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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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 21
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005642 Oleic acid Substances 0.000 claims abstract description 21
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 21
- 239000004480 active ingredient Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims description 25
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims description 25
- 229940055577 oleyl alcohol Drugs 0.000 claims description 25
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 22
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 9
- 239000004317 sodium nitrate Substances 0.000 claims description 9
- 235000010344 sodium nitrate Nutrition 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- -1 p-methyl benzenesulfonic acid ester Chemical class 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 abstract description 6
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 239000002585 base Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 6
- 101150065749 Churc1 gene Proteins 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 102100038239 Protein Churchill Human genes 0.000 description 6
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 6
- 229940073769 methyl oleate Drugs 0.000 description 6
- 239000008154 viscoelastic solution Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of a low-concentration viscoelastic surfactant solution. The structure of an active ingredient is shown in the specifications. The preparation method of the surfactant solution comprises the following steps of: synthesizing an oleic acid-based Gemini quaternary ammonium salt surfactant in the ratio 18:(1-2)-18:1; performing ion exchange; neutralizing with acid and alkali; and compounding. The surfactant solution is characterized in that: the surfactant solution shows higher viscoelasticity at an extremely low concentration, and can be applied to oil field fracturing fluids, drag reduction agents and daily detergent formulas. The invention contributes to facilitating the application of oleic acid to a surfactant viscoelastic system.
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:
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.
(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%.
Claims (4)
1. the preparation method of a viscoelastic surfactant solution, first prepare Gemini surfactant, and then process and obtain corresponding quaternary ammonium base with strong basic ion exchange resin, through acid-base neutralization, obtain surfactant active ingredient again, last viscoelastic surfactant described in obtaining with inorganic salts are composite, is characterized in that, described inorganic salts are sodium nitrate, described Gemini surfactant is oleic acid base Gemini surfactant 18:1-2-18:1, is to obtain by following formula reaction:
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 ℃;
The viscoelastic surfactant solution of described low concentration is by surfactant active ingredient and inorganic salts are composite obtains, and wherein the active ingredient of surfactant is oleic acid base Gemini quaternary surfactant 18:1-2-18:12NO
3, structural formula is as follows:
2. the preparation method of viscoelastic surfactant solution according to claim 1, is characterized in that, described paratoluensulfonyl chloride reacts with oleyl alcohol after being first dissolved in carrene again.
3. the preparation method of viscoelastic surfactant solution according to claim 1, is characterized in that, 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.
4. the preparation method of viscoelastic surfactant solution according to claim 1, is characterized in that, adds anhydrous propanone as reaction dissolvent when adding lithium bromide.
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