CN1557535A - Gemini quaternary surfactant containing pyridine rings and preparing method thereof - Google Patents
Gemini quaternary surfactant containing pyridine rings and preparing method thereof Download PDFInfo
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- CN1557535A CN1557535A CNA2004100216553A CN200410021655A CN1557535A CN 1557535 A CN1557535 A CN 1557535A CN A2004100216553 A CNA2004100216553 A CN A2004100216553A CN 200410021655 A CN200410021655 A CN 200410021655A CN 1557535 A CN1557535 A CN 1557535A
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Abstract
The present invention is one kind of quaternary ammonium salt surfactant containing pyridine ring and its preparation process. The preparation process includes: adding bromoalkane and metal lithium into anhydrous ethyl ether and reaction for 0.5-2 hr at temperature controlled near the freezing point; maintaining the temperature and adding excessive pyridine and toluene solution to react for 0.5-3 hr, raising temperature and reflux for hours; mixing alkyl pyridine and haloalkane dibromide in the ratio of 1-4 into alcohol solvent for reflux reaction for 15-72 hr; and re-crystallizing the product and drying. The surfactant of the present invention has very high surface activity, high sterilizing effect, high corrosion resistance, simple preparation process, mild reaction condition and other advantages.
Description
Technical field
The present invention relates to nitrogenous heterocyclic gemini quaternary ammonium salt surfactant of a class and preparation method thereof.
Background technology
1. the application of surfactant in tertiary oil recovery
Crude oil is non-renewable resource, and conventional oil recovery technique only can the extraction crude oil reserve 1/3, and the seventies, oil crisis bred the growth of tertiary oil recovery.Wherein, ternary composite driving is the tertiary oil recovery new technology that grows up the eighties.And surfactant has been played the part of the key player in this process.The surfactant that is used for tertiary oil recovery must meet the following conditions: (1) at the surface-active height of oil/water termination, oil water interfacial tension is reduced to (0.01～0.001) * 10
-5Below the N/cm.Have certain solubility, and reduce the adsorbance of rock crude oil; (2) little in the rock surface adsorbance; (3) in the stratum, suitable diffusion velocity should be arranged, can not be too big and too little; (4) when concentration is low, stronger oil-displacement capacity should be arranged; (5) has the ability of high temperature resistance, high salinity; (6) have higher economic worth, input and output have advantage.The gemini quaternary ammonium salt surfactant is compared with conventional surfactant, has the ability of higher surface activity and reduction oil/water termination tension force, crude oil is had good solubilising, good anti-salt and antisolvent precipitation and wetting power.Be used for tertiary oil recovery so synthesize the high performance gemini quaternary ammonium salt surfactant of inexpensive valency, will bring very high economic worth.
Quaternary ammonium salt sterilizing and anticorrosion aspect application
In the secondary oil recovery technology, need a large amount of re-injection water, often contain sulfatereducting bacteria (SRB), saprophytic bacteria etc. in the re-injection water, these bacteriums can cause that metal erosion, formation blockage, chemicals go bad, wherein the corrosion that especially causes with SRB is very serious, brings about great losses for oil field industry.Therefore oil field reinjection water being carried out preliminary treatment such as sterilization and anticorrosion is a most important step in the secondary oil recovery technology.Adding bactericide in re-injection water is a kind of more convenient effective way.The surfactant of quaternary comprises single linked list surface-active agent and dimeric surfactant, the protein molecule of complexity can be split into some polypeptide chains, to the activity generation inhibitory action of bacterium.Lien and Perrin discover that along with the reduction of cmc value, the sterilizing ability of quaternary surfactant linearly increases.But in actual applications, the mono-quaternaries surfactant exposes its intrinsic weakness, promptly uses for a long time, owing to the resistance to the action of a drug of microorganisms obviously descends its result of use, further application is restricted.For example present China's widely used a kind of mono-quaternaries series bactericidal agent 1227 in oil field (dodecyl benzyl dimethyl ammonium chloride), its using dosage rises to 100mg/L from 30mg/L.
Show that according to the study the gemini quaternary ammonium salt surfactant is compared with the mono-quaternaries surfactant that ion head base is connected the same carbon atoms number chain, its critical micelle concentration cmc value that characterizes physical property is than low 2 orders of magnitude of mono-quaternaries.The host that becomes new type bactericide in the oil field flood pattern so the gemini quaternary ammonium salt surfactant is expected to replace the mono-quaternaries surfactant.
The economic loss that metal erosion causes is very huge, and only it just accounts for 3%～4.5% of gross national product in China, estimate the domestic this respect of China in 1993 with a toll of more than 1,000 hundred million yuan.People are just seeking all ways makes metal erosion drop to minimum degree, and therefore various corrosion inhibiter arise at the historic moment.Quaternary ammonium salt and nitrogen-containing organic compound such as amine and pyridines are the materials that a class is widely used in fields such as corrosion inhibition for metal, the gemini quaternary ammonium salt compound is compared with general mono-quaternaries, have characteristics such as low toxicity and wide biological activity and good water-solubility, be expected in the corrosion inhibition for metal field, to be widely used
Summary of the invention
The object of the present invention is to provide the gemini quaternary ammonium salt surfactant that contains pyridine ring.This surfactant has the advantage of Gemini surface active agent, and promptly high surface-active and low critical micelle concentration also embody the sterilization and the multi-functional such as anticorrosion of quaternary ammonium salt simultaneously.
Another object of the present invention also is to provide the preparation method of this gemini quaternary ammonium salt surfactant that contains pyridine ring.This method is easy to operate, and step is less, and the reaction condition gentleness.
For reaching above technical purpose, the invention provides following technical scheme.
Contain the gemini quaternary ammonium salt surfactant of pyridine ring, this surfactant has following structure:
n＝8，10，12，14，16，18????m＝2，4，6，8，10
Contain the preparation method of the gemini quaternary ammonium salt surfactant of pyridine ring, may further comprise the steps successively:
(1) the control temperature adds bromoalkane and lithium metal in absolute ether near freezing point, and its mol ratio is a bromoalkane: lithium metal=1: 5～1: 1, reacted 0.5～2 hour;
(2) insulation and adding excess pyridine and toluene solution, question response was warming up to about 110 ℃ after 0.5～3 hour, refluxed 2～5 hours, had promptly synthesized the alpha-alkyl pyridine;
(3) in alcohols solvent with alkyl pyridine and dibromo alkyl halide in molar ratio 1～4: 1 ratio mix back flow reaction 15～72 hours;
(4) with the product recrystallization, drying promptly obtains the gemini quaternary ammonium salt surfactant that the present invention contains pyridine ring.
Alcohols solvent can be ethanol, propyl alcohol described in preparation method's step of the present invention (3), and the ratio of alkyl pyridine and dibromo alkyl halide is 2～3: 1 o'clock the best.
Can be in preparation method's step of the present invention (4) earlier with product anhydrous propanone frozen recrystallization 1 time, with acetone and absolute ethyl alcohol recrystallization, the target compound purity that obtains is higher again.
This reaction mechanism of gemini quaternary ammonium salt surfactant that contains pyridine ring is as follows:
(1) the alpha-alkyl pyridine is synthetic
(2) the gemini quaternary ammonium salt surfactant is synthetic
Compared with prior art, the present invention has following beneficial effect:
(1) new varieties of gemini quaternary ammonium salt surfactant have been increased;
(2) gemini quaternary ammonium salt surfactant provided by the invention has very high surface-active;
(3) gemini quaternary ammonium salt surfactant bactericidal effect provided by the invention is good, and erosion resistance is strong;
(4) method step provided by the invention is few, and is simple to operate, the reaction condition gentleness, so cost is low, market application foreground is wide.
Description of drawings
Fig. 1 is the relation that contains gemini quaternary ammonium salt surfactant GP5, GP6 consumption and the corrosion inhibition rate of pyridine ring
Fig. 2 is the infrared spectrum that contains the gemini quaternary ammonium salt surfactant GP5 of pyridine ring
Fig. 3 is the hydrogen spectrogram that contains the gemini quaternary ammonium salt surfactant GP5 of pyridine ring
The specific embodiment
Embodiment 1
In the three-neck flask of the 500ml of the reflux condensing tube of being furnished with dropping funel, nitrogen ingress pipe, band drying tube, earlier with after the purging with nitrogen gas, add 100ml absolute ether and 2.45g lithium (0.35mol), splash into the C of 0.2mol during stirring
10H
21The mixture of Br and 40～60ml absolute ether reacted about 1 hour, and most of lithium bits are reacted completely, and the control reaction temperature drips 21g (0.26mol) pyridine and 50ml toluene near freezing point, and question response was warming up to 110 ℃ after 2 hours, refluxed 3 hours.Separatory, washing, drying.Boil off low-boiling compound on rotary evaporator, corresponding cut is collected in decompression distillation, passes through column chromatography (eluant, eluent: benzinum: ethyl acetate=4: 1), obtain the alpha-decyl pyridine again.
In the three-neck flask that agitator, reflux condensing tube are housed, add decyl pyridine and 1,4-dibromobutane (or 1, the 6-dibromobutane), its mol ratio is 2.4: 1, and the mass fraction of solvent in the reactant mixture (absolute ethyl alcohol) is 40%, back flow reaction 48 hours, steam absolute ethyl alcohol with rotary evaporator, add the anhydrous propanone frozen recrystallization then 1 time, be recrystallized 1 time with acetone and absolute ethyl alcohol again, with the white solid of gained at P
2O
5Existence under, drying under reduced pressure is 24 hours under the room temperature, obtains target compound, promptly contains the gemini quaternary ammonium salt surfactant GP5 (if add 1, the 6-dibromobutane then obtains GP6) of pyridine ring.
Embodiment 2
In the three-neck flask of the 500ml of the reflux condensing tube of being furnished with dropping funel, nitrogen ingress pipe, band drying tube, earlier with after the purging with nitrogen gas, add 50ml absolute ether and 2.45g lithium (0.35mol), start stirring, splash into 0.2molC
12H
25The mixture of Br and 50ml absolute ether reacted about 2 hours, and most of lithium bits are reacted completely, and the control reaction temperature drips 0.3mol pyridine and 60ml toluene about freezing point, and question response was warming up to about 110 ℃ after 2 hours, refluxed 3 hours.Separatory, washing, drying.Boil off low-boiling compound on rotary evaporator, corresponding cut is collected in decompression distillation, passes through column chromatography again, obtains α-dodecyl pyridine.
In the three-neck flask that agitator, reflux condensing tube are housed, add dodecyl pyridine and 1, the 6-dibromo-hexane, its mol ratio is 2.4: 1, the mass fraction of solvent in the reactant mixture (absolute ethyl alcohol) is 40%, back flow reaction 20 hours steams absolute ethyl alcohol with rotary evaporator, recrystallization, the white solid of dry gained promptly obtains containing the gemini quaternary ammonium salt surfactant GP7 of pyridine ring.
In the three-neck flask that agitator, reflux condensing tube are housed, add the dodecyl pyridine and 1 that embodiment 2 synthesizes, 4-dibromobutane (its mol ratio is 3: 1), the mass fraction of solvent in the reactant mixture (absolute ethyl alcohol) is 60%, back flow reaction 20 hours, steam absolute ethyl alcohol with rotary evaporator, recrystallization, the white solid of dry gained promptly obtains containing the gemini quaternary ammonium salt surfactant GP8 of pyridine ring.
Embodiment 4 contains the bactericidal activity of the gemini quaternary ammonium salt surfactant of pyridine ring and measures (sizing technique GB15981-1995)
(1) bactericide is made into the solution of 30ppm concentration.
(2) bacterium liquid is carried out count plate, and to be diluted to bacteria containing amount with sterile distilled water be 5 * 10
5-6 * 10
6The bacteria suspension of cfu/ml is made as original bacteria liquid, do 10 times increase progressively the dilution be 10
-3, 10
-4, 10
-5The dilution of 3 kinds of concentration is drawn 0.5ml in different sterilization plates with pipette respectively, and each each dilution factor is made two plates, in time pours cold to 45 a ℃ left and right sides meat soup protein culture medium into plate about 7ml then, and forwards plate to and make it to mix.After treating that agar solidifies, the upset plate, put 37 ℃ down cultivate 24h after, calculate dull and stereotyped in the bacterium colony number, multiply by extension rate, multiply by 2 again, promptly get the total plate count among every ml, use N
AlwaysExpression.
(3) get microbicide solution that 4ml prepared in test tube, add the 1ml original bacteria liquid, mix, act on to the stipulated time (1h), take out an amount of bacterium soup, do suitably dilution, get 0.5ml in aseptic plate,, add culture medium by the method in above-mentioned (2), cultivate the back counting, bacterium colony number in dull and stereotyped multiply by extension rate, multiply by 10 again, promptly get the clump count of surviving in every ml bacterium soup, use N
LiveExpression.Be calculated as follows killing rate:
Killing rate (%)=[(N
Always-N
Live)/N
Always] * 100
Gemini quaternary ammonium salt surfactant GP5, GP6, GP7, GP8 and the common quaternary surfactant P2, P3, the P16 that contain pyridine ring see Table 1 to the bactericidal effect contrast of bacteriums such as hay bacillus.
The structure of P2, P3, P16 is respectively:
The different bactericide of table 1 are to the killing rate of each bacterioid
Bactericide hay bacillus escherichia coli and staphylococcus aureus Candida albicans
GP5????????89.4??????98.2???????????80.1???????????99.99
GP6????????79.7??????95.3???????????80.7???????????96.1
GP7????????94.3??????93.1???????????79.5???????????99.9
GP8????????92.0??????95.0???????????77.5???????????99.8
P2?????????72.0??????93.8???????????76.5???????????97.6
P3?????????62.1??????94.8???????????75.1???????????90.5
P16????????86.2??????76.9???????????77.7???????????76.0
The gemini quaternary ammonium salt surfactant (GP5, GP7, GP8) that embodiment 5 will contain pyridine ring is mixed with the certain density aqueous solution with redistilled water, adopts the suspension ring method to measure the surface tension of aqueous surfactant solution, and its surface-active sees Table 2.
Table 2 contains the surface-active of pyridine ring gemini quaternary ammonium salt surfactant
| Surfactant | ??GP5 | ???GP6 | ???GP7 | ???GP8 |
| ????CMC(mmol/l | ??3.0 | ???2.9 | ???1.3 | ???0.99 |
| ????γ CMC(m?N/m) | ??38.5 | ???41 | ???41 | ???43.2 |
(1) test piece pre-treatment
Test piece is milled to light, cleans, dries up with cold wind with absolute ethyl alcohol, acetone successively with 400#, 500#, 800# abrasive paper for metallograph successively.Survey its size with slide measure, it is standby to put into drying box, claims initial weight before the experiment on assay balance.
(2) test piece experiment
100ml (corrosion inhibiter of hydrochloric acid solution+variable concentrations of 0.1% NaCl+10%) solution is packed in the 100ml single port flask, the steel disc of handling well is immersed and be suspended from the water.Flask constant temperature 90 degree, and constant temperature 5 hours.
(3) test piece post processing
Press from both sides a small amount of absorbent cotton wiping test piece surface product with tweezers,, dry, put into absolute ethyl alcohol and steep 5min with hospital gauze with the clear water flushing, slough moisture content, in acetone, steep 5-10min, cleaning by degreasing again, clean once with ethanol, with clean silk wiping, cold wind dries up again.Drying, assay balance is weighed.
Calculate inhibition speed and inhibition efficiency by following fruit
V＝(m
0-m
1)/(A×t)
η(％)＝(V
0-V)/V×100
In the formula: m
0---metal testing plate initial mass, g;
m
1---remove the metal testing plate quality of corrosion product, g;
A---metal testing plate area, m
2
V
0---do not contain the corrosion rate in the corrosive medium of corrosion inhibiter, (g/m
2.h)
V---the inhibition speed in the corrosive medium of interpolation corrosion inhibiter, (g/m
2.h)
η (%)---inhibition efficiency
Referring to Fig. 1, the consumption of gemini quaternary ammonium salt surfactant GP5, GP6 that contains pyridine ring is when 20ppm, and inhibition efficiency reaches more than 70%.
The gemini quaternary ammonium salt surfactant structure that embodiment 7 contains pyridine ring characterizes
Referring to Fig. 2, as can be seen from the figure, at 3435cm
-1, 2029cm
-1, 1639cm
-1The place is the characteristic absorption peak of water, and this is owing to the quaternary ammonium salt moisture absorption causes.At 3055cm
-1, 1489cm
-1, 1175cm
-1, 774cm
-1, 682cm
-1The place is the characteristic absorption peak of pyridine.
Referring to Fig. 3, following absworption peak is arranged as can be seen from the figure:
Absworption peak δ (ppm) peak area number of hydrogen atoms ratio
1?????????9.95???????1.000?????1
2?????????8.25???????1.006?????1
3?????????7.73-7.80??2.025?????2
4?????????4.97???????2.002?????2
5?????????3.38???????2.005?????2
6?????????2.47???????2.011?????2
7?????????1.76???????2.020?????2
8?????????1.48???????2.143?????2
9?????????1.21???????12.371???12
10????????0.83???????3.113?????3
1,2,3 group of absworption peak that the peak is a hydrogen on the pyridine ring in more than showing, remaining peak is CH
2Or CH
3Absworption peak.
Claims (5)
1 contains the gemini quaternary ammonium salt surfactant of pyridine ring, it is characterized in that this surfactant has following structure:
n＝8，10，12，14，16，18????m＝2，4，6，8，10
2 contain the preparation method of the gemini quaternary ammonium salt surfactant of pyridine ring, may further comprise the steps successively:
(1) the control temperature adds bromoalkane and lithium metal in absolute ether near freezing point, and its mol ratio is a bromoalkane: lithium metal=1: 5～1: 1, reacted 0.5～2 hour;
(2) insulation and adding excess pyridine and toluene solution, question response was warming up to about 110 ℃ after 0.5～3 hour, refluxed 2～5 hours, had promptly synthesized the alpha-alkyl pyridine;
(3) in alcohols solvent with alkyl pyridine and dibromo alkyl halide in molar ratio 1～4: 1 ratio mix back flow reaction 15～72 hours;
(4) with the product recrystallization, drying promptly obtains the gemini quaternary ammonium salt surfactant that the present invention contains pyridine ring.
3 methods as claimed in claim 2 is characterized in that, alcohols solvent is ethanol or propyl alcohol described in the step (3).
4 methods as claimed in claim 2 is characterized in that, the ratio of alkyl pyridine and dibromo alkyl halide is 2～3: 1 in the step (3).
5 methods as claimed in claim 2 is characterized in that, the recrystallization in the step (4) comprises earlier with product anhydrous propanone frozen recrystallization, again with acetone and absolute ethyl alcohol recrystallization.
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| CN100363096C (en) * | 2005-12-02 | 2008-01-23 | 西南石油学院 | Novel gemini surfactants and its synthesis method |
| CN100364650C (en) * | 2005-12-29 | 2008-01-30 | 华东理工大学 | Cation fluoride Gemini surface activator |
| CN100376316C (en) * | 2005-11-22 | 2008-03-26 | 华东理工大学 | Gemini surface active agent |
| CN101205212B (en) * | 2007-10-22 | 2010-04-07 | 西华师范大学 | Gemini nicotinate quaternary ammonium salt and method for making same |
| CN101695642B (en) * | 2009-11-09 | 2011-09-21 | 蚌埠丰原医药科技发展有限公司 | Cationic surfactant and preparation method thereof |
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| CN100363096C (en) * | 2005-12-02 | 2008-01-23 | 西南石油学院 | Novel gemini surfactants and its synthesis method |
| CN100364650C (en) * | 2005-12-29 | 2008-01-30 | 华东理工大学 | Cation fluoride Gemini surface activator |
| CN101205212B (en) * | 2007-10-22 | 2010-04-07 | 西华师范大学 | Gemini nicotinate quaternary ammonium salt and method for making same |
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| CN101695641B (en) * | 2009-11-09 | 2012-09-26 | 蚌埠丰原医药科技发展有限公司 | Cationic surfactant and preparation method thereof |
| CN103289671B (en) * | 2013-05-28 | 2016-10-05 | 四川安东油气工程技术服务有限公司 | Corrosion inhibiter and preparation method thereof |
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| CN103599729A (en) * | 2013-11-13 | 2014-02-26 | 中国林业科学研究院林产化学工业研究所 | Rosinyl quaternary ammonium salt dimeric surfactant as well as preparation method and application thereof |
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