CN102319550B - Low-concentration viscoelastic surfactant solution and preparation method thereof - Google Patents
Low-concentration viscoelastic surfactant solution and preparation method thereof Download PDFInfo
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Abstract
Description
Technical field
The present invention relates to a kind of viscoelastic surfactant solution, particularly a kind ofly take low concentration viscoelastic surfactant solution that natural products oleic acid is raw material and preparation method thereof.
Background technology
Surfactant viscoelastic solution has a wide range of applications in daily life and industrial production, as the fracturing fluid that oil extraction in oil field is used, towing drag reducer and daily cleaning agent prescription etc.Common surfactant viscoelastic solution can be by adding a large amount of inorganic salts or organic salt to obtain in the surfactant solution to single head list tail.This system needs surfactant to reach higher concentration conventionally, has increased cost on the one hand, also can cause unnecessary pollution to system on the other hand, has increased the difficulty of post processing.
The viscoplasticity of surfactant solution and the molecular structure of surfactant, the kind of counter ion, concentration etc. is relevant.Gemini surfactant can show very strong viscoplasticity under low concentration, caused people broad interest (Zana, R.Adv.Colloid Interface Sci.2002,97,205-253).Utilize the molecular skeleton of Gemini, then by regulating the kind of hydrophobic chain, the kind of length and counter ion and ratio, be expected to obtain the better molecular species of viscoplasticity.
Oleic acid is extensively present in occurring in nature with the form of glyceride, easily obtains.After oleic acid is separated from natural products, purifying, through ester exchange or esterification, reduction, can obtain oleyl alcohol.Oleyl alcohol, after halo, just can be widely used in the preparation process of surfactant.
Summary of the invention
In order to solve in the solution that prior art exists, need to add a large amount of salt, and the concentration of surfactant is higher, the problem of post processing difficulty, the invention provides a kind of preparation method of low concentration viscoelastic surfactant solution.The Gemini surfactant of preparing with oleyl alcohol is basis, and the surfactant solution of composite rear acquisition has high viscoplasticity under very low concentrations.
Technical scheme of the present invention is: the viscoelastic surfactant solution of a kind of low concentration, be by surfactant active ingredient and inorganic salts are composite obtains, wherein the active ingredient of surfactant is oleic acid base Gemini quaternary surfactant 18: 1-2-18: 12NO 3, structural formula is as follows:
described inorganic salts are sodium nitrate, and the mol ratio of surfactant active ingredient and sodium nitrate is 1: 1～5.
A kind of preparation method of described viscoelastic surfactant solution, first prepare Gemini surfactant, and then process and obtain corresponding quaternary ammonium base with strong basic ion exchange resin, obtain surfactant active ingredient through acid-base neutralization again, last viscoelastic surfactant described in obtaining with inorganic salts are composite; Wherein, described inorganic salts are sodium nitrate, and described Gemini surfactant is oleic acid base Gemini surfactant 18: 1-2-18: 1, be to obtain by following formula reaction:
Described solvent is the mixed solvent of any one or any several arbitrary proportions of ethanol, isopropyl alcohol, acetonitrile, acetone etc.
During acid-base neutralization, acid used is nitric acid.
The mol ratio of oleyl alcohol and paratoluensulfonyl chloride is 1: 1～3, and reaction temperature is-20 ℃～-5 ℃.
Described paratoluensulfonyl chloride reacts with oleyl alcohol after being first dissolved in carrene again.
The p-methyl benzenesulfonic acid ester of oleyl alcohol and the mol ratio of lithium bromide are 1: 1～5, and reaction temperature is room temperature.
When adding lithium bromide, add anhydrous propanone as reaction dissolvent.
Beneficial effect:
The surfactant viscoelastic solution obtaining, when surfactant active ingredient concentration is lower, has good viscoplasticity at 1.7wt%, can obviously reduce use cost.
Accompanying drawing explanation
The dynamic shearing figure of Fig. 1 surfactant viscoelastic solution (0.023mol/L, G ' (●), G " (zero)).
The steady state shearing figure (0.023mol/L, 1.7wt%) of Fig. 2 surfactant viscoelastic solution.
The specific embodiment
A viscoelastic surfactant solution is by surfactant active ingredient and inorganic salts are composite obtains, and the structural formula of its active ingredient is as follows:
for oleic acid base Gemini quaternary surfactant 18: 1-2-18: 12NO 3, described inorganic salts are sodium nitrate, the mol ratio of surfactant active ingredient and sodium nitrate is 1: 1～5.
A kind of preparation method of low-concentration viscoelastic surfactant solution, first prepare Gemini surfactant, and then process and obtain corresponding quaternary ammonium base with strong basic ion exchange resin, obtain surfactant active ingredient through acid-base neutralization again, last viscoelastic surfactant described in obtaining with inorganic salts are composite; Wherein, described inorganic salts are sodium nitrate, and described Gemini surfactant is oleic acid base Gemini surfactant 18: 1-2-18: 1, be to obtain by following formula reaction:
Wherein oleyl alcohol can directly be bought commercially availablely, also can take natural products oleic acid as raw material, through over-churning, reduction, prepares, and preparation feedback formula is as follows:
In the bromination step of alcohol, be that oleyl alcohol is first reacted with paratoluensulfonyl chloride, then reaction make with anhydrous lithium bromide.The mol ratio of oleyl alcohol and paratoluensulfonyl chloride is 1: 1～3, with the mol ratio of anhydrous lithium bromide be 1: 1～5.
In quaternized step, N, N, N ', the mol ratio of the bromo-cis-9-of N '-tetramethylethylenediamine and 1-octadecylene is 1: 2～5.Solvent is ethanol, isopropyl alcohol, and acetonitrile, acetone, n-butanol, the mixed solvent of any one in DMF or several arbitrary proportion reacts 24 to 120 hours at 80～100 ℃.
Take oleic acid as initiation material, the low-concentration viscoelastic surfactant solution that preparation is described, specifically can react by following formula:
The esterification of oleic acid:
The methyl alcohol of oleic acid and 10 times of molal quantitys is mixed, under the catalysis of the concentrated sulfuric acid, at 80～90 ℃, reflux 5～8 hours.After removing methyl alcohol, washing, being dried, decompression distillation obtains methyl oleate.
Methyl oleate is reduced to oleyl alcohol:
Methyl oleate is reacted 3～10 hours at-15～0 ℃ with the lithium aluminium hydride of equimolar amounts in anhydrous tetrahydro furan.Through post processing, the dry oleyl alcohol that obtains.Described lithium aluminium hydride can also be that red aluminium etc. does not reduce two keys, only reduces the reducing agent of ester group
The bromination of oleyl alcohol:
The mol ratio of oleyl alcohol and paratoluensulfonyl chloride is 1: 1～3, and under the triethylamine of 2～10 times of moles exists ,-20～-5 ℃ are reacted 2～15 hours.Through washing, the dry p-methyl benzenesulfonic acid ester that obtains oleyl alcohol.The mol ratio of p-methyl benzenesulfonic acid ester and anhydrous lithium bromide is 1: 1～5, at room temperature reacts 2～50 hours.Desolventize after filtration,, column chromatography obtains the bromo-cis-9-of 1-octadecylene.
Quaternized:
N, N, N ', the mol ratio of the bromo-cis-9-of N '-tetramethylethylenediamine and 1-octadecylene is 1: 2～5, with ethanol, makees solvent, at 90 ℃, refluxes 96 hours.Cooling rear steaming desolventizes, and with Ethanol-Acetic Acid ethyl ester, is recrystallized three times, and vacuum drying obtains product oleic acid base Gemini surfactant 18: 1-2-18: 1.Described solvent is the mixed solvent of any one or any several arbitrary proportions of ethanol, isopropyl alcohol, acetonitrile, acetone etc.
Ion-exchange:
By strong basic ion exchange resin through acid soak-washing-sodium hydroxide solution wash-wash-pickling-washing-sodium hydroxide solution washes-washes processing.3g oleic acid base Gemini surfactant 18: 1-2-18: 1 is dissolved in 20mL distilled water, adds ion exchange column, the flow velocity wash-out with distilled water with 5mL/min.With the check of phenolphthalein test solution, when reddening phenolphthalein, efflux starts to collect, obtain oleic acid base Gemini surfactant 18: 1-2-18: 1 quaternary ammonium alkali solution.
Acid-base neutralization and composite:
Prepare finite concentration salpeter solution, with constant-current titration, determine the accurate concentration of quaternary ammonium base and salpeter solution.Acid, alkali are neutralized according to mol ratio at 1: 1, then the surfactant viscoelastic solution described in obtaining with a certain proportion of sodium nitrate is composite.
Embodiment 1
(1) methyl oleate is synthetic
By oleic acid (120g), absolute methanol (120g) and the concentrated sulfuric acid (1g) added in the mono-neck bottle of 500mL, 82 ℃ of stirring and refluxing 6 hours.After cooling, remove low-boiling point material, extremely neutral with dilute sodium bicarbonate solution washing organic layer.Add anhydrous magnesium sulfate drying to spend the night.After filtration, crude product decompression distillation is obtained to methyl oleate.176～178 ℃/6mmHg (uncorrected) productive rates: 90.0%
1H?NMR(300MHz，CDCl 3，Me 4Si)δ(ppm)：5.35(m，2H，CH＝CH)，3.66(s，3H，OCH 3)，2.30(t，2H，CH 2COOCH 3)，2.02(t，4H，CH 2CH＝CHCH 2)，1.62(t，2H，CH 2CH 2COOCH 3)，1.30～1.27(m，20H，CH 3(CH 2) 6CH 2CH＝CHCH 2(CH 2) 4)，0.88(t，3H，CH 3)
(2) oleyl alcohol is synthetic
By methyl oleate (52g), the oxolane (207g) refluxing after dewatering through sodium-benzophenone adds in the mono-neck bottle of 500mL.Single neck bottle is put into low-temp reaction device, and temperature is controlled at below-10 ℃.Lithium aluminium hydride (8g) is slowly added, start to have more γ-ray emission.Add rear stirring half an hour, then transfer to room temperature and continue reaction 4 hours.Mixture is cooled to-15 ℃, first and, first slowly add wherein 8mL water, then add 8mL 10%wt sodium hydroxide solution.Add rear stirring at room half an hour, suction filtration obtains clear filtrate.By filtrate anhydrous magnesium sulfate drying, after filtering, decompression is removed solvent and is obtained product oleyl alcohol.Productive rate: 86.3%
1H?NMR(400MHz，CDCl 3，Me 4Si)δ(ppm)：5.34(t，2H，CH＝CH)，3.63(t，2H，CH 2OH)，2.00(d，4H，CH 2CH＝CHCH 2)，1.85(s，1H，OH)，1.58～1.21(m，24H，CH 3(CH 2) 6CH 2CH＝CHCH 2(CH 2) 6)，0.88(t，3H，CH 3)
(3) the bromo-cis-9-of 1-octadecylene is synthetic:
In 500mL three-necked bottle, add oleyl alcohol (70.4g, 0.26mol), triethylamine (53g, 0.52mol) and 100mL carrene, be cooled to-10 ℃.Stir the lower dichloromethane solution (65g, 0.34mol) that slowly drips p-methyl benzene sulfonic chloride, the muddy generation of dropping process adularescent.Add rear stirring at room 5 hours.Reactant liquor is first washed with dilute hydrochloric acid solution, then be washed with distilled water to neutrality.With anhydrous magnesium sulfate drying, suction filtration obtains light yellow filtrate; Removal of solvents is obtained to buff liquid.Liquid rotating is moved on in the mono-neck bottle of 500mL, add 300mL anhydrous propanone and anhydrous lithium bromide (35g, 0.4mol) simultaneously, stirring at room 32 hours.By acetone evaporate to dryness, add 200mL benzinum, standing 4 hours at-5 ℃.Sedimentation and filtration is obtained to clear filtrate, steam and desolventize to obtain head product.By first product purification by silica gel column chromatography, eluant, eluent is benzinum.Finished product is colourless transparent liquid.Productive rate: 51.2%.
1H?NMR(300MHz，CDCl 3)δ5.35(d，2H，CH＝CH)，3.39(t，2H，CH 2Br)，2.01(d，4H，CH 2CH＝CHCH 2)，1.90～1.77(m，2H，CH 2CH 2Br)，1.35(m，22H，CH 3(CH 2) 6CH 2CH＝CHCH 2(CH 2) 6)，0.88(t，3H，CH 3).
(4) oleic acid base Gemini surfactant 18: 1-2-18: 1 synthetic
By 1-bromo-cis-9-octadecylene (44g, 0.13mol), tetramethylethylenediamine (7g, 0.06mol) and 200mL ethanol add in the mono-neck bottle of 500mL and reflux 96 hours.Cooling rear steaming desolventizes, and with Ethanol-Acetic Acid ethyl ester, is recrystallized three times, and vacuum drying obtains product, is white waxy solid.Productive rate: 25.1%.
1H?NMR(300MHz，CDCl 3)δ5.34(s，4H)，4.76(s，4H)，3.71(s，4H)，3.52(s，12H)，2.01(m，8H)，1.82(m，4H)，1.37～1.27(m，44H)，0.88(t，6H).
(5) preparation of quaternary ammonium base
The processing of strong basic ion exchange resin: 717 type anion exchange resin (chlorine type) 400g is soaked two days with dilute hydrochloric acid solution, pack in post, be washed till neutrality with distilled water.With the sodium hydroxide solution of 1mol/L, exchange first, flow velocity 10mL/min, until the check of the liquor argenti nitratis ophthalmicus of nitric acid acidifying is without precipitation.With distilled water, be washed till after neutrality, then the flow velocity exchange with 20mL/min with the hydrochloric acid solution of 1mol/L, then be washed till neutrality with distilled water.Finally with the sodium hydroxide solution of 1.5mol/L, the flow velocity with 10mL/min exchanges, until the check of the liquor argenti nitratis ophthalmicus of nitric acid acidifying is without precipitation.With distilled water, be washed till neutrality, be disposed.
By 3g oleic acid base Gemini surfactant 18: 1-2-18: 1 is dissolved in 100mL distilled water, adds ion exchange column, the flow velocity wash-out with distilled water with 5mL/min.With the check of phenolphthalein test solution, when reddening phenolphthalein, efflux starts to collect, obtain 18: 1-2-18: 1 quaternary ammonium alkali solution.
(6) acid-base neutralization and composite
Prepare certain density salpeter solution, with sodium carbonate standard liquid, calibrate accurate concentration.With Potassium Hydrogen Phthalate standard liquid, calibrate the accurate concentration of quaternary ammonium alkali solution.Get respectively salpeter solution and the quaternary ammonium alkali solution distilled water diluting of certain volume, according to the acid-base neutralization ratio of 1: 1, mix, the concentration of the viscoelastic surfactant active ingredient finally obtaining is 0.023mol/L (1.7wt%).After the solid nitric acid sodium (0.6wt%) that takes 3 times of amount of substances adds and dissolves in this solution, obtain described low-concentration viscoelastic surfactant solution.
(7) gained solution is at room temperature carried out to dynamic and stable state flow measurement, obtain related data, concrete data are shown in Fig. 1 and Fig. 2, and as seen from Figure 1, this solution shows obvious viscoelastic property, presents the feature of Maxwell fluid.As seen from Figure 2, the zero-shear viscosity of this solution can reach 7.4Pas, far above the viscosity of conventional surfactants solution under similar concentration.
The contrast of table 1 embodiment and common CTAB-inorganic salt system
Control systems r:Candau, S.J., Hirsch, E., Zana, R., Delsanti, M.Langmuir 1989,5, and 1225.
By upper table, can clearly find out that system of the present invention just can have good zero-shear viscosity in very low concentration, the consumption of inorganic salts is also very low.
Embodiment 2
Synthesizing of the bromo-cis-9-of 1-octadecylene:
Adopt commercially available oleyl alcohol, get 50g oleyl alcohol and 36g paratoluensulfonyl chloride, both mol ratios are 1: 1, and under the triethylamine of 10 times of moles exists ,-20 ℃ are reacted 15 hours.Through washing, the dry p-methyl benzenesulfonic acid ester that obtains oleyl alcohol.The anhydrous lithium bromide 80g that adds 5 times of moles adds acetone simultaneously, at room temperature reacts 2 hours.By acetone evaporate to dryness, add benzinum ,-5 ℃ standing after, after filtration, desolventize, column chromatography obtains the bromo-cis-9-of 1-octadecylene, productive rate 21.5%.
Quaternized:
By 1-bromo-cis-9-octadecylene (40g, 0.12mol), N, N, N ', N '-tetramethylethylenediamine (5g, 0.04mol), both mol ratios are 3: 1,150mL anhydrous acetonitrile adds in the mono-neck bottle of 500mL and refluxes 100 hours.Cooling rear steaming desolventizes, and with Ethanol-Acetic Acid ethyl ester, is recrystallized three times, and vacuum drying obtains product, is white waxy solid.Productive rate: 38.5%.
Embodiment 3
Synthesizing of the bromo-cis-9-of 1-octadecylene:
In 500mL three-necked bottle, add oleyl alcohol (50g, 0.186mol), triethylamine (56g, 0.56mol) and carrene 220mL, be cooled to-10 ℃.Stir the lower dichloromethane solution that slowly drips p-methyl benzene sulfonic chloride (71g, 0.37mol), the mol ratio of oleyl alcohol and paratoluensulfonyl chloride is 1: 2, the muddy generation of dropping process adularescent.Add rear stirring at room 15 hours.Reactant liquor is first washed with dilute hydrochloric acid solution, then be washed with distilled water to neutrality.With anhydrous magnesium sulfate drying, suction filtration obtains light yellow filtrate; Removal of solvents is obtained to buff liquid.Liquid rotating is moved on in the mono-neck bottle of 500mL, add 300mL anhydrous propanone and anhydrous lithium bromide simultaneously, the mol ratio of p-methyl benzenesulfonic acid ester and anhydrous lithium bromide is 1: 3, stirring at room 50 hours.By acetone evaporate to dryness, add 200mL benzinum, standing 4 hours at-5 ℃.Sedimentation and filtration is obtained to clear filtrate, steam and desolventize to obtain head product.By first product purification by silica gel column chromatography, eluant, eluent is benzinum.Finished product is colourless transparent liquid, productive rate 64.8%.
Quaternized:
By 1-bromo-cis-9-octadecylene (66.3g, 0.2mol), N, N, N ', N '-tetramethylethylenediamine (5g, 0.04mol), both mol ratios are 5: 1,150mL isopropyl alcohol adds in the mono-neck bottle of 500mL and refluxes 100 hours.Cooling rear steaming desolventizes, and with Ethanol-Acetic Acid ethyl ester, is recrystallized three times, and vacuum drying obtains product, is white waxy solid.Productive rate: 25.3%.
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| CN103933893A (en) * | 2014-04-28 | 2014-07-23 | 河南师范大学 | Choline ionic liquid surfactant and preparation method thereof |
| CN104801233B (en) * | 2014-12-16 | 2016-05-25 | 江南大学 | A kind of viscoelastic solution and preparation method who contains trimerization anion surface active agent composition |
| CN106588591A (en) * | 2016-11-25 | 2017-04-26 | 江苏恒盛药业有限公司 | Salmeterol intermediate ionic liquid catalytic bromination technology |
| CN108837771A (en) * | 2018-06-25 | 2018-11-20 | 江南大学 | A kind of dimeric surfactant vermiculate glues and preparation method thereof |
| CN108837770A (en) * | 2018-06-25 | 2018-11-20 | 江南大学 | The four poly- surfactant worm-like micelle systems containing azobenzene group |
| CN108970535A (en) * | 2018-06-25 | 2018-12-11 | 江南大学 | A kind of dimeric surfactant vermiculate glues and preparation method thereof |
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