CN101229496B - Method of preparing gemini surface active agent with chelating capacity - Google Patents
Method of preparing gemini surface active agent with chelating capacity Download PDFInfo
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Abstract
The present invention relates to a preparation method of a surface active agent, in particular to a preparation method of a surface active agent of gemini type with chelating property. The present invention employs haloalkane to respectively substitute the hydrogen on two nitrogens of dibasic amine molecule to obtain an intermediate of diamine of N, N-dialkyl which then reacts with halogenated carboxylic acid to generate diacetyl sodiums of binary amine of N, N-double-stranded alkyl. The compounds have excellent surface active agent and good performance of chelating metal ionic, and the wetting and emulsification performances are superior to the ordinary surface active agent. The novel surface active agent is expected to be applied to the emulsion polymerization industry; at the same time, the invention can be used as printing and dyeing agent, pesticide wetting agent, spreader, penetrating agent, mobile agent, wetting agent and stabilizer in detergent formula and used in the field of metallurgical ore processing chain, heavy metal waste disposal, etc. The target product has the performances of high-temperature stability and anti-electrolyte; therefore, the invention also has potential application value in the aspects of tertiary oil recovery, soil hygiene, sub-surface repairing, etc.
Description
Technical field
The present invention relates to the preparation method of surfactant, be meant a kind of preparation method especially with double type surfactant of sequestering power.
Background technology
Effects such as that surfactant has is wetting, absorption, infiltration, emulsification, breakdown of emulsion, dispersion, cohesion, foaming, froth breaking, solubilising, decontamination, antistatic, sterilization, waterproof, anticorrosion, except being used for synthetic detergent and cosmetics industry in a large number, just be widely used in many fields such as industry such as weaving, printing and dyeing, plastics, rubber, process hides, papermaking, pharmacy, oil, metal processing, mining, ore dressing, building, electronics and water technology.Though its consumption is few, can play the improvement production technology, increase product variety, energy savings is improved the quality of products, and reduces production costs, and the title of " industrial monosodium glutamate " is enjoyed in key effect such as raise labour productivity.
Chelating-double type surfactant has the remarkable advantage that the other types surfactant is not had.On the one hand, chelating-double type surfactant belongs to the double type surfactant, and CMC is very little, can reduce the surface tension of water efficiently, strengthen cementitiousness, have remarkable resistance to hard water and excellent potential resistance to electrolyte contamination ability, can in abominable acid, alkali lye environment, stablize use; Owing to two hydrophilic and oleophilic groups are arranged in the molecule, have extremely strong amphiphilicly, the solubility in water is bigger, so the rinsing ability is better than traditional anion surfactant.Has better sterilization effect than general quaternary ammonium salt cationic surfactant.Can be used in emulsion polymerization industry, simultaneously also as printing and dyeing, levelling agent, agricultural chemicals wetting agent, spreader-sticker, bleeding agent and flowable, the wetting agent in cosmetic products, the detergent compositions, coupling agent and stabilizing agent etc.
On the other hand, chelating-double type surfactant has the ability of the distinctive chelating grappling of chelate surfactant metal ion, can form stable water soluble chelate compound with metal ion-chelant.Be suitable for flotation ore deposit concentration and separation heavy metal ion, heavy metal ion offal treatment in the metallurgical industry; environmental protection, printing and dyeing, the oxygen that also is used in simultaneously textile industry are floated, are soaped etc. and strengthen the nutrient solution preparation of resistance to hard water, animals and plants trace element in technology and the washing agent washing powder.
Summary of the invention
The objective of the invention is to seek a kind of preparation method with double type surfactant of sequestering power, adopt the reaction of alkyl group alkyl halide and diamine to obtain N, N-dialkyl group diamine intermediate, this intermediate generate dialkyl group diamine oxalic acid sodium salt with the halogenated carboxylic acid reaction again.The preparation method is simple and feasible, and the gained compound has good thermal stability and potential resistance to electrolyte contamination ability, and has good wetting, emulsification performance.
According to technical scheme provided by the invention, obtain N with chain alkyl alkyl halide and diamine reaction, N-dialkyl group diamine intermediate, N, N-dialkyl group diamine intermediate generates with the halogenated carboxylic acid reaction again has the double type surfactant dialkyl group diamine oxalic acid that the huge legendary turtle cooperation is used, and the general formula of described dialkyl group diamine oxalic acid is:
N=2 in the formula～20, m=1～4, y=2～6, R is H, Na, K.
Described preparation method with double type surfactant that the huge legendary turtle cooperation uses comprises: obtain N with chain alkyl alkyl halide and diamine reaction, N-dialkyl group diamine intermediate, the mol ratio of chain alkyl alkyl halide and diamine is 1: 0.02～0.50,25～120 ℃ of reaction temperatures; Again with N, N-dialkyl group diamine and halogenated carboxylic acid are packed in the reaction bulb, N-dialkyl group diamine is 1: 3～6 with the ratio of halogenated carboxylic acid, add 50～200mL solvent cyclohexane again, add 2～40g powdered sodium hydroxide then, stirring reaction 1～3h under elder generation's room temperature, be heated to 40～120 ℃ of back flow reaction again 4～12 hours, stop reaction, transfer pH=8～14 with sodium hydroxide solution, leave standstill, separate out precipitation, obtain slightly yellow solid behind the suction filtration and be dialkyl group diamine oxalic acid, the general formula of described dialkyl group diamine oxalic acid is:
N=2 in the formula～20, m=1～4, y=2～6, R is H, Na, K.
Obtain the double type surfactant that has the huge legendary turtle cooperation to use of different wetting, emulsifying capacity by the length of regulating alkyl chain in the chain alkyl alkyl halide; The general formula of described chain alkyl alkyl halide is:
CnH
2n-1X, CnH
2NX, n=2～20 wherein, X is Cl, Br.
Obtain different big or small sequestration ligand rings by diamine and the halogenated carboxylic acid that utilizes different length;
Described diamine general formula is: H
2N (CH
2) yNH
2, y=2～6 wherein;
Described halogenated carboxylic acid general formula is: X (CH
2) mCOOH, m=1～4 wherein, X is Cl, Br.
After chain alkyl alkyl halide and diamine reaction end, be that 70～90 ℃ hot wash obtains yellowy N earlier with temperature, N-dialkyl group diamine crude product, obtain the N of white solid again with the absolute ethyl alcohol recrystallization, N-dialkyl group diamine crude product, crude product yield 40～99%, dry back is recrystallized with absolute ethyl alcohol.
Described have double type surfactant that the huge legendary turtle cooperation uses and can be widely used in the ore deposit in the printing and dyeing levelling agent of emulsion polymerization industry, textile printing and dyeing industry, wetting agent, spreader-sticker, bleeding agent and flowable, cosmetic products, tertiary oil recovery, wastewater treatment, new material preparation, the technics of metallurgy mineral dressing refining of wetting agent, coupling agent and stabilizing agent, washing powder and agricultural chemicals in the detergent compositions.
At preparation N, during N-dialkyl group diamine intermediate, characterize by methods such as infrared spectrum, elemental analyser, nuclear magnetic resonance, compound has the structure of expection.
At first step N, in the preparation of N-dialkyl group diamine, regulate alkyl chain segment length short (be alkyl carbon atoms number what), can make surfactant with different wetting, emulsifying capacity.Second step selected for use sequestration ligand part that different halogenated carboxylic acids obtain to form with metal ion to stablize the median size cyclic complex.
Select for use the alkyl group of C2～C20 to generate and have surfactant necessarily wetting, emulsifying capacity, can be applicable to fields such as emulsion polymerization industry, textile printing and dyeing industry, washing agent washing powder, tertiary oil recovery, wastewater treatment, new material preparation, technics of metallurgy mineral dressing refining ore deposit.
Chelating-double type the surfactant of the present invention preparation combines the two advantage of chelate surfactant and double type surfactant, two hydrophilic and oleophilic groups are arranged in the molecular structure and have better surface-active, and the existence of chelatingligand makes product have the ability of chelated metal ions, and products obtained therefrom will have bigger range of application and more wide application prospect.The chelating of being developed-double type surfactant can be used in emulsion polymerization industry, textile printing and dyeing industry, washing agent washing powder, agricultural chemicals wetting agent, spreader-sticker, bleeding agent and flowable, the wetting agent in cosmetic products and the detergent compositions, coupling agent and stabilizing agent etc.; Also be suitable for simultaneously the flotation ore deposit concentration and separation heavy metal ion of metallurgical industry; carry out the heavy metal ion offal treatment in the environmental protection; technologies such as printing and dyeing, the oxygen of textile industry floats, soaps; strengthen resistance to hard water in the washing agent washing powder, aspects such as the microelement nutritious liquid preparation in the animals and plants nutriment.Particularly its high stability that has and potential resistance to electrolyte contamination ability make the potential application of aspects such as it is repaired on tertiary oil recovery, wastewater treatment, soil sanitation, technics of metallurgy mineral dressing refining ore deposit, inferior surface, preparation new material more cause people's attention.
The specific embodiment
Embodiment 1
Add bromododecane in the three-necked bottle that reflux condensing tube, dropping funel and thermometer are housed, the ethylenediamine that splashes into new steaming carries out stirring reaction, allows both ratios of quality be 1: 0.04, dropwises under 60 ℃ of temperature reaction 5 hours, stops reaction.Tell lower floor's (processing in addition) while hot, the upper strata organic liquor is placed with about about 80 ℃ hot wash 2～3 times, room temperature.Get light yellow waxy solid,, get the white solid crude product with the absolute ethyl alcohol recrystallization.Crude product yield 94%.
Again with gained crude product N, N-dialkyl group ethylenediamine, excessive 3 times monoxone are packed in the reaction bulb, add the solvent cyclohexane, add powdered sodium hydroxide then, stirring reaction 1h under the first room temperature, heating reflux reaction is 8 hours then, stop reaction, transfer pH=10, place with sodium hydroxide solution, separate out precipitation, suction filtration.Dry back gets final product with the absolute ethyl alcohol recrystallization.
Embodiment 2
Add bromotetradecane in the three-necked bottle that reflux condensing tube, dropping funel and thermometer are housed, the ethylenediamine that splashes into new steaming carries out stirring reaction, allows the ratio of amount of the two be 1: 0.10, dropwises under 70 ℃ of temperature reaction 5 hours, stops reaction.Tell lower floor's (processing in addition) while hot, the upper strata organic liquor is placed with about about 80 ℃ hot wash 2～3 times, room temperature.Get light yellow waxy solid,, get the white solid crude product with the absolute ethyl alcohol recrystallization.Crude product yield 89%.
Again with gained crude product N, N-dialkyl group ethylenediamine, excessive 3.5 times monoxone are packed in the reaction bulb, add the solvent cyclohexane, add powdered sodium hydroxide then, stirring reaction 1h under the first room temperature, heating reflux reaction is 8 hours then, stop reaction, transfer pH=10, place with sodium hydroxide solution, separate out precipitation, suction filtration.Dry back gets final product with the absolute ethyl alcohol recrystallization.
Embodiment 3
Add bromododecane in the three-necked bottle that reflux condensing tube, dropping funel and thermometer are housed, the propane diamine that splashes into new steaming carries out stirring reaction, allows both ratios of quality be 1: 0.20, dropwises under 80 ℃ of temperature reaction 6 hours, stops reaction.Tell lower floor's (processing in addition) while hot, the upper strata organic liquor is placed with about about 80 ℃ hot wash 2～3 times, room temperature.Get light yellow waxy solid,, get the white solid crude product with the absolute ethyl alcohol recrystallization.Crude product yield 86%.
Again with gained crude product N, N-dialkyl group propane diamine, excessive 4 times 3-chloropropionic acid are packed in the reaction bulb, add the solvent cyclohexane, add powdered sodium hydroxide then, stirring reaction 1h under the first room temperature, heating reflux reaction is 8 hours then, stop reaction, transfer pH=10, place with sodium hydroxide solution, separate out precipitation, suction filtration.Dry back gets final product with the absolute ethyl alcohol recrystallization.
Embodiment 4
Add bromo-octadecane in the three-necked bottle that reflux condensing tube, dropping funel and thermometer are housed, the butanediamine that splashes into new steaming carries out stirring reaction, allows both ratios of quality be 1: 0.40, dropwises under 120 ℃ of temperature reaction 8 hours, stops reaction.Tell lower floor's (processing in addition) while hot, the upper strata organic liquor is placed with about about 80 ℃ hot wash 2～3 times, room temperature.Get light yellow waxy solid,, get the white solid crude product with the absolute ethyl alcohol recrystallization.Crude product yield 45%.
Again with gained crude product N, N-dialkyl group ethylenediamine, excessive 4.5 times 4-chloro-butyric acid are packed in the reaction bulb, add the solvent cyclohexane, add powdered sodium hydroxide then, stirring reaction 1h under the first room temperature, heating reflux reaction is 8 hours then, stop reaction, transfer pH=10, place with sodium hydroxide solution, separate out precipitation, suction filtration.Dry back gets final product with the absolute ethyl alcohol recrystallization.
Embodiment 5
Add the chloro decane in the three-necked bottle that reflux condensing tube, dropping funel and thermometer are housed, the ethylenediamine that splashes into new steaming carries out stirring reaction, allows both ratios of quality be 1: 0.10, dropwises under 100 ℃ of temperature reaction 6 hours, stops reaction.Tell lower floor's (processing in addition) while hot, the upper strata organic liquor is placed with about about 80 ℃ hot wash 2～3 times, room temperature.Get light yellow waxy solid,, get the white solid crude product with the absolute ethyl alcohol recrystallization.Crude product yield 51%.
Again with gained crude product N, N-dialkyl group ethylenediamine, excessive 5 times 3-chloropropionic acid are packed in the reaction bulb, add the solvent cyclohexane, add powdered sodium hydroxide then, stirring reaction 1h under the first room temperature, heating reflux reaction is 8 hours then, stop reaction, transfer pH=10, place with sodium hydroxide solution, separate out precipitation, suction filtration.Dry back gets final product with the absolute ethyl alcohol recrystallization.
Claims (2)
1. preparation method with double type surfactant that the huge legendary turtle cooperation uses, it is characterized in that: in the three-necked bottle that reflux condensing tube, dropping funel and thermometer are housed, add bromododecane, the propane diamine that splashes into new steaming carries out stirring reaction, allow both ratios of quality be 1: 0.20, dropwise under 80 ℃ of temperature and reacted 6 hours, stop reaction; Tell lower floor while hot, the upper strata organic liquor is placed with about 80 ℃ hot wash 2～3 times, room temperature; Get light yellow waxy solid,, get the white solid crude product with the absolute ethyl alcohol recrystallization; Crude product yield 86%;
Again with gained crude product N, N-two (dodecane) propane diamine, excessive 4 times 3-chloropropionic acid are packed in the reaction bulb, add the solvent cyclohexane, add powdered sodium hydroxide then, stirring reaction 1h under the first room temperature, heating reflux reaction is 8 hours then, stop reaction, transfer pH=10, place with sodium hydroxide solution, separate out precipitation, suction filtration; Dry back gets final product with the absolute ethyl alcohol recrystallization.
2. preparation method with double type surfactant that the huge legendary turtle cooperation uses, it is characterized in that: in the three-necked bottle that reflux condensing tube, dropping funel and thermometer are housed, add bromo-octadecane, the butanediamine that splashes into new steaming carries out stirring reaction, allow both ratios of quality be 1: 0.40, dropwise under 120 ℃ of temperature and reacted 8 hours, stop reaction; Tell lower floor while hot, the upper strata organic liquor is placed with about 80 ℃ hot wash 2～3 times, room temperature; Get light yellow waxy solid,, get the white solid crude product with the absolute ethyl alcohol recrystallization; Crude product yield 45%;
Again with gained crude product N, N-two (octadecane) butanediamine, excessive 4.5 times 4-chloro-butyric acid are packed in the reaction bulb, add the solvent cyclohexane, add powdered sodium hydroxide then, stirring reaction 1h under the first room temperature, heating reflux reaction is 8 hours then, stop reaction, transfer pH=10, place with sodium hydroxide solution, separate out precipitation, suction filtration; Dry back gets final product with the absolute ethyl alcohol recrystallization.
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| CN101711959B (en) * | 2009-11-19 | 2012-02-01 | 蚌埠丰原医药科技发展有限公司 | Polymerizable ester-group Gemini cation gemini surfactant and preparation method thereof |
| CN101972613B (en) * | 2010-09-25 | 2012-07-04 | 长江大学 | Carboxylate type gemini surfactant and synthesis method thereof |
| CN107442287B (en) * | 2017-08-14 | 2019-08-27 | 江西理工大学 | A kind of Gemini surface active agent for mineral floating |
| CN110079290B (en) * | 2019-05-16 | 2021-10-29 | 长江大学 | Low surface tension viscosity-increasing carboxylate gemini surfactant and preparation method thereof |
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