CN105561864A - Imidazoline amphoteric surfactant and preparation method thereof - Google Patents
Imidazoline amphoteric surfactant and preparation method thereof Download PDFInfo
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
- C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D233/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Abstract
The invention provides an imidazoline amphoteric surfactant and a preparation method thereof. The method comprises the steps: stirring and mixing cinnamic acid and diethylenetriamine in the presence of a water carrying agent and a catalyst, and carrying out amidation reaction and cyclization reaction dehydrating, so as to obtain an imidazoline intermediate; introducing a thiourea group into the imidazoline intermediate, and carrying out quaternization by using sodium chloroacetate, thereby obtaining the imidazoline amphoteric surfactant. According to the imidazoline amphoteric surfactant and the preparation method thereof, by taking sodium chloroacetate as a quaternization reagent, the reaction is easy to carry out, the product quality is good, and the water solubility of the product is improved. The imidazoline amphoteric surfactant provided by the invention is easy to synthesize and has good stability, and the raw materials are cheap and readily available.
Description
Technical field
The present invention relates to a kind of quaternary ammonium salt corrosion inhibiter, be specifically related to a kind of imidazoline amophoteric surface active agent and preparation method.
Background technology
At water treatment corrosion inhibitors field purposes imidazolidine derivatives mainly carboxylic acid type and sulfuric acid ester type etc. more widely, be mainly used as corrosion inhibitor for oil field, bactericide, restrainer; And imidazoline quaternary ammonium salt synthesis technique is simple, product good water solubility, there is higher surface-active.At present, a lot of to the synthesis report of imidazolidine derivatives both at home and abroad, most employing has the organic acid of chain alkyl as reactive agent, and this organic acid is owing to having long chain hydrophobic group, water-soluble generally poor, and time quaternized to it, many employings chlorination Bian or dimethyl suflfate are as quaternizing agent, and these two kinds of reagent toxicities are extremely strong, volatile, large to harm, unfriendly to environment.Therefore, select the quaternizing agent synthesizing new water-soluble imidazoline quaternary ammonium salt of low toxicity can produce certain environmental benefit, there is broad mass market prospect.
Bai Li, Feng Lajun, Lu Yongbin (corrosion and protection, 2014,35 (8): 812-818) with diethylenetriamine and oleic acid for raw material, the method adopting solvent method and vacuum method to work in coordination with use has synthesized a kind of imidazoline inhibitor, this kind of product water-soluble poor.By (corrosion and protections such as celebrating, Wang Yefei, 2006,27 (3): 122-125) with palmitic acid, diethylenetriamine, maleic anhydride a kind of Imidazoline corrosion inhibitor that has been Material synthesis, and palmitic acid is a kind of higher fatty acids with Long carbon chain.Fan Guodong, Ge Jun, bavin tinkling of pieces of jades, Li Xuekun, An Jiaolong, Cheng Xitao (Speciality Petrochemicals, 2011,28 (1): 73-76; Application chemical industry, 2013,42 (11): 2005-2008) with oleic acid, diethylenetriamine for raw material, benzyl chloride, epoxychloropropane are quaternizing agent, synthesize Novel Imidaoline Inhibition, these two kinds of quaternizing agents have certain toxicity to people, also endanger to some extent environment simultaneously.
In sum, above expert has carried out research in various degree to corrosion inhibiter, many employings Long carbon chain organic acid is as reactant, time quaternized, many employings chlorination Bian or dimethyl suflfate are as quaternizing agent, and these two kinds of reagent toxicities are strong, volatile, endanger greatly to producers, unfriendly to environment, therefore, above-mentioned research does not solve environmental friendliness and hypotoxic problem.
Summary of the invention
For overcoming the problems of the prior art, the object of this invention is to provide a kind of imidazoline amophoteric surface active agent and preparation method, the amphoteric surfactant that the method obtains has environmental friendliness, and the advantage that cost is low.
For achieving the above object, the present invention adopts following technical scheme:
A kind of imidazoline amophoteric surface active agent, the structural formula of this surfactant is as follows:
A preparation method for imidazoline amophoteric surface active agent, comprises the following steps:
1) cinnamic acid, diethylenetriamine, azeotropic agent and catalyst are added water knockout drum and N are housed
2in the reactor of protective device, after dehydration, obtain imidazoline intermediate;
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:(1.1 ~ 1.3), azeotropic agent addition is 20% ~ 30% of cinnamic acid and diethylenetriamine gross mass; Catalyst charge is 0.1% ~ 0.3% of cinnamic acid quality;
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 140 ~ 160 DEG C, react 2 ~ 4h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the mol ratio of imidazoline intermediate and thiosemicarbazide is 1:(1 ~ 2);
3) under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 80 ~ 100 DEG C of reaction 2 ~ 4h, obtain imidazoline amophoteric surface active agent;
Wherein, in thioureido-imidazoline and sodium chloroacetate solution, the mol ratio of sodium chloroacetate is 1:(2 ~ 3).
Described step 1) in azeotropic agent be dimethylbenzene or toluene.
Described step 1) in catalyst be Al
2o
3or magnesium chips.
Described step 1) in the detailed process of dehydration be: prior to 150 DEG C ~ 160 DEG C of dehydration 4 ~ 5h, be then warmed up to 210 DEG C ~ 220 DEG C, dehydration 4 ~ 6h.
Described step 2) in the addition of n-octyl alcohol be imidazoline intermediate, thiosemicarbazide gross mass 50% ~ 70%.
Described step 3) in sodium chloroacetate solution obtain by the following method: be that monoxone, the NaOH of 1:1 is added to the water by mol ratio, obtain sodium chloroacetate solution.
The mass concentration of gained sodium chloroacetate solution is 16%.
Compared with prior art, beneficial effect of the present invention is: this compound with cinnamic acid, diethylenetriamine for raw material, by amidation process and cyclization dehydration synthesis imidazoline intermediate, then the thioureido-imidazoline intermediate of synthesis is obtained a kind of imidazoline amophoteric surface active agent through quaternized.This imidazoline amophoteric surface active agent can allow corrosion inhibiter have good adsorption capacity in metal surface, because of the atom N on phenyl ring and imidazoline ring, all there is higher cloud density, can combine with the empty d track of metal and form firmly coordinate bond, and hydrophobic grouping is defining one deck hydrophobic membrane away from metal surface, peripheral shield effect is being played to electrode surface.After imidazoline is quaternized, atom N is positively charged in conjunction with a proton or a group, forms quaternary ammonium salt in conjunction with an anion simultaneously.Due to electrostatic attraction, quaternary ammonium cation is just attracted to metal surface, and metal surface is become positively charged lotus, prevents hydrogen ion in acid solution further close to metal surface, thus slow down corrosion of metal.And this product has lower cost and more favourable to environment, thus this corrosion inhibiter is made to have superior corrosion inhibition.Cinnamic acid imidazoline provided by the invention is a kind of amphoteric surfactant, and the thiourea group containing corrosion-resisting function in product, greatly can improve the corrosion mitigating effect of product, be worth promoting in course of industrialization; In addition, reaction raw materials cinnamic acid belongs to green material, containing benzene radicals in molecule, stronger in the suction-operated of metal surface, corrosion inhibition connects branched chain type group higher than it, and this is owing to phenyl ring having large π key, can with the C=N key generation conjugation on imidazoline ring, stability increases greatly, thus promotes corrosion inhibition.The present invention by dripping sodium chloroacetate solution in thioureido-imidazoline, and obtained imidazoline amophoteric surface active agent, because sodium chloroacetate toxicity is less, overcomes in prior art and endanger greatly to producers, to the disagreeableness problem of environment.
Further, the present invention selects that toxicity is low, the sodium chloroacetate that is cheaply easy to get as quaternizing agent, synthesized water-soluble imidazoline quaternary ammonium salt corrosion inhibiter.This corrosion inhibiter has hydrophilic radical, better water-soluble, and corrosion inhibition rate is high, production process environmental friendliness, reaches and reduces corrosion inhibiter cost, improves processing safety object.
Accompanying drawing explanation
Fig. 1 is synthetic route chart of the present invention.
Fig. 2 is infrared spectrogram of the present invention.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further details, but is not limited to practical range of the present invention.
The structural formula of imidazoline amophoteric surface active agent of the present invention is as follows:
See Fig. 1, the preparation of above-mentioned imidazoline amophoteric surface active agent, comprises the following steps:
1) cinnamic acid, diethylenetriamine, azeotropic agent, catalyst are added reflux condensing tube, agitator, thermometer, water knockout drum and N are housed
2in the reactor of protective device, in 150 DEG C ~ 160 DEG C dehydration 4 ~ 5h, in course of reaction, can see that water is taken out of by solvent successively; reaction 4 ~ 5h water yield is basicly stable; then be warming up to 210 DEG C ~ 230 DEG C, dehydration 4 ~ 6h, obtains imidazoline intermediate after decompression distillation.
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:(1.1 ~ 1.3), azeotropic agent addition is 20% ~ 30% of cinnamic acid and diethylenetriamine gross mass, and azeotropic agent is dimethylbenzene or toluene; The addition of catalyst is 0.1% ~ 0.3% of cinnamic acid quality, and catalyst is Al
2o
3or magnesium chips.
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 140 ~ 160 DEG C, react 2 ~ 4h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the mol ratio of imidazoline intermediate and thiosemicarbazide is 1:(1 ~ 2); N-octyl alcohol addition be imidazoline intermediate, thiosemicarbazide gross mass 50% ~ 70%.
3) be the monoxone of 1:1 by mol ratio, NaOH is added to the water, and obtains the sodium chloroacetate solution that mass concentration is 16%.Under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 80 ~ 100 DEG C of reaction 2 ~ 4h, obtain imidazoline amophoteric surface active agent;
Wherein, in thioureido-imidazoline and sodium chloroacetate solution, the mol ratio of sodium chloroacetate is 1:(2 ~ 3).
Further illustrate embodiment of the present invention below by specific embodiment.
Embodiment 1
The preparation method of imidazoline amophoteric surface active agent, comprises the following steps:
1) by cinnamic acid, diethylenetriamine, dimethylbenzene, Al
2o
3add and reflux condensing tube, agitator, thermometer, water knockout drum and N are housed
2in the four-hole boiling flask of protective device, in 150 DEG C of dehydration 4h, can see that water is taken out of by solvent successively in course of reaction, reaction 4h water yield is basicly stable, is then warmed up to 210 DEG C, dehydration 4h, after decompression distillation, obtains imidazoline intermediate.
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:1.1, and dimethylbenzene addition is 20% of cinnamic acid and diethylenetriamine gross mass; Al
2o
3addition be 0.1% of cinnamic acid quality.
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 140 DEG C, react 2h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the imidazoline intermediate after purifying and the mol ratio of thiosemicarbazide are 1:1; N-octyl alcohol addition be imidazoline intermediate, thiosemicarbazide gross mass 50%.
3) be the monoxone of 1:1 by mol ratio, NaOH is added to the water, and obtains the sodium chloroacetate solution that mass concentration is 16%.Under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 80 DEG C of reaction 2h, obtain imidazoline amophoteric surface active agent;
Wherein, the mol ratio of the sodium chloroacetate in thioureido-imidazoline and sodium chloroacetate solution is 1:2.
Embodiment 2
The preparation method of imidazoline amophoteric surface active agent, comprises the following steps:
1) cinnamic acid, diethylenetriamine, dimethylbenzene, magnesium chips are added reflux condensing tube, agitator, thermometer, water knockout drum and N are housed
2in the four-hole boiling flask of protective device, in 150 DEG C of dehydration 4h, can see that water is taken out of by solvent successively in course of reaction, reaction 4h water yield is basicly stable, is then warmed up to 220 DEG C, dehydration 5h, obtains imidazoline intermediate after decompression distillation.
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:1.2, and dimethylbenzene addition is 25% of cinnamic acid and diethylenetriamine gross mass; The addition of magnesium chips is 0.2% of cinnamic acid quality.
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 150 DEG C, react 3h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the mol ratio of imidazoline intermediate and thiosemicarbazide is 1:1.5; N-octyl alcohol addition be imidazoline intermediate, thiosemicarbazide gross mass 60%.
3) be the monoxone of 1:1 by mol ratio, NaOH is added to the water, and obtains the sodium chloroacetate solution that mass concentration is 16%.Under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 90 DEG C of reaction 3h, obtain imidazoline amophoteric surface active agent;
Wherein, the mol ratio of thioureido-imidazoline and sodium chloroacetate solution is 1:2.5.
Embodiment 3
The preparation method of imidazoline amophoteric surface active agent, comprises the following steps:
1) by cinnamic acid, diethylenetriamine, dimethylbenzene, Al
2o
3add and reflux condensing tube, agitator, thermometer, water knockout drum and N are housed
2in the four-hole boiling flask of protective device, in 160 DEG C of dehydration 4h, can see that water is taken out of by solvent successively in course of reaction, reaction 4h water yield is basicly stable, is then warmed up to 230 DEG C, dehydration 6h, obtains imidazoline intermediate after decompression distillation.
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:1.3, and dimethylbenzene addition is 30% of cinnamic acid and diethylenetriamine gross mass; Al
2o
3addition be 0.3% of cinnamic acid quality.
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 160 DEG C, react 4h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the mol ratio of imidazoline intermediate and thiosemicarbazide is 1:2; N-octyl alcohol addition be imidazoline intermediate, thiosemicarbazide gross mass 70%.
3) be the monoxone of 1:1 by mol ratio, NaOH is added to the water, and obtains the sodium chloroacetate solution that mass concentration is 16%.Under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 90 DEG C of reaction 3h, obtain imidazoline amophoteric surface active agent;
Wherein, the mol ratio of thioureido-imidazoline and sodium chloroacetate solution is 1:2.5.
Embodiment 4
The preparation method of imidazoline amophoteric surface active agent, comprises the following steps:
1) cinnamic acid, diethylenetriamine, dimethylbenzene, magnesium chips are added reflux condensing tube, agitator, thermometer, water knockout drum and N are housed
2in the four-hole boiling flask of protective device, in 160 DEG C of dehydration 4h, can see that water is taken out of by solvent successively in course of reaction, reaction 4h water yield is basicly stable, is then warmed up to 230 DEG C, dehydration 6h, obtains imidazoline intermediate after decompression distillation.
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:1.1, and dimethylbenzene addition is 30% of cinnamic acid and diethylenetriamine gross mass; The addition of magnesium chips is 0.3% of cinnamic acid quality.
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 140 DEG C, react 3h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the mol ratio of imidazoline intermediate and thiosemicarbazide is 1:1.5; N-octyl alcohol addition be imidazoline intermediate, thiosemicarbazide gross mass 60%.
3) be the monoxone of 1:1 by mol ratio, NaOH is added to the water, and obtains the sodium chloroacetate solution that mass concentration is 16%.Under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 90 DEG C of reaction 3h, obtain imidazoline amophoteric surface active agent;
Wherein, the mol ratio of thioureido-imidazoline and sodium chloroacetate solution is 1:2.
Embodiment 5
The preparation method of imidazoline amophoteric surface active agent, comprises the following steps:
1) cinnamic acid, diethylenetriamine, dimethylbenzene, magnesium chips are added reflux condensing tube, agitator, thermometer, water knockout drum and N are housed
2in the four-hole boiling flask of protective device, in 160 DEG C of dehydration 5h, can see that water is taken out of by solvent successively in course of reaction, reaction 5h water yield is basicly stable, is then warmed up to 220 DEG C, dehydration 5h, obtains imidazoline intermediate after decompression distillation.
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:1.2, and dimethylbenzene addition is 20% of cinnamic acid and diethylenetriamine gross mass; The addition of magnesium chips is 0.1% of cinnamic acid quality.
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 150 DEG C, react 3h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the mol ratio of imidazoline intermediate and thiosemicarbazide is 1:2; N-octyl alcohol addition be imidazoline intermediate, thiosemicarbazide gross mass 70%.
3) be the monoxone of 1:1 by mol ratio, NaOH is added to the water, and obtains the sodium chloroacetate solution that mass concentration is 16%.Under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 100 DEG C of reaction 2h, obtain imidazoline amophoteric surface active agent;
Wherein, the mol ratio of thioureido-imidazoline and sodium chloroacetate solution is 1:2.5.
Embodiment 6
The preparation method of imidazoline amophoteric surface active agent, comprises the following steps:
1) cinnamic acid, diethylenetriamine, toluene, magnesium chips are added reflux condensing tube, agitator, thermometer, water knockout drum and N are housed
2in the four-hole boiling flask of protective device, in 150 DEG C of dehydration 4h, can see that water is taken out of by solvent successively in course of reaction, reaction 4h water yield is basicly stable, and be then warmed up to 210 DEG C, dehydration 4h, decompression distillation obtains imidazoline intermediate.
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:1.3, and toluene addition is 20% of cinnamic acid and diethylenetriamine gross mass; The addition of magnesium chips is 0.1% of cinnamic acid quality.
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 150 DEG C, react 3h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the mol ratio of imidazoline intermediate and thiosemicarbazide is 1:2; N-octyl alcohol addition be imidazoline intermediate, thiosemicarbazide gross mass 70%.
3) be the monoxone of 1:1 by mol ratio, NaOH is added to the water, and obtains the sodium chloroacetate solution that mass concentration is 16%.Under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 100 DEG C of reaction 2h, obtain imidazoline amophoteric surface active agent;
Wherein, the mol ratio of thioureido-imidazoline and sodium chloroacetate solution is 1:2.5.
Embodiment 7
The preparation method of imidazoline amophoteric surface active agent, comprises the following steps:
1) cinnamic acid, diethylenetriamine, toluene, magnesium chips are added reflux condensing tube, agitator, thermometer, water knockout drum and N are housed
2in the four-hole boiling flask of protective device, in 150 DEG C of dehydration 4.5h, can see that water is taken out of by solvent successively in course of reaction, reaction 5h water yield is basicly stable, is then warmed up to 230 DEG C, dehydration 6h, obtains imidazoline intermediate after decompression distillation.
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:1.1, and toluene addition is 25% of cinnamic acid and diethylenetriamine gross mass; The addition of magnesium chips is 0.2% of cinnamic acid quality.
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 160 DEG C, react 4h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the mol ratio of imidazoline intermediate and thiosemicarbazide is 1:1; N-octyl alcohol addition be imidazoline intermediate, thiosemicarbazide gross mass 50%.
3) be the monoxone of 1:1 by mol ratio, NaOH is added to the water, and obtains the sodium chloroacetate solution that mass concentration is 16%.Under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 90 DEG C of reaction 4h, obtain imidazoline amophoteric surface active agent;
Wherein, the mol ratio of thioureido-imidazoline and sodium chloroacetate solution is 1:3.
See Fig. 2, as can be seen from infrared spectrum of the present invention, 1646cm
-1for C=N stretching vibration absorbs, be the characteristic absorption peak of imidazoline ring, at 1100cm
-1there is the absworption peak of C=S key in place, this characteristic peak shows to be obtained by reacting target product.
Cinnamic acid, diethylenetriamine are uniformly mixed under the effect of azeotropic agent, catalyst, obtain imidazoline intermediate by amidation process and cyclization dehydration; By introducing thiourea group and quaternizedly obtaining a kind of amphoteric surfactant, this material both containing ghiourea group, had carboxylic acid group again, added the water-soluble of product, and made it have good adsorption capacity in metal surface, improved the performance of product.Imidazoline amophoteric surface active agent of the present invention easily synthesizes, and raw material is cheap and easy to get, and is organic inhibitor, nontoxic.
The invention solves and allow corrosion inhibiter can adsorb and have lower cost and environment amenable inhibition problem preferably in metal surface, thus make corrosion inhibiter have superior corrosion inhibition.Thioureido-imidazoline provided by the invention, carry out quaternized with sodium chloroacetate to it, the thioureido-imidazoline quaternary ammonium salt obtained is a kind of amphoteric surfactant, and containing carboxylic acid group's hydrophilic radical in product, the water-soluble requirement of imidazoline products can be met, be worth promoting in course of industrialization.Cinnamic acid belongs to green material simultaneously, and containing benzene radicals in molecule, corrosion inhibition connects branched chain type group higher than it, this is owing to phenyl ring having large π key, can with the C=N key generation conjugation on imidazoline ring, stability increases greatly, thus causes the lifting of corrosion inhibition.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention; can not assert that the specific embodiment of the present invention is only limitted to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to the present invention by submitted to claims determination scope of patent protection.
Claims (8)
1. an imidazoline amophoteric surface active agent, is characterized in that, the structural formula of this surfactant is as follows:
2. a preparation method for imidazoline amophoteric surface active agent as claimed in claim 1, is characterized in that, comprise the following steps:
1) cinnamic acid, diethylenetriamine, azeotropic agent and catalyst are added water knockout drum and N are housed
2in the reactor of protective device, after dehydration, obtain imidazoline intermediate;
Wherein, the mol ratio of cinnamic acid and diethylenetriamine is 1:(1.1 ~ 1.3), azeotropic agent addition is 20% ~ 30% of cinnamic acid and diethylenetriamine gross mass; Catalyst charge is 0.1% ~ 0.3% of cinnamic acid quality;
2) in imidazoline intermediate, add thiosemicarbazide and n-octyl alcohol, at 140 ~ 160 DEG C, react 2 ~ 4h, obtain bronzing viscous liquid after decompression distillation, oven dry, be thioureido-imidazoline;
Wherein, the mol ratio of imidazoline intermediate and thiosemicarbazide is 1:(1 ~ 2);
3) under room temperature, in thioureido-imidazoline, drip sodium chloroacetate solution, drip after finishing and be warming up to 80 ~ 100 DEG C of reaction 2 ~ 4h, obtain imidazoline amophoteric surface active agent;
Wherein, in thioureido-imidazoline and sodium chloroacetate solution, the mol ratio of sodium chloroacetate is 1:(2 ~ 3).
3. the preparation method of imidazoline amophoteric surface active agent according to claim 2, is characterized in that: described step 1) in azeotropic agent be dimethylbenzene or toluene.
4. the preparation method of imidazoline amophoteric surface active agent according to claim 2, is characterized in that: described step 1) in catalyst be Al
2o
3or magnesium chips.
5. the preparation method of imidazoline amophoteric surface active agent according to claim 2, it is characterized in that: described step 1) in the detailed process of dehydration be: prior to 150 DEG C ~ 160 DEG C of dehydration 4 ~ 5h, then 210 DEG C ~ 220 DEG C are warmed up to, dehydration 4 ~ 6h.
6. the preparation method of imidazoline amophoteric surface active agent according to claim 2, is characterized in that: described step 2) in the addition of n-octyl alcohol be imidazoline intermediate, thiosemicarbazide gross mass 50% ~ 70%.
7. the preparation method of imidazoline amophoteric surface active agent according to claim 2, it is characterized in that: described step 3) in sodium chloroacetate solution obtain by the following method: be that monoxone, the NaOH of 1:1 is added to the water by mol ratio, obtain sodium chloroacetate solution.
8. the preparation method of imidazoline amophoteric surface active agent according to claim 7, is characterized in that: the mass concentration of gained sodium chloroacetate solution is 16%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107385449A (en) * | 2017-08-11 | 2017-11-24 | 中国石油大学(华东) | A kind of corrosion inhibiter preparation method and application for suppressing carbon steel sour corrosion |
| CN108559979A (en) * | 2018-01-24 | 2018-09-21 | 永星化工(上海)有限公司 | A kind of chemical nickel-plating liquid and preparation method thereof |
| CN109913875A (en) * | 2019-03-12 | 2019-06-21 | 陕西科技大学 | A kind of preparation method of polyethylene glycol imidazoline inhibitor |
| CN113430597A (en) * | 2021-08-26 | 2021-09-24 | 深圳市板明科技股份有限公司 | Application of hole-filling electroplating leveling agent for circuit board |
| CN113430040A (en) * | 2021-06-23 | 2021-09-24 | 煤炭科学技术研究院有限公司 | Multifunctional additive for hydraulic support concentrated solution and preparation method thereof |
| CN115490620A (en) * | 2022-09-30 | 2022-12-20 | 陕西科技大学 | Anion-cation adjustable surfactant and preparation method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102311A (en) * | 2011-11-11 | 2013-05-15 | 中国科学院海洋研究所 | Cinnamyl imidazoline derivative and its preparation method and use |
| CN103529657A (en) * | 2013-10-23 | 2014-01-22 | 杨桂望 | Photoresist stripping agent |
| CN103881697A (en) * | 2014-03-14 | 2014-06-25 | 杭州央力科技有限公司 | Imidazoline compound corrosion inhibitor and preparation method thereof |
| CN104693124A (en) * | 2013-12-05 | 2015-06-10 | 青岛惠城石化科技有限公司 | Synthesis and application of lauric acid imidazoline ampholytic surfactant |
| CN104775123A (en) * | 2015-04-13 | 2015-07-15 | 成都石大力盾科技有限公司 | Preparation method of thiosemicarbazide imidazoline derivative corrosion inhibitor |
| CN104830299A (en) * | 2015-05-20 | 2015-08-12 | 广西经正科技开发有限责任公司 | Imidazoline-quaternary ammonium salt compound corrosion inhibitor and preparation method thereof |
-
2015
- 2015-12-14 CN CN201510937750.6A patent/CN105561864B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102311A (en) * | 2011-11-11 | 2013-05-15 | 中国科学院海洋研究所 | Cinnamyl imidazoline derivative and its preparation method and use |
| CN103529657A (en) * | 2013-10-23 | 2014-01-22 | 杨桂望 | Photoresist stripping agent |
| CN104693124A (en) * | 2013-12-05 | 2015-06-10 | 青岛惠城石化科技有限公司 | Synthesis and application of lauric acid imidazoline ampholytic surfactant |
| CN103881697A (en) * | 2014-03-14 | 2014-06-25 | 杭州央力科技有限公司 | Imidazoline compound corrosion inhibitor and preparation method thereof |
| CN104775123A (en) * | 2015-04-13 | 2015-07-15 | 成都石大力盾科技有限公司 | Preparation method of thiosemicarbazide imidazoline derivative corrosion inhibitor |
| CN104830299A (en) * | 2015-05-20 | 2015-08-12 | 广西经正科技开发有限责任公司 | Imidazoline-quaternary ammonium salt compound corrosion inhibitor and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107385449A (en) * | 2017-08-11 | 2017-11-24 | 中国石油大学(华东) | A kind of corrosion inhibiter preparation method and application for suppressing carbon steel sour corrosion |
| CN108559979A (en) * | 2018-01-24 | 2018-09-21 | 永星化工(上海)有限公司 | A kind of chemical nickel-plating liquid and preparation method thereof |
| CN108559979B (en) * | 2018-01-24 | 2020-05-08 | 永星化工(上海)有限公司 | Chemical nickel plating solution and preparation method thereof |
| CN109913875A (en) * | 2019-03-12 | 2019-06-21 | 陕西科技大学 | A kind of preparation method of polyethylene glycol imidazoline inhibitor |
| CN113430040A (en) * | 2021-06-23 | 2021-09-24 | 煤炭科学技术研究院有限公司 | Multifunctional additive for hydraulic support concentrated solution and preparation method thereof |
| CN113430597A (en) * | 2021-08-26 | 2021-09-24 | 深圳市板明科技股份有限公司 | Application of hole-filling electroplating leveling agent for circuit board |
| CN113430597B (en) * | 2021-08-26 | 2021-11-09 | 深圳市板明科技股份有限公司 | Application of hole-filling electroplating leveling agent for circuit board |
| CN115490620A (en) * | 2022-09-30 | 2022-12-20 | 陕西科技大学 | Anion-cation adjustable surfactant and preparation method and application thereof |
| CN115490620B (en) * | 2022-09-30 | 2023-09-26 | 陕西科技大学 | Anionic and cationic adjustable surfactant and preparation method and application thereof |
| CN115613036A (en) * | 2022-10-11 | 2023-01-17 | 常州大学 | Corrosion inhibitor with flocculation function and preparation method thereof |
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