CN103951581B - A kind of synthesis of positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt - Google Patents
A kind of synthesis of positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt Download PDFInfo
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Abstract
The invention discloses a kind of synthesis of positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt, it is characterized in that: take ethyl acetate as solvent, positive DC11 carries out back flow reaction with the sulfur oxychloride newly steamed under catalyst action, generates positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydride mixtures; Under acid binding agent exists, the mixture of positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides, reacts with Asparagus cochinchinensis ammonia acid sodium in the mixed solvent of acetone and water, generates positive 11 carbon diacyls pair Asparagus cochinchinensis ammonia acid sodium; After resultant of reaction dilute with water, pickling and washing; obtain the two aspartic acid of just 11 carbon diacyls; then join in diglycolamine; stirring and dissolving; obtained positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt; the effect of the stable comple having excellent rust inhibition and is formed with calcium, magnesium ion, operation is simple, applicable suitability for industrialized production.
Description
Technical field
The present invention relates to rust-inhibiting additive synthesis technical field, espespecially a kind of synthesis of positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt.
Background technology
Inhibiter is as a kind of additive; the effect preventing from corroding and wearing and tearing is played in intermetallic composite coating; inhibiter is owing to containing one or more eluting group in molecule; by physical adsorption or the protective membrane being chemisorbed on the arrangement of metallic surface formation molecular orientation; thus slow down or inhibit the corrosion of metallic matrix, receive much concern.The alcohol amine salt of carboxylic acid and derivative all has certain rust-preventing characteristic, resistance to abrasion and antifriction quality, major cause is the carboxyl all in the hydramine molecules of salt of carboxylic acid and derivative with strong polarity, their molecular adsorption is in the surface of iron, form firmly chemisorbed layer, play antirust effect, in addition, rub under being chemisorbed on high load condition and react, generate the friction chemical reaction film of high strength, this is that they have the major cause of better wear-resistant, antifriction and supporting capacity.
When working fluid preparation uses, generally adopt tap water under normal circumstances, present underground water is banned just gradually to be adopted, due to contacted surrounding environment and medium different, therefore impurity liquid contained in water is not quite similar, water hardness is also different, surface water impurities comprises oxygen, nitrogen, carbonic acid gas, dust, microorganism, solubility salt, suspended substance and erosion etc., when the alcohol amine salt of aliphatic carboxylic acid and derivative contacts with hard water, namely calcium ion and magnesium ion form insoluble calcium soap and magnesium soap with the effect of aliphatic carboxylic acid radical ion, thus too much consumption is caused, water hardness is higher, the consumption of lipid acid also just the more, therefore, water hardness has a strong impact on the rustless property of inhibiter.
Summary of the invention
The object of the present invention is to provide a kind of synthesis of positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt.
Technical solution of the present invention is: take ethyl acetate as solvent, and positive DC11 carries out back flow reaction with the sulfur oxychloride newly steamed under catalyst action, generates positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydride mixtures; Under acid binding agent exists, the mixture of positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides, reacts with Asparagus cochinchinensis ammonia acid sodium in the mixed solvent of acetone and water, generates positive 11 carbon diacyls pair Asparagus cochinchinensis ammonia acid sodium; After reaction mass dilute with water, pickling and washing, obtain the two aspartic acid of just 11 carbon diacyls, then join in diglycolamine, stirring and dissolving, obtained positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt.Specifically comprise following steps:
1). take ethyl acetate as solvent, positive DC11 (I) and the sulfur oxychloride newly steamed in molar ratio 1 ﹕ 1.5 ~ 2.5 feed intake, N, dinethylformamide is catalyzer, 80 DEG C ~ 85 DEG C back flow reaction 4 ~ 7 hours under stirring, and tail gas alkali liquor absorption, generate positive 11 carbon diacid chlorides (II) and positive 11 carbon dicarboxylic anhydrides (III), after completion of the reaction, Distillation recovery ethyl acetate, its main chemical reactions is:
2). under acid binding agent exists, the mixture of positive 11 carbon diacid chlorides (II) and positive 11 carbon dicarboxylic anhydrides (III), slowly join in the acetone of Asparagus cochinchinensis ammonia acid sodium (IV) and the mixed solvent of water in batches, temperature of reaction system is made to control at 5 DEG C ~ 10 DEG C, after the mixture of positive 11 carbon diacid chlorides (II) and positive 11 carbon dicarboxylic anhydrides (III) adds, be warming up to 25 DEG C ~ 35 DEG C and carry out reaction 2 ~ 3 hours, be warming up to 45 DEG C ~ 65 DEG C again and continue reaction 2 ~ 3 hours, generate the two Asparagus cochinchinensis ammonia acid sodium (V) of positive 11 carbon diacyls, after completion of the reaction, Distillation recovery acetone, its main chemical reactions is:
3). resultant of reaction water dilutes, and slowly adds acid solution, adjusts about pH to 1.0, separates out solid product, and with water repetitive scrubbing product, obtain the two aspartic acid (VI) of just 11 carbon diacyls, its main chemical reactions is:
4). join in diglycolamine by two for positive 11 carbon diacyls aspartic acid, be heated to 40 DEG C ~ 50 DEG C, stirring and dissolving, obtained positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt (VII), its main chemical reactions is:
Further, described ethyl acetate consumption is 100% ~ 120% of positive DC11 quality.
Described DMF catalyst levels is 1% ~ 5% of positive DC11 quality; .
Described alkali lye is aqueous sodium carbonate.
Described acid binding agent to be concentration be 20% aqueous sodium hydroxide solution.
Described acetone and the volume ratio of water are 1 ﹕ 1.
The mol ratio of described Asparagus cochinchinensis ammonia acid sodium and positive DC11 is 1 ﹕ 1.5 ~ 2.
Described acid solution is sulphuric acid soln or hydrochloric acid soln.
The mol ratio of the two aspartic acid of described positive 11 carbon diacyls and diglycolamine is 1 ﹕ 4 ~ 6.
The synthetic method of a kind of positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt of the present invention, its feature and advantage are: sufficient raw, and cost is lower; Reduce the consumption of sulfur oxychloride, reduce the corrosion to equipment; Synthetics is a kind of organic polycarboxylic acid, has the characteristic of multiple carboxyl and melts combine, can play excellent rust inhibition, and have the effect of the stable comple formed with calcium, magnesium ion, can softening of water; Operation is simple, is applicable to suitability for industrialized production.
Embodiment
Embodiment 1
30 grams of positive DC11s and 36 grams of ethyl acetate are put in corrosion-resistant reactor, 0.3 gram of N, dinethylformamide, add 41 grams of sulfur oxychlorides newly steamed, 80 DEG C ~ 85 DEG C back flow reaction 4 hours under stirring, tail gas alkali liquor absorption, generates positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides, after completion of the reaction, Distillation recovery ethyl acetate, whipping appts is being housed, in the four-hole bottle of reflux condensate device and thermometer, add the mixed solvent of 33 grams of Asparagus cochinchinensis ammonia acid sodiums and 50 milliliters of acetone and water, pH is regulated to be 10 with the sodium hydroxide solution that concentration is 20%, under abundant stirring, slowly add positive 11 carbon diacid chlorides and the positive mixture of 11 carbon dicarboxylic anhydrides and the sodium hydroxide solution of 20% more in batches, temperature of reaction system is made to control at 5 DEG C ~ 10 DEG C, it is 9 ~ 10 that pH controls, after the mixture of positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides adds, be warming up to 25 DEG C ~ 35 DEG C and carry out reaction 2 hours, it is 9 ~ 10 that pH controls, be warming up to 45 DEG C ~ 65 DEG C again and continue reaction 3 hours, it is 9 ~ 10 that pH controls, generate the two Asparagus cochinchinensis ammonia acid sodium of positive 11 carbon diacyls, after completion of the reaction, Distillation recovery acetone, reaction mass water dilutes, and slowly adds acid solution, adjusts about pH to 1.0, separates out solid product, with water repetitive scrubbing product, obtains the two aspartic acid of just 11 carbon diacyls, two for positive 11 carbon diacyls aspartic acid is joined in 45 grams of diglycolamines, stirring and dissolving, obtained positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt.
Embodiment 2
36 grams of positive DC11s and 36 grams of ethyl acetate are put in corrosion-resistant reactor, add 1.8 grams of N, dinethylformamide, add 30 grams of sulfur oxychlorides newly steamed again, 80 DEG C ~ 85 DEG C back flow reaction 7 hours under stirring, tail gas alkali liquor absorption, generates positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides, after completion of the reaction, Distillation recovery ethyl acetate, whipping appts is being housed, in the four-hole bottle of reflux condensate device and thermometer, add the mixed solvent of 50 grams of Asparagus cochinchinensis ammonia acid sodiums and 60 milliliters of acetone and water, pH is regulated to be 10 with the sodium hydroxide solution that concentration is 20%, under abundant stirring, slowly add positive 11 carbon diacid chlorides and the positive mixture of 11 carbon dicarboxylic anhydrides and the sodium hydroxide solution of 20% more in batches, temperature of reaction system is made to control at 5 DEG C ~ 10 DEG C, it is 9 ~ 10 that pH controls, after the mixture of positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides adds, be warming up to 25 DEG C ~ 35 DEG C and carry out reaction 3 hours, it is 9 ~ 10 that pH controls, be warming up to 45 DEG C ~ 65 DEG C again and continue reaction 2 hours, it is 9 ~ 10 that pH controls, generate the two Asparagus cochinchinensis ammonia acid sodium of positive 11 carbon diacyls, after completion of the reaction, Distillation recovery acetone, reaction mass water dilutes, and slowly adds acid solution, adjusts about pH to 1.0, separates out solid product, with water repetitive scrubbing product, obtains the two aspartic acid of just 11 carbon diacyls, two for positive 11 carbon diacyls aspartic acid is joined in 80 grams of diglycolamines, stirring and dissolving, obtained positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt.
Embodiment 3
40 grams of positive DC11s and 44 grams of ethyl acetate are put in corrosion-resistant reactor, add 1.2 grams of N, dinethylformamide, add 44 grams of sulfur oxychlorides newly steamed, 80 DEG C ~ 85 DEG C back flow reaction 5 hours under stirring, tail gas alkali liquor absorption, generates positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides, after completion of the reaction, Distillation recovery ethyl acetate, whipping appts is being housed, in the four-hole bottle of reflux condensate device and thermometer, add the mixed solvent of 45 grams of Asparagus cochinchinensis ammonia acid sodiums and 55 milliliters of acetone and water, pH is regulated to be 10 with the sodium hydroxide solution that concentration is 20%, under abundant stirring, slowly add positive 11 carbon diacid chlorides and the positive mixture of 11 carbon dicarboxylic anhydrides and the sodium hydroxide solution of 20% more in batches, temperature of reaction system is made to control at 5 DEG C ~ 10 DEG C, it is 9 ~ 10 that pH controls, after the mixture of positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides adds, be warming up to 25 DEG C ~ 35 DEG C and carry out reaction 3 hours, it is 9 ~ 10 that pH controls, be warming up to 45 DEG C ~ 65 DEG C again and continue reaction 3 hours, it is 9 ~ 10 that pH controls, generate the two Asparagus cochinchinensis ammonia acid sodium of positive 11 carbon diacyls, after completion of the reaction, Distillation recovery acetone, reaction mass water dilutes, and slowly adds acid solution, adjusts about pH to 1.0, separates out solid product, with water repetitive scrubbing product, obtains the two aspartic acid of just 11 carbon diacyls, two for positive 11 carbon diacyls aspartic acid is joined in 78 grams of diglycolamines, stirring and dissolving, obtained positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt.
The above; embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under the prerequisite of spirit not departing from the technology of the present invention; the various distortion that this area engineering technical personnel make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (2)
1. the synthesis of positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt, it is characterized in that: take ethyl acetate as solvent, positive DC11 carries out back flow reaction with the sulfur oxychloride newly steamed under catalyst action, generates positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydride mixtures; Under acid binding agent exists, the mixture of positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides, reacts with Asparagus cochinchinensis ammonia acid sodium in the mixed solvent of acetone and water, generates positive 11 carbon diacyls pair Asparagus cochinchinensis ammonia acid sodium; After reaction mass dilute with water, pickling and washing, obtain the two aspartic acid of just 11 carbon diacyls, then join in diglycolamine, stirring and dissolving, obtained positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt; Specifically comprise following steps:
1). take ethyl acetate as solvent, positive DC11 and the sulfur oxychloride newly steamed in molar ratio 1 ﹕ 1.5 ~ 2.5 feed intake, N, dinethylformamide is catalyzer, 80 DEG C ~ 85 DEG C back flow reaction 4 ~ 7 hours under stirring, tail gas alkali liquor absorption, generates positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides, after completion of the reaction, Distillation recovery ethyl acetate;
2). under acid binding agent exists, the mixture of positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides, slowly join in the acetone of Asparagus cochinchinensis ammonia acid sodium and the mixed solvent of water in batches, temperature of reaction system is made to control at 5 DEG C ~ 10 DEG C, after the mixture of positive 11 carbon diacid chlorides and positive 11 carbon dicarboxylic anhydrides adds, be warming up to 25 DEG C ~ 35 DEG C and carry out reaction 2 ~ 3 hours, be warming up to 45 DEG C ~ 65 DEG C again and continue reaction 2 ~ 3 hours, generate the two Asparagus cochinchinensis ammonia acid sodium of positive 11 carbon diacyls, after completion of the reaction, Distillation recovery acetone;
3). resultant of reaction water dilutes, and slowly adds acid solution, adjusts about pH to 1.0, separates out solid product, with water repetitive scrubbing product, obtains the two aspartic acid of just 11 carbon diacyls;
4). two for positive 11 carbon diacyls aspartic acid is joined in diglycolamine, is heated to 40 DEG C ~ 50 DEG C, stirring and dissolving, obtained positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt.
2. the synthesis of a kind of positive 11 carbon diacyl two aspartic acids-bis--glycol ether amine salt according to claim 1, is characterized in that: described ethyl acetate consumption is 100% ~ 120% of positive DC11 quality; Described DMF catalyst levels is 1% ~ 5% of positive DC11 quality; Described alkali lye is aqueous sodium carbonate; Described acetone and the volume ratio of water are 1 ﹕ 1; The mol ratio of described Asparagus cochinchinensis ammonia acid sodium and positive DC11 is 1 ﹕ 1.5 ~ 2; Described acid solution is sulphuric acid soln or hydrochloric acid soln; The mol ratio of the two aspartic acid of described positive 11 carbon diacyls and diglycolamine is 1 ﹕ 4 ~ 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101903336A (en) * | 2007-11-20 | 2010-12-01 | 科莱恩金融(Bvi)有限公司 | Method for producing acylglycinates |
| CN102863348A (en) * | 2012-09-05 | 2013-01-09 | 长沙普济生物科技有限公司 | Synthesis method of palmitoyl amino acid sodium |
| CN103130675A (en) * | 2011-11-23 | 2013-06-05 | 苏州维美生物科技有限公司 | Industrial production method of high-purity N-lauroyl-L-alanine surfactant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101903336A (en) * | 2007-11-20 | 2010-12-01 | 科莱恩金融(Bvi)有限公司 | Method for producing acylglycinates |
| CN103130675A (en) * | 2011-11-23 | 2013-06-05 | 苏州维美生物科技有限公司 | Industrial production method of high-purity N-lauroyl-L-alanine surfactant |
| CN102863348A (en) * | 2012-09-05 | 2013-01-09 | 长沙普济生物科技有限公司 | Synthesis method of palmitoyl amino acid sodium |
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Effective date of registration: 20191204 Address after: Haiyan County of Jiaxing City, Zhejiang province 314311 Shendang Town Industrial Park Patentee after: JIAXING RIFENG METAL PRODUCTS Co.,Ltd. Address before: 226500, No. 8, Suijiang Road, Shi Zhuang Town, Nantong City, Jiangsu Province, Rugao Patentee before: JIANGSU TAICANG AGRICULTURAL CHEMICALS CO.,LTD. |