CN103464050A - Positive ion Gemini surfactants with head base region including hydroxyl radicals and preparation method thereof - Google Patents
Positive ion Gemini surfactants with head base region including hydroxyl radicals and preparation method thereof Download PDFInfo
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- CN103464050A CN103464050A CN2013104610011A CN201310461001A CN103464050A CN 103464050 A CN103464050 A CN 103464050A CN 2013104610011 A CN2013104610011 A CN 2013104610011A CN 201310461001 A CN201310461001 A CN 201310461001A CN 103464050 A CN103464050 A CN 103464050A
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Abstract
The invention relates to quaternary ammonium salt type positive ion Gemini surfactants with a head base region including multiple hydroxyl radicals and a preparation method of the quaternary ammonium salt type positive ion Gemini surfactants. According to the structural formula of the quaternary ammonium salt type positive ion Gemini surfactants, m (2OH)-3 (OH)-m (2OH)R=n-CmH2m+1, m=6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, and the synthesis of the surfactants comprises the synthesis of N-alkyl diethanolamine and the quaterisation of coupling links including hydroxyl radicals. In the molecular structure of the surfactants, the head base region comprises the five hydroxyl radicals, and the surfactants are novel quaternary ammonium salt positive ion Gemini surfactants. The hydroxyl radicals can obviously improve the self-organizing properties of the surfactants, and the surfactants of the structure are beneficial for enriching the related knowledge of the self-origination of the Gemini surfactants.
Description
Technical field
The present invention relates to Cationic Gemini Surfactant and the synthetic method thereof of a class base containing a plurality of hydroxyls, belong to surfactant science and application.
Background technology
The Gemini surfactant is that the surfactant of two traditional single head list tails is being connected and forming by coupling link near a Ji Chu.With conventional surfactant, compare, its molecular structure is more complicated, but also therefore shows unique performance.With respect to conventional surfactant, the Gemini surfactant has higher surface-active and abundanter self-organizing behavior.In addition, it also has the stronger effect of peeling off, and removes the culture medium of bacterium at the metal surface apposition growth, and, by absorption film-forming, has blocked the passage of bacterium and metal surface, shows excellent sterilization, corrosion inhibition etc.Sneaking into the Gemini surfactant in dyestuff can also promote the dispersion of dyestuff and increase the adsorbance of fabric to dyestuff.With Gemini, surfactant-modified material can be driven away on-aqueous liquid and the pollutant adsorbed in deep soil in underground water.
A base of ionic surface active agent plays an important role in its absorption and accumulation process.When the base ionic surface active agent, with after hydroxyl modified, the self-organizing behavior generation of meeting Surfactant more significantly affects.The position of functional group in surfactant molecule also determining the mode of intermolecular interaction.While in molecule, containing a plurality of hydroxyl, compound may also can show some special performance.Therefore, be necessary to adopt synthetic method, consider the many factors such as molecular structure, hydroxy position, quantity, prepare the functional surface activating agent of novel hydroxyl group, make the more importantly effect of aggregation system performance of this class surfactant.
Summary of the invention
The present invention relates to preparation and the surface-active mensuration of a base containing the Cationic Gemini Surfactant of a plurality of hydroxyls.Use bromoalkane, diethanol amine and 1,3-dibromo isopropyl alcohol are initiation material, and the surfactant of acquisition has very strong ability of aggregation.
Base is containing the Cationic Gemini Surfactant of a plurality of hydroxyls, and structural formula is as follows: the structural formula of m (2OH)-3 (OH)-m (2OH):
R＝n-C
mH
2m+1，m＝6，7，8，9，10，11，12，13，14，15，16
A kind of method of described base containing the Cationic Gemini Surfactant of a plurality of hydroxyls that prepare, react the alkyl tertiary amine that obtains long-chain with diethanol amine with bromoalkane, the N-alkyl diethanol amine obtained obtains target product with 1,3-dibromo isopropanol reaction again, and concrete reaction equation is as follows:
The synthetic route of m (2OH)-3 (OH)-m (2OH):
R＝n-C
mH
2m+1，m＝6，7，8，9，10，11，12，13，14，15，16
Described bromoalkane, diethanol amine and 1,3-dibromo isopropyl alcohol are commercially available.
In N-alkyl diethanol amine synthesis step, first, with bromoalkane and diethanol amine reaction, the mol ratio of bromoalkane and diethanol amine is 1:2～5.
In quaterisation, N-alkyl diethanol amine and 1,3-dibromo isopropyl alcohol mol ratio are 2～5:1.
In N-alkyl diethanol amine synthesis step, reaction condition is under 50～80 ℃, to react 24～72 hours.
In quaterisation, reaction condition is that reaction condition is under 70～130 ℃ 48～96 hours.
Use the method for described base containing the Cationic Gemini Surfactant of a plurality of hydroxyls, solvent used is absolute ethyl alcohol, acetone, DMF, any in acetonitrile or several mixed solvents that mix with arbitrary proportion arbitrarily wherein.
The present invention obtains following effect:
1. the present invention is with diethanol amine, and bromoalkane and 1,3-dibromo isopropyl alcohol are raw material, the Cationic Gemini Surfactant through the synthetic base of two-step reaction containing a plurality of hydroxyls.Explore the actual conditions of reaction, rationally controlled reaction time and reaction condition, be conducive to improve reaction yield, reduced the difficulty of final products purifying.
2. synthetic Sets of Quaternary Gemini Surfactants head base contains five hydroxyls, and from 30 ℃, can to obtain its critical micelle concentration be 6.7 * 10 to electric lead curve
-4mol/L, have stronger ability of aggregation.
The accompanying drawing explanation
The nuclear magnetic resonance that Fig. 1 is embodiment product 12 (2OH)-3 (OH)-12 (2OH)
1the HNMR spectrogram.
Fig. 2 is the electrical conductivity curve of embodiment product 12 (2OH)-3 (OH)-12 (2OH) in the time of 30 ℃.
The specific embodiment
Base is containing a plurality of hydroxyls, and alkane chain is containing the Cationic Gemini Surfactant of 12 carbon atoms, and structural formula is as follows:
The structural formula of 12 (2OH)-3 (OH)-12 (2OH)
Synthetic route is as follows:
The synthetic route of 12 (2OH)-3 (OH)-12 (2OH)
Take bromododecane and diethanol amine as raw material, synthetic mesophase product N-dodecyl diethanol amine; Intermediate product contains the Cationic Gemini Surfactant of a plurality of hydroxyls again with the synthetic base of 1,3-dibromo isopropanol reaction.
The reaction of synthetic mesophase product N-dodecyl diethanol amine:
The mol ratio of bromododecane and diethanol amine is 1:4, and by bromododecane, diethanol amine and absolute ethyl alcohol stir 24 hours at 60 ℃, and cooling back end hydrogenation sodium oxide molybdena continues to stir 1 hour.Rotary evaporation is removed ethanol, in residue, adds 150mL distilled water, then adds 100mL ether, system layering.The upper strata organic layer is separated, and lower floor continues to use twice of extracted with diethyl ether.Extract is merged, with twice of distillation washing.The diethyl ether solution anhydrous magnesium sulfate drying, after filtration, the ether rotary evaporation is removed and is obtained thick product.Thick product is carried out to decompression distillation, and to obtain last sterling be colourless liquid.
The reaction of synthetic end-product:
N-dodecyl diethanol amine and 1,3-dibromo isopropyl alcohol mol ratio are 2.5:1, and by N-dodecyl diethanol amine, 1,3-dibromo isopropyl alcohol and a small amount of ethanol were 90 ℃ of reactions 72 hours.Rotary evaporation is removed ethanol, then to obtain sterling for three times with ethanol/ethyl acetate mixed solvent recrystallization be white solid.
Synthesizing of N-dodecyl diethanol amine
Dodecyl Bromide is mixed according to the amount of mol ratio 1:4 with diethanol amine, add absolute ethyl alcohol, 60 ℃ of reactions 24 hours.After cooling, then add NaOH to continue to stir 1 hour.After rotary evaporation is removed ethanol, in residue, add 150mL distilled water, then add 100mL ether, system layering.The upper strata organic layer is separated, and lower floor continues to use twice of extracted with diethyl ether.Extract is merged, with twice of distillation washing.The diethyl ether solution anhydrous magnesium sulfate drying, after filtration, the ether rotary evaporation is removed and is obtained thick product.Thick product is carried out to decompression distillation, and to obtain last sterling be colourless liquid (180 ℃/5mmHg), productive rate: 73.1%.
Embodiment 2
Synthesizing of 12 (2OH)-3 (OH)-12 (2OH)
N-dodecyl diethanol amine and 1,3-dibromo isopropyl alcohol are mixed according to mol ratio 2.5:1, add absolute ethyl alcohol, 90 ℃ of reactions 72 hours.Reactant is cooling, and rotary evaporation is removed ethanol.Residue re-crystallizing in ethyl acetate three times obtain finished product after vacuum drying, are white solid, yield 28%.
The mensuration of the electrical conductivity of embodiment product 12 (2OH)-3 (OH)-12 (2OH), adopt electrical conductivity method to be measured product electrical conductivity of solution under variable concentrations, make 12 (2OH)-3 (OH)-12 (2OH) aqueous solution electrical conductivity under 30 ℃ and, with concentration curve, see Fig. 2.From figure, curve break obtains critical micelle concentration value (cmc), from the slope ratio of two straight lines in turning point front and back, obtains degree of dissociation.The experiment discovery, the critical micelle concentration of the Cationic Gemini Surfactant of coupling link hydroxyl is lower, is 0.67mmol/L, and degree of dissociation is 0.25.
Embodiment 4
The end-product hydrogen nuclear magnetic resonance 1HNMR spectrum obtained by embodiment 1 is shown in Fig. 1.
According to Fig. 1 hydrogen nuclear magnetic resonance spectrum analysis, embodiment product 12 (2OH)-3 (OH)-12 (2OH) dissolves with DMSO, records
1the HNMR spectrum.The peak at δ in Fig. 1=2.5 and 3.3 places is peaks of DMSO solvent.All the other proton displacement δ are: 6.05 (d, 1H), 5.3 (m, 4H), 4.81 (m, 1H), (3.76-3.92 m, 8H), 3.6 (d, 8H), 3.3-3.4 (m, 4H), (1.69 d, 4H), 1.25 (s, 36H), 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. Cationic Gemini Surfactant of coupling link and an equal hydroxyl of base and preparation method thereof, its structural formula is as follows:
m(2OH)-3(OH)-m(2OH)
R＝n-C
mH
2m+1，m＝6，7，8，9，10，11，12，13，14，15，16。
2. one kind prepares the method for claimed in claim 1 base containing the Cationic Gemini Surfactant of a plurality of hydroxyls, it is characterized in that, bromoalkane reacts and obtains alkyl tertiary amine with diethanol amine, the N-alkyl diethanol amine obtained is again with 1,3-dibromo isopropanol reaction obtains target product, and concrete reaction equation is as follows:
The synthetic route of m (2OH)-3 (OH)-m (2OH):
R＝n-C
mH
2m+1，m＝6，7，8，9，10，11，12，13，14，15，16。
3. a preparation according to claim 2 base, containing the method for the Cationic Gemini Surfactant of a plurality of hydroxyls, is characterized in that, described bromoalkane, and diethanol amine and 1,3-dibromo isopropyl alcohol are commercially available.
4. a preparation according to claim 2 base is containing the method for the Cationic Gemini Surfactant of a plurality of hydroxyls, it is characterized in that, the mol ratio of bromoalkane and diethanol amine is 1:2～5, and long-chain alkyl tertiary amine and 1,3-dibromo isopropyl alcohol mol ratio are 2～5:1.
5. a preparation according to claim 2 base, containing the method for the Cationic Gemini Surfactant of a plurality of hydroxyls, is characterized in that, in the reaction of bromoalkane and diethanol amine, reaction condition is under 50～80 ℃, to react 24～72 hours.
6. according to claim 2 base, containing the method for the cation Gemini surfactant of a plurality of hydroxyls, is characterized in that, in the reaction of alkylol tertiary amine and 1,3-dibromo isopropyl alcohol, reaction condition is under 70～130 ℃ 48～96 hours.
7. the method for the Cationic Gemini Surfactant of coupling link according to claim 2 and an equal hydroxyl of base, 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 (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104645875A (en) * | 2014-12-16 | 2015-05-27 | 江南大学 | Viscoelastic system constructed by functional Gemini surfactants and preparation method of viscoelastic system |
| CN107352548A (en) * | 2017-08-22 | 2017-11-17 | 江南大学 | A kind of bar-shaped mesoporous silica nano-particle of two-dimentional hexagonal phase and preparation method thereof |
| 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 |
| US10563042B2 (en) | 2016-12-14 | 2020-02-18 | Ecolab Usa Inc. | Quaternary cationic polymers |
| CN113331218A (en) * | 2021-05-19 | 2021-09-03 | 安徽达尔美生物科技有限公司 | Household sterilizing disinfectant and preparation method thereof |
| CN114854390A (en) * | 2022-04-14 | 2022-08-05 | 西南石油大学 | Polyhydroxy super-large hydrophilic head-based viscoelastic surfactant and synthesis method thereof |
| US11427964B2 (en) | 2018-06-12 | 2022-08-30 | Ecolab Usa Inc. | Quaternary cationic surfactants and polymers for use as release and coating modifying agents in creping and tissue papers |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104645875A (en) * | 2014-12-16 | 2015-05-27 | 江南大学 | Viscoelastic system constructed by functional Gemini surfactants and preparation method of viscoelastic system |
| US10563042B2 (en) | 2016-12-14 | 2020-02-18 | Ecolab Usa Inc. | Quaternary cationic polymers |
| US11319427B2 (en) | 2016-12-14 | 2022-05-03 | Ecolab Usa Inc. | Quaternary cationic polymers |
| CN107352548A (en) * | 2017-08-22 | 2017-11-17 | 江南大学 | A kind of bar-shaped mesoporous silica nano-particle of two-dimentional hexagonal phase and preparation method thereof |
| CN107352548B (en) * | 2017-08-22 | 2019-12-24 | 江南大学 | Two-dimensional hexagonal-phase rod-like mesoporous silica nanoparticle and preparation method thereof |
| US11427964B2 (en) | 2018-06-12 | 2022-08-30 | Ecolab Usa Inc. | Quaternary cationic surfactants and polymers for use as release and coating modifying agents in creping and tissue papers |
| 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 |
| CN113331218A (en) * | 2021-05-19 | 2021-09-03 | 安徽达尔美生物科技有限公司 | Household sterilizing disinfectant and preparation method thereof |
| CN114854390A (en) * | 2022-04-14 | 2022-08-05 | 西南石油大学 | Polyhydroxy super-large hydrophilic head-based viscoelastic surfactant and synthesis method thereof |
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Application publication date: 20131225 |