CN103480298A - Positive ion Gemini surface active agent with coupling link containing hydroxyl radical and preparation method of surface active agent - Google Patents
Positive ion Gemini surface active agent with coupling link containing hydroxyl radical and preparation method of surface active agent Download PDFInfo
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- CN103480298A CN103480298A CN201310460894.8A CN201310460894A CN103480298A CN 103480298 A CN103480298 A CN 103480298A CN 201310460894 A CN201310460894 A CN 201310460894A CN 103480298 A CN103480298 A CN 103480298A
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Abstract
The invention relates to a positive ion Gemini surface active agent with a coupling link containing a hydroxyl radical and a preparation method of the surface active agent. A structural formula of the surface active agent is as follows: R1=n-CmH2m+1, m=6,7,8,9,10,11,12,13,14,15,16, R2=CH3CH2-,CH3CH2CH2-, CH3CH2CH2CH2-, and synthesis of the series of surface active agents comprises a reaction of synthesizing tertiary amine by bromoalkane and secondary amine and a quaternization reaction of connecting tertiary amine and the coupling link containing the hydroxyl radical. In a molecular structure of the series of surface active agents, a head radical of tertiary amine contains a hydroxyl radical, the coupling link contains the hydroxyl, and the surface active agent is a quaternary ammonium salt type positive ion Gemini surface active agent provided with a complex head radical structure. The structure can enrich related knowledge of self-organization of the Gemini surface active agent, and the unique performance is beneficial to applications in industrial production.
Description
Technical field
The present invention relates to Cationic Gemini Surfactant and the synthetic method thereof of a class coupling link hydroxyl, belong to surfactant science and application.
Background technology
The Gemini surfactant is that the surfactant of two traditional single head list tails is being formed by connecting by coupling link near a Ji Chu.With conventional surfactant, compare, its molecular structure is more complicated, but also therefore shows unique performance, as lower critical micelle concentration, is easy to form novel aggregation, better acts synergistically etc.Application study to the Gemini surfactant relates to a plurality of fields, as Micellar catalysis, and nano particle preparation, gene transfection, corrosion inhibition for metal etc.It is synthetic that to have highly active novel surfactant be the emphasis that people pay close attention to always.
The surfactant of hydroxyl group has shown the performance different from conventional surfactant aspect self-organizing.Introduce hydroxy functional group in the surfactant molecule structure after, molecule likely produces additional intermolecular hydrogen bonding effect in process of self-organization.Because hydrogen bond has directionality, so the position of hydroxyl in molecule must affect intermolecular interaction mode.The position difference, the property and morphology of the aggregation of generation is just likely different.From current research, can find out, the research that has Surfactant self-organizing rule of hydroxyl is significant.Further explore the character of the Gemini surfactant of hydroxyl on coupling link, contribute to enrich the relevant knowledge of Gemini surfactant self-organizing, to usining surfactant, as the new material of template is synthetic important using value also arranged.
Summary of the invention
The present invention relates to preparation and the surface-active of the Cationic Gemini Surfactant of coupling link hydroxyl.Use bromoalkane, secondary amine and 1,3-dibromo isopropyl alcohol are initiation material, and the surfactant of acquisition has very high surface-active.
The Cationic Gemini Surfactant of coupling link hydroxyl, structural formula is as follows:
R
1＝n-C
mH
2m+1，m=6，7，8，9，10，11，12，13，14，15，16
R
2=CH
3CH
2-,CH
3CH
2CH
2-,CH
3CH
2CH
2CH
2-
A kind of method for preparing the Cationic Gemini Surfactant of described coupling link hydroxyl, react the alkyl tertiary amine that obtains long-chain with secondary amine with bromoalkane, the N-alkyl tertiary amine obtained obtains target product with 1,3-dibromo isopropanol reaction again, and concrete reaction equation is as follows:
M (2R
2)-3 (OH)-m (2R
2) synthetic route:
R
1＝n-C
mH
2m+1，m=6，7，8，9，10，11，12，13，14，15，16
R
2=CH
3CH
2-,CH
3CH
2CH
2-,CH
3CH
2CH
2CH
2-
Described bromoalkane, secondary amine and 1,3-dibromo isopropyl alcohol are commercially available.
In the synthesis step of N-alkyl tertiary amine, be that the mol ratio of bromoalkane and secondary amine is 1: 2～10 with bromoalkane and secondary amine reaction.
In quaterisation, the mol ratio of N-alkyl tertiary amine and 1,3-dibromo isopropyl alcohol is 2～6: 1.
In the synthesis step of N-alkyl tertiary amine, reaction condition is under 50～80 ℃, to react 24～72 hours.
In quaterisation, reaction condition is under 70～100 ℃ 48～96 hours.
Solvent for use is absolute ethyl alcohol, acetone, DMF, any in acetonitrile or any several mixed solvents that mix with arbitrary proportion wherein.
The present invention obtains following effect:
1. the present invention is with secondary amine, and bromoalkane and 1,3-dibromo isopropyl alcohol are raw material, through the novel cation Gemini surfactant of the synthetic coupling link hydroxyl of two-step reaction, has explored the actual conditions of reaction.By reasonable control reaction time and reaction condition, be conducive to improve reaction yield, reduce the difficulty of final products purifying.
2. synthetic quaternary ammonium salt Gemini surfactant coupling link hydroxy functional groups, have a more complicated based structures.Its critical micelle concentration cmc can reach 5.9 * 10
-4mo1/L, shown stronger ability of aggregation.
The accompanying drawing explanation
The nuclear magnetic resonance that Fig. 1 is embodiment product 12 (2Et)-3 (OH)-12 (2Et)
1the HNMR spectrogram.
Fig. 2 is the electrical conductivity curve of embodiment product 12 (2Et)-3 (OH)-12 (2Et) in the time of 30 ℃.
The specific embodiment
The Cationic Gemini Surfactant of coupling link hydroxyl
12 (2Et)-3 (OH)-12 (2Et), structural formula is as follows:
Synthetic route is as follows:
The synthetic route of 12 (2Et)-3 (OH)-12 (2Et)
Take bromododecane and diethylamine as raw material, synthetic mesophase product N, N-diethyl lauryl amine; Intermediate product again with a base of the synthetic coupling link hydroxyl of 1, the 3-dibromo isopropyl alcohol quaterisation novel cation Gemini surfactant that is ethyl.
Synthetic mesophase product N, the reaction of N-diethyl lauryl amine:
Mix according to the mol ratio ratio of 1: 5 with diethylamine in bromododecane, add absolute ethyl alcohol, stir 24 hours under 50 ℃, cooling back end hydrogenation sodium oxide molybdena continues to stir 1 hour.Rotary evaporation is removed ethanol.Add ether, in system, have solid to separate out.After filtration, the filtrate rotary evaporation is removed to ether and obtain thick product.Thick product being carried out to decompression distillation and obtain finished product, is colourless liquid.
The reaction of synthetic end-product:
By N, the ratio that N-diethyl lauryl amine and 1,3-dibromo isopropyl alcohol are 2.5: 1 according to mol ratio is mixed, and adds absolute ethyl alcohol, and under 80 ℃, reaction is 72 hours.Rotary evaporation is removed ethanol, then obtains finished product three times with ethanol/ethyl acetate mixed solvent recrystallization, is white solid.
N, N-diethyl lauryl amine synthetic
Dodecyl Bromide is mixed according to the mol ratio ratio of 1: 5 with diethylamine, add Dodecyl Bromide, diethylamine reacts 24 hours at 50 ℃ with absolute ethyl alcohol.After cooling, then add NaOH to continue to stir 1 hour.Rotary evaporation is removed low-boiling point material, in residue, adds the 100mL ether, in system, has solid to separate out, and after filtration, the filtrate rotary evaporation is removed to ether.Residue obtains product through decompression distillation, is colourless liquid (128 ℃/5mmHg).Productive rate: 62.8%.
Embodiment 2
Synthesizing of 12 (2Et)-3 (OH)-12 (2Et)
In reactor, by N, N-diethyl lauryl amine and 1,3-dibromo isopropyl alcohol mix according to mol ratio at 2.5: 1, and under 80 ℃, reaction is 72 hours.After reactant is cooling, rotary evaporation is removed ethanol.Residue ethanol/re-crystallizing in ethyl acetate three times obtain finished product after vacuum drying, are white solid, yield 35.3%.
The mensuration of the Cationic Gemini Surfactant electrical conductivity of coupling link hydroxyl, adopt conductance method to be measured the electrical conductivity of the product solution of variable concentrations, under doing 30 ℃, 12 (2Et)-3 (OH)-12 (2Et) aqueous solution electrical conductivity, with the change curve of solution concentration, are shown in Fig. 2.The ratio of the critical micelle concentration (cmc) that the concentration that in figure, curve break is corresponding is this surfactant slope of two straight lines before and after curve break from figure can obtain the degree of dissociation of this surfactant.The experiment discovery, the critical micelle concentration of the Cationic Gemini Surfactant of coupling link hydroxyl is lower, and cmc is 5.9 * 10
-4mo1/L, the degree of dissociation of the surfactant 12 (2Et)-3 (OH)-12 (2Et) under critical micelle concentration is 0.22.
Embodiment 4
The end-product nuclear magnetic resonance that embodiment obtains
1the HNMR spectrum is shown in Fig. 1.
According to the map analysis of Fig. 1 nuclear magnetic resoance spectrum, end product 12 (2Et)-3 (OH)-12 (2Et) dissolves with DMSO, records
1the HNMR spectrum.δ in Fig. 1=2.5 and 3.3 places are solvent peaks of DMSO.All the other proton displacement δ are: 6.19 (d, 1H), 4.65 (m, 1H), 3.25-3.5 (m, 18H), 1.62 (d, 4H), 1.15-1.35 (m, 48H), 0.85 (t, 6H).The data cases analysis of processing from spectrogram, can learn that end product is consistent with the design object product.
Claims (7)
1. the Cationic Gemini Surfactant of coupling link hydroxyl, its structural formula is as follows:
m(2R
2)-3(OH)-m(2R
2)
R
1=n-C
mH
2m+1，m=6，7，8，9，10，11，12，13，14，15，16
R
2=CH
3CH
2-,CH
3CH
2CH
2-,CH
3CH
2CH
2CH
2-。
2. a method for preparing the Cationic Gemini Surfactant of coupling link hydroxyl claimed in claim 1, is characterized in that, bromoalkane reacts the alkyl tertiary amine that obtains long-chain with secondary amine.Long chain tertiary amine obtains target product with 1,3-dibromo isopropanol reaction again, and concrete reaction equation is as follows:
M (2R
2)-3 (OH)-m (2R
2) synthetic route:
R
1=n-C
mH
2m+1，m=6，7，8，9，10，11，12，13，14，15，16
R
2=CH
3CH
2-,CH
3CH
2CH
2-,CH
3CH
2CH
2CH
2-。
3. the method for preparing the Cationic Gemini Surfactant of coupling link hydroxyl according to claim 2, is characterized in that, described bromoalkane, and secondary amine and 1,3-dibromo isopropyl alcohol are commercially available.
4. the method for preparing the Cationic Gemini Surfactant of coupling link hydroxyl according to claim 2, is characterized in that, the mol ratio of bromoalkane and secondary amine is 1: 2～10, and the mol ratio of long-chain alkyl tertiary amine and 1,3-dibromo isopropyl alcohol is 2～6: 1.
5. the method for preparing the Cationic Gemini Surfactant of coupling link hydroxyl according to claim 2, is characterized in that, in the reaction of bromoalkane and secondary amine, reaction condition is under 50～80 ℃, to react 24～72 hours.
6. the method for the Cationic Gemini Surfactant of coupling link hydroxyl according to claim 2, is characterized in that, in the reaction of long-chain alkyl tertiary amine and 1,3-dibromo isopropyl alcohol, reaction condition is under 70～100 ℃ 48～96 hours.
7. the method for the Cationic Gemini Surfactant of coupling link hydroxyl according to claim 2, is characterized in that, solvent for use is absolute ethyl alcohol, acetone, DMF, any in acetonitrile or any several mixed solvents that mix with arbitrary proportion wherein.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128120A (en) * | 2014-07-22 | 2014-11-05 | 武汉工程大学 | Preparation method of cationic gemini surfactant with connection chain containing hydroxy group |
| CN104959070A (en) * | 2015-06-19 | 2015-10-07 | 武汉工程大学 | Cationic gemini surfactant and preparing method thereof |
| CN105964185A (en) * | 2016-05-24 | 2016-09-28 | 江南大学 | Asymmetric cationic Gemini surfactant containing hydroxyl group in coupling link |
| CN108794340A (en) * | 2017-04-27 | 2018-11-13 | 南京科技职业学院 | A kind of quaternary surfactant and preparation method thereof of major part base |
| CN109535015A (en) * | 2018-11-11 | 2019-03-29 | 广州市金浪星非织造布有限公司 | A kind of four ethoxy dibromo propane-diammonium of double octadecyls and preparation method thereof |
| CN112592705A (en) * | 2020-12-22 | 2021-04-02 | 西南石油大学 | Ecological safety type scale and corrosion inhibitor and preparation method thereof |
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2013
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128120A (en) * | 2014-07-22 | 2014-11-05 | 武汉工程大学 | Preparation method of cationic gemini surfactant with connection chain containing hydroxy group |
| CN104959070A (en) * | 2015-06-19 | 2015-10-07 | 武汉工程大学 | Cationic gemini surfactant and preparing method thereof |
| CN105964185A (en) * | 2016-05-24 | 2016-09-28 | 江南大学 | Asymmetric cationic Gemini surfactant containing hydroxyl group in coupling link |
| CN108794340A (en) * | 2017-04-27 | 2018-11-13 | 南京科技职业学院 | A kind of quaternary surfactant and preparation method thereof of major part base |
| CN109535015A (en) * | 2018-11-11 | 2019-03-29 | 广州市金浪星非织造布有限公司 | A kind of four ethoxy dibromo propane-diammonium of double octadecyls and preparation method thereof |
| CN112592705A (en) * | 2020-12-22 | 2021-04-02 | 西南石油大学 | Ecological safety type scale and corrosion inhibitor and preparation method thereof |
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