CN102049213B - Propargyl alcohol type quaternary ammonium salt surfactant and preparation method thereof - Google Patents
Propargyl alcohol type quaternary ammonium salt surfactant and preparation method thereof Download PDFInfo
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- CN102049213B CN102049213B CN201010541986.5A CN201010541986A CN102049213B CN 102049213 B CN102049213 B CN 102049213B CN 201010541986 A CN201010541986 A CN 201010541986A CN 102049213 B CN102049213 B CN 102049213B
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Abstract
The invention relates to a propargyl alcohol type quaternary ammonium salt surfactant and a preparation method thereof, and the structural formula of quaternary ammonium salt is as follows: n is equal to 8, 10, 12, 14 or 16, and X is Cl or Br; and a substituent is positioned in the ortho-position, interposition or para-position. The preparation method is as follows: (1) adding 3-5g of NaH into a reactor, introducing nitrogen, adding 60-90ml of THF (tetrahydrofuran), stirring at room temperature, dropping 4-6g of propiolic alcohol, further slowly dropping 10-15g of chloromethylpyridine, stirring for 15-30h, separating water phase from organic phase, washing, drying, performing column chromatography, and then getting pyridyl-2-butynol; and (2) adding the pyridyl-2-butynol and alkyl halide into the reactor according to the molar ratio of 1: 1.5-1: 4, further adding 10ml-15ml of acetonitrile, refluxing and stirring for 20-30h at the temperature of 50-80 DEG C, washing, performing the column chromatography, and then getting the alkynol type quaternary ammonium salt surfactant. The series of the propargyl alcohol type quaternary ammonium salt surfactants have very high surface activity and very strong corrosion inhibition performance, the preparation method is simple and feasible, the operation is easy, the yield is higher, and the environmental pollution can be avoided.
Description
Technical field
The present invention relates to propargyl alcohol type quaternary ammonium salt surfactant, the invention still further relates to the preparation method of such surfactant.
Background technology
The harm of metal erosion is very huge, according to document announcement, in the annual metal aggregate tonnage of producing in the whole world, approximately there are the goods of 10%-20% to scrap fully because of corrosion, therefore about 30% hardware damages, and the loss that the corrosion of metal plant equipment causes is considerably beyond the price of metal itself.Material has not only been wasted in metal erosion, also tends to bring the accidents such as stopping production, personal safety and environmental pollution.According to relevant expert's introduction, the whole world each minute half just has 1 ton of steel corrosion to become iron rust, at present the corrosion loss that brings due to metal material and surrounding environment generation chemistry or electrochemical reaction of China is annual about 5,000 hundred million yuans, accounts for 6% left and right of China's gross national product.Approximately 10,000,000,000 yuan of the losses that is caused by corrosion in China's oil and natural gas every year, the annual corrosion loss of coal industry is about 55.6 hundred million yuan, nearly 1,700,000,000 yuan of the corrosion loss in power system every year.The corrosion inhibiter technology is due to simple to operate, and instant effect can be protected the advantages such as whole system and be widely used in various production processes, and therefore, rationally using corrosion inhibiter is the effective ways that prevent metal and alloy corrosion in surrounding medium.
The appearance of corrosion inhibiter starts from the application of pickling of metal and restrainer, and is initial, due to the development of metallurgical industry, for the scale removal of ferrous materials acid pickling and rust removing and equipment, developed restrainer.Subsequently, because of the needs of petroleum industry oil well acidation technology, acidifying corrosion inhibitor for oil well and oil gas field corrosion inhibiter have been researched and developed.Since the nineties in last century, the development of organic inhibitor and use the extremely concern of Chinese scholars.
The kinds of surfactants that can be used as metal inhibitor is a lot, but application study is maximum is cationic surfactant, non-ionic surface active agent and contains multi-functional surfactant, quaternary ammonium salt cationic surfactant particularly, owing to having the inhibition bactericidal action concurrently, use very extensive in oil field recharged waste water aspect the inhibition of iron and steel.In addition for the surfactant that a plurality of functional groups are arranged in molecule; thereby because can forming insoluble chelate film with the metal surface, a plurality of functional groups have high corrosion inhibiting ability; and multi-functional surfactant usually can have two kinds or over-all properties in inhibition, scale inhibition, three kinds of performances of sterilization concurrently; the formula of water treatment agent is simplified, so become focus synthetic and application study.
The inorganic inhibitor that once used in early stage oil field has: (1) chromate: high temperature resistance, but have carcinogenicity, its oxide precipitation easily to stop up the gap, lower oil yield; (2) oxidation ammonia: its nitrogen-atoms is adsorbed on iron surface, forms coverlay, prevents the corrosion of acid-soluble oil Pump for well; (3) Quadrafos: prevent the formation of dirt, can suppress the spot corrosion of dirt layer bottom, with organic sequestering agent and the use such as ETDA, can improve corrosion mitigating effect; (4) arsenic compound: be a kind of inorganic inhibitor in the past the most frequently used in oil well, often in NaOH and use, then add boric acid can improve corrosion mitigating effect, its disadvantage is that toxicity is high.Present multiplex organic inhibitor is as (1) formaldehyde; (2) chain organic amine and derivative thereof; (3) imidazoline and its derivative; (4) quaternary ammonium salt; (5) rosin amine derivative; (6) sulfonate, imines acetogenin and alkynol class etc.; These organic compounds are especially effective oil well corrosion inhibiter by the ethylene oxide compound of the synthetic rosin amine of rosin acid.
Find in research and application practice, the inorganic inhibitor that contains arsenic and chromium is more high temperature resistant, but toxicity is very large, and is large to the harmfulness of environment; Corrosion mitigating effect is good at normal temperatures for organic inhibitor commonly used, but this class corrosion inhibiter mostly is adsorption corrosion inhibitor, often take physical absorption as main, very responsive to corrosive medium and temperature, very easily come off from metal material surface when high temperature, decompose, thereby lose its corrosion inhibitive function, therefore general organic inhibitor just is difficult to bring into play its corrosion inhibition in the environment more than 60 ℃.At present domestic also do not have a kind of corrosion inhibiter or inhibition system can effectively suppress the steel surface corrosion in high temperature and high acidity situation.
Enter 21st century, very fast for research and development and the application development of corrosion inhibiter both at home and abroad, with the enhancing of human environment protection consciousness, sustainable development has become the common recognition of various countries.Realize the harmonious development of man and nature, necessary energy savings reduces the wasting of resources that causes because of corrosion.The corrosion inhibiter the reach of science provides favourable necessary condition and guarantee for sustainable development.In the last few years, with the reinforcement of environmental protection and awareness of safety, some poisonous and hazardous corrosion inhibiter will be limited and forbid making, as chromate, arsenate, stannate, mercury salt etc.Organic phosphate, poly-polyphosphate, microcosmic salt are class corrosion-and scaling-inhibiting water treating agents preferably, but easily cause the eutrophication at water source due to phosphorus-containing compound, the red tide of some marine site occurrence of large-area of China coast harm in recent years and lake algal bloom and water quality deterioration are all because of due to phosphorus-containing compound.Thereby protection of the environment, research and develop out the nontoxic environmental friendliness corrosion inhibiter of public hazards, be the corrosion inhibiter research and development direction in future.Should strengthen manually synthesizing the research work of low toxicity or the nontoxic organic inhibitor of Mobyneb, the effect study that acts synergistically between exploitation organic inhibitor and inorganic inhibitor is developed the better composite corrosion inhibitor of performance.
Serial propargyl alcohol type quaternary ammonium salt surfactant provided by the invention has good surface-active; This series of surfactants has better corrosion inhibition, compares with the present widely used WD-11 in oil field (Manny alkene bases), and its inhibition efficiency is more than 5 times of WD-11, and the high temperature resistant property of this corrosion inhibiter is better.
Summary of the invention
The object of the present invention is to provide propargyl alcohol type quaternary ammonium salt surfactant and preparation method thereof, this series propargyl alcohol type quaternary ammonium salt surfactant has very high surface-active and very strong corrosion inhibition, and its preparation method is simple and feasible, easy operating, yield is higher, and non-environmental-pollution.
For reaching above technical purpose, the invention provides following technical scheme:
Propargyl alcohol type quaternary ammonium salt surfactant, its structural formula is as follows:
Substituting group position is (o-), a position (m-) or contraposition (p-) at the ortho position.
When n is 8, the substituting group of pyridine ring be adjacent,, contraposition, called after o-8 respectively, m-8, p-8.The rest may be inferred.
The preparation method of this propargyl alcohol type quaternary ammonium salt surfactant mainly comprises the following steps:
(1) add NaH3-5g in reactor, logical nitrogen 20-30 minute, add THF60-90ml, stirred 25-40 minute under room temperature, slowly drip propilolic alcohol 4-6g, dropwise rear stirring 1-3 hour, more slowly drip PMC 10-15g, continue to stir 15-30 hour, react complete after, water phase separated and organic phase through washing, dry, column chromatography, obtain pyridine radicals-2-butynol;
(2) add pyridine radicals-2-butynol and alkyl halide in reactor, its mol ratio is 1: 1.5-1: 4, the C atomicity of described alkyl halide is 8,10,12,14 or 16, add again acetonitrile 10ml-15ml in 50-80 ℃ of lower return stirring 20-30 hour, react complete after, through washing, column chromatography, obtain bromination-(4-hydroxyl-2-butynyl)-N-alkyl pyridine, i.e. alkynol class quaternary surfactant of the present invention.
In (1) step, described washing, drying, column chromatography use saturated NaCl solution washing to neutral exactly, use anhydrous Na
2SO
4Drying with benzinum and ethyl acetate (20: 1) column chromatography, obtains pyridine radicals-2-butynol.
In (2) step, described alkyl halide is bromoalkane, and described washing, column chromatography are used petroleum ether exactly, and (15-25: 1) column chromatography obtains bromination-(4-hydroxyl-2-butynyl)-N-eight alkyl pyridines to use carrene and methyl alcohol.
The present invention be with adjacent, or p-chloromethyl pyridine hydrochloride, propilolic alcohol, bromoalkane are that raw material has synthesized serial alkynol class quaternary ammonium salt, the neighbour, or p-chloromethyl pyridine hydrochloride at NaHCO
3And CH
2Cl
2Exist lower generate adjacent, or p-PMC, its course of reaction is as follows:
Compared with prior art, beneficial effect of the present invention is: 1) propargyl is introduced in molecule, and the corrosion inhibition of this corrosion inhibiter is better, and the performance of high temperature resistance and high acidity is stronger.General corrosion inhibiter is after temperature is higher than 60 ℃, and its inhibition efficiency increases along with temperature and sharply descends.Corrosion inhibiter provided by the invention in 15% HCl solution, at 2-12 hour, to the inhibition speed of X70 steel more than 97%.2) due to the existence of unsaturated bond, this corrosion inhibiter has polymerizability.
Description of drawings
Fig. 1 is the infared spectrum of P16
Fig. 2 is P16
1The HNMR collection of illustrative plates
Fig. 3 is P16
13CNM R collection of illustrative plates
Fig. 4-6 are respectively that the surface tension of propargyl alcohol type quaternary ammonium salt surfactant is with concentration curve
Fig. 7-9 are respectively that the corrosion inhibition rate of propargyl alcohol type quaternary ammonium salt surfactant is with concentration curve
The scanning electron microscope (SEM) photograph (without corrosion inhibiter) of Figure 10 to be the X70 steel disc soak 3 hours in 60 ℃, 20%HCl after
The scanning electron microscope (SEM) photograph of Figure 11 to be the X70 steel disc soak 3 hours in 60 ℃, 20%HCl after (contains 9 * 10
-5The 0-16 surfactant of mol/L)
Figure 12 is that acid concentration and soak time are on the impact of the rate of corrosion of X70 steel disc in 0-16 solution
The specific embodiment
Further illustrate the present invention below in conjunction with accompanying drawing.
The preparation of embodiment 1 propargyl alcohol type quaternary ammonium salt surfactant
(1), the preparation of bromination-2-(4-hydroxyl-2-butynyl)-N-cetyl pyridinium (brief note o-16)
Add NaH (3.6g) in the 250ml three-neck flask, logical nitrogen adds the THF (70ml) of new distillation after 20 minutes, stirs 30 minutes under room temperature, adds the propilolic alcohol (5.6g) of new distillation, stirs 2 hours.Add O-PMC (12.75g), dropwise rear continuation and stirred 24 hours.Slowly add 60ml H
2O, water phase separated and organic phase with a small amount of extracted with diethyl ether water 3 times, merge organic phase.Be washed till neutrality, anhydrous Na with the saturated NaCl aqueous solution
2SO
4Dried overnight, evaporating solvent with benzinum and ethyl acetate (20: 1) column chromatography, obtains oily liquids.
Add 4-(2-pyridine radicals)-2-butynol (2.94g) in the 100ml round-bottomed flask, bromohexadecane and acetonitrile (10ml) were in 75 ℃ of lower return stirrings 30 hours, get viscous liquid after evaporating solvent, use petroleum ether, and then with getting target compound, yield 23% after carrene and methyl alcohol (20: 1) column chromatography.
(2), the preparation of bromination-3-(4-hydroxyl-2-butynyl)-N-cetyl pyridinium (brief note m-16)
Slowly drip m-PMC (12.75g) in the propine sodium alkoxide of (1) preparation, dropwise rear continuation and stirred 24 hours.The H that slowly adds 60ml after reaction finishes
2O, then water phase separated and organic phase with a small amount of extracted with diethyl ether water 3 times, merge organic phase.Be washed till neutrality with the saturated NaCl aqueous solution, use anhydrous Na
2SO
4Dried overnight, evaporating solvent gets oily liquids with benzinum and ethyl acetate (20: 1) column chromatography.
Add 4-(3-pyridine radicals)-2-butynol (2.94g) in the 100ml round-bottomed flask, bromohexadecane and acetonitrile (10ml) were in 80 ℃ of lower return stirrings 20 hours, obtain viscous liquid, use petroleum ether, and then with obtaining target product, yield 46% after carrene and methyl alcohol (20: 1) column chromatography.
(3), the preparation of bromination-4-(4-hydroxyl-2-butynyl)-N-cetyl pyridinium ((brief note P-16))
Slowly drip p-PMC (12.94g) in the propine sodium alkoxide of (1) preparation, dropwise rear continuation and stirred 24 hours.The H that slowly adds 60ml after reaction finishes
2O removes unreacted NaH, then separately water and organic phase, water merges organic phase with after a small amount of extracted with diethyl ether 3 times, then is washed till neutrality with the saturated NaCl aqueous solution, with anhydrous Na 2SO4 dried overnight, get oily liquids with benzinum and ethyl acetate (20: 1) column chromatography.
Add 4-(4-pyridine radicals)-2-butynol (2.94g) in the 100ml round-bottomed flask, bromohexadecane and acetonitrile (10ml-15ml) were in 70 ℃ of lower return stirrings 24 hours, obtain viscous liquid, use petroleum ether, obtain target compound, yield 34% after using again carrene and methyl alcohol (25: 1) column chromatography.
Use said method, synthesized respectively 0-8, m-8, p-8,0-10, m-10, p-10,0-12, m-12, p-12,0-14, m-14, p-14.
The structural characterization of embodiment 2 propargyl alcohol type quaternary ammonium salt surfactants
Fig. 1 is the infrared spectrum of P16, and Fig. 1 is analyzed, and obtains the result of table 1.
The infrared spectrum of table 1P-16 is resolved
| cm -1. | Ownership | cm -1. | Ownership | cm -1. | Ownership |
| 3433， | H 2O | 3043 | OH | 2917，2850 | CH
3， |
| 2101， | C≡C | 1639 | C＝N | 1570，1513 | Pyridine ring |
| 1464，1384 | CH 3，CH 2 | 1345 | |
1113，914， | Pyridine ring |
Fig. 2 is P16
1The HNMR collection of illustrative plates is analyzed Fig. 2, obtains the result of table 2.
The hydrogen spectrum of table 2P-16 is resolved
Fig. 3 is P16
13CNM R collection of illustrative plates is analyzed Fig. 3, obtains the result of table 3.
The carbon spectrum of table 3P-16 is resolved
Can find out from the analysis of table 1, table 2, table 3, synthetic target product is propargyl alcohol type quaternary ammonium salt surfactant really, i.e. bromination-(4-hydroxyl-2-butynyl)-N-alkyl pyridine.
The surface tension test of embodiment 3 propargyl alcohol type quaternary ammonium salt surfactants
The surfactant of measuring is mixed with certain density Series of Water solution with redistilled water, under 20 ℃, adopts the suspension ring method to measure the surface tension of aqueous surfactant solution.Measurement result is as shown in Fig. 4, Fig. 5, Fig. 6 and table 4.
Can find out that by Fig. 4-6 and table 4 this series compound all has the ability of good reduction water surface tension, along with alkyl chain increases, solution surface tension reduces, it is 12 o'clock at the side chain carbon number, surface tension drops to minimum, and alkyl chain further increases subsequently, and surface tension rises again.As: the surface tension of p-12 is 29.4mN/m, compares with the surface tension of pure water, has reduced 43mN/m, illustrates that the ability of p-12 reduction water surface tension is the strongest; Along with alkyl chain increases, its critical micelle concentration reduces, and the cmc value of o-16 and m-16 is respectively 0.13mmol/L and 0.14mmol/L.
Cmc, γ cmc and the C of table 4 alkynol class quaternary ammonium salt monomer
20
The inhibition efficiency of embodiment 4 propargyl alcohol type quaternary ammonium salt surfactants
Experimental technique is as follows:
1) lacing film pre-treatment:
A3 steel disc sample abrasive paper for metallograph 200#, 600#, 800# polish step by step and are mirror-smooth to each surface and corner angle, then use distilled water flushing, and acetone and absolute ethyl alcohol oil removing are at last with well drying for standby in drier at room temperature of filter paper packet.
2) coupon test
The hydrochloric acid solution of 100mL 20% is placed in 100mL ground conical flask, and adds respectively the quaternary ammonium salt of variable concentrations in bottle, then measure the size of A3 cuboid carbon steel coupon with slide measure, calculate its area.Electronic balance weighs up its weight.With the cord of carrying out mark, the A3 steel disc is hung in 100mL ground conical flask, carbon steel coupon hangs on the middle part of solution, does simultaneously blank assay (not being added with blank 20% hydrochloric acid solution of corrosion inhibiter).The ground conical flask is placed in water bath with thermostatic control, soaks 3h under uniform temperature.
3) lacing film post processing
Takes out carbon steel coupon after experiment finishes from solution, distilled water flushing is then with the soaked in absolute ethyl alcohol cleaning of dewatering in 5 minutes.Carbon steel coupon after dehydration is put into the acetone oil removing, then dry up with cold wind, dry and weigh under room temperature.Weight loss before and after being soaked in solution by A3 cuboid carbon steel coupon calculates its corrosion rate V (g/cm in hydrochloric acid
2H) and inhibition efficiency IE%.
4) calculating of corrosion rate
According to the weightlessness of test piece, can calculate the inhibition efficiency of absolute corrosion rate and quaternary ammonium salt:
V＝(W
0-W)/St
In formula: W
0, the weight (g) before and after W-test piece experiment;
Surface area (the m of S-test piece
2);
T-inhibition experimental period (h);
V-corrosion rate (g/m
2h)
The calculating of corrosion inhibition rate:
In formula: V
0-do not add the absolute corrosion rate (g/m of the A3 carbon steel of propargyl alcohol class quaternary ammonium salt
2H);
V-is added with the absolute corrosion rate (g/m of the A3 carbon steel of propargyl alcohol class quaternary ammonium salt
2H);
The inhibition efficiency of IE%-quaternary ammonium salt
IE％＝(V
0-V)/V
0×100％
According to above-mentioned experimental technique, estimated the propargyl alcohol class quaternary ammonium salt that synthesized in 20%HCl, under 60 ℃ of experiment conditions to X
70The corrosion inhibition of carbon steel the results are shown in Figure 7, Fig. 8, Fig. 9.
By in Fig. 7-9 as can be known: this series quaternary ammonium salt all has good corrosion inhibition to the X70 carbon steel in 60 ℃, 20% hydrochloric acid, inhibition efficiency is along with density of corrosion inhibitor increases and increases, along with alkyl chain in molecule increases and increases; But the position of alkyl chain on pyridine ring is influential, and be general, ortho position＞position～contraposition.For ten O-series more than carbon atom of alkyl chain, surpass 3 * 10 in its concentration
-5During mol/L, corrosion inhibition rate reaches more than 90%, reaches as high as 99%.
Figure 10, Figure 11 scanning electron microscope (SEM) photograph to be the X70 steel disc soak 3 hours in 60 ℃, 20%HCl after, Figure 10 is without corrosion inhibiter, and the X70 steel disc is subject to the heavy corrosion of HCl, and the corrosion product that the steel surface coverage is a large amount of has many holes.Figure 11 contains 9 * 10
-5The O-16 surfactant of mol/L, the surperficial smoother of X70 steel is smooth, and extent of corrosion descends greatly.
The high temperature resistant property of embodiment 5 propargyl alcohol type quaternary ammonium salt surfactants
In order to investigate the high temperature resistant property of propargyl alcohol type quaternary ammonium salt surfactant, contrast test O-16 in 60 and 90 ℃, 3 hours, 20%HCl solution to the corrosion mitigating effect of X70 steel disc, result is listed table 5 in.Find from table 5 kind of Data Comparison, when surfactant concentration was low, temperature was very large on its corrosion inhibition impact, and along with dosage of surfactant increases, impact reduces temperature on corrosion inhibition rate.Surpass 7 * 10 in concentration
-5After mol/L, under 60 and 90 ℃, (98.83,60 ℃ of slight difference of corrosion inhibition rate; 97.19,90 ℃), illustrate that this surfactant has high temperature resistant property preferably.
The corrosion inhibition rate (20%HCl, 3h) of table 5O-16 under different temperatures
The impact on propargyl alcohol class quaternary ammonium salt corrosion inhibition of embodiment 6 acidity and soak time
Investigate acidity and soak time to the impact of propargyl alcohol class quaternary ammonium salt corrosion inhibition, take O-16 as example, result as shown in figure 12.
As can be seen from Fig. 12, be 7 * 10 in O-16 concentration
-5Mol/L, 90 ℃ the time, along with acidity strengthens, the corrosion rate of X70 steel increases; Lower than 15%, along with soak time increases, from 2-12 hour, corrosion rate changed slowly, illustrates that this surfactant has stronger corrosion inhibition when concentration of hydrochloric acid.When HCl concentration large 20%, corrosion rate is along with soak time increases sharply.
Claims (3)
1. propargyl alcohol type quaternary ammonium salt surfactant has following structural formula:
2. propargyl alcohol type quaternary ammonium salt surfactant as claimed in claim 1, is characterized in that, X is Br.
3. the preparation method of propargyl alcohol type quaternary ammonium salt surfactant as claimed in claim 1 comprises the following steps:
(1) add NaH3-5g in reactor, logical nitrogen 20-30 minute, add THF60-90mL, stir under room temperature, drip propilolic alcohol 4-6g, stirred 1-3 hour, drip again PMC 10-15g, continue to stir 15-30 hour water phase separated and organic phase, through washing, dry, column chromatography, obtain pyridine radicals-2-butynol;
(2) add pyridine radicals-2-butynol and bromoalkane in reactor, its mol ratio is 1:1.5-1:4, the C atomicity of described bromoalkane is 8,10,12,14 or 16, add again acetonitrile 10mL-15mL in 50-80 ℃ of lower return stirring 20-30 hour, through washing, column chromatography, obtain bromination-(4-hydroxyl-2-butynyl)-N-alkyl pyridine, i.e. propargyl alcohol type quaternary ammonium salt surfactant.
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| CN104005035B (en) * | 2014-05-08 | 2016-04-20 | 西华师范大学 | Polymerization inhibiter and preparation method thereof |
| GB2532990A (en) * | 2014-12-05 | 2016-06-08 | Schlumberger Holdings | Corrosion inhibition |
| GB2543498A (en) | 2015-10-19 | 2017-04-26 | Schlumberger Holdings | Corrosion inhibition |
| CN114276521A (en) * | 2022-03-04 | 2022-04-05 | 西陇科学股份有限公司 | Preparation method of high-purity epoxy resin applied to flip chip packaging |
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