CN103611467B - The tensio-active agent containing double connection group prepared with N, N ˊ-bis-(2-hydroxyethyl) piperazidine and preparation method - Google Patents
The tensio-active agent containing double connection group prepared with N, N ˊ-bis-(2-hydroxyethyl) piperazidine and preparation method Download PDFInfo
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- CN103611467B CN103611467B CN201310633220.3A CN201310633220A CN103611467B CN 103611467 B CN103611467 B CN 103611467B CN 201310633220 A CN201310633220 A CN 201310633220A CN 103611467 B CN103611467 B CN 103611467B
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- piperazidine
- hydroxyethyl
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Abstract
The present invention relates to the tensio-active agent containing double connection group and preparation method prepared with N, N ˊ-bis-(2-hydroxyethyl) piperazidine.This surfactant base component is as follows, is molfraction: N, N ˊ-bis-(2-hydroxyethyl) piperazidine 1 part, bromoalkane 1.5 ~ 4 parts.The invention still further relates to the preparation method of this tensio-active agent.The Gemini surface active that the present invention obtains is the Gemini surface active containing double connection group quaternary ammonium salt, more existing Gemini surface active has better surfactivity and interface performance, in material preparation, germ killing drugs etc., have potential using value.
Description
Technical field
The present invention relates to N, tensio-active agent containing double connection group prepared by N ˊ-bis-(2-hydroxyethyl) piperazidine and preparation method, in particular to one N, the preparation of N ˊ-bis-(2-hydroxyethyl) piperazidine, containing double connection group Quaternary ammonium gemini surfactants and preparation method thereof, belongs to chemical material technical field.
Background technology
Gemini surface active is as a kind of novel tensio-active agent, be formed by connecting by chemical bond via spacer group by the polar group of two parents, usually have higher surfactivity, it is all widely used in tertiary oil recovery, material are prepared etc.
The Gemini surface active of current report is connect with a spacer group to form mostly.As Chinese patent literature CN102614805A(application number 201210042527.1) disclose a kind of Quaternary Ammonium Gemini Surfactants.Primarily of fat tertiary amine (shown in formula III compound), in organic solvent, back flow reaction obtains described Quaternary Ammonium Gemini Surfactants at least 24 hours with halohydrocarbon (formula I institute V shows compound).
Chinese patent literature CN101279219A(application number 200810052006.8) disclose a kind of GEMINI quaternary ammonium salt cationic surfactant with sterilization effect.Two halides and aliphatic amide are reacted by the preparation method of GEMINI quaternary cationics of the present invention in organic solvent, namely dibromo is used for thing and alkyl tertiary amine in ethanol (or acetone, ethyl acetate) solution, under room temperature or low-heat, condition of normal pressure, carry out the method for chemical reaction, synthesize a series of GEMINI quaternary ammonium salt cationic surfactant.
But the report of the Gemini surface active of also not useful double connection group connection at present.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, one N is provided, the tensio-active agent containing double connection group prepared by N ˊ-bis-(2-hydroxyethyl) piperazidine and preparation method.
Technical solution of the present invention is as follows:
A kind of containing double connection group Quaternary ammonium gemini surfactants, feed composition is as follows, is molfraction:
N, N ˊ-bis-(2-hydroxyethyl) piperazidine 1 part, bromoalkane 1.5 ~ 4 parts.
Preferred according to the present invention, feed composition is as follows, is molfraction:
N, N ˊ-bis-(2-hydroxyethyl) piperazidine 1 part, bromoalkane 2 ~ 3 parts.
Preferred according to the present invention, described bromoalkane is bromo-decane.
The above-mentioned preparation method containing double connection group Quaternary ammonium gemini surfactants, step is as follows:
Be dissolved in by bromoalkane in ethanol, obtained bromoalkane solution, then drips N, N ˊ-bis-(2-hydroxyethyl) piperazidine solution, heating reflux reaction 12 ~ 72h, purifying, obtained containing double connection group Quaternary ammonium gemini surfactants.
In above-mentioned reaction, the mol ratio of N, N ˊ-bis-(2-hydroxyethyl) piperazidine and bromoalkane is 1:(1.5 ~ 4).
Preferred according to the present invention, in described bromoalkane solution, the mass concentration of bromoalkane is 386 ~ 488g/L;
Preferred according to the present invention, in described N, N ˊ-bis-(2-hydroxyethyl) piperazidine solution, solvent is alcohol or ketone, and N, N ˊ-bis-(2-hydroxyethyl) piperazidine mass concentration is 96 ~ 304g/L;
Preferred according to the present invention, described heating reflux reaction temperature is 78 DEG C.
Preferred according to the present invention, described purification step is: ethanol unnecessary in first distillation removing product, then adds acetone recrystallization three times, filter, washing, dry.
Preferred according to the present invention, the mol ratio of N, N ˊ-bis-(2-hydroxyethyl) piperazidine and bromoalkane is 1:(2 ~ 3).
In the present invention, the amount of bromoalkane is at least N, 1.5 ~ 4 times of N ˊ-bis-(2-hydroxyethyl) piperazidine, and object allows in the atom N at piperazidine two ends all connect alkyl chain, prevents the quaternary surfactant generating strand.Piperazidine reactant takes the mode dropwise instilled to add, and the speed started when instilling is slow, makes the N of instillation, and N ˊ-bis-(2-hydroxyethyl) piperazidine is energy complete reaction all; In addition, the initial quaternary ammonium salt product generated also as the catalyzer of reaction, can be conducive to the carrying out of subsequent reactions.
Beneficial effect
1, the Gemini surface active that the present invention obtains is the Gemini surface active containing double connection group quaternary ammonium salt, more existing Gemini surface active has better surfactivity and interface performance, in material preparation, germ killing drugs etc., have potential using value;
2, the Gemini surface active containing double connection group quaternary ammonium salt that the present invention obtains has stronger self-assembly ability, can prepare orderly Metaporous silicon dioxide material;
3, the Gemini surface active low in raw material price containing double connection group quaternary ammonium salt of the present invention, preparation technology is simple, and Production Flow Chart is few, and reaction conditions is gentle, easy and simple to handle, has that production cost is low, toxicity is little, the feature little to environmental hazard.
Accompanying drawing explanation
Fig. 1 is the 300M hydrogen nuclear magnetic resonance spectrogram containing double connection group Quaternary ammonium gemini surfactants that the embodiment of the present invention 1 obtains.
Fig. 2 is the surface tension graphic representation containing double connection group Quaternary ammonium gemini surfactants that the embodiment of the present invention 1 obtains.
Fig. 3 is the small angle X-ray diffraction graphic representation of the white powder that test example 1 obtains;
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further elaborated, but institute of the present invention protection domain is not limited thereto.
Raw material explanation
Bass special reagent company limited in N, N ˊ-bis-(2-hydroxyethyl) piperazidine Chengdu is on sale;
Bromo-decane West Asia Reagent Company is on sale.
Embodiment 1
Containing the preparation method of double connection group Quaternary ammonium gemini surfactants, synthetic route is as follows:
Synthesis step is as follows:
Bromo-decane 89g is dissolved in 100mL ethanol, obtained bromoalkane solution, then N is dripped, N ˊ-bis-(2-hydroxyethyl) piperazidine solution 32mL, the solvent of N, N ˊ-bis-(2-hydroxyethyl) piperazidine solution is ethanol, and mass concentration is 161g/L, heating reflux reaction 72h, 78 DEG C of distillation 30min remove ethanol.Add acetone 100r/min and stir 20min, hold over night, inclines and supernatant liquor, repeats above operation three times, after 50 DEG C of vacuum-dryings, obtained containing double connection group Quaternary ammonium gemini surfactants; This product is viscous brown thing.Because it contains two hydroxyls, during high density, easily form intermolecular hydrogen bonding, therefore product display is dope state, instead of solid state body.
Through 300M proton nmr spectra detect, containing double connection group Quaternary ammonium gemini surfactants structural confirmation collection of illustrative plates as shown in Figure 1.
With reference to QB/T1323-1991, by the surface tension of annulus pull-up liquid film chart surface-active agent.At 25 DEG C, the obtained micelle-forming concentration (cmc) containing double connection group Quaternary ammonium gemini surfactants is 9.6 × 10
-4mol/L, γ
cmc=36.1mN/m, as shown in Figure 2.
Embodiment 2
Containing the preparation method of double connection group Quaternary ammonium gemini surfactants, step is as follows:
Bromo-decane 66g is dissolved in 60mL acetone, obtained bromoalkane solution, then N is dripped, N ˊ-bis-(2-hydroxyethyl) piperazidine solution 32mL, the solvent of N, N ˊ-dimethyl piperazidine solution is acetone, and mass concentration is 136g/L, heating reflux reaction 72h, 56 DEG C of distillation 20min remove acetone.Add ether 100r/min and stir 20min, leave standstill 5h, incline and supernatant liquor, repeat above operation three times, after 50 DEG C of vacuum-dryings, obtained containing double connection group Quaternary ammonium gemini surfactants;
With reference to QB/T1323-1991, by the surface tension of annulus pull-up liquid film chart surface-active agent.At 25 DEG C, the obtained micelle-forming concentration (cmc) containing double connection group Quaternary ammonium gemini surfactants is 9.6 × 10
-4mol/L, γ
cmc=36.1mN/m.
Embodiment 3
Containing the preparation method of double connection group Quaternary ammonium gemini surfactants, step is as follows:
Bromo-decane 133g is dissolved in 130mL ethanol, obtained bromoalkane solution, then N is dripped, N ˊ-bis-(2-hydroxyethyl) piperazidine solution 32mL, the solvent of N, N ˊ-dimethyl piperazidine solution is ethanol, and mass concentration is 136g/L, heating reflux reaction 72h, 78 DEG C of distillation 35min remove ethanol.Add acetone 100r/min and stir 20min, hold over night, inclines and supernatant liquor, repeats above operation three times, after 50 DEG C of vacuum-dryings, obtained containing double connection group Quaternary ammonium gemini surfactants;
With reference to QB/T1323-1991, by the surface tension of annulus pull-up liquid film chart surface-active agent.At 25 DEG C, the obtained micelle-forming concentration (cmc) containing double connection group Quaternary ammonium gemini surfactants is 9.6 × 10
-4mol/L, γ
cmc=36.1mN/m.
Comparative example
A kind of novel simply connected reported see Song Liangli etc. connects Gemini surface active PR-J(science and technology and engineering, 13rd volume the 4th phase in 2013 1003 pages), described Gemini surface active is prepared by α, ω-dibromoalkane and N-Alkyl Dimethylamine, its γ
cmcfor 39.55mN/m.
The micelle-forming concentration (cmc) containing double connection group Quaternary ammonium gemini surfactants obtained by the embodiment of the present invention 1 ~ 3 is 9.6 × 10
-4mol/L, 2 ~ 4 orders of magnitude lower than the micelle-forming concentration value of comparative example, corresponding γ
cmc=36.1mN/m is also lower.Illustrate that product of the present invention can under lower micelle-forming concentration, significantly reducing the surface tension of solution, is high performance tensio-active agent.
Test example 1
Get 0.93g embodiment 2 obtained containing double connection group Quaternary ammonium gemini surfactants, be placed in 56mL deionized water, the NaOH solution adding 2mL massfraction 20% makes it to dissolve; Under ultrasonic, dropwise instilling the tetraethyl orthosilicate of 1.25g, is 9.7 with dilute sulphuric acid regulator solution pH afterwards, ageing 3 days in 80 DEG C of baking ovens.After cooling, filtering and washing obtains white powder;
Small angle X-ray diffraction sign is carried out to obtained material, can find to have occurred a spike at a ° place, 2 θ=2.310, as shown in Figure 3, define orderly mesoporous in the earth silicon material prepared by explanation.
Claims (6)
1. the preparation method containing double connection group Quaternary ammonium gemini surfactants, it is characterized in that, step is as follows: be dissolved in by bromoalkane in ethanol, obtained bromoalkane solution, then N is dripped, N ˊ-bis-(2-hydroxyethyl) piperazidine solution, heating reflux reaction 12 ~ 72h, purifying, obtained containing double connection group Quaternary ammonium gemini surfactants;
In above-mentioned reaction, the mol ratio of N, N ˊ-bis-(2-hydroxyethyl) piperazidine and bromoalkane is 1:(1.5 ~ 4);
In described N, N ˊ-bis-(2-hydroxyethyl) piperazidine solution, solvent is alcohol or ketone, and N, N ˊ-bis-(2-hydroxyethyl) piperazidine mass concentration is 96 ~ 304g/L.
2. preparation method as claimed in claim 1, it is characterized in that, in described bromoalkane solution, the mass concentration of bromoalkane is 386 ~ 488g/L.
3. preparation method as claimed in claim 1, it is characterized in that, described heating reflux reaction temperature is 78 DEG C.
4. preparation method as claimed in claim 1, it is characterized in that, described purification step is: ethanol unnecessary in first distillation removing product, then adds acetone recrystallization three times, filter, washing, dry.
5. preparation method as claimed in claim 1, it is characterized in that, the mol ratio of N, N ˊ-bis-(2-hydroxyethyl) piperazidine and bromoalkane is 1:(2 ~ 3).
6. preparation method as claimed in claim 1, it is characterized in that, described bromoalkane is bromo-decane.
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| ZA806992B (en) * | 1979-11-13 | 1981-10-28 | Johannesburg Cons Invest | Organic diammonium and related compounds as solvent extractants |
| US6890496B2 (en) * | 2002-02-07 | 2005-05-10 | Lynntech, Inc. | Extraction of metals with diquaternary amines |
| US7175818B2 (en) * | 2002-02-07 | 2007-02-13 | Lynntech, Inc. | Extraction of metals with diquaternary ammonium salts |
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