CN108250095A - A kind of synthetic method of acid amide type gemini surfactant - Google Patents
A kind of synthetic method of acid amide type gemini surfactant Download PDFInfo
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- CN108250095A CN108250095A CN201810034996.6A CN201810034996A CN108250095A CN 108250095 A CN108250095 A CN 108250095A CN 201810034996 A CN201810034996 A CN 201810034996A CN 108250095 A CN108250095 A CN 108250095A
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- amide type
- gemini surfactant
- acid amide
- type gemini
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/145—Amides; N-substituted amides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of synthetic methods of acid amide type gemini surfactant.This method is in anhydrous conditions first with 1,3 propane diamine carry out reacting intermediate of the synthesis with bisamide base with double chlorine atoms with chloracetyl chloride, and the intermediate is recycled to react synthesis with Dodecyl Dimethyl Amine and obtains the final product for belonging to Quaternary ammonium gemini surfactants.This method synthesizes target product using two-step method, and easy reaction and product have the advantages that high surface activity, good water solubility, irritation are small degradable.Final product can be applied in aviation alloyed aluminium inhibition system, and experiment proves corrosion inhibition of the corrosion inhibition better than the single-stranded quaternary ammonium salt corrosion inhibitor of tradition.
Description
Technical field
The invention belongs to technical field of fine, more particularly to a kind of acid amide type gemini surfactant
Synthetic method.
Technical background
Gemini surface active agent is in ion by chemical bond by two traditional single head base list alkane chain surfactants
The surfactant of new generation that head Ji Chu is linked up with spacer group.In recent years, with the development of Chemical Engineering Technology and economy
Demand, traditional surfactant have been unable to meet the demand of people due to many limitations present in self structure.With biography
System surfactant is compared, since gemini surfactant is more with high surface-active, good water solubility and rheological characteristic etc.
Kind advantage, therefore with extensive industrialized production and commercial application prospect.With the rise of green revolution tide, the ring of people
Consciousness gradually enhancing is protected, developing the high efficiency gemini quaternary ammonium salt of novel easily biological-degradable has become the research hotspot in the field.Containing acyl
The Gemini of amido not only possesses the surface-active better than conventional surfactant, also with nontoxic, biodegradable spy
Point has powerful application potential in numerous areas such as detergents and cosmetic, industrial separations.
Conventional single-chain quaternary ammonium salt corrosion inhibitor has many applications in terms of corrosion protection, but corrosion mitigating effect is bad, there is use
Concentration is high, forms the problems such as inhibition film persistence is poor.The imidazolines of dominant contribution and quaternary ammonium salt inhibition are accounted for currently on the market
The problem of agent generally existing antiseptic property can not be taken into account with no pollution discharge.Therefore it is a kind of be readily synthesized and efficient pollution-free it is new
Type double type corrosion inhibiter undoubtedly has broad application prospects.
Invention content
For deficiencies of the prior art, the purpose of the present invention is to provide a kind of environmentally protective and surfaces
The synthetic method of the high acid amide type gemini surfactant of activity.
In order to achieve the above object, the synthetic method of acid amide type gemini surfactant provided by the invention includes
The following steps carried out in order：
1) prepared by intermediate：1,3- propane diamine is dissolved in the dichloromethane as solvent, in ice bath and stirring condition
Under be slowly dropped among enough chloracetyl chlorides, after being added dropwise, heating reacts 4-6 hours, then in 35 DEG C of water-bath
1-2 hours are evaporated under reduced pressure to remove solvent and excessive chloracetyl chloride using rotary evaporator in 60 DEG C of water-bath, it will be remaining
Object water dissolution, filtering once obtain the intermediate of white needle-like crystals, i.e. 1,3-, bis- (2- with absolute ethyl alcohol recrystallization later
Chloroacetamide) propylamine；Reaction equation is as follows：
2) synthesizing amide type gemini surfactant：The 1,3- bis- (2- chloroacetamides) third that step 1) is obtained
Amine solvent adds in Dodecyl Dimethyl Amine in the ethyl acetate as solvent, and it is small that reaction 10-14 is stirred at room temperature
When, 1-2 hours are then evaporated under reduced pressure in 80 DEG C of water-bath to remove solvent and excessive Dodecyl Dimethyl Amine, it will be surplus
Excess n-hexane dissolution, a layer substance is removed in liquid separation, then by the matter utilization re-crystallizing in ethyl acetate twice, is done naturally after taking-up
It is dry to constant weight, obtain final product, i.e. acid amide type gemini surfactant.
During above-mentioned intermediate and Dodecyl Dimethyl Amine react, Dodecyl Dimethyl Amine tertiary amine
In nitrogen-atoms attack intermediate in chlorine atom, and replace, and then generate acid amide type gemini surfactant,
Reaction equation is as follows：
In step 1), the molar ratio of 1, the 3- propane diamine and chloracetyl chloride is 1.0:2.0—3.0.
In step 2), the molar ratio of 1, the 3- bis- (2- chloroacetamides) propylamine and Dodecyl Dimethyl Amine is
1.0:2.0—3.0。
The synthetic method of acid amide type gemini surfactant provided by the invention be in anhydrous conditions first with 1,
3- propane diamine and chloracetyl chloride carry out reacting intermediate of the synthesis with bisamide base with double chlorine atoms, recycle the intermediate with
Dodecyl Dimethyl Amine reaction synthesis obtains the final product for belonging to Quaternary ammonium gemini surfactants.This method utilizes
It is small degradable with high surface activity, good water solubility, irritation that two-step method synthesizes target product, easy reaction and product
The advantages of.Final product can be applied in aviation alloyed aluminium inhibition system, and experiment proves corrosion inhibition better than tradition single-stranded season
The corrosion inhibition of ammonium salt corrosion inhibiter.
Description of the drawings
Fig. 1 is intermediate1H NMR hydrogen spectrograms.
Fig. 2 is final product1H NMR hydrogen spectrograms.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1：
The synthetic method of acid amide type gemini surfactant provided in this embodiment includes carrying out down in order
Row step：
1) prepared by intermediate：50ml dichloromethane is added in beaker, the chloracetyl chloride of 11.3g is dissolved in dichloromethane
Among, 3.7g1 is taken, 3- propane diamine is slowly dropped into beaker with the speed of every five seconds one drops under ice bath and stirring condition, waits to be added dropwise
After, heating reacts 4 hours in 35 DEG C of water-bath, is then evaporated under reduced pressure 1 using rotary evaporator in 60 DEG C of water-bath
Hour, by residue water dissolution, filtering was recrystallized once later with absolute ethyl alcohol to remove solvent and excessive chloracetyl chloride
Obtain intermediate 4.7g, i.e. 1,3- bis- (2- chloroacetamides) propylamine.
2) synthesizing amide type gemini surfactant：The 1,3- bis- (2- chloroacetamides) third that step 1) is obtained
Amine 4.7g is dissolved in the ethyl acetate of 50ml, adds in 10.7g Dodecyl Dimethyl Amines, and it is small that reaction 10 is stirred at room temperature
When, 1 hour is then evaporated under reduced pressure in 80 DEG C of water-bath to remove solvent and excessive Dodecyl Dimethyl Amine, it will be remaining
Object n-hexane dissolution, a layer substance is removed in liquid separation, then by the matter utilization re-crystallizing in ethyl acetate twice, is spontaneously dried after taking-up
To constant weight, final product 9.1g, i.e. acid amide type gemini surfactant are obtained.
Embodiment 2：
The synthetic method of acid amide type gemini surfactant provided in this embodiment includes carrying out down in order
Row step：
1) prepared by intermediate：50ml dichloromethane is added in beaker, the chloracetyl chloride of 14.1g is dissolved in dichloromethane
Among, 3.7g1 is taken, 3- propane diamine is slowly dropped into beaker with the speed of every five seconds one drops under ice bath and stirring condition, waits to be added dropwise
After, heating is reacted 5 hours in 35 DEG C of water-bath, is then evaporated under reduced pressure in 60 DEG C of water-bath using rotary evaporator
To remove solvent and excessive chloracetyl chloride, by residue water dissolution, filtering is recrystallized later with absolute ethyl alcohol within 1.5 hours
Once obtain intermediate 4.9g, i.e. 1,3- bis- (2- chloroacetamides) propylamine.
2) synthesizing amide type gemini surfactant：1,3- bis- (2 chloroamide) propylamine that step 1) is obtained
4.9g is dissolved in the ethyl acetate of 50ml, adds in 13.3g Dodecyl Dimethyl Amines, and it is small that reaction 12 is stirred at room temperature
When, 1.5 hours are then evaporated under reduced pressure in 80 DEG C of water-bath to remove solvent and excessive Dodecyl Dimethyl Amine, it will be surplus
Excess n-hexane dissolution, a layer substance is removed in liquid separation, then by the matter utilization re-crystallizing in ethyl acetate twice, is done naturally after taking-up
It is dry to constant weight, obtain final product 9.3g, i.e. acid amide type gemini surfactant.
Embodiment 3：
The synthetic method of acid amide type gemini surfactant provided in this embodiment includes carrying out down in order
Row step：
1) prepared by intermediate：50ml dichloromethane is added in beaker, the chloracetyl chloride of 17.0g is dissolved in dichloromethane
Among, 3.7g1 is taken, 3- propane diamine is slowly dropped into beaker with the speed of every five seconds one drops under ice bath and stirring condition, waits to be added dropwise
After, heating reacts 6 hours in 35 DEG C of water-bath, is then evaporated under reduced pressure 2 using rotary evaporator in 60 DEG C of water-bath
Hour, by residue water dissolution, filtering was recrystallized once later with absolute ethyl alcohol to remove solvent and excessive chloracetyl chloride
Obtain intermediate 5.0g, i.e. 1,3- bis- (2- chloroacetamides) propylamine.
2) synthesizing amide type gemini surfactant：The 1,3- bis- (2- chloroacetamides) third that step 1) is obtained
Amine 5.0g is dissolved in the ethyl acetate of 50ml, adds in 16.0g Dodecyl Dimethyl Amines, and it is small that reaction 14 is stirred at room temperature
When, 2 hours are then evaporated under reduced pressure in 80 DEG C of water-bath to remove solvent and excessive Dodecyl Dimethyl Amine, it will be remaining
Object n-hexane dissolution, a layer substance is removed in liquid separation, then by the matter utilization re-crystallizing in ethyl acetate twice, is spontaneously dried after taking-up
To constant weight, final product 9.3g, i.e. acid amide type gemini surfactant are obtained.
The present inventor is detected white needles intermediate made from step 1) using Nuclear Magnetic Resonance, and Fig. 1 is this
Intermediate1H NMR hydrogen spectrograms, as can be seen from Figure, the structure of the intermediate is 1,3- bis- (2- chloroacetamides) propylamine.
The present inventor is detected final product made from step 2) using Nuclear Magnetic Resonance, and Fig. 2 is the final production
Object1H NMR hydrogen spectrograms, as can be seen from Figure, the structure of the final product is acid amide type gemini surfactant,
Belong to Quaternary ammonium gemini surfactants.
Claims (3)
1. a kind of synthetic method of acid amide type gemini surfactant, it is characterised in that：The synthetic method includes
The following steps carried out in order：
1) prepared by intermediate：1,3- propane diamine is dissolved in the dichloromethane as solvent, is delayed under ice bath and stirring condition
Slowly it is added drop-wise among enough chloracetyl chlorides；After being added dropwise, heating is reacted 4-6 hours in 35 DEG C of water-bath, then 60
DEG C water-bath in using rotary evaporator be evaporated under reduced pressure 1-2 hour with remove solvent and excess chloracetyl chloride, residue is used
Water dissolution, filtering once obtain the intermediate of white needle-like crystals, i.e. (the 2- chloroethenes of 1,3- bis- with absolute ethyl alcohol recrystallization later
Amide) propylamine；Reaction equation is as follows：
2) synthesizing amide type gemini surfactant：1,3- bis- (2- chloroacetamides) propylamine dissolving that step 1) is obtained
In the ethyl acetate as solvent, Dodecyl Dimethyl Amine is added in, reaction 10-14 hours is stirred at room temperature, then
1-2 hours are evaporated under reduced pressure in 80 DEG C of water-bath to remove solvent and excessive Dodecyl Dimethyl Amine, residue is used
N-hexane dissolution, a layer substance is removed in liquid separation, then by the matter utilization re-crystallizing in ethyl acetate twice, perseverance is naturally dried to after taking-up
Weight, obtains final product, i.e. acid amide type gemini surfactant；Reaction equation is as follows：
2. the synthetic method of acid amide type gemini surfactant according to claim 1, it is characterised in that：In step
It is rapid 1) in, the molar ratio of 1, the 3- propane diamine and chloracetyl chloride is 1.0:2.0—3.0.
3. the synthetic method of acid amide type gemini surfactant according to claim 1, it is characterised in that：In step
It is rapid 2) in, the molar ratio of 1, the 3- bis- (2- chloroacetamides) propylamine and Dodecyl Dimethyl Amine is 1.0:2.0—
3.0。
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| CN201810034996.6A CN108250095A (en) | 2018-01-15 | 2018-01-15 | A kind of synthetic method of acid amide type gemini surfactant |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823577A (en) * | 2018-07-02 | 2018-11-16 | 中国民航大学 | The corrosion inhibiter of amide containing type gemini surfactant |
| CN109232300A (en) * | 2018-11-05 | 2019-01-18 | 扬州工业职业技术学院 | A kind of dodecyl Gemini surface active agent and its application in emulsion of crude oil demulsification |
| CN109232299A (en) * | 2018-11-05 | 2019-01-18 | 扬州工业职业技术学院 | A kind of n-decane base Gemini surface active agent and its application in emulsion of crude oil demulsification |
| CN109261068A (en) * | 2018-09-26 | 2019-01-25 | 扬州蓝色生物医药科技有限公司 | A kind of new type of Gemini surfactant and its and application of the ultrasonic synergistic in dirty oil dewatering |
| CN110055045A (en) * | 2019-04-26 | 2019-07-26 | 中国石油化工股份有限公司 | A kind of low poly-cationic quaternary surfactant Synergistic type oil displacement agent |
| CN110105234A (en) * | 2019-05-13 | 2019-08-09 | 中国民航大学 | A kind of synthetic method of asymmetrical type gemini surfactant |
| CN111117787A (en) * | 2019-12-23 | 2020-05-08 | 万华化学集团股份有限公司 | Bactericidal acaricidal surfactant, preparation method thereof and laundry detergent |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823577A (en) * | 2018-07-02 | 2018-11-16 | 中国民航大学 | The corrosion inhibiter of amide containing type gemini surfactant |
| CN109261068A (en) * | 2018-09-26 | 2019-01-25 | 扬州蓝色生物医药科技有限公司 | A kind of new type of Gemini surfactant and its and application of the ultrasonic synergistic in dirty oil dewatering |
| CN109232300A (en) * | 2018-11-05 | 2019-01-18 | 扬州工业职业技术学院 | A kind of dodecyl Gemini surface active agent and its application in emulsion of crude oil demulsification |
| CN109232299A (en) * | 2018-11-05 | 2019-01-18 | 扬州工业职业技术学院 | A kind of n-decane base Gemini surface active agent and its application in emulsion of crude oil demulsification |
| CN109232299B (en) * | 2018-11-05 | 2022-03-01 | 扬州工业职业技术学院 | N-decyl gemini surfactant and application thereof in demulsification of crude oil emulsion |
| CN109232300B (en) * | 2018-11-05 | 2022-03-01 | 扬州工业职业技术学院 | N-dodecyl gemini surfactant and application thereof in demulsification of crude oil emulsion |
| CN110055045A (en) * | 2019-04-26 | 2019-07-26 | 中国石油化工股份有限公司 | A kind of low poly-cationic quaternary surfactant Synergistic type oil displacement agent |
| CN110105234A (en) * | 2019-05-13 | 2019-08-09 | 中国民航大学 | A kind of synthetic method of asymmetrical type gemini surfactant |
| CN111117787A (en) * | 2019-12-23 | 2020-05-08 | 万华化学集团股份有限公司 | Bactericidal acaricidal surfactant, preparation method thereof and laundry detergent |
| CN111117787B (en) * | 2019-12-23 | 2021-05-14 | 万华化学集团股份有限公司 | Bactericidal acaricidal surfactant, preparation method thereof and laundry detergent |
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