CN102319550A - 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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- CN102319550A CN102319550A CN201110191927A CN201110191927A CN102319550A CN 102319550 A CN102319550 A CN 102319550A CN 201110191927 A CN201110191927 A CN 201110191927A CN 201110191927 A CN201110191927 A CN 201110191927A CN 102319550 A CN102319550 A CN 102319550A
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005642 Oleic acid Substances 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
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 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 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 16
- 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
- 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
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 9
- 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
- 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
- 239000002253 acid Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000012459 cleaning agent Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 238000003786 synthesis reaction Methods 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 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
- 239000007788 liquid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001035 drying Methods 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
- 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
- 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
- 239000003513 alkali Substances 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
- 238000001816 cooling Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007787 solid Substances 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
- 238000010992 reflux 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
- 238000004440 column chromatography Methods 0.000 description 2
- 230000008021 deposition Effects 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
- 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
- 230000002194 synthesizing effect Effects 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
- 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
- 239000000084 colloidal system 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
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000007789 gas Substances 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 238000012856 packing Methods 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
- 238000011084 recovery Methods 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
- 238000005303 weighing Methods 0.000 description 1
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Abstract
本发明涉及一种低浓度粘弹性表面活性剂溶液的制备方法，其有效成分的结构如下：
The present invention relates to a kind of preparation method of low-concentration viscoelastic surfactant solution, the structure of its active ingredient is as follows:
Description
Technical field
The present invention relates to a kind of viscoelastic surfactant solution, particularly a kind of is the low concentration viscoelastic surfactant solution and preparation method thereof of raw material with natural products oleic acid.
Background technology
Surfactant viscoelastic solution has a wide range of applications in daily life and commercial production, like the fracturing fluid of oil field oil recovery usefulness, and towing drag reducer and daily cleaning agent prescription etc.Common surfactant viscoelastic solution can obtain through a large amount of inorganic salts of adding or organic salt in the surfactant solution of single head list tail.This system needs surfactant to reach higher concentration usually, has increased cost on the one hand, also can cause unnecessary pollution to system on the other hand, has increased difficulty of post-processing.
The viscoplasticity of surfactant solution and the molecular structure of surfactant, the kind of counter ion, concentration or the like is relevant.The Gemini surfactant can show very strong viscoplasticity under low concentration, caused people extensive interest (Zana, R.Adv.Colloid Interface Sci.2002,97,205-253).Utilize the molecular skeleton of Gemini, through regulating the kind of hydrophobic chain, the kind of length and counter ion and ratio promptly are expected to obtain the better molecular species of viscoplasticity again.
Oleic acid extensively is present in occurring in nature with the form of glyceride, obtains easily.Oleic acid is separated from natural products, behind the purifying, can obtain oleyl alcohol through ester exchange or esterification, reduction.Oleyl alcohol just can be widely used in the preparation process of surfactant behind halo.
Summary of the invention
Need to add a large amount of salt in order to solve in the solution that prior art exists, and surfactant concentrations is than higher, the problem that post processing is difficult the invention provides a kind of preparation method of low concentration viscoelastic surfactant solution.Use the Gemini surfactant of oleyl alcohol preparation to be the basis, the surfactant solution that composite back obtains promptly has high viscoplasticity under the low concentration very much.
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 following:
A kind of preparation method of described viscoelastic surfactant solution; Prepare the Gemini surfactant earlier; And then handle with strong basic ion exchange resin and to obtain corresponding quaternary ammonium base; Obtain surfactant active ingredient through acid-base neutralization again, last and inorganic salts are composite to obtain described viscoelastic surfactant; 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 the following formula reaction:
Described solvent is the mixed solvent of any one or any several kinds of arbitrary proportions of ethanol, isopropyl alcohol, acetonitrile, acetone etc.
Used acid is nitric acid during acid-base neutralization.
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 dissolved in carrene earlier 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 a room temperature.
When adding lithium bromide, add anhydrous propanone as reaction dissolvent.
Beneficial effect:
The surfactant viscoelastic solution that is obtained promptly has viscoplasticity preferably at 1.7wt% when surfactant active ingredient concentration is low, can obviously reduce use cost.
Description of drawings
The dynamic shearing figure of Fig. 1 surfactant viscoelastic solution (0.023mol/L, G ' (●), G " (zero)).
The steady state shearing figure of Fig. 2 surfactant viscoelastic solution (0.023mol/L, 1.7wt%).
The specific embodiment
A kind of low concentration viscoelastic surfactant solution is by surfactant active ingredient and inorganic salts are composite obtains, and the structural formula of its active ingredient is following:
A kind of preparation method of low concentration viscoelastic surfactant solution; Prepare the Gemini surfactant earlier; And then handle with strong basic ion exchange resin and to obtain corresponding quaternary ammonium base, obtaining surfactant active ingredient through acid-base neutralization again, last and inorganic salts are composite to obtain described viscoelastic surfactant; 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 the following formula reaction:
Wherein oleyl alcohol can directly be bought commercially availablely, can be raw material with natural products oleic acid also, prepares through over-churning, reduction, and the preparation feedback formula is following:
In the bromination step of alcohol, be that oleyl alcohol is reacted with paratoluensulfonyl chloride earlier, reaction makes with anhydrous lithium bromide again.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 N '-tetramethylethylenediamine and 1-bromo-cis-9-octadecylene is 1: 2～5.Solvent is an ethanol, isopropyl alcohol, and acetonitrile, acetone, n-butanol, N, the mixed solvent of any one in the dinethylformamide or some kinds of arbitrary proportions reacted 24 to 120 hours down at 80～100 ℃.
With oleic acid is initiation material, prepares described low concentration viscoelastic surfactant solution, specifically can react by following formula:
The esterification of oleic acid:
With the methanol mixed of oleic acid and 10 times of molal quantitys, under the catalysis of the concentrated sulfuric acid, refluxed 5～8 hours at 80～90 ℃.After removing methyl alcohol, washing, drying, decompression distillation obtains methyl oleate.
Methyl oleate is reduced to oleyl alcohol:
The lithium aluminium hydride of methyl oleate and equimolar amounts was reacted in anhydrous tetrahydro furan 3～10 hours at-15～0 ℃.Through post processing, drying obtains oleyl alcohol.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 in the presence of the triethylamine of 2～10 times of moles ,-20～-5 ℃ were reacted 2～15 hours.Obtain the p-methyl benzenesulfonic acid ester of oleyl alcohol through washing, drying.The mol ratio of p-methyl benzenesulfonic acid ester and anhydrous lithium bromide is 1: 1～5, at room temperature reacts 2～50 hours.Through filter, desolventize, column chromatography obtains 1-bromo-cis-9-octadecylene.
Quaternized:
N, N, N ', the mol ratio of N '-tetramethylethylenediamine and 1-bromo-cis-9-octadecylene is 1: 2～5, makees solvent with ethanol, refluxes 96 hours at 90 ℃.Cooling back is steamed and is desolventized, and with ethanol-re-crystallizing in ethyl acetate three times, vacuum drying gets product oleic acid base Gemini surfactant 18: 1-2-18: 1.Described solvent is the mixed solvent of any one or any several kinds of arbitrary proportions of ethanol, isopropyl alcohol, acetonitrile, acetone etc.
Ion-exchange:
With strong basic ion exchange resin through 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 the 20mL distilled water, adds ion exchange column, with the flow velocity wash-out of distilled water with 5mL/min.With the check of phenolphthalein test solution, begin to collect when liquid reddens phenolphthalein when flowing out, obtain oleic acid base Gemini surfactant 18: 1-2-18: 1 quaternary ammonium alkali solution.
Acid-base neutralization and composite:
Prepare the finite concentration salpeter solution, confirm the accurate concentration of quaternary ammonium base and salpeter solution with constant-current titration.Acid, alkali are neutralized according to mol ratio at 1: 1, promptly obtain described surfactant viscoelastic solution with a certain proportion of sodium nitrate is composite again.
(1) methyl oleate is synthetic
With oleic acid (120g), absolute methanol (120g) and the concentrated sulfuric acid (1g) added in the single neck bottle of 500mL, 82 ℃ of stirring and refluxing 6 hours.After the cooling, remove low-boiling point material, extremely neutral with dilute sodium bicarbonate solution washing organic layer.Adding anhydrous magnesium sulfate drying spends the night.After the filtration, the bullion decompression distillation is got 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
With methyl oleate (52g), the oxolane (207g) that refluxes after dewatering through sodium-benzophenone adds in the single neck bottle of 500mL.Single neck bottle is put into the low-temp reaction device, and temperature is controlled at below-10 ℃.Lithium aluminium hydride (8g) is slowly added, begin to have more gas to produce.Add the back and stir half an hour, transfer to room temperature again and continue reaction 4 hours.Mixture is cooled to-15 ℃, earlier with, earlier to wherein slowly adding 8mL water, add 8mL 10%wt sodium hydroxide solution again.Add back stirring at room half an hour, suction filtration gets clear filtrate.To filtrate and use anhydrous magnesium sulfate drying, decompression is removed solvent and is promptly got the product oleyl alcohol after filtering.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) 1-bromo-cis-9-octadecylene is synthetic:
(70.4g, 0.26mol), (53g 0.52mol) with the 100mL carrene, is cooled to-10 ℃ to triethylamine in the 500mL three-necked bottle, to add oleyl alcohol.(65g 0.34mol), drips the muddy generation of process adularescent to the dichloromethane solution of slow dropping p-methyl benzene sulfonic chloride under stirring.Added the back stirring at room 5 hours.Reactant liquor is washed with dilute hydrochloric acid solution earlier, be washed with distilled water to neutrality again.Use anhydrous magnesium sulfate drying, suction filtration gets light yellow filtrating; Removal of solvents is got buff liquid.Liquid is transferred in the single neck bottle of 500mL, add simultaneously 300mL anhydrous propanone and anhydrous lithium bromide (35g, 0.4mol), stirring at room 32 hours.With the acetone evaporate to dryness, add the 200mL benzinum, left standstill 4 hours at-5 ℃.Sedimentation and filtration is got clear filtrate, steam desolventize head product.First product is used purification by silica gel column chromatography, and eluant, eluent is a benzinum.Finished product is a 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
(44g, 0.13mol), (7g's tetramethylethylenediamine 0.06mol) with in the single neck bottle of 200mL ethanol adding 500mL refluxed 96 hours with 1-bromo-cis-9-octadecylene.Cooling back is steamed and is desolventized, and with ethanol-re-crystallizing in ethyl acetate three times, vacuum drying gets 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 was soaked two days with dilute hydrochloric acid solution, in the post of packing into, be washed till neutrality with distilled water.Sodium hydroxide solution with 1mol/L exchanges first, and flow velocity 10mL/min is not till the liquor argenti nitratis ophthalmicus check of nitric acid acidifying has deposition.After being washed till neutrality with distilled water, with the flow velocity exchange of the hydrochloric acid solution of 1mol/L, be washed till neutrality with distilled water more again with 20mL/min.Exchange with the sodium hydroxide solution of 1.5mol/L flow velocity at last, till the liquor argenti nitratis ophthalmicus check of nitric acid acidifying does not have deposition with 10mL/min.Be washed till neutrality with distilled water, dispose.
With 3g oleic acid base Gemini surfactant 18: 1-2-18: 1 is dissolved in the 100mL distilled water, adds ion exchange column, with the flow velocity wash-out of distilled water with 5mL/min.With the check of phenolphthalein test solution, begin to collect when liquid reddens phenolphthalein when flowing out, obtain 18: 1-2-18: 1 quaternary ammonium alkali solution.
(6) acid-base neutralization and composite
Prepare certain density salpeter solution, calibrate accurate concentration with the sodium carbonate standard liquid.Calibrate the accurate concentration of quaternary ammonium alkali solution with the Potassium Hydrogen Phthalate standard liquid.Get the salpeter solution and the quaternary ammonium alkali solution of certain volume respectively and use distilled water diluting, according to 1: 1 mixed of acid-base neutralization, the concentration of the viscoelastic surfactant active ingredient that obtains at last is 0.023mol/L (1.7wt%).The solid nitric acid sodium (0.6wt%) that takes by weighing 3 times of amount of substances adds in this solution after the dissolving, promptly obtains described low concentration viscoelastic surfactant solution.
(7) gained solution is at room temperature carried out dynamically and the stable state flow measurement, obtain related data, concrete data are seen Fig. 1 and Fig. 2, can be found out that by Fig. 1 this solution shows tangible viscoelastic property, demonstrate the characteristic of Maxwell fluid.Can find out that by Fig. 2 the zero-shear viscosity of this solution can reach 7.4Pas, far above the viscosity of conventional surfactants solution under the 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.
Can find out clearly that by last table 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 1-bromo-cis-9-octadecylene:
Adopt commercially available oleyl alcohol, get 50g oleyl alcohol and 36g paratoluensulfonyl chloride, both mol ratios are 1: 1, and in the presence of the triethylamine of 10 times of moles ,-20 ℃ were reacted 15 hours.Obtain the p-methyl benzenesulfonic acid ester of oleyl alcohol through washing, drying.Add the anhydrous lithium bromide 80g of 5 times of moles, add acetone simultaneously, at room temperature reacted 2 hours.With the acetone evaporate to dryness, add benzinum ,-5 ℃ leave standstill after, through filter, desolventize, column chromatography obtains 1-bromo-cis-9-octadecylene, productive rate 21.5%.
Quaternized:
With 1-bromo-cis-9-octadecylene (40g, 0.12mol), N, N, N ', N '-tetramethylethylenediamine (5g, 0.04mol), both mol ratios are 3: 1, the 150mL anhydrous acetonitrile adds in the single neck bottle of 500mL and refluxed 100 hours.Cooling back is steamed and is desolventized, and with ethanol-re-crystallizing in ethyl acetate three times, vacuum drying gets product, is white waxy solid.Productive rate: 38.5%.
Synthesizing of 1-bromo-cis-9-octadecylene:
In the 500mL three-necked bottle, add oleyl alcohol (50g, 0.186mol), triethylamine (56g, 0.56mol) with carrene 220mL, be cooled to-10 ℃.(mol ratio of oleyl alcohol and paratoluensulfonyl chloride is 1: 2 for 71g, dichloromethane solution 0.37mol), the muddy generation of dropping process adularescent to stir slow down dropping p-methyl benzene sulfonic chloride.Added the back stirring at room 15 hours.Reactant liquor is washed with dilute hydrochloric acid solution earlier, be washed with distilled water to neutrality again.Use anhydrous magnesium sulfate drying, suction filtration gets light yellow filtrating; Removal of solvents is got buff liquid.Liquid is transferred in the single neck bottle of 500mL, added 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.With the acetone evaporate to dryness, add the 200mL benzinum, left standstill 4 hours at-5 ℃.Sedimentation and filtration is got clear filtrate, steam desolventize head product.First product is used purification by silica gel column chromatography, and eluant, eluent is a benzinum.Finished product is a colourless transparent liquid, productive rate 64.8%.
Quaternized:
With 1-bromo-cis-9-octadecylene (66.3g, 0.2mol), N, N, N ', N '-tetramethylethylenediamine (5g, 0.04mol), both mol ratios are 5: 1, the 150mL isopropyl alcohol adds in the single neck bottle of 500mL and refluxed 100 hours.Cooling back is steamed and is desolventized, and with ethanol-re-crystallizing in ethyl acetate three times, vacuum drying gets product, is white waxy solid.Productive rate: 25.3%.
Claims (8)
1. viscoelastic surfactant solution of low concentration is by surfactant active ingredient and inorganic salts are composite obtains, and it is characterized in that wherein the active ingredient of surfactant is oleic acid base Gemini quaternary surfactant 18: 1-2-18: 12NO
3, structural formula is following:
2. the preparation method of the described viscoelastic surfactant solution of claim 1; Prepare the Gemini surfactant earlier; And then handle with strong basic ion exchange resin and to obtain corresponding quaternary ammonium base; Obtain surfactant active ingredient through acid-base neutralization again, last and inorganic salts are composite to obtain described viscoelastic surfactant.It is characterized in that described inorganic salts are sodium nitrate, described Gemini surfactant is oleic acid base Gemini surfactant 18: 1-2-18: 1, be to obtain by the following formula reaction:
3. the preparation method of viscoelastic surfactant solution according to claim 2 is characterized in that, the solvent described in the quaternized step is the mixed solvent of any one or any several kinds of arbitrary proportions of ethanol, isopropyl alcohol, acetonitrile, acetone etc.
4. the preparation method of viscoelastic surfactant solution according to claim 2 is characterized in that, used acid is nitric acid during acid-base neutralization.
5. the preparation method of viscoelastic surfactant solution according to claim 2 is characterized in that, the mol ratio of oleyl alcohol and paratoluensulfonyl chloride is 1: 1～3, and reaction temperature is-20 ℃～-5 ℃.
6. the preparation method of viscoelastic surfactant solution according to claim 5 is characterized in that, described paratoluensulfonyl chloride reacts with oleyl alcohol after being dissolved in carrene earlier again.
7. the preparation method of viscoelastic surfactant solution according to claim 2 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 a room temperature.
8. the preparation method of viscoelastic surfactant solution according to claim 7 is characterized in that, when adding lithium bromide, adds anhydrous propanone as reaction dissolvent.
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| 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 |
| CN108837770A (en) * | 2018-06-25 | 2018-11-20 | 江南大学 | The four poly- surfactant worm-like micelle systems containing azobenzene group |
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| 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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