CN104447321A - Alcohol ether ester carboxylate (AEEC) and synthetic process thereof - Google Patents
Alcohol ether ester carboxylate (AEEC) and synthetic process thereof Download PDFInfo
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- CN104447321A CN104447321A CN201410653041.0A CN201410653041A CN104447321A CN 104447321 A CN104447321 A CN 104447321A CN 201410653041 A CN201410653041 A CN 201410653041A CN 104447321 A CN104447321 A CN 104447321A
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- alcohol ether
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- ether ester
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- oxalic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/36—Oxalic acid esters
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Abstract
The invention discloses alcohol ether ester carboxylate (AEEC). AEEC is a compound with a structure shown in a formula in the specification, wherein in the formula, n is equal to 6, 8, 10, 12, 14 or 16; m is equal to 1-9; M is Na, K, Ca, Mg or Zn. A synthetic process of AEEC comprises the following steps in sequence: (1) preparation of mono-alcohol ether oxalate, namely mixing alkyl alcohol ether with oxalic acid in a certain ratio to undergo esterification reaction to obtain corresponding alcohol ether ester oxalate; and (2) synthesis of alcohol ether ester metal oxalates, namely carrying out neutralization salt forming reaction on an obtained alcohol ether ester oxalate intermediate by using specific alkali metals to obtain various corresponding alcohol ether ester metal carboxylates. The compound is easy to synthesize and low in toxicity, is beneficial to biodegradation and has good decontaminating, dispersing and emulsifying properties.
Description
Technical field
The present invention relates to surfactant field, particularly a kind of alcohol ether ester group carboxylate salt (AEEC) and synthesis technique thereof.
Background technology
Alcohol ether carboxylate AEC is the novel multi-functional anion surfactant of a class, and its general structure formula is: R-(OCH
2cH
2)
noCH
2cOONa (H), quite similar with soap, but the EO chain embedded makes it have both the feature of negatively charged ion and nonionogenic tenside, can use under pH condition widely, and show remarkable performance, such as remarkable solubilising, good soil release performance, wettability, emulsifying property, dispersiveness and dispersion of calcium soap, good foaminess and froth stability, to eyes and skin as mild as a dove, resistance to hard water, acid and alkali-resistance, electrolyte-resistant, high temperature resistant, readily biodegradable etc.Due to the above-mentioned character of AEC, it is made to be widely used in the fields such as washing, makeup, weaving, personal cleanliness's articles for use.As CN103805365A discloses a kind of washing liquid containing alcohol ether carboxylate.
But, alcohol ether carboxylate has the shortcomings such as not easily degraded, and the performances such as detersive power, dispersion force and emulsifying property also exist very large room for promotion, therefore, be necessary to develop one and be easy to synthesis, toxicity is low, be conducive to biological degradation and there is the novel alcohol ether carboxylate surfactant of better performance.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of alcohol ether ester group carboxylate salt, this compound is easy to synthesis, and toxicity is low, be conducive to biological degradation and have good decontamination, dispersion, emulsifying property.
A kind of alcohol ether ester group carboxylate salt provided by the invention, for having the compound of structure as follows:
N=6,8,10,12,14 or 16 in formula;
m＝1～9；
M is Na, K, Ca, Mg or Zn.
The synthesis technique of above-mentioned alcohol ether ester group carboxylate salt, in turn includes the following steps:
(1) preparation of oxalic acid single methanol ether-ether: alkyl ethoxylated and oxalic acid are mixed in certain proportion, add appropriate catalyst for esterification reaction, under condition of no solvent, or react under certain reaction conditions, obtain corresponding alcohol ether ester group oxalic acid, reaction equation is as follows:
(2) synthesis of alcohol ether ester group oxalic acid metal-salt: by alcohol ether ester group oxalic acid intermediate obtained above, is undertaken by using specific metal base being neutralized into reactant salt, and obtain corresponding various alcohol ether ester group carboxylic metallic salts, its reaction equation is as follows:
Preferably, in step (1), the mol ratio of alkyl ethoxylated and oxalic acid is 1: 1 ~ 1: 1.2, reaction is solvent-free reaction, not only or alcohol ether itself makes reactant but also as solvent, temperature of reaction is 100 ~ 180 DEG C, catalysts is tosic acid, methylsulfonic acid, trifluoromethanesulfonic acid, thionamic acid, trifluoromethanesulfonic acid rare-earth salts (RE (OTf)
3) in the mixture of one or more, the reaction times is 2h ~ 8h.
Preferably, in step (2), the adding proportion of metal base maintains between 6-10 for controlling pH value of reaction system, fully stirs in reaction process, ensures to exist without solid sediment.
More preferably, the temperature of reaction in step (2) is 80 DEG C, and the reaction times is 3h.
More preferably, temperature of reaction is 100 ~ 120 DEG C, and the reaction times is 3h.
A kind of alcohol ether ester group carboxylate salt provided by the invention and synthesis technique thereof, have following beneficial effect:
(1) by using oxalic acid and alkyl ethoxylated as raw material, as connection base, alcohol ether chain and hydroxy-acid group coupled together using the ester group of easily degrading, toxicity is low, be conducive to biological degradation.
(2) the method raw material is simple and easy to get, compared to the advantage using the Mono Chloro Acetic Acid of severe toxicity to have larger environmental protection aspect in traditional technology.In addition, the esterification involved by this technique and acid-base neutralisation reaction all have comparatively ripe industrialized producing technology and equipment support, and be easy to realize industrialization, production cost is lower.
(3) in synthesis technique of the present invention, the first step esterification can be carried out under condition of no solvent, decreases three waste discharge;
(4) most importantly, this product can at detersive power, dispersive ability, and the alcohol ether carboxylate of many-sided beyond tradition such as emulsifying property, has application prospect comparatively widely.
Embodiment
In order to make those skilled in the art person understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Take 61.1g (0.105mol) dodecyl alcohol ether (EO
9) and 9g (0.1mol) oxalic acid, join in 250mL there-necked flask, oil bath is heated to 100 DEG C, after solid reactant is melted completely, taking 172mg (1mmol) tosic acid joins in above-mentioned reaction system, raising temperature of reaction is 120 DEG C, and reaction 3h, stops heating.Take 4g (0.1mol) sodium hydroxide to add in above-mentioned solution, be warming up to 80 DEG C, stirring reaction 3h, stop heating, cooling after product is separated out with white solid forms.
Embodiment 2
61.1g (0.105mol) dodecyl alcohol ether (EO
9) and 9g (0.1mol) oxalic acid, join in 250mL there-necked flask, oil bath is heated to 100 DEG C, after solid reactant is melted completely, takes 172mg (1mmol) tosic acid and joins in above-mentioned reaction system, raising temperature of reaction is 120 DEG C, reaction 3h, is cooled to 80 DEG C, and slowly drips the aqueous sodium hydroxide solution of 10N in system, controlling reaction end by pH meter is pH=9, obtains pale yellow transparent thick liquid.
Embodiment 3
Take 66.6g (0.11mol) octadecyl alcohol ether (EO
9) and 9g (0.1mol) oxalic acid, join in 250mL there-necked flask, oil bath is heated to 100 DEG C, after solid reactant is melted completely, taking 172mg (1mmol) tosic acid joins in above-mentioned reaction system, raising temperature of reaction is 120 DEG C, and reaction 3h, stops heating.Take 4.4g (0.11mol) sodium hydroxide to add in above-mentioned solution, be warming up to 80 DEG C, stirring reaction 3h, stop heating, cooling after product is separated out with white solid forms.
Embodiment 4
Take 66.6g (0.11mol) octadecyl alcohol ether (EO
9) and 9g (0.1mol) oxalic acid, join in 250mL there-necked flask, oil bath is heated to 100 DEG C, after solid reactant is melted completely, taking 172mg (1mmol) tosic acid joins in above-mentioned reaction system, raising temperature of reaction is 120 DEG C, and reaction 3h, stops heating.Take 5.6g (0.11mol) potassium hydroxide to add in above-mentioned solution, be warming up to 80 DEG C, stirring reaction 3h, stop heating, cooling after product is separated out with white solid forms.
Embodiment 5
Take 31.9g (0.11mol) isomery ten polyoxyethylenated alcohol (EO
3) and 9g (0.1mol) oxalic acid, join in 100mL there-necked flask, oil bath is heated to 100 DEG C, after solid reactant is melted completely, taking 150mg (1mmol) joins in above-mentioned reaction system to trifluoromethanesulfonic acid, raising temperature of reaction is 120 DEG C, and reaction 3h, stops heating.Take 5.6g (0.11mol) potassium hydroxide to add in above-mentioned solution, be warming up to 80 DEG C, stirring reaction 3h, stop heating, cooling after product is separated out with white solid forms.
Embodiment 6
Take 64.6g (0.105mol) Nonoxynol-9 (EO
9) and 9g (0.1mol) oxalic acid, join in 100mL there-necked flask, oil bath is heated to 100 DEG C, after solid reactant is melted completely, taking 150mg (1mmol) joins in above-mentioned reaction system to trifluoromethanesulfonic acid, raising temperature of reaction is 120 DEG C, and reaction 3h, stops heating.Take 4.4g (0.11mol) sodium hydroxide to add in above-mentioned solution, be warming up to 80 DEG C, stirring reaction 3h, stop heating, cooling after product is separated out with white solid forms.
Embodiment 7
Take 60.6g (0.105mol) oleth-9 (EO
5) and 9g (0.1mol) oxalic acid, join in 100mL there-necked flask, oil bath is heated to 100 DEG C, after solid reactant is melted completely, takes 150mg (1mmol) and joins in above-mentioned reaction system to trifluoromethanesulfonic acid, raising temperature of reaction is 120 DEG C, reaction 3h, is cooled to 80 DEG C, and slowly drips the aqueous sodium hydroxide solution of 10N in system, controlling reaction end by pH meter is pH=8, obtains pale yellow transparent thick liquid.
Reaction expression in the various embodiments described above is as follows:
(1) alkyl ethoxylated and oxalic acid react:
Reaction equation is as follows:
(2) synthesis of alcohol ether ester group oxalic acid metal-salt:
Test example 1
Measure the soil removability of embodiment 1 ~ 7 product according to GB/T13174-2008 " mensuration of dress material washing composition detersive power and circulation cleaning performance ", active concentration 0.2wt%, result is as follows:
| Product | Relative standard's powder decontamination ratio |
| Embodiment 1 | 3.7 |
| Embodiment 2 | 3.4 |
| Embodiment 3 | 4.2 |
| Embodiment 4 | 4.1 |
| Embodiment 5 | 3.8 |
| Embodiment 6 | 4.3 |
| Embodiment 7 | 3.6 |
Test example 2
Measure product emulsifying property, testing method is as follows: measure: the surfactant soln and the 40mL Witco 70 (chemical pure) that add 40mL0.1% in 100mL tool plug graduated cylinder, cover stopper, leave standstill after fiercely vibrating 30 times up and down, record and separate the 10mL time to aqueous phase from leaving standstill.Time, longer emulsifying property was better.Outcome record is in following table:
| Product | Time/min |
| Embodiment 1 | 8.2min |
| Embodiment 2 | 8.5min |
| Embodiment 3 | 8.2min |
| Embodiment 4 | 9.5min |
| Embodiment 5 | 9min |
| Embodiment 6 | 9.2min |
| Embodiment 7 | 8.3min |
Above a kind of alcohol ether ester group carboxylate salt provided by the present invention and synthesis technique thereof are described in detail.Apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands core concept of the present invention for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention.These improve and modify and also should fall in the protection domain of the claims in the present invention.
Claims (6)
1. an alcohol ether ester group carboxylate salt, is characterized in that, for having the compound of structure as follows:
N=6,8,10,12,14 or 16 in formula;
m＝1～9；
M is Na, K, Ca, Mg or Zn.
2. a synthesis technique for alcohol ether ester group carboxylate salt described in claim 1, is characterized in that, in turn include the following steps:
(1) preparation of oxalic acid single methanol ether-ether: alkyl ethoxylated and oxalic acid are mixed in certain proportion, add appropriate catalyst for esterification reaction, under condition of no solvent, or react under certain reaction conditions, obtain corresponding alcohol ether ester group oxalic acid, reaction equation is as follows:
(2) synthesis of alcohol ether ester group oxalic acid metal-salt: by alcohol ether ester group oxalic acid intermediate obtained above, is undertaken by using specific metal base being neutralized into reactant salt, and obtain corresponding various alcohol ether ester group carboxylic metallic salts, its reaction equation is as follows:
3. the synthesis technique of alcohol ether ester group carboxylate salt according to claim 2, it is characterized in that, in step (1), the mol ratio of alkyl ethoxylated and oxalic acid is 1: 1 ~ 1: 1.2, reaction is solvent-free reaction, not only or alcohol ether itself makes reactant but also as solvent, temperature of reaction is 100 ~ 180 DEG C, and catalysts is tosic acid, methylsulfonic acid, trifluoromethanesulfonic acid, thionamic acid, trifluoromethanesulfonic acid rare-earth salts (RE (OTf)
3) in the mixture of one or more, the reaction times is 2h ~ 8h.
4. the synthesis technique of alcohol ether ester group carboxylate salt according to claim 2, it is characterized in that, in step (2), the adding proportion of metal base maintains between 6-10 for controlling pH value of reaction system, fully stirs in reaction process, ensures to exist without solid sediment.
5. the synthesis technique of alcohol ether ester group carboxylate salt according to claim 4, is characterized in that, the temperature of reaction in step (2) is 80 DEG C, and the reaction times is 3h.
6. the synthesis technique of alcohol ether ester group carboxylate salt according to claim 3, is characterized in that, temperature of reaction is 100 ~ 120 DEG C, and the reaction times is 3h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410653041.0A CN104447321A (en) | 2014-11-17 | 2014-11-17 | Alcohol ether ester carboxylate (AEEC) and synthetic process thereof |
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|---|---|---|---|
| CN201410653041.0A CN104447321A (en) | 2014-11-17 | 2014-11-17 | Alcohol ether ester carboxylate (AEEC) and synthetic process thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999717A (en) * | 2019-04-11 | 2019-07-12 | 中国日用化学研究院有限公司 | A kind of fatty alcohol ether succinate surfactant and preparation method thereof |
| CN110903476A (en) * | 2019-12-26 | 2020-03-24 | 上海雅运新材料有限公司 | Preparation method of polyoxyalkylene ether sulfate surfactant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108804A (en) * | 2007-07-17 | 2008-01-23 | 中国日用化学工业研究院 | Technique of manufacturing lemon acid monoester salt |
| CN101475469A (en) * | 2009-01-20 | 2009-07-08 | 南京林业大学 | Method for synthesizing diatomic alcohol ether acid ester |
| CN102167665A (en) * | 2011-02-21 | 2011-08-31 | 中国人民解放军第二炮兵工程学院 | High-grade fatty acid ester ether compound |
-
2014
- 2014-11-17 CN CN201410653041.0A patent/CN104447321A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108804A (en) * | 2007-07-17 | 2008-01-23 | 中国日用化学工业研究院 | Technique of manufacturing lemon acid monoester salt |
| CN101475469A (en) * | 2009-01-20 | 2009-07-08 | 南京林业大学 | Method for synthesizing diatomic alcohol ether acid ester |
| CN102167665A (en) * | 2011-02-21 | 2011-08-31 | 中国人民解放军第二炮兵工程学院 | High-grade fatty acid ester ether compound |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999717A (en) * | 2019-04-11 | 2019-07-12 | 中国日用化学研究院有限公司 | A kind of fatty alcohol ether succinate surfactant and preparation method thereof |
| CN110903476A (en) * | 2019-12-26 | 2020-03-24 | 上海雅运新材料有限公司 | Preparation method of polyoxyalkylene ether sulfate surfactant |
| CN110903476B (en) * | 2019-12-26 | 2022-05-13 | 太仓宝霓实业有限公司 | Preparation method of polyoxy alkenyl ether sulfate surfactant |
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Application publication date: 20150325 |