后冷却至0℃,冰盐浴下,依次加入4.2mLH2O,4.2mL15%NaOH水溶液及12.6mLH2O淬灭过量的LiAlH4,过滤,滤饼用20ml乙酸乙酯充分洗涤,滤液经无水硫酸镁干燥,减压浓缩得到粗产品,最后经柱分离得到产物。(2) 90 mL of tetrahydrofuran dried with metallic sodium was added to a 250 mL three-necked flask, cooled to 0° C. with an ice-salt bath, 4.18 g LiAlH 4 was slowly added in batches, and the imide dissolved in tetrahydrofuran was slowly added after stirring for 3 min. It was added dropwise to a three-necked flask, and after the addition was completed, it was raised to 30° C. for reaction for 5 hours. The completion of the reaction was monitored by TLC (ThinLayerChromatography). After the reaction was completed, it was cooled to 0°C, and under an ice-salt bath, 4.2 mL of H 2 O, 4.2 mL of 15% NaOH aqueous solution and 12.6 mL of H 2 O were sequentially added to quench the excess LiAlH 4 , filtered, and the filter cake was washed with 20 mL of ethyl acetate. The filtrate was dried over anhydrous magnesium sulfate, concentrated under reduced pressure to obtain the crude product, and finally the product was obtained by column separation.
(3)将上述产物及40mL蒸馏水加入到250mL三口烧瓶中,置于冰盐浴冷却至0℃,缓慢加入高锰酸钾KMnO4(15.8g,添加时间为40min),待全部加完后缓慢升温至100℃下反应10h。向三口烧瓶中加入80mL饱和亚硫酸钠水溶液淬灭过量的KMnO4;待紫色褪去后,缓慢降温并趁热用硅藻土过滤掉反应中生成的MnO2,得到澄清滤液;然后用乙酸乙酯将滤液萃取3次除去杂质,收集水相,采用稀盐酸将水相pH调至3析出固体,过滤干燥得到纯净的最终产物。(3) above-mentioned product and 40mL distilled water were added in 250mL three-necked flask, placed in ice-salt bath and cooled to 0°C, slowly added potassium permanganate KMnO 4 (15.8g, addition time was 40min), slowly after adding all The temperature was raised to 100 °C and the reaction was carried out for 10 h. Add 80 mL of saturated aqueous sodium sulfite solution to the three-necked flask to quench the excess KMnO 4 ; after the purple color fades, slowly lower the temperature and filter out the MnO 2 generated in the reaction with diatomaceous earth while hot to obtain a clear filtrate; then the filtrate is washed with ethyl acetate. Extracted 3 times to remove impurities, collected the aqueous phase, adjusted the pH of the aqueous phase to 3 with dilute hydrochloric acid, and precipitated a solid, filtered and dried to obtain a pure final product.
实施例2所得产物的产率为51%。The yield of the product obtained in Example 2 was 51%.
实施例3Example 3
(1)在装有回流冷凝管的250mL三口烧瓶中依次滴加十二胺(18.5g,0.1mol)和环丁-3-烯二甲酸酐(24.8g,0.2mol),通氮气3次,然后加热至200℃反应5h,TLC(Thin LayerChromatography,薄层色谱)监测反应完成。待反应完成后冷却至室温,加入50mL蒸馏水,采用80mL乙酸乙酯萃取3次,经无水硫酸镁干燥,过滤,减压浓缩得到粗产品,最后经柱分离得到无色油状酰亚胺。(1) Dodecylamine (18.5g, 0.1mol) and cyclobut-3-ene dicarboxylic anhydride (24.8g, 0.2mol) were successively added dropwise in a 250mL three-necked flask equipped with a reflux condenser, and nitrogen was passed 3 times, Then, it was heated to 200° C. to react for 5 h, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction was completed, it was cooled to room temperature, 50 mL of distilled water was added, extracted three times with 80 mL of ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which was finally separated by column to obtain a colorless oily imide.
(2)将100mL用金属钠干燥过的四氢呋喃加入到250mL三口烧瓶中,采用冰盐浴冷却至0℃,分批缓慢加入3.99gLiAlH4,搅拌3min后再将溶解在四氢呋喃中的酰亚胺缓慢滴加至三口烧瓶中,待加完后升至35℃反应6h。TLC(ThinLayerChromatography,薄层色谱)监测反应完成。待反应完成后冷却至0℃,冰盐浴下,依次加入4mLH2O,4mL15%NaOH水溶液及12mLH2O淬灭过量的LiAlH4,过滤,滤饼用20ml乙酸乙酯充分洗涤,滤液经无水硫酸镁干燥,减压浓缩得到粗产品,最后经柱分离得到产物。(2) 100 mL of tetrahydrofuran dried with metallic sodium was added to a 250 mL three-necked flask, cooled to 0° C. using an ice-salt bath, 3.99 g of LiAlH 4 was slowly added in batches, and the imide dissolved in tetrahydrofuran was slowly added after stirring for 3 min. It was added dropwise to a three-necked flask, and after the addition was completed, it was raised to 35° C. for reaction for 6 hours. The completion of the reaction was monitored by TLC (ThinLayerChromatography). After the reaction was completed, it was cooled to 0°C, and under an ice-salt bath, 4 mL of
(3)将上述产物及40mL蒸馏水加入到250mL三口烧瓶中,置于冰盐浴冷却至0℃,缓慢加入高锰酸钾KMnO4(25g,添加时间为40min),待全部加完后缓慢升温至90℃下反应12h。向三口烧瓶中加入80mL饱和亚硫酸钠水溶液淬灭过量的KMnO4;待紫色褪去后,缓慢降温并趁热用硅藻土过滤掉反应中生成的MnO2,得到澄清滤液;然后用乙酸乙酯将滤液萃取3次除去杂质,收集水相,采用稀盐酸将水相pH调至4析出固体,过滤干燥得到纯净的最终产物。(3) above-mentioned product and 40mL distilled water were added in 250mL there-necked flask, placed in ice-salt bath and cooled to 0°C, slowly added potassium permanganate KMnO 4 (25g, addition time was 40min), slowly heat up after adding all Reaction at 90°C for 12h. Add 80 mL of saturated aqueous sodium sulfite solution to the three-necked flask to quench the excess KMnO 4 ; after the purple color fades, slowly lower the temperature and filter out the MnO 2 generated in the reaction with diatomaceous earth while hot to obtain a clear filtrate; then the filtrate is washed with ethyl acetate. Extracted 3 times to remove impurities, collected the aqueous phase, adjusted the pH of the aqueous phase to 4 with dilute hydrochloric acid, and precipitated a solid, filtered and dried to obtain a pure final product.
实施例3所得产物的产率为53%。The yield of the product obtained in Example 3 was 53%.
实施例4Example 4
(1)在装有回流冷凝管的250mL三口烧瓶中依次滴加十二胺(18.5g,0.1mol)和环丁-3-烯二甲酸酐(24.8g,0.2mol),通氮气3次,然后加热至190℃反应5h,TLC(Thin LayerChromatography,薄层色谱)监测反应完成。待反应完成后冷却至室温,加入50mL蒸馏水,采用80mL乙酸乙酯萃取3次,经无水硫酸镁干燥,过滤,减压浓缩得到粗产品,最后经柱分离得到无色油状酰亚胺。(1) Dodecylamine (18.5g, 0.1mol) and cyclobut-3-ene dicarboxylic anhydride (24.8g, 0.2mol) were successively added dropwise in a 250mL three-necked flask equipped with a reflux condenser, and nitrogen was passed 3 times, Then it was heated to 190° C. to react for 5 h, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction was completed, it was cooled to room temperature, 50 mL of distilled water was added, extracted three times with 80 mL of ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which was finally separated by column to obtain a colorless oily imide.
(2)将80mL用金属钠干燥过的四氢呋喃加入到250mL三口烧瓶中,采用冰盐浴冷却至0℃,分批缓慢加入4.56gLiAlH4,搅拌3min后再将溶解在四氢呋喃中的酰亚胺缓慢滴加至三口烧瓶中,待加完后升至20℃反应6h。TLC(ThinLayerChromatography,薄层色谱)监测反应完成。待反应完成后冷却至0℃,冰盐浴下,依次加入4.6mLH2O,4.6mL15%NaOH水溶液及13.8mLH2O淬灭过量的LiAlH4,过滤,滤饼用20ml乙酸乙酯充分洗涤,滤液经无水硫酸镁干燥,减压浓缩得到粗产品,最后经柱分离得到产物。(2) 80 mL of tetrahydrofuran dried with metallic sodium was added to a 250 mL three-necked flask, cooled to 0° C. with an ice-salt bath, 4.56 g of LiAlH 4 was slowly added in batches, and the imide dissolved in tetrahydrofuran was slowly added after stirring for 3 min. It was added dropwise to a three-necked flask, and after the addition was completed, it was raised to 20° C. for reaction for 6 hours. The completion of the reaction was monitored by TLC (ThinLayerChromatography). After the reaction was completed, it was cooled to 0°C, and under an ice-salt bath, 4.6 mL of H 2 O, 4.6 mL of 15% NaOH aqueous solution and 13.8 mL of H 2 O were sequentially added to quench excess LiAlH 4 , filtered, and the filter cake was washed with 20 mL of ethyl acetate. The filtrate was dried over anhydrous magnesium sulfate, concentrated under reduced pressure to obtain the crude product, and finally the product was obtained by column separation.
(3)将上述产物及40mL蒸馏水加入到250mL三口烧瓶中,置于冰盐浴冷却至0℃,缓慢加入高锰酸钾KMnO4(31.6g,添加时间为40min),待全部加完后缓慢升温至100℃下反应10h。向三口烧瓶中加入80mL饱和亚硫酸钠水溶液淬灭过量的KMnO4;待紫色褪去后,缓慢降温并趁热用硅藻土过滤掉反应中生成的MnO2,得到澄清滤液;然后用乙酸乙酯将滤液萃取3次除去杂质,收集水相,采用稀盐酸将水相pH调至2析出固体,过滤干燥得到纯净的最终产物。(3) above-mentioned product and 40mL distilled water were added in 250mL three-necked flask, placed in ice-salt bath and cooled to 0°C, slowly added potassium permanganate KMnO 4 (31.6g, addition time was 40min), slowly after adding all The temperature was raised to 100 °C and the reaction was carried out for 10 h. Add 80 mL of saturated aqueous sodium sulfite solution to the three-necked flask to quench the excess KMnO 4 ; after the purple color fades, slowly lower the temperature and filter out the MnO 2 generated in the reaction with diatomaceous earth while hot to obtain a clear filtrate; then the filtrate is washed with ethyl acetate. Extracting 3 times to remove impurities, collecting the aqueous phase, using dilute hydrochloric acid to adjust the pH of the aqueous phase to 2 to precipitate solids, filtering and drying to obtain the pure final product.
实施例4所得产物的产率为60%。The yield of the product obtained in Example 4 was 60%.
为了表征一种具有阴阳离子反转能力的双羧基表面活性剂的结构特征,对实施例4中合成的具有阴阳离子反转能力的双羧基表面活性剂进行了核磁氢谱测试,结果如下所示:In order to characterize the structural characteristics of a biscarboxyl surfactant with anion and cation inversion ability, the biscarboxyl surfactant with anion and cation inversion ability synthesized in Example 4 was tested by hydrogen NMR, and the results are as follows :
1H NMR(300MHz,DMSO):δ12.13(s,2H),2.78-2.43(m,8H),1.36-1.26(m,20H),0.88(t,J=7.4Hz,3H)ppm。 1 H NMR (300 MHz, DMSO): δ 12.13 (s, 2H), 2.78-2.43 (m, 8H), 1.36-1.26 (m, 20H), 0.88 (t, J=7.4 Hz, 3H) ppm.
为了表征一种具有阴阳离子反转能力的双羧基表面活性剂的表面张力。采用JK99C型全自动表面张力仪测试实施例4中表面活性剂溶液的表面张力。首先配置浓度为0.01mol/L的表面活性剂溶液,在25℃下测试其表面张力。在测试过程中连续读取5个有升有降的数据,且5个数据之差小于1,取这些数据的平均值作为溶液的最终表面张力值,测试方法为白金环法。表面活性剂溶液的表面张力随pH的变化如图2所示。由图可知,随着表面活性剂溶液pH值增大,其表面张力先增加后降低。当pH为6时,表面张力达到最大为65.2mN/m,说明在酸性或碱性条件下,该表面活性剂具有较强的表面活性。To characterize the surface tension of a biscarboxyl surfactant with anion-cation inversion ability. The surface tension of the surfactant solution in Example 4 was measured by using a JK99C automatic surface tensiometer. First, a surfactant solution with a concentration of 0.01 mol/L was prepared, and its surface tension was tested at 25 °C. During the test, continuously read 5 data with rising and falling, and the difference between the 5 data is less than 1, take the average value of these data as the final surface tension value of the solution, and the test method is the platinum ring method. The surface tension of the surfactant solution as a function of pH is shown in Figure 2. It can be seen from the figure that as the pH value of the surfactant solution increases, its surface tension first increases and then decreases. When the pH is 6, the surface tension reaches a maximum of 65.2 mN/m, indicating that the surfactant has strong surface activity under acidic or alkaline conditions.
以上内容是对本发明所作的进一步详细说明,不能认定本发明的具体实施方式仅限于此,对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单的推演或替换,都应当视为属于本发明由所提交的权利要求书确定保护范围。The above content is a further detailed description of the present invention, and it cannot be considered that the specific embodiments of the present invention are limited to this. Several simple deductions or substitutions should be regarded as belonging to the protection scope of the present invention determined by the submitted claims.
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