CN101121671B - Technique for synthesizing ester amine and quaternary ammonium salt thereof - Google Patents
Technique for synthesizing ester amine and quaternary ammonium salt thereof Download PDFInfo
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- CN101121671B CN101121671B CN 200710062343 CN200710062343A CN101121671B CN 101121671 B CN101121671 B CN 101121671B CN 200710062343 CN200710062343 CN 200710062343 CN 200710062343 A CN200710062343 A CN 200710062343A CN 101121671 B CN101121671 B CN 101121671B
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Abstract
The invention relates to a technology for the synthetic ester amine and the quaternary ammonium salt; in the technology, fatty acid, ethanolamine and acidic catalyst are added into a loop reactor; thesystem carries out the nitrogen replacement under the 0.01 to 1.0 Mpa nitrogen pressure; the material begins to react when the temperature of the material is up to150 to 210 Celsius system and laststo react for five to ten hours; when the acid value of the ester amine of the reaction products is less than 5 milligrams of potassium hydroxide in one gram, the reaction is stopped to get the ester amine; after lowering the temperature of the ester amine in the loop reactor to 50 to 90 Celsius system, the pressure of the loop reaction system is lowered to the normal pressure; the isopropanol is added in the loop reactor and the loop system is closed; uniformly the quaternary ammonium reagent is added into the loop reactor within 0.5 to 2 hours; the reaction is kept for 4 to 6 hours; when thecontent of the free amine in the products is less than 0.025 mmol per gram, the reaction is stopped and the quaternary ammonium salt is obtained. The invention has the advantages of the reduced reaction time, the guarantee of the color of the product, the improvement of the product quality, and the reduction of the production cost.
Description
Technical field
The invention belongs to the preparation technology of a kind of ester amine and quarternary ammonium salt compound thereof.
Background technology
The main manufacturer of ester amine and quaternary ammonium salt thereof is Stepan company, the P﹠amp of the U.S. in the world at present; G company, companies such as Henkel KGaA company and Dutch Acker assistant Nobel.The main method that they produce ester based quaternary ammonium salt is to adopt lipid acid and thanomin synthesizing ester amine under the condition that is catalyzer with acid, carries out quaterisation then.From existing ester amine and quaternary ammonium salt synthetic patent such as CN 1419006A, EP0295385, WO 91/01295 grade their synthesis route as can be seen all adopts still formula stirring reaction technology to carry out.Do not appear in the newspapers for the method that adopts loop reactor prepared ester amine and quaternary ammonium salt thereof.
Summary of the invention
The purpose of this invention is to provide a kind of synthesis technique that adopts loop reactor to prepare ester amine and quaternary ammonium salt thereof.
Synthesis technique of the present invention is a certain proportion of lipid acid and thanomin to be joined carry out the ester amination reaction in the loop reactor, and then add quaternizing agent and carry out quaterisation in the loop reactor and obtain the ester-amine series quaternary ammonium salt, concrete preparation method is as follows:
(1) ester amination reaction: a certain amount of lipid acid, thanomin and an acidic catalyst are joined in the loop reactor, after system carried out nitrogen replacement, make the reaction pressure of whole loop reaction system keep the nitrogen pressure of 0.01～1.0Mpa, start the outer circulation pump, utilizing outer circulation interchanger and loop reactor to make material be warming up to temperature of reaction reacts for 150～210 ℃, 5～10 hours reaction times, when the acid value that records reaction product ester amine is lower than 5mgKOH/g, stopped reaction obtains ester amine;
(2) quaterisation: after the temperature of ester amine in the loop reactor reduced to 50～90 ℃, make whole loop reaction system reduce to normal pressure, again that whole cyclic system is airtight after joining Virahol in the loop reactor, in 0.5～2 hour, at the uniform velocity quaternizing agent is joined in the loop reactor, reacted 4～6 hours, when free amine content is less than 0.025mmol/g in recording product, get final product stopped reaction, obtain quaternary ammonium salt;
The each component add-on is:
The mol ratio of lipid acid, thanomin and quaternizing agent: 1.4～2.5: 1: 0.9～1.2, the an acidic catalyst consumption is that an acidic catalyst accounts for lipid acid and thanomin weight sum 0.05%～0.5%, and the Virahol consumption is that Virahol accounts for lipid acid and thanomin weight sum 5%～15%.
Described lipid acid is: the saturated fatty acid of C6～C22 or unsaturated fatty acids and composition thereof.As: one or more in sad, lauric acid, palmitinic acid, oleic acid, stearic acid, mountain Yu acid or the tallow acid.
Described thanomin is: dimethylethanolamine, methyldiethanolamine or trolamine etc.
Described an acidic catalyst is organic acid or mineral acid: organic acid is alkyl benzene sulphonate (ABS) or tosic acid etc.Mineral acid is sulfuric acid, phosphoric acid, phosphorous acid or hydrochloric acid etc.
Described quaternizing agent is methyl chloride, monobromethane, methyl-sulfate, ethyl sulfate or methylcarbonate etc.
The present invention compared with prior art has following advantage:
1, the loop reaction device is by the material circulation of himself, not only can reinforcing mass transfer, and shorten the reaction times, and utilize the self-circulation of its gassy system water generation reaction can be taken out of, do not need additionally to carry out nitrogen and replenish or vacuumize.
2, the outer circulation heating unit of loop reaction process using has greatly been strengthened the heat transfer efficiency of system, and can adjust temperature, the gas phase internal circulating load of system rapidly according to the actual process condition, is very suitable for the ester amination reaction.
3, loop reactor is when carrying out the ester amination reaction, and its reaction system is relatively independent, does not exist owing to entering of air and to problems such as product color impact.
4, adopt loop reaction technology can shorten the reaction times, reduce nitrogen use level, guarantee product color, improve the quality of products, reduce production costs.
Description of drawings
Fig. 1 is the process flow diagram of synthesizing ester amine of the present invention and quaternary ammonium salt thereof.
As shown in the figure: the 1st, outer circulation pump, the 2nd, loop reactor, the 3rd, catalyst feeds, the 4th, material opening for feed, the 5th, nitrogen inlet, the 6th, vacuum orifice, the 7th, hot oil inlet, the 8th, outer circulation interchanger, the 9th, hot oil outlet, the 10th, gas phase condenser, the 11st, reflux exchanger, the 12nd, hot oil outlet, the 13rd, hot oil inlet, the 14th, hot oil inlet, the 15th, hot oil outlet.
Embodiment
Embodiment 1
The ester amination reaction: the stearic acid, 14.9Kg trolamine and the 200g alkyl benzene sulphonate (ABS) that take by weighing the 57Kg fusing join in the loop reactor 2 of 200L, use nitrogen replacement, make whole cyclic system keep the nitrogen pressure of reaction pressure 0.2MPa, start outer circulation pump 1, utilize outer circulation interchanger 8 and loop reactor 2 to make material be warming up to 180 ℃ of temperature of reaction, begin reaction.After 6 hours reaction times, when recording ester amine product acid value 2.8mgKOH/g, stopped reaction obtains ester amine.
Quaterisation: utilize outer circulation interchanger 8 and loop reactor 2 that ester amine temperature is reduced to 70 ℃ of temperature of reaction, system pressure is reduced to normal pressure, add Virahol 10Kg in loop reactor by material inlet 4, make the loop reaction system airtight then, in 1.5 hours reinforced time, at the uniform velocity join the 12.1Kg methyl-sulfate in the loop reactor, carry out quaterisation, react after 4 hours, record when free amine content is 0.018mmol/g in the product, get final product stopped reaction, obtain quaternary ammonium salt.
Embodiment 2
Ester amination reaction: the stearic acid 100Kg of fusing, methyldiethanolamine 20.9Kg, phosphorous acid 100g, reaction pressure 0.5MPa, 170 ℃ of temperature of reaction, 5 hours reaction times, product acid value 3mgKOH/g.
Quaterisation: 60 ℃ of temperature of reaction, Virahol consumption 14.2Kg, methyl-sulfate consumption 22Kg, the reinforced 2 hours time, after 6 hours reaction times, free amine content is 0.016mmol/g in the product.Other condition is with embodiment 1.
Embodiment 3
Ester amination reaction: oleic acid 56.4Kg, trolamine 14Kg, alkyl benzene sulphonate (ABS) 200g, reaction pressure 0.4MPa, 200 ℃ of temperature of reaction, 4 hours reaction times, product acid value 2.5mgKOH/g.
Quaterisation: 80 ℃ of temperature of reaction, Virahol consumption 10Kg, methyl chloride consumption 5.3Kg, the reinforced 1 hour time, after 5 hours reaction times, free amine content is 0.015mmol/g in the product.Other condition is with embodiment 1.
Embodiment 4
Ester amination reaction: lauric acid 80Kg, methyldiethanolamine 23.4Kg, phosphatase 11 00g,, reaction pressure 0.4MPa, 200 ℃ of temperature of reaction, 6 hours reaction times, product acid value 1.8mgKOH/g.
Quaterisation: 70 ℃ of temperature of reaction, Virahol consumption 8Kg, methyl chloride consumption 10Kg, the reinforced 1 hour time, after 6 hours reaction times, free amine content is 0.017mmol/g in the product.Other condition is with embodiment 1.
Embodiment 5
Ester amination reaction: palmitinic acid 51.2Kg, trolamine 14.9Kg, tosic acid 107g, reaction pressure 0.4MPa, 190 ℃ of temperature of reaction, 8 hours reaction times, product acid value 1.7mgKOH/g.
Quaterisation: 85 ℃ of temperature of reaction, Virahol consumption 7.2Kg, ethyl sulfate consumption 15.3Kg, the reinforced 2 hours time, after 5 hours reaction times, free amine content is 0.023mmol/g in the product.Other condition is with embodiment 1.
Embodiment 6
Ester amination reaction: tallow acid 23Kg, palmitinic acid 36Kg, oleic acid 41Kg, methyldiethanolamine 22Kg, alkyl benzene sulphonate (ABS) 200g, reaction pressure 0.4MPa, 200 ℃ of temperature of reaction, 9 hours reaction times, product acid value 1.1mgKOH/g.
Quaterisation: 70 ℃ of temperature of reaction, Virahol consumption 14.3Kg, methyl-sulfate consumption 23.3Kg, the reinforced 1 hour time, after 6 hours reaction times, free amine content is 0.024mmol/g in the product.Other condition is with embodiment 1.
Claims (9)
1. the technology of synthesizing ester amine and quaternary ammonium salt thereof is characterized in that comprising the steps:
(1) ester amination reaction: a certain amount of lipid acid, thanomin and an acidic catalyst are joined in the loop reactor, after system carried out nitrogen replacement, make the reaction pressure of whole loop reaction system keep the nitrogen pressure of 0.01～1.0Mpa, start the outer circulation pump, utilizing outer circulation interchanger and loop reactor to make material be warming up to temperature of reaction reacts for 150～210 ℃, 5～10 hours reaction times, when the acid value that records reaction product ester amine is lower than 5mgKOH/g, stopped reaction obtains ester amine;
(2) quaterisation: after the temperature of ester amine in the loop reactor reduced to 50～90 ℃, make whole loop reaction system reduce to normal pressure, again that whole cyclic system is airtight after joining Virahol in the loop reactor, in 0.5～2 hour, at the uniform velocity quaternizing agent is joined in the loop reactor, reacted 4～6 hours, when free amine content is less than 0.025mmol/g in recording product, get final product stopped reaction, obtain quaternary ammonium salt;
The each component add-on is:
The mol ratio of lipid acid, thanomin and quaternizing agent: 1.4～2.5: 1: 0.9～1.2, the an acidic catalyst consumption is that an acidic catalyst accounts for lipid acid and thanomin weight sum 0.05%～0.5%, and the Virahol consumption is that Virahol accounts for lipid acid and thanomin weight sum 5%～15%.
2. the technology of a kind of synthesizing ester amine as claimed in claim 1 and quaternary ammonium salt thereof is characterized in that described lipid acid is: the saturated fatty acid of C6～C22 or unsaturated fatty acids and composition thereof.
3. the technology of a kind of synthesizing ester amine as claimed in claim 2 and quaternary ammonium salt thereof, the saturated fatty acid that it is characterized in that described C6～C22 are one or more in sad, lauric acid, mountain Yu acid, palmitinic acid or the stearic acid.
4. the technology of a kind of synthesizing ester amine as claimed in claim 2 and quaternary ammonium salt thereof, the unsaturated fatty acids that it is characterized in that described C6～C22 are one or more in oleic acid or the tallow acid.
5. the technology of a kind of synthesizing ester amine as claimed in claim 1 and quaternary ammonium salt thereof is characterized in that described thanomin is dimethylethanolamine, methyldiethanolamine or trolamine.
6. the technology of a kind of synthesizing ester amine as claimed in claim 1 and quaternary ammonium salt thereof is characterized in that described an acidic catalyst is organic acid or mineral acid.
7. the technology of a kind of synthesizing ester amine as claimed in claim 6 and quaternary ammonium salt thereof is characterized in that described organic acid is alkyl benzene sulphonate (ABS) or tosic acid.
8. the technology of a kind of synthesizing ester amine as claimed in claim 6 and quaternary ammonium salt thereof is characterized in that described mineral acid is sulfuric acid, phosphoric acid, phosphorous acid or hydrochloric acid.
9. the technology of a kind of synthesizing ester amine as claimed in claim 1 and quaternary ammonium salt thereof is characterized in that described quaternizing agent is methyl chloride, monobromethane, methyl-sulfate, ethyl sulfate or methylcarbonate.
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| CN102336675A (en) * | 2010-07-21 | 2012-02-01 | 博兴华润油脂化学有限公司 | Production method of esterquats |
| CN102503841A (en) * | 2011-10-08 | 2012-06-20 | 中国日用化学工业研究院 | Ethoxylate ester quaternary ammonium salt and its preparation method |
| CN102850228A (en) * | 2012-08-24 | 2013-01-02 | 陕西科技大学 | Preparation method of cationic fatty acid ester |
| CN103835132B (en) * | 2012-11-26 | 2017-09-29 | 五邑大学 | A kind of biodegradable antistatic finishing agent and preparation method thereof |
| CN102962005A (en) * | 2012-11-27 | 2013-03-13 | 中国日用化学工业研究院 | Ethoxylated trimester-group quaternary ammonium salt and preparation method thereof |
| CN103849360A (en) * | 2012-11-28 | 2014-06-11 | 中国石油化工股份有限公司 | Preparation method of water-based drilling fluid lubricant |
| CN103030622B (en) * | 2013-01-15 | 2014-04-23 | 中国日用化学工业研究院 | Method for preparing glyceride carbonate by using loop reaction device |
| WO2015156256A1 (en) | 2014-04-09 | 2015-10-15 | 花王株式会社 | Efficacy-enhancing composition for amino acid-based agrochemical |
| CN104131461B (en) * | 2014-08-04 | 2016-03-09 | 广东妮可儿服饰有限公司 | A kind of composition and method of making the same for field of textiles and purposes |
| CN107541942A (en) * | 2017-09-16 | 2018-01-05 | 常州道博化工有限公司 | A kind of preparation method of biodegradation type ester quat softening agent |
| CN108221374A (en) * | 2018-03-09 | 2018-06-29 | 广州科丰达化工科技有限公司 | A kind of softener and preparation method thereof |
| CN108252090A (en) * | 2018-03-12 | 2018-07-06 | 江苏海云花新材料有限公司 | A kind of preparation method weaved with softening agent consistent lubricant essence |
| CN108396555A (en) * | 2018-03-27 | 2018-08-14 | 东莞市恩科化工有限公司 | A kind of washable nylon moisture control agent and preparation method thereof |
| CN109180489B (en) * | 2018-09-21 | 2022-02-18 | 中国日用化学研究院有限公司 | Process for preparing methyl carbonate quaternary ammonium salt or ethyl carbonate quaternary ammonium salt by loop reaction device |
| CN109575260B (en) * | 2018-11-30 | 2021-12-14 | 中建西部建设股份有限公司 | Quaternary ammonium salt type concrete anti-mud agent and preparation method thereof |
| CN115260125A (en) * | 2022-07-01 | 2022-11-01 | 青海百能汇通新能源科技有限公司 | Synthetic process and device of bromine complexing agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562960A (en) * | 2004-03-29 | 2005-01-12 | 中国日用化学工业研究院 | Quaternary ammonium salt in ester-amines and synthetic method |
| CN1846843A (en) * | 2005-01-08 | 2006-10-18 | 戈尔德施米特有限公司 | Equilibrium reactions and gas/liquid reaction in a loop reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562960A (en) * | 2004-03-29 | 2005-01-12 | 中国日用化学工业研究院 | Quaternary ammonium salt in ester-amines and synthetic method |
| CN1846843A (en) * | 2005-01-08 | 2006-10-18 | 戈尔德施米特有限公司 | Equilibrium reactions and gas/liquid reaction in a loop reactor |
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Assignee: Shanghai Fine Chemical Co., Ltd. Assignor: Chinese Daily Use Chemical Industry Research Inst. Contract record no.: 2011310000098 Denomination of invention: Technique for synthesizing ester amine and quaternary ammonium salt thereof Granted publication date: 20100519 License type: Exclusive License Open date: 20080213 Record date: 20110712 |
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