CN104437235A - Long-chain cationic gemini surfactant and preparation method thereof - Google Patents
Long-chain cationic gemini surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a long-chain cationic gemini surfactant and a preparation method thereof. During preparation of a traditional gemini surfactant, when a tertiary amine hydrochloride intermediate is prepared, hydrogen chloride gas is introduced into tertiary amine, so that corrosion to equipment can be caused, and in addition, in the presence of a residual solvent, the rheological property of the gemini surfactant can be lowered. The preparation method comprises the following step: with epichlorohydrin and fatty acyl amide ethyl/propyl/butyl dimethylamine as raw materials, preparing a series of saturated and unsaturated cationic gemini surfactants with 2-hydroxy-1, 3-propylidene as a linking group, wherein a molecular structure contains an amido bond which is easy in biodegradation and hydroxyl which is easy in hydrolysis, and a hydrophobic chain is formed by alkyl chains of saturated or unsaturated long-chain fatty acids. According to the preparation method disclosed by the invention, under the condition of solvent-free alkaline catalysis, epoxyhalopropane and long-chain tertiary amine are adopted to further react to prepare a final product, so that the reaction yield is increased, the reaction process is simplified, the reaction period is shortened, and the long-chain cationic gemini surfactant is suitable for large-scale industrial production.
Description
Technical field
the present invention relates to a kind of surfactant, be specifically related to a kind of long chain cation gemini surfactant and preparation method thereof.
Background technology
Surfactant, as the important fine chemicals of a class, has a wide range of applications in production and each field of living.Particularly Gemini surface active, because its molecule is by two hydrophobic chains, two hydrophilic groups and an interval group composition, the structure that the surfactant list hydrophobic group single parent that breaks traditions is water base, fundamentally overcome the separation tendency that traditional single ionic surfactant causes due to the charge repulsion between ion head base or hydration, promote its close-packed arrays in interface or molecule aggregate, make it have lower critical micelle concentration (CMC) and the rheological property of higher surface-active and uniqueness, various advantage makes Gemini surface active agent in tertiary oil recovery, fracturing fluid, drilling fluid, emulsion polymerisation, gene transfection, washing, sterilization, emulsification, dispersion, the fields such as the synthesis of anticorrosion and ordered mesoporous material have larger application potential.These advantages have attracted numerous scientific research personnel to be devoted to the Synthesis and application research of Gemini surface active agent.
Along with the enhancing of people's environmental protection consciousness and the rise of Green Chemistry, green syt can have great importance by biological (or environment) Gemini surface active agent of degrading.Ikeda merit etc. manages facile hydrolysis group amide groups and ester group to be incorporated in the alkyl chain of cationic Gemini surfactant, example is synthesized, the first step: 2-(acid amides) dimethylamine being obtained by reacting serial single molecular chain with the fatty acid methyl ester of different alkyl chain length and 2-amino-ethyl dimethylamine with what be with the Gemini surface active agent of amide groups; Second step: namely single molecular chain 2-(acid amides) dimethylamine obtains with epichlorohydrin reaction bimolecular 2-(acid amides) dimethylamine that product spacer group is 2-hydroxyl-1,3 propylidene under its hydrochloride exists.There is following defect in this reaction: when first this reaction need prepare Amine from Tertiary Amine Hydrochloride intermediate, is passed in tertiary amine by hydrogen chloride gas, and hydrogen chloride gas cognition causes very large corrosion to production equipment.Its secondary response introduces solvent normal propyl alcohol, need pressure reducing and steaming solvent, and the existence of residual solvent can reduce the rheological property of Gemini surface active agent.
When the connecting group of Gemini surface active agent is 2-hydroxyl-1,3 propylidene, because epichlorohydrin reaction activity is higher, be widely used in the preparation of Gemini surface active agent.For improving reaction yield, usually make that epoxychloropropane is excessive or tertiary amine is excessive, this method not only causes material waste, and Gemini surface active agent product must be obtained by separating-purifying, follow-up separating-purifying process is complicated, epoxychloropropane is noxious material in addition, remains bring negative effect by the application of finished product quaternaries cation Gemini surface active agent if a large amount of.
Summary of the invention
The object of this invention is to provide a kind of long chain cation gemini surfactant and preparation method thereof, improve reaction yield, simplify reaction process, shorten reaction time, reduce costs.
The technical solution adopted in the present invention is:
Long chain cation gemini surfactant, is characterized in that:
It has following molecular structure:
Wherein:
R is saturated or undersaturated aliphatic acid long-chain, and in carbochain, carbon number is 17≤n≤27;
X is Cl or Br;
M=2,3 or 4.
The preparation method of described long chain cation gemini surfactant, is characterized in that:
Realized by following steps:
Fatty acid amide second/the third/butyldimethylamine and coupling reagent epoxyhalopropane are under solvent-free base catalysis condition, directly carry out diquaternary amine reaction, after through ethanol washing, the obtained bronzing lotion of dry cooling, namely obtain end-product long chain cation gemini surfactant, synthesis equation is as follows:
Wherein:
R is saturated or undersaturated aliphatic acid long-chain, and in carbochain, carbon number is 17≤n≤27;
X is Cl or Br;
M=2,3 or 4.
The catalyst of described base catalysis is potassium hydroxide or NaOH, and consumption is 0.15-0.20 g.
The rate of charge of the amount of substance of described fatty acid amide second/the third/butyldimethylamine and epoxyhalopropane is χ, 1.8≤χ≤2.3.
The reaction temperature of described diquaternary amineization reaction is 70-100 DEG C, and the reaction time is 5-8 hour.
The long chain cation gemini surfactant that the preparation method of described long chain cation gemini surfactant obtains is as the application of surfactant.
The present invention has the following advantages:
The present invention is that connecting group prepares quaternaries cation Gemini surface active agent with epoxyhalopropane, adopts solvent-free base catalysis method, and existing specifically have following advantage for prior art:
(1) this synthetic method is without the need to preparing Amine from Tertiary Amine Hydrochloride intermediate, does not introduce hydrogen chloride, reduces the corrosion to equipment and the particular/special requirement to equipment material.
(2) this synthetic method is solventless one-step synthetic method, does not use solvent, without the need to follow-up decompression distillation except desolventizing, reduces Product formation cost, simplifies synthesis technique, solve the difficult problem that organic solvent causes environmental pollution; And the remnants of part organic solvent can affect the rheological property of Gemini surface active agent, solventless method can fundamentally be avoided.
(3) building-up process is with potassium hydroxide/NaOH for catalyst, is beneficial to epoxide group open loop, strengthens the activity of spacer group, effectively improves reaction conversion ratio.
(4) this synthetic method, reaction condition is gentle, and simple to operate, conversion ratio is high, do not need to rely on that a kind of material is excessive in a large number improves conversion ratio, avoid simultaneously and must carry out separating-purifying owing to there being a large amount of residual a certain raw material in reaction system and could obtain product.
Accompanying drawing explanation
Fig. 1 is the γ-C curve of the double-type cationic surfactant that embodiment 1 obtains.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention will be described in detail.
The present invention has taken into full account the problem of sustainable development, develops the Gemini surface active agent meeting green chemical concept, selects the Gemini surface active agent containing group of easily degrading, fundamentally prevents environmental pollution; Adopt solventess ore-step process synthesis Bis-quaternary Ammonium Surfactants, reduce Product formation cost, simplify synthesis technique, solve the difficult problem that organic solvent causes environmental pollution; Use base catalyst, improve reaction yield, realize green syt.The green syt of this Gemini surface active agent is beneficial to promoting the use of of Gemini surface active agent.
Involved long chain cation gemini surfactant, has following molecular structure:
Wherein:
R is saturated or undersaturated aliphatic acid long-chain, and in carbochain, carbon number is 17≤n≤27;
X is Cl or Br;
M=2,3 or 4.
The surfactant of said structure is for raw material with epoxychloropropane and fatty acid amide second/the third/butyldimethylamine, preparation with 2-hydroxyl-1,3-propylidene is a series of saturated of connecting group and undersaturated cation Gemini surfactant (E/Sm-n-3 (OH)-n-m-E/S), and concrete synthesis step is as follows:
Fatty acid amide second/the third/butyldimethylamine and coupling reagent epoxyhalopropane are under solvent-free base catalysis condition, directly carry out diquaternary amine reaction, after through ethanol washing, the obtained bronzing lotion of dry cooling, obtain end-product long chain cation gemini surfactant, synthesis equation is as follows:
Wherein:
R is saturated or undersaturated aliphatic acid long-chain, and in carbochain, carbon number is 17≤n≤27;
X is Cl or Br;
M=2,3 or 4.
The catalyst of described base catalysis is potassium hydroxide or NaOH, and consumption is 0.15-0.20 g;
The reaction temperature of described diquaternary amineization reaction is 70-100 DEG C, and the reaction time is 5-8 hour;
The rate of charge of the amount of substance of described fatty acid amide second/the third/butyldimethylamine and epoxyhalopropane is χ, 1.8≤χ≤2.3.
Embodiment 1:
Long chain cation gemini surfactant E18-3-3 (OH)-3-E18 has following molecular structure:
Its preparation method is:
Oleamide diemethylamine (40mmol, 14.96g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or NaOH) 0.15-0.20g is placed in reaction bulb, 80 DEG C of reaction 6h, add ethanol washing, namely obtain product 14.65g after drying, yield is 90.9%, through MS,
1h NMR identifies that product is consistent with target compound molecular structure.
When Cl in above-mentioned molecular structure is replaced by Br, the epoxychloropropane in preparation method changes to epoxy bromopropane.
Embodiment 2:
Long chain cation gemini surfactant E18-2-3 (OH)-2-E18 has following molecular structure:
Its preparation method is:
Oleamide dimethylamine (40mmol, 14.48g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or NaOH) 0.15-0.20g is placed in reaction bulb, 70 DEG C of reaction 5h, add ethanol washing, namely obtain product 14.19g after drying, yield is 91.2%, through MS,
1h NMR identifies that product is consistent with target compound molecular structure.
When Cl in above-mentioned molecular structure is replaced by Br, the epoxychloropropane in preparation method changes to epoxy bromopropane.
Embodiment 3:
Long chain cation gemini surfactant E22-3-3 (OH)-3-E22 has following molecular structure:
Its preparation method is:
Erucyl amide diemethylamine (40mmol, 16.88g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or NaOH) 0.15-0.20g is placed in reaction bulb, 90 DEG C of reaction 8h, add ethanol washing, namely obtain product 16.31g after drying, yield is 90.4%, through MS,
1h NMR identifies that product is consistent with target compound molecular structure.
When Cl in above-mentioned molecular structure is replaced by Br, the epoxychloropropane in preparation method changes to epoxy bromopropane.
Embodiment 4:
Long chain cation gemini surfactant E22-2-3 (OH)-2-E22 has following molecular structure:
Its preparation method is:
Acid acid amides dimethylamine (40mmol, 16.32g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or NaOH) 0.15-0.20 g is placed in reaction bulb, 90 DEG C of reaction 7h, add ethanol washing, namely obtain product 15.87g after drying, yield is 90.8%, through MS,
1h NMR identifies that product is consistent with target compound molecular structure.
When Cl in above-mentioned molecular structure is replaced by Br, the epoxychloropropane in preparation method changes to epoxy bromopropane.
Embodiment 5:
Long chain cation gemini surfactant S18-3-3 (OH)-3-S18 has following molecular structure:
Its preparation method is:
Stearamidopropyl dimethylamine (40mmol, 14.72g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or NaOH) 0.15-0.20g is placed in reaction bulb, 90 DEG C of reaction 7h, add ethanol washing, namely obtain product 14.67g after drying, yield is 92.4%, through MS,
1h NMR identifies that product is consistent with target compound molecular structure.
When Cl in above-mentioned molecular structure is replaced by Br, the epoxychloropropane in preparation method changes to epoxy bromopropane.
Embodiment 6:
Long chain cation gemini surfactant S22-3-3 (OH)-3-S22 has following molecular structure:
Its preparation method is:
Mountain Yu amido propyl dimethylamine (40mmol, 16.96g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or NaOH) 0.15-0.20 g is placed in reaction bulb, 100 DEG C of reaction 8h, add ethanol washing, namely obtain product 16.63g after drying, yield is 91.8%, through MS,
1h NMR identifies that product is consistent with target compound molecular structure.
When Cl in above-mentioned molecular structure is replaced by Br, the epoxychloropropane in preparation method changes to epoxy bromopropane.
Content of the present invention is not limited to cited by embodiment, and the conversion of those of ordinary skill in the art by reading description of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Claims (6)
1. long chain cation gemini surfactant, is characterized in that:
It has following molecular structure:
Wherein:
R is saturated or undersaturated aliphatic acid long-chain, and in carbochain, carbon number is 17≤n≤27;
X is Cl or Br;
M=2,3 or 4.
2. the preparation method of long chain cation gemini surfactant according to claim 1, is characterized in that:
Realized by following steps:
Fatty acid amide second/the third/butyldimethylamine and coupling reagent epoxyhalopropane are under solvent-free base catalysis condition, directly carry out diquaternary amine reaction, after through ethanol washing, the obtained bronzing lotion of dry cooling, namely obtain end-product long chain cation gemini surfactant, synthesis equation is as follows:
Wherein:
R is saturated or undersaturated aliphatic acid long-chain, and in carbochain, carbon number is 17≤n≤27;
X is Cl or Br;
M=2,3 or 4.
3. the preparation method of long chain cation gemini surfactant according to claim 2, is characterized in that:
The catalyst of described base catalysis is potassium hydroxide or NaOH, and consumption is 0.15-0.20 g.
4. the preparation method of long chain cation gemini surfactant according to claim 3, is characterized in that:
The rate of charge of the amount of substance of described fatty acid amide second/the third/butyldimethylamine and epoxyhalopropane is χ, 1.8≤χ≤2.3.
5. the preparation method of long chain cation gemini surfactant according to claim 4, is characterized in that:
The reaction temperature of described diquaternary amineization reaction is 70-100 DEG C, and the reaction time is 5-8 hour.
6. the long chain cation gemini surfactant that obtains of the preparation method of long chain cation gemini surfactant according to claim 5 is as the application of surfactant.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106799191A (en) * | 2017-01-04 | 2017-06-06 | 汕头大学 | One class fluorine-carbon sufactant and its synthetic method |
| CN108707089A (en) * | 2018-06-29 | 2018-10-26 | 广州市润研基因科技有限公司 | A kind of novel gemini star quaternary ammonium salt, preparation method and application |
| CN108745197A (en) * | 2018-05-16 | 2018-11-06 | 中国日用化学研究院有限公司 | A kind of degradable gemini quaternary ammonium salt and preparation method thereof |
| CN109836512A (en) * | 2019-03-04 | 2019-06-04 | 西南石油大学 | A kind of novel β-CD Gemini surface active agent is the clean fracturing fluid of thickening agent |
| CN111471445A (en) * | 2020-04-03 | 2020-07-31 | 中国石油天然气股份有限公司 | Oil displacement agent of ligand gemini surfactant, preparation method and application thereof |
| CN116143728A (en) * | 2022-10-18 | 2023-05-23 | 智仑超纯环氧树脂(西安)有限公司 | Reactive epoxy hydrophobic modifier and preparation method and application thereof |
| CN116355598A (en) * | 2023-03-30 | 2023-06-30 | 甘肃省水利水电勘测设计研究院有限责任公司 | Low-dosage viscoelastic solid-free water-based drilling fluid and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106799191A (en) * | 2017-01-04 | 2017-06-06 | 汕头大学 | One class fluorine-carbon sufactant and its synthetic method |
| CN108745197A (en) * | 2018-05-16 | 2018-11-06 | 中国日用化学研究院有限公司 | A kind of degradable gemini quaternary ammonium salt and preparation method thereof |
| CN108745197B (en) * | 2018-05-16 | 2020-09-22 | 中国日用化学研究院有限公司 | Easily degradable gemini quaternary ammonium salt and preparation method thereof |
| CN108707089A (en) * | 2018-06-29 | 2018-10-26 | 广州市润研基因科技有限公司 | A kind of novel gemini star quaternary ammonium salt, preparation method and application |
| CN109836512A (en) * | 2019-03-04 | 2019-06-04 | 西南石油大学 | A kind of novel β-CD Gemini surface active agent is the clean fracturing fluid of thickening agent |
| CN111471445A (en) * | 2020-04-03 | 2020-07-31 | 中国石油天然气股份有限公司 | Oil displacement agent of ligand gemini surfactant, preparation method and application thereof |
| CN111471445B (en) * | 2020-04-03 | 2022-08-05 | 中国石油天然气股份有限公司 | Oil displacement agent of ligand gemini surfactant, preparation method and application thereof |
| CN116143728A (en) * | 2022-10-18 | 2023-05-23 | 智仑超纯环氧树脂(西安)有限公司 | Reactive epoxy hydrophobic modifier and preparation method and application thereof |
| CN116355598A (en) * | 2023-03-30 | 2023-06-30 | 甘肃省水利水电勘测设计研究院有限责任公司 | Low-dosage viscoelastic solid-free water-based drilling fluid and application thereof |
| CN116355598B (en) * | 2023-03-30 | 2024-04-26 | 甘肃省水利水电勘测设计研究院有限责任公司 | Low-dosage viscoelastic solid-free water-based drilling fluid and application thereof |
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