CN104437235B - Long chain cation gemini surfactant and preparation method thereof - Google Patents
Long chain cation gemini surfactant and preparation method thereof Download PDFInfo
- Publication number
- CN104437235B CN104437235B CN201410598920.8A CN201410598920A CN104437235B CN 104437235 B CN104437235 B CN 104437235B CN 201410598920 A CN201410598920 A CN 201410598920A CN 104437235 B CN104437235 B CN 104437235B
- Authority
- CN
- China
- Prior art keywords
- preparation
- long chain
- gemini surfactant
- cation gemini
- fatty acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a kind of long chain cation gemini surfactant and preparation method thereof.Hydrogen chloride gas need to be passed through in tertiary amine, cause equipment corrosion when preparing Amine from Tertiary Amine Hydrochloride intermediate, and the existence of residual solvent can reduce the rheological property of Gemini surface active agent by the preparation of existing Gemini surface active agent.The present invention is with epoxychloropropane and fatty acid amide second/the third/butyldimethylamine as raw material, preparation with 2 hydroxyls 1,3 propylidene are a series of saturated and undersaturated cation Gemini surfactant of connecting group, comprising the amido link of easily biological-degradable and the hydroxyl of facile hydrolysis in molecular structure, hydrophobic chain is made up of the alkyl chain of saturated or unsaturated long-chain fatty acid.The preparation method of the present invention, under the conditions of solvent-free base catalysis, uses epoxyhalopropane and a kind of long chain tertiary amine to prepare end product through single step reaction, improves reaction yield, simplify reaction process, shorten and be suitable for commercial scale production reaction time.
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 an important fine chemicals of 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 a spacer groups 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 higher surface activity and the rheological property of uniqueness, various advantages make Gemini surface active agent in tertiary oil recovery, fracturing fluid, drilling fluid, emulsion is polymerized, gene transfects, washing, sterilization, emulsifying, dispersion, the fields such as the synthesis of anticorrosion and ordered mesoporous material have bigger application potential.These advantages have attracted numerous scientific research personnel to be devoted to synthesis and the applied research of Gemini surface active agent.
Along with enhancing and the rise of Green Chemistry of people's environmental protection consciousness, green syt can have great importance by biological (or environment) degraded Gemini surface active agent.Ikeda merit etc. manages to be incorporated in the alkyl chain of cationic Gemini surfactant facile hydrolysis group amide groups and ester group, as a example by the synthesis of the Gemini surface active agent of band amide groups, the first step: react 2-(amide) dimethylamine obtaining serial single molecular chain with the fatty acid methyl ester of different alkyl chain lengths with 2-amino-ethyl dimethylamine；Second step: single molecular chain 2-(amide) dimethylamine i.e. obtains bimolecular 2-(amide) dimethylamine that product spacer group is 2-hydroxyl-1,3 propylidene in the presence of its hydrochlorate with epichlorohydrin reaction.There is following defect in this reaction: when first this reaction need to prepare Amine from Tertiary Amine Hydrochloride intermediate, is passed through in tertiary amine by hydrogen chloride gas, and production equipment is caused the biggest corrosion by hydrogen chloride gas cognition.Its secondary response introduces solvent normal propyl alcohol, need to reduce pressure and boil off 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, during 3 propylidene, because epichlorohydrin reaction activity is higher, it is widely used in the preparation of Gemini surface active agent.For improving reaction yield, generally make epoxychloropropane excess or tertiary amine excess, this method does not only result in material waste, and Gemini surface active agent product must be obtained by separating-purifying, follow-up separating-purifying process is complicated, additionally epoxychloropropane is noxious substance, if the application of finished product quaternaries cation Gemini surface active agent will be negatively affected by a large amount of residual.
Summary of the invention
It is an object of the invention to provide a kind of long chain cation gemini surfactant and preparation method thereof, improve reaction yield, simplify reaction process, shorten reaction time, reduce cost.
The technical solution adopted in the present invention is:
Long chain cation gemini surfactant, it is characterised in that:
It has a following molecular structure:
Wherein:
R is saturated or undersaturated fatty 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, it is characterised in that:
Realized by following steps:
Fatty acid amide second/the third/butyldimethylamine and coupling reagent epoxyhalopropane are under the conditions of solvent-free base catalysis, directly carry out diquaternary amine reaction, after through washing with alcohol, be dried cooling prepare bronzing mastic, i.e. obtaining end-product long chain cation gemini surfactant, synthesis equation is as follows:
Wherein:
R is saturated or undersaturated fatty 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 sodium hydroxide, and consumption is 0.15-0.20 g.
Described fatty acid amide second/the third/butyldimethylamine is χ with the rate of charge of the amount of the material of epoxyhalopropane, 1.8≤χ≤2.3.
The reaction temperature of described diquaternary amineization reaction is 70-100 DEG C, and the response time is 5-8 hour.
The long chain cation gemini surfactant that the preparation method of described long chain cation gemini surfactant prepares is as the application of surfactant.
The invention have the advantages that
The present invention prepares quaternaries cation Gemini surface active agent with epoxyhalopropane for connecting group, uses solvent-free base catalysis method, specifically has the advantage that referring now to prior art
(1) this synthetic method is without 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, it is not necessary to follow-up decompression is distilled off solvent, reduces Product formation cost, simplifies synthesis technique, solves organic solvent and causes a difficult problem for 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/sodium hydroxide as catalyst, beneficially epoxide group open loop, strengthens the activity of spacer group, is effectively improved reaction conversion ratio.
(4) this synthetic method, reaction condition is gentle, simple to operate, and conversion ratio is high, need not rely on a kind of material excess in a large number to improve conversion ratio, avoid in reaction system simultaneously and must carry out separating-purifying could obtain product owing to there being a certain raw material of a large amount of residual.
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 degradable group, fundamentally prevents environmental pollution；Use solventess ore-step process synthesis Bis-quaternary Ammonium Surfactants, reduce Product formation cost, simplify synthesis technique, solve organic solvent and cause a difficult problem for environmental pollution；Use base catalyst, improve reaction yield, it is achieved green syt.Promoting the use of of the green syt of this Gemini surface active agent beneficially Gemini surface active agent.
Involved long chain cation gemini surfactant, has a following molecular structure:
Wherein:
R is saturated or undersaturated fatty 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 with epoxychloropropane and fatty acid amide second/the third/butyldimethylamine as raw material, preparation with 2-hydroxyl-1,3-propylidene is a series of saturated and undersaturated cation Gemini surfactant (E/Sm-n-3 (OH)-n-m-E/S) of connecting group, and concrete synthesis step is as follows:
Fatty acid amide second/the third/butyldimethylamine and coupling reagent epoxyhalopropane are under the conditions of solvent-free base catalysis, directly carry out diquaternary amine reaction, after through washing with alcohol, be dried cooling and prepare bronzing mastic, obtain end-product long chain cation gemini surfactant, synthesis equation is as follows:
Wherein:
R is saturated or undersaturated fatty 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 sodium hydroxide, and consumption is 0.15-0.20 g；
The reaction temperature of described diquaternary amineization reaction is 70-100 DEG C, and the response time is 5-8 hour；
Described fatty acid amide second/the third/butyldimethylamine is χ with the rate of charge of the amount of the material of epoxyhalopropane, 1.8≤χ≤2.3.
Embodiment 1:
Long chain cation gemini surfactant E18-3-3 (OH)-3-E18 has a following molecular structure:
Its preparation method is:
Oleamide diemethylamine (40mmol, 14.96g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or sodium hydroxide) 0.15-0.20g is placed in reaction bulb, 80 DEG C of reaction 6h, add washing with alcohol, i.e. obtaining 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 is changed to epoxy bromopropane.
Embodiment 2:
Long chain cation gemini surfactant E18-2-3 (OH)-2-E18 has a following molecular structure:
Its preparation method is:
Oleamide dimethylamine (40mmol, 14.48g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or sodium hydroxide) 0.15-0.20g is placed in reaction bulb, 70 DEG C of reaction 5h, add washing with alcohol, i.e. obtaining 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 is changed to epoxy bromopropane.
Embodiment 3:
Long chain cation gemini surfactant E22-3-3 (OH)-3-E22 has a following molecular structure:
Its preparation method is:
Erucyl amide diemethylamine (40mmol, 16.88g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or sodium hydroxide) 0.15-0.20g is placed in reaction bulb, 90 DEG C of reaction 8h, add washing with alcohol, i.e. obtaining 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 is changed to epoxy bromopropane.
Embodiment 4:
Long chain cation gemini surfactant E22-2-3 (OH)-2-E22 has a following molecular structure:
Its preparation method is:
Acid amide dimethylamine (40mmol, 16.32g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or sodium hydroxide) 0.15-0.20 g is placed in reaction bulb, 90 DEG C of reaction 7h, add washing with alcohol, i.e. obtaining 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 is changed to epoxy bromopropane.
Embodiment 5:
Long chain cation gemini surfactant S18-3-3 (OH)-3-S18 has a following molecular structure:
Its preparation method is:
Stearamidopropyl dimethylamine (40mmol, 14.72g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or sodium hydroxide) 0.15-0.20g is placed in reaction bulb, 90 DEG C of reaction 7h, add washing with alcohol, i.e. obtaining 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 is changed to epoxy bromopropane.
Embodiment 6:
Long chain cation gemini surfactant S22-3-3 (OH)-3-S22 has a following molecular structure:
Its preparation method is:
Behenyl amido propyl dimethylamine (40mmol, 16.96g), epoxychloropropane (20mmol, 1.85g), potassium hydroxide (or sodium hydroxide) 0.15-0.20 g is placed in reaction bulb, 100 DEG C of reaction 8h, add washing with alcohol, i.e. obtaining 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 is changed to epoxy bromopropane.
Present disclosure is not limited to cited by embodiment, and the conversion of any equivalence that technical solution of the present invention is taked by those of ordinary skill in the art by reading description of the invention, the claim being the present invention is contained.
Claims (5)
1. the preparation method of long chain cation gemini surfactant, it is characterised in that:
Described long chain cation gemini surfactant has a following molecular structure:
Wherein:
R is saturated or undersaturated fatty acid long-chain, and in carbochain, carbon number is 17≤n≤27；
X is Cl or Br；
M=2,3 or 4；
Described long chain cation gemini surfactant is realized by following steps:
Fatty acid amide second/the third/butyldimethylamine and coupling reagent epoxyhalopropane are under the conditions of solvent-free base catalysis, directly carry out double quaterisation, after through washing with alcohol, be dried cooling prepare bronzing mastic, i.e. obtain end-product long chain cation gemini surfactant, synthetic route is as follows:
Wherein:
R is saturated or undersaturated fatty 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 long chain cation gemini surfactant the most according to claim 1, it is characterised in that:
The catalyst of described base catalysis is potassium hydroxide or sodium hydroxide, and consumption is 0.15-0.20 g.
The preparation method of long chain cation gemini surfactant the most according to claim 2, it is characterised in that:
Described fatty acid amide second/the third/butyldimethylamine is χ with the rate of charge of the amount of the material of epoxyhalopropane, 1.8≤χ≤2.3.
The preparation method of long chain cation gemini surfactant the most according to claim 3, it is characterised in that:
The reaction temperature of described pair of quaterisation is 70-100 DEG C, and the response time is 5-8 hour.
The long chain cation gemini surfactant that the preparation method of long chain cation gemini surfactant the most according to claim 4 prepares is as the application of surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410598920.8A CN104437235B (en) | 2014-10-31 | 2014-10-31 | Long chain cation gemini surfactant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410598920.8A CN104437235B (en) | 2014-10-31 | 2014-10-31 | Long chain cation gemini surfactant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104437235A CN104437235A (en) | 2015-03-25 |
| CN104437235B true CN104437235B (en) | 2016-08-17 |
Family
ID=52884447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410598920.8A Active CN104437235B (en) | 2014-10-31 | 2014-10-31 | Long chain cation gemini surfactant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437235B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11795374B2 (en) | 2021-09-30 | 2023-10-24 | Saudi Arabian Oil Company | Composition and method of making cationic surfactants with two quaternary ammonium head groups |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106799191A (en) * | 2017-01-04 | 2017-06-06 | 汕头大学 | One class fluorine-carbon sufactant and its synthetic method |
| 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 |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005503431A (en) * | 2001-09-28 | 2005-02-03 | エルジー ハウスホールド アンド ヘルス ケア エルティーディー． | Method for producing cationic surfactant and fiber softener composition containing the same |
| WO2007056284A2 (en) * | 2005-11-07 | 2007-05-18 | Stepan Company | Polycationic viscoelastic compositions |
| CN101929074B (en) * | 2009-12-23 | 2012-07-18 | 东华大学 | Water-soluble chitosan quaternary ammonium salt antibiotic finishing agent and preparation and application thereof |
| CN102631864B (en) * | 2012-03-31 | 2013-12-25 | 陕西科技大学 | Amphoteric Gemini surfactant and method for preparing same |
-
2014
- 2014-10-31 CN CN201410598920.8A patent/CN104437235B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11795374B2 (en) | 2021-09-30 | 2023-10-24 | Saudi Arabian Oil Company | Composition and method of making cationic surfactants with two quaternary ammonium head groups |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104437235A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104437235B (en) | Long chain cation gemini surfactant and preparation method thereof | |
| CN103965861B (en) | A kind of high temperature resistance Gemini cationic viscoelastic surfactants and synthetic method thereof | |
| CN104607094B (en) | Asymmetric cation Gemini surfactant and preparation method thereof | |
| CN104803889A (en) | Fatty amine polyoxyethylene ether disulfonate and preparation method thereof | |
| CN109627195A (en) | A method of heavy alkylbenzene sulfonate is prepared using microreactor | |
| CN112812076B (en) | Bis-sulfonic acid-based surfactant, clean fracturing fluid and preparation method thereof | |
| CN110791273A (en) | Gas well foam scrubbing agent composition, preparation method and application thereof | |
| CN103173197B (en) | Gemini surfactant, preparation method thereof, and application thereof in tertiary oil recovery | |
| CN102500087A (en) | Method for preparing perfluorohexane surfactant serving as main agent of aqueous film-forming extinguishing agent directly | |
| CN107384357B (en) | Polyoxyethylene-sub- surfactant of benzene sulfonic acid salt form Composite Double and preparation method thereof | |
| CN101428206A (en) | Double-tail quaternary ammonium salt cation surface active agent and preparation method thereof | |
| CN104190314A (en) | Fatty amine polyoxyethylene ether diethyl disulfonate surfactant and preparation method thereof | |
| CN110354755A (en) | A kind of novel fluorine betaine type amphoteric surfactant and its preparation method and application | |
| CN107814755B (en) | Anionic gemini surfactant and preparation method thereof | |
| CN106117027B (en) | The method for preparing cyclocitral using micro-structured reactor | |
| CN101912745A (en) | Sulfamic acid amphoteric surfactant and synthesis method thereof | |
| CN108440251A (en) | A kind of method of light/nickel concerted catalysis list arylation glycol | |
| CN102603549B (en) | Method for synthesizing erucamide propyl betaine | |
| CN115895684A (en) | Preparation method of epoxidized cardanol amphoteric surfactant | |
| CN103305261A (en) | Synthesis method of novel ionic liquid and application of novel ionic liquid to oil product denitrification | |
| CN106566510B (en) | A kind of ternary composite driving composition and its application in chemical flooding | |
| CN105771789B (en) | A kind of phosphate-based quaternary cationics and its synthetic method | |
| CN104672105B (en) | The preparation method of L-3-(3,4-Dimethoxyphenyl)-2-amino-2-methyl propionitrile hydrochlorate | |
| CN104151170A (en) | 4-nitrophenethylamine hydrochloride and preparation method thereof | |
| CN105294506A (en) | Guanidyl long chain gemini quaternary ammonium salt and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190905 Address after: 710016 8 floors of Jingkaiwanke Center, Weiyang District, Xi'an City, Shaanxi Province Patentee after: Xi'an Yipu Eco-technology Co., Ltd. Address before: 710021 Shaanxi city of Xi'an province Weiyang University City Patentee before: Shaanxi University of Science and Technology |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 710016 8 floors of Jingkaiwanke Center, Weiyang District, Xi'an City, Shaanxi Province Patentee after: Xi'an Yipu Digital Agriculture Co., Ltd Address before: 710016 8 floors of Jingkaiwanke Center, Weiyang District, Xi'an City, Shaanxi Province Patentee before: Xi'an Yipu Eco-technology Co.,Ltd. |