CN102516109A - Synthesis method of high-purity fatty acid monoethanolamine - Google Patents
Synthesis method of high-purity fatty acid monoethanolamine Download PDFInfo
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- CN102516109A CN102516109A CN2011103737497A CN201110373749A CN102516109A CN 102516109 A CN102516109 A CN 102516109A CN 2011103737497 A CN2011103737497 A CN 2011103737497A CN 201110373749 A CN201110373749 A CN 201110373749A CN 102516109 A CN102516109 A CN 102516109A
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Abstract
The invention belongs to the technical field of synthesis of a surfactant in organic chemistry, and particularly relates to a synthesis method of a high-purity fatty acid monoethanolamine, which comprises the following steps of: 1) preparation of a fatty acid methyl ester; 2) post-treatment refining of the fatty acid methyl ester; and 3) amidation reaction. The fatty acid monoethanolamine prepared by the method has the advantages of high purity, light odor, low amine value, light color and the like.
Description
Technical field
The invention belongs to tensio-active agent synthesis technical field in the organic chemistry, be specifically related to the compound method of high purity fatty acid single ethanol amide.
Background technology
Fatty monoethanol amide is a kind of nonionogenic tenside.Because the existence of amido linkage makes it in wider pH value scope, have good chemical stability in its molecule, excellent dispersion, solubilising, emulsification, thickening reach performances such as lubricated.In the daily use chemicals industry, fatty monoethanol amide is everlasting and is used as thickening material in the liquid washing agent, plays surely bubble effect of thickening.At present; Most widely used thickening material is a fatty diglycollic amide in the liquid washing agent; But research shows; Free diethylolamine contained in the fatty diglycollic amide series of surfactants has obvious carcinogenic activity, is expected to become the surrogate of fatty diglycollic amide tensio-active agent as the fatty monoethanol amide of similar alkylolamide class.
Both at home and abroad fatty monoethanol amide synthetic mainly contains three routes: 1) made 150～180 ℃ of reactions by coco-nut oil fatty acid and monoethanolamine, temperature of reaction is higher, and product color deepens, and by products such as carboxylic acid amide esters and amino ester are arranged; Also have and adopt two-step process to prepare, though can improve the fatty monoethanol amide yield, on the suitability for industrialized production; Still exist temperature of reaction high, the time is long, and color and luster is dark; By product is more, and product amine value is high, the shortcoming that smell is heavy; 2) make by Oleum Cocois and monoethanolamine direct reaction.This route reaction is difficult for fully, and the glycerine of generation can form a series of by products, and the by-product glycerin of product residue is up to about 10%; 3) react under the basic catalyst effect with monoethanolamine after the coconut oil methyl esterization and make; The processing condition of this route suitability for industrialized production and quality product are all not mature enough; Purity is not high enough, and amide content is between 92～97% mostly, and product contains other more impurity.Existing technology is after carrying out esterification, and the aftertreatment of being carried out is simple standing demix, and the glycerine branch of lower floor is fallen, and methyl esters is not carried out further refining the purification.But simple standing demix aftertreatment can not be removed the soap in the product, glycerine and other water-soluble impurities totally, can contain a certain amount of fatty acid soaps in the product, and the glycerine of about 0.5～2% content is residual.In addition, the product ester too high levels of producing is mostly between 2～7%.Product amine value is too high, between 5～20mgKOH/g, is converted between the unhindered amina about 0.6～2.2% mostly, and this has caused the amine flavor of product heavier.
Summary of the invention
In order to overcome the deficiency of prior art, the object of the present invention is to provide a kind of compound method of high purity fatty acid single ethanol amide, the product that is prepared by this method possesses the purity height, and smell is light, and the amine value is low, lighter color, advantage such as temperature of reaction is low.
For realizing above-mentioned purpose, the technical scheme that the present invention adopted is following:
A kind of compound method of high purity fatty acid single ethanol amide may further comprise the steps:
(1) preparation of fatty acid methyl ester: with vegetables oil and methanol mixed, and add a certain amount of basic catalyst, heated and stirred stoichiometric number hour obtains the fatty acid methyl ester bullion;
(2) the fatty acid methyl ester aftertreatment is refining, may further comprise the steps:
1. after reaction finishes, left standstill several hours, the glycerine of lower floor is separated;
2. the excessive methanol in the methyl esters is distilled;
3. add washed twice in certain density salt solution to the methyl esters, add the clear water washing more once, the soap in the bullion, glycerine and some other water-soluble impurities are removed;
4. be heated to certain temperature, the small amount of methanol in the methyl esters, moisture content underpressure distillation are fallen, obtain the purified fatty acid methyl ester;
(3) amidate action: the fatty acid methyl ester that back is obtained mixes with a certain amount of monoethanolamine, and adds a certain amount of basic catalyst, at a certain temperature vacuum reaction for some time, obtains the high purity fatty acid single ethanol amide;
Particularly, the compound method of high purity fatty acid single ethanol amide of the present invention may further comprise the steps:
(1) preparation of fatty acid methyl ester: with mol ratio is the vegetables oil and the methanol mixed of 1.0:3.0～9.0; And add a certain amount of basic catalyst; Catalyst levels accounts for vegetables oil mass ratio 0.01～1%, and heated and stirred obtains the fatty acid methyl ester bullion in 50～90 ℃ of reactions 1～6 hour;
Wherein, vegetables oil is one or more in plam oil, palm-kernel oil, Oleum Cocois, VT 18, rapeseed oil and the hydrogenate thereof;
Basic catalyst is a kind of in sodium methylate, sodium hydroxide and the Pottasium Hydroxide, and catalyzer can be solid, also can be certain density catalyzer methanol solution;
(2) the fatty acid methyl ester aftertreatment is refining, may further comprise the steps:
1. after reaction finishes, left standstill 1～6 hour, the glycerine of lower floor is separated;
2. the excessive methanol in the methyl esters is distilled;
3. add washed twice in certain density salt solution to the methyl esters, add the clear water washing more once, with the soap in the bullion, glycerine, and some other water-soluble impurities remove; 20-100 ℃ of salt solution and clear water wash temperature, water consumption are 20～100% of methyl esters volume;
4. be heated to 80～140 ℃, the small amount of methanol in the methyl esters, moisture content underpressure distillation are fallen, obtain the purified fatty acid methyl ester;
(3) amidate action: fatty acid methyl ester and monoethanolamine that back is obtained are that 1.0:1.0～1.1 are mixed with the mol ratio, and add a certain amount of basic catalyst, at 60～140 ℃ of vacuum reactions, obtain the high purity fatty acid single ethanol amide;
Wherein, the preferred 1.0:1.0 of the mol ratio of fatty acid methyl ester and monoethanolamine～1.05;
Wherein, basic catalyst is a kind of in sodium methylate, sodium hydroxide, the Pottasium Hydroxide, and catalyzer can be solid, also can be certain density catalyzer methanol solution; It is 0.01 ~ 1% that catalyst levels accounts for the methyl esters mass ratio, preferred 0.02 ~ 0.1%, and catalyzer can be catalyst solid, also can be diluted to certain density catalyzer methanol solution;
Wherein, 1～5 hour vacuum reaction time, preferred 2 ~ 3 hours, vacuum tightness is-0.05～-0.1Mpa.
Fatty acid methyl ester after the present invention makes with extra care through aftertreatment is when carrying out amidate action, and speed of response is faster, can react at 2 ~ 3 hours to finish, and prior art generally needs ability reaction in 5 ~ 7 hours to finish.
When the fatty acid methyl ester after the present invention makes with extra care through aftertreatment carries out amidate action, react required catalyzer still less, only need 0.02-0.1%, and the prior art catalyst levels generally will be more than 0.5%.
The present invention is when the fatty acid methyl ester after refining carries out amidate action through aftertreatment, and reaction efficiency is higher, and it is excessive 0～5% that monoethanolamine only needs, and in the prior art, monoethanolamine wants excessive 10～30%.
In addition, the amine value of the fatty monoethanol amide that existing amidation technology is synthesized is generally up to 5-20mgKOH/g, and the product amine value that the inventive method is synthesized can be low to moderate below the 2mgKOH/g.And, compare that the high purity fatty acid single ethanol amide impurity that prior art compound method of the present invention prepares is few, lighter color, the amine value is low, smell is light.
Embodiment
Below in conjunction with embodiment the present invention is done further explain, should be understood that these embodiment only be used to the present invention is described and be not used in the restriction range of application of the present invention.
Embodiment 1:
400g palm-kernel oil is mixed with the 100g anhydrous methanol, and add 2g Pottasium Hydroxide,, leave standstill after 2 hours lower floor's glycerine branch is fallen, obtain upper strata palm-kernel oil methyl esters bullion in 70 ℃ of heated and stirred reactions 4 hours.Methyl alcohol excessive in the bullion is distilled, then in 60 ℃ with 200g 5% concentration weak brine washed twice, with 200g clear water washing once, be warming up to 100 ℃ of underpressure distillation 1h then again, obtain 395.0g palm-kernel oil methyl esters.Add 104.0g monoethanolamine and 0.2g sodium methylate, in 100 ℃ of following vacuum reaction 2h, vacuum tightness-0.095Mpa.Obtain high purity palm-kernel oleic acid single ethanol amide, purity 98.3%, amine value 1.1 (being converted into unhindered amina 0.12%), ester content 1.58%.
Embodiment 2:
400g palm-kernel oil is mixed with the 150g anhydrous methanol, and add 2g Pottasium Hydroxide,, leave standstill after 1 hour lower floor's glycerine branch is fallen, obtain upper strata palm-kernel oil methyl esters bullion in 70 ℃ of heated and stirred reactions 2 hours.Methyl alcohol excessive in the bullion is distilled, then in 60 ℃ with 200g 5% concentration weak brine washed twice, with 200g clear water washing once, be warming up to 100 ℃ of underpressure distillation 1h then again, obtain 397.2g palm-kernel oil methyl esters.Add 107.2g monoethanolamine and 0.2g sodium methylate, in 100 ℃ of following vacuum reaction 2h, vacuum tightness-0.095Mpa.Obtain high purity palm-kernel oleic acid single ethanol amide, purity 98.5%, amine value 1.2 (being converted into unhindered amina 0.13%), ester content 1.36%.
Embodiment 3:
The 400g Oleum Cocois is mixed with the 120g anhydrous methanol, and add the 1g sodium methylate,, leave standstill after 1 hour lower floor's glycerine branch is fallen, obtain upper strata palm fibre coconut oil methyl ester bullion in 70 ℃ of heated and stirred reactions 3 hours.Methyl alcohol excessive in the bullion is distilled, then in 60 ℃ with 200g 5% concentration weak brine washed twice, with 200g clear water washing once, be warming up to 100 ℃ of underpressure distillation 1h then again, obtain 397.1g cocinic acid methyl esters.Add 110.1g monoethanolamine and 0.2g sodium methylate, in 100 ℃ of following vacuum reaction 2h, vacuum tightness-0.095Mpa.Obtain the high purity coconut monoethanolamide, purity 98.3%, amine value 1.8 (being converted into unhindered amina 0.12%), ester content 1.63%.
Embodiment 4:
The 400g Oleum Cocois is mixed with the 120g anhydrous methanol, and add the 1g sodium methylate,, leave standstill after 1 hour lower floor's glycerine branch is fallen, obtain upper strata palm fibre coconut oil methyl ester bullion in 70 ℃ of heated and stirred reactions 3 hours.Methyl alcohol excessive in the bullion is distilled, then in 60 ℃ with 200g 5% concentration weak brine washed twice, with 200g clear water washing once, be warming up to 100 ℃ of underpressure distillation 1h then again, obtain 396.5g cocinic acid methyl esters.Add 109.9g monoethanolamine and 0..4g sodium methylate, in 100 ℃ of following vacuum reaction 2h, vacuum tightness-0.095Mpa.Obtain the high purity coconut monoethanolamide, purity 98.5%, amine value 1.8 (being converted into unhindered amina 0.20%), ester content 1.33%.
Embodiment 5:
The 400g hydrogenated coconut oil is mixed with the 120g anhydrous methanol, and add the 1g sodium methylate,, leave standstill after 1 hour lower floor's glycerine branch is fallen, obtain upper strata hydrogenated coconut oil methyl esters bullion in 70 ℃ of heated and stirred reactions 3 hours.Methyl alcohol excessive in the bullion is distilled, then in 60 ℃ with 200g 5% concentration weak brine washed twice, with 200g clear water washing once, be warming up to 100 ℃ of underpressure distillation 1h then again, obtain 398.0g hydrogenated coconut oleic acid methyl esters.Add 109.4g monoethanolamine and 0.3g sodium methylate, in 100 ℃ of following vacuum reaction 2h, vacuum tightness-0.095Mpa.Obtain high purity hydrogenation coconut monoethanolamide, purity 98.3%, amine value 1.5 (being converted into unhindered amina 0.17%), ester content 1.53%.
Embodiment 6:
The 400g hydrogenated coconut oil is mixed with the 120g anhydrous methanol, and add the 1g sodium methylate,, leave standstill after 1 hour lower floor's glycerine branch is fallen, obtain upper strata hydrogenated coconut oil methyl esters bullion in 70 ℃ of heated and stirred reactions 3 hours.Methyl alcohol excessive in the bullion is distilled, then in 60 ℃ with 200g 5% concentration weak brine washed twice, with 200g clear water washing once, be warming up to 80 ℃ of underpressure distillation 1h then again, obtain 396g hydrogenated coconut oleic acid methyl esters.The methanol solution of sodium methylate that adds 108.8g monoethanolamine and 1.5g30% concentration is in 80 ℃ of following vacuum reaction 4h, vacuum tightness-0.095Mpa.Obtain high purity hydrogenation coconut monoethanolamide, purity 98.4%, amine value 1.7 (being converted into unhindered amina 0.19%), ester content 1.40%.
Claims (10)
1. the compound method of a high purity fatty acid single ethanol amide may further comprise the steps:
(1) preparation of fatty acid methyl ester: with vegetables oil and methanol mixed, and add a certain amount of basic catalyst, heated and stirred stoichiometric number hour obtains the fatty acid methyl ester bullion;
(2) the fatty acid methyl ester aftertreatment is refining, may further comprise the steps:
1. after reaction finishes, left standstill several hours, the glycerine of lower floor is separated;
2. the excessive methanol in the methyl esters is distilled;
3. add washed twice in certain density salt solution to the methyl esters, add the clear water washing more once, with the soap in the bullion, glycerine, and some other water-soluble impurities remove;
4. be heated to certain temperature, with the small amount of methanol in the methyl esters, the moisture content underpressure distillation is fallen, and obtains the purified fatty acid methyl ester;
(3) amidate action: fatty acid methyl ester and a certain amount of monoethanolamine that back obtains is mixed, and add a certain amount of basic catalyst, at a certain temperature vacuum reaction for some time, obtain the high purity fatty acid single ethanol amide.
2. the compound method of high purity fatty acid single ethanol amide according to claim 1 is characterized in that: in the said preparation fatty acid methyl ester step, the vegetables oil of employing is a plam oil; Palm-kernel oil; Oleum Cocois, VT 18, one or more in rapeseed oil and the hydrogenate thereof.
3. the compound method of high purity fatty acid single ethanol amide according to claim 1; It is characterized in that: in said esterification and the amidation step; The basic catalyst that is adopted is a kind of in sodium methylate, sodium hydroxide and the Pottasium Hydroxide; Catalyzer can be solid, also can be certain density catalyzer methanol solution.
4. the compound method of high purity fatty acid single ethanol amide according to claim 1; It is characterized in that: in the said preparation fatty acid methyl ester step; Vegetables oil and methyl alcohol mol ratio are 1.0:3.0～9.0; 50～90 ℃ of temperature of reaction, reaction times 1～6h, catalyst levels account for vegetables oil mass ratio 0.01～1%.
5. the compound method of high purity fatty acid single ethanol amide according to claim 1 is characterized in that: during said fatty acid methyl ester aftertreatment was refining, leaving standstill the branch glycerine time was 1～6 hour.
6. the compound method of high purity fatty acid single ethanol amide according to claim 1 is characterized in that: during said fatty acid methyl ester aftertreatment was refining, 20-100 ℃ of salt solution and clear water wash temperature, water consumption were 20～100% of methyl esters volume.
7. the compound method of high purity fatty acid single ethanol amide according to claim 1 is characterized in that: during said fatty acid methyl ester aftertreatment was refining, temperature was 80～140 ℃ when underpressure distillation methyl alcohol and moisture content.
8. the compound method of high purity fatty acid single ethanol amide according to claim 1 is characterized in that: in the said amidation step, the mol ratio of fatty acid methyl ester and monoethanolamine is 1.0:1.0～1.1.
9. the compound method of high purity fatty acid single ethanol amide according to claim 1; It is characterized in that: in the said amidation step; It is 0.01 ~ 1% that catalyst levels accounts for the methyl esters mass ratio, and catalyzer can be catalyst solid, also can be diluted to certain density catalyzer methanol solution.
10. the compound method of high purity fatty acid single ethanol amide according to claim 1 is characterized in that: in the said amidation step, and 60～140 ℃ of temperature of reaction, reaction times 1～5h, vacuum tightness-0.05～-0.1Mpa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382762A (en) * | 2017-07-18 | 2017-11-24 | 钟千里 | A kind of synthetic method of fatty diglycollic amide |
| CN108048180A (en) * | 2017-12-06 | 2018-05-18 | 田秋珍 | A kind of preparation method of biodegradation type wire drawing oil |
| CN109232296A (en) * | 2018-10-25 | 2019-01-18 | 江南大学 | Oleic monoethanolamide polyoxyethylene ether and its synthetic method |
| CN112608249A (en) * | 2020-12-22 | 2021-04-06 | 赞宇科技集团股份有限公司 | Preparation method of fatty acid monoethanolamide |
| CN114907225A (en) * | 2022-04-28 | 2022-08-16 | 广东丽臣奥威实业有限公司 | Production method of coconut oil fatty acid monoethanolamide |
| WO2024083770A1 (en) * | 2022-10-18 | 2024-04-25 | Clariant International Ltd | An additive for anti-scratch composition |
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2011
- 2011-11-22 CN CN2011103737497A patent/CN102516109A/en active Pending
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| 金传玲: "生物柴油及其衍生物烷醇酰胺的制备和应用", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382762A (en) * | 2017-07-18 | 2017-11-24 | 钟千里 | A kind of synthetic method of fatty diglycollic amide |
| CN108048180A (en) * | 2017-12-06 | 2018-05-18 | 田秋珍 | A kind of preparation method of biodegradation type wire drawing oil |
| CN109232296A (en) * | 2018-10-25 | 2019-01-18 | 江南大学 | Oleic monoethanolamide polyoxyethylene ether and its synthetic method |
| CN112608249A (en) * | 2020-12-22 | 2021-04-06 | 赞宇科技集团股份有限公司 | Preparation method of fatty acid monoethanolamide |
| CN114907225A (en) * | 2022-04-28 | 2022-08-16 | 广东丽臣奥威实业有限公司 | Production method of coconut oil fatty acid monoethanolamide |
| WO2024083770A1 (en) * | 2022-10-18 | 2024-04-25 | Clariant International Ltd | An additive for anti-scratch composition |
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Application publication date: 20120627 |