CN106588706B - The synthetic method of castor oil acid formicester ethoxylate sulfonates - Google Patents
The synthetic method of castor oil acid formicester ethoxylate sulfonates Download PDFInfo
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- CN106588706B CN106588706B CN201610996808.9A CN201610996808A CN106588706B CN 106588706 B CN106588706 B CN 106588706B CN 201610996808 A CN201610996808 A CN 201610996808A CN 106588706 B CN106588706 B CN 106588706B
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- castor oil
- ethoxylates
- ethoxylate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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Abstract
A kind of synthetic method of castor oil acid formicester ethoxylate sulfonates is that castor oil acid formicester ethoxylate, sodium hydrogensulfite, catalyst, deionized water, low-carbon alcohols are added in reactor, under strong stirring, reaction, the wherein molar ratio of castor oil acid formicester ethoxylate and sodium hydrogensulfite are 1:1.5‑2.5；The dosage of catalyst is the 1.5 2.5% of castor oil acid formicester ethoxylation amount of substance, low-carbon alcohols, and the mass ratio of deionized water and castor oil acid formicester ethoxylate is 0.9 3：0.9‑3:1, after reaction, vacuum distillation removes water and low-carbon alcohols, is dissolved with excessive absolute ethyl alcohol, removes unreacted sodium hydrogensulfite and the sodium sulfite of generation, and vacuum distillation removes ethanol and obtains product.The present invention has that synthesis technique is simple and safe, and the advantages of spent acid and salkali waste will not be produced.
Description
Technical field
The present invention relates to a kind of preparation method of anion surfactant, relates in particular to a kind of castor oil acid formicester
The synthetic method of ethoxylate sulfonates.
Background technology
In recent years, as people are to environmental problem pay attention to day by day, develop new environmentally protective Mobyneb surface and live
Property agent is increasingly valued by people.Castor oil acid formicester ethoxylate is a kind of typical nonionic surfactant,
Have the characteristics that cost is low, be readily biodegradable, Environmental compatibility is good and small to skin irritation.Its molecular structure compares
It is special, compared with common Fatty acid methyl ester ethoxylate, more one are similar to fatty alcohol polyoxyethylene ether on side chain
Structure, intramolecular also has a carbon-carbon double bond in addition, therefore gets more and more people's extensive concerning.
Ethoxylates of Castor Oil sulfonate/Ethoxylates of Castor Oil sulfate is with castor oil acid
Formicester ethoxylate is raw material, and use is SO 3 sulfonated, then obtained with alkali neutralization.Because sulfonic group can be with ester appended
α hydrogen, can also substitute the end hydrogen of side chain polyoxyethylene ether, so sulfonate and sulfate can be generated.React obtained castor-oil plant
Methyl oleate ethoxylate sulfonates/Ethoxylates of Castor Oil sulfate has low bubble property, emulsifying capacity is strong, goes
Dirty power is by force, easy the advantages that rinsing, (Li Jie, Yang Xiaoyi, Sun Yongqiang, intelligence found winged Ethoxylates of Castor Oil sulfonate/sulphur
The synthesis of hydrochlorate and physical and chemical performance [J] printing and dyeing assistants, 2016,34 (4):7-10.).
Using castor oil acid formicester ethoxylate as raw material, under the action of catalyst and sodium hydrogensulfite Direct Sulfonation can
To obtain a kind of new anion surfactant ----castor oil acid formicester ethoxylate sulfonates, sodium hydrogensulfite add
Into on carbon-carbon double bond in the molecule, the preparation method of such a surfactant at home and abroad has not been reported.
The content of the invention
The purpose of the invention is to provide a kind of synthetic method of castor oil acid formicester ethoxylate sulfonates.
The molecular structural formula of raw material castor oil acid formicester ethoxylate provided by the invention is as follows：
Wherein：X+y=15-20
Present invention reaction synthetic route is as follows：
The synthetic method of anion surfactant castor oil acid formicester ethoxylate sulfonates provided by the invention, bag
Include following steps：
Castor oil acid formicester ethoxylate, sodium hydrogensulfite, catalyst, deionized water, low-carbon alcohols are added to reaction
In device, under strong stirring, 60-80 DEG C is heated to, reacts 6-8h；Wherein castor oil acid formicester ethoxylate and sodium hydrogensulfite
Molar ratio be 1:1.5-2.5；The dosage of catalyst be castor oil acid formicester ethoxylation amount of substance 1.5-2.5%, low-carbon
The mass ratio of alcohol, deionized water and castor oil acid formicester ethoxylate is 0.9-3：0.9-3:1, after reaction, decompression is steamed
Water and low-carbon alcohols are removed in distillation, are dissolved with excessive absolute ethyl alcohol, and heat filtering removes the Asia of unreacted sodium hydrogensulfite and generation
Sodium sulphate, vacuum distillation remove ethanol and obtain product.
In above-mentioned reaction, the average adduct number of castor oil acid formicester ethoxylate ethylene oxide is 15-20, intramolecular
Containing undersaturated carbon-carbon double bond, because on the carbon-carbon double bond of sodium hydrogensulfite addition in the molecule, so castor oil acid formicester second
Carbon-carbon double bond is not contained in epoxide compound sulfonate.
Catalyst in above-mentioned reaction is azodiisobutyronitrile.
Low-carbon alcohols in above-mentioned reaction are the alcohol of some short carbon chains such as methanol, ethanol, propyl alcohol, isopropanol or butanol.
The molar ratio of castor oil acid formicester ethoxylate and sodium hydrogensulfite is preferably 1 in above-mentioned reaction:1.8-2.2；
The dosage of catalyst is preferably the 1.9-2.3% of the quality of castor oil acid formicester ethoxylate, low-carbon alcohols, deionized water and castor
The mass ratio of sesame oil acid formicester ethoxylate is preferably 0.9-1.5：0.9-1.5:1.
Product in above-mentioned reaction is castor oil acid formicester ethoxylate sulfonates and castor oil acid formicester ethoxylation
The mixture of thing, analysis is carried out to product can prove to have synthesized castor oil acid formicester ethoxylate sulfonates.By product point
From castor oil acid formicester ethoxylate sulfonates are obtained, castor oil acid formicester ethoxylate recycles.
In above-mentioned reaction can first in advance sodium hydrogensulfite dissolving in deionized water, then by castor oil acid formicester second
Epoxide compound, catalyst and low-carbon alcohols are added in ionized water, are so conducive to being smoothed out for reaction.
It is an object of the invention to synthesize a kind of new anion surfactant castor oil acid formicester ethoxylate sulphur
Hydrochlorate, it is the anion surfactant that a kind of special anion-nonionic is combined, and intramolecular has three hydrophilic group functions
Group, is obtained, the position of addition is intramolecular by sodium hydrogensulfite and the direct addition of castor oil acid formicester ethoxylate
Carbon-carbon double bond.
The present invention has the following advantages that compared with prior art：
1 has synthesized a kind of new sulfosalt surfactant, there is multiple hydrophilic functional groups, have it is low bubble property, easily rinse,
The advantages that alkali resistance is strong.
2 synthesis techniques are simple and safe, and will not produce spent acid and salkali waste.
Brief description of the drawings
Fig. 1 is the infrared spectrum after the castor oil acid formicester ethoxylate sulfonates purification that the present invention synthesizes
In Fig. 1,1178cm-1,1034cm-1,620cm-1And 519cm-1The absworption peak at place represents that intramolecular has sulfonic group function
Group, 717cm-1Absworption peak be carbon-carbon double bond absworption peak because also remaining castor oil acid formicester ethoxylate does not have
Remove.
Embodiment
Present invention employs following test method：(1) determine to contain sulfonate functional groups in product by infrared spectrum.
(2) using diphasic titration measure anionic surfactant concentration.(3) measure product iodine number, and with castor oil acid formicester
Ethoxylate iodine number contrasts, by calculating finally definite sodium hydrogensulfite addition on the carbon-carbon double bond of intramolecular.
Embodiment 1
By 50g (0.051mol) castor oil acid formicester ethoxylate, (average molecular weight 976, X average values are put down for 10.9, Y
Average is 4.2, iodine number 26.1g/100g), 100g deionized waters, 100g isopropanols, 8g (0.077mol) sodium hydrogensulfites with
And 1.1g azodiisobutyronitriles are added in the four-hole boiling flask of 500ml, 80 DEG C are heated to, reacts 6.5h.After reaction, rotate
Evaporate and remove water and isopropanol, dissolved with excessive absolute ethyl alcohol, heat filtering removes unreacted sodium hydrogensulfite and generation
Sodium sulfite, rotary evaporation remove ethanol and obtain product.Product leading indicator is as follows：(1) iodine number is 22.1g/100g；(2) castor
The mass fraction of sesame oil acid formicester ethoxylate sodium sulfonate is 14.7%.
Embodiment 2
By 30g (0.030mol) castor oil acid formicester ethoxylate, (average molecular weight 976, X average values are put down for 10.9, Y
Average is 4.2, iodine number 26.1g/100g), 60g deionized waters, 60g ethanol, 4.8g (0.046mol) sodium hydrogensulfites and
0.6g azodiisobutyronitriles are added in the four-hole boiling flask of 250ml (is dissolved in deionized water in advance before charging sodium hydrogensulfite
In), 78 DEG C are heated to, reacts 6h.After reaction, rotary evaporation removes water and ethanol, is dissolved with excessive absolute ethyl alcohol, heat
Unreacted sodium hydrogensulfite and the sodium sulfite of generation are filtered to remove, rotary evaporation removes ethanol and obtains product.Product is main
Index is as follows：(1) iodine number is 21.6g/100g；(2) mass fraction of castor oil acid formicester ethoxylate sodium sulfonate is
17.9%.
Embodiment 3
By 30g (0.026mol) castor oil acid formicester ethoxylate, (average molecular weight 1151, X average values are 13.2, Y
Average value is 5.9, iodine number 22.5g/100g), 55g deionized waters, 55g methanol, 5.4g (0.052mol) sodium hydrogensulfites with
And 0.5g azodiisobutyronitriles are added in the four-hole boiling flask of 250ml, 60 DEG C are heated to, reacts 8h.After reaction, rotation is steamed
Hair removes water and methanol, is dissolved with excessive absolute ethyl alcohol, and heat filtering removes unreacted sodium hydrogensulfite and the sulfurous of generation
Sour sodium, rotary evaporation remove ethanol and obtain product.Product leading indicator is as follows：(1) iodine number is 18.5g/100g；(2) castor oil
The mass fraction of sour formicester ethoxylate sodium sulfonate is 18.9%.
Embodiment 4
By 30g (0.026mol) castor oil acid formicester ethoxylate, (average molecular weight 1151, X average values are 13.2, Y
Average value is 5.9, iodine number 22.5g/100g), 80g deionized waters, 80g isopropanols, 6.5g (0.064mol) sodium hydrogensulfite
And 0.4g azodiisobutyronitriles be added in the four-hole boiling flask of 500ml (charging before sodium hydrogensulfite is dissolved in advance from
In sub- water), 78 DEG C are heated to, reacts 6h.After reaction, rotary evaporation removes water and isopropanol, with excessive absolute ethyl alcohol
Dissolving, heat filtering remove unreacted sodium hydrogensulfite and the sodium sulfite of generation, and rotary evaporation removes ethanol and obtains product.Production
Thing leading indicator is as follows：(1) iodine number is 17.6g/100g；(2) mass fraction of castor oil acid formicester ethoxylate sodium sulfonate
For 20.4%.
Embodiment 5
By 30g (0.029mol) castor oil acid formicester ethoxylate, (average molecular weight 1037, X average values are 11.9, Y
Average value is 4.5, iodine number 25g/100g), 70g deionized waters, 70g ethanol, 6g (0.058mol) sodium hydrogensulfites and
0.7g azodiisobutyronitriles are added in the four-hole boiling flask of 500ml, are heated to 75 DEG C, react 6.5h.After reaction, rotation is steamed
Hair removes water and ethanol, is dissolved with excessive absolute ethyl alcohol, and heat filtering removes unreacted sodium hydrogensulfite and the sulfurous of generation
Sour sodium, rotary evaporation remove ethanol and obtain product.Product leading indicator is as follows：(1) iodine number is 18.4g/100g；(2) castor oil
The mass fraction of sour formicester ethoxylate sodium sulfonate is 24.2%.
Embodiment 6
By 30g (0.029mol) castor oil acid formicester ethoxylate, (average molecular weight 1037, X average values are 11.9, Y
Average value is 4.5, iodine number 25g/100g), 90g deionized waters, 90g isopropanols, 6g (0.058mol) sodium hydrogensulfites and
0.7g azodiisobutyronitriles are added in the four-hole boiling flask of 500ml, are heated to 80 DEG C, react 6.5h.After reaction, rotation is steamed
Hair removes water and isopropanol, is dissolved with excessive absolute ethyl alcohol, and heat filtering removes the Asia of unreacted sodium hydrogensulfite and generation
Sodium sulphate, rotary evaporation remove ethanol and obtain product.Product leading indicator is as follows：(1) iodine number is 18.8g/100g；(2) castor-oil plant
The mass fraction of oleic acid formicester ethoxylate sodium sulfonate is 23.1%.
Embodiment 7
By 30g (0.029mol) castor oil acid formicester ethoxylate, (average molecular weight 1037, X average values are 11.9, Y
Average value is 4.5, iodine number 24.6g/100g), 30g deionized waters, 30g ethanol, 6g (0.058mol) sodium hydrogensulfites and
0.7g azodiisobutyronitriles are added in the four-hole boiling flask of 250ml, are heated to 78 DEG C and (sodium hydrogensulfite are dissolved in advance before charging
In deionized water), 7h is reacted.After reaction, rotary evaporation removes water and ethanol, is dissolved with excessive absolute ethyl alcohol, heat
Unreacted sodium hydrogensulfite and the sodium sulfite of generation are filtered to remove, rotary evaporation removes ethanol and obtains product.Product is main
Index is as follows：(1) iodine number is 18.2g/100g；(2) mass fraction of castor oil acid formicester ethoxylate sodium sulfonate is
25.2%.
Claims (4)
1. a kind of synthetic method of Ethoxylates of Castor Oil sulfonate, it is characterised in that include the following steps：
Ethoxylates of Castor Oil, sodium hydrogensulfite, catalyst, deionized water, low-carbon alcohols are added in reactor,
Under strong stirring, 60-80 DEG C is heated to, reacts 6-8h；Wherein Ethoxylates of Castor Oil and sodium hydrogensulfite rubs
You are than being 1:1.5-2.5；The dosage of catalyst is the 1.5-2.5% of Ethoxylates of Castor Oil quality, and low-carbon alcohols, go
The mass ratio of ionized water and Ethoxylates of Castor Oil is 0.9-3：0.9-3:1, after reaction, vacuum distillation removes
Water and low-carbon alcohols, are dissolved with excessive absolute ethyl alcohol, and heat filtering removes unreacted sodium hydrogensulfite and the sodium sulfite of generation,
Vacuum distillation removes ethanol and obtains product；
The molecular structural formula of the raw material Ethoxylates of Castor Oil is as follows：
Wherein：x+y=15-20；
The catalyst is azodiisobutyronitrile；
The low-carbon alcohols are methanol, ethanol, propyl alcohol, isopropanol or butanol.
A kind of 2. synthetic method of Ethoxylates of Castor Oil sulfonate as claimed in claim 1, it is characterised in that
The molar ratio of Ethoxylates of Castor Oil and sodium hydrogensulfite is 1:1.8-2.2；The dosage of catalyst is castor oil acid
The quality of the 1.9-2.3% of the quality of methyl ester ethoxylates, low-carbon alcohols, deionized water and Ethoxylates of Castor Oil
Than for 0.9-1.5：0.9-1.5:1.
A kind of 3. synthetic method of Ethoxylates of Castor Oil sulfonate as claimed in claim 1, it is characterised in that
First in advance sodium hydrogensulfite dissolving in deionized water, then by Ethoxylates of Castor Oil, catalyst and low-carbon alcohols
Add in ionized water.
A kind of 4. synthetic method of Ethoxylates of Castor Oil sulfonate as claimed in claim 1, it is characterised in that
Product is Ethoxylates of Castor Oil sulfonate and the mixture of Ethoxylates of Castor Oil, and product is separated
Ethoxylates of Castor Oil sulfonate is obtained, Ethoxylates of Castor Oil recycles.
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| CN108484450B (en) * | 2018-03-29 | 2020-12-01 | 中国日用化学研究院有限公司 | Synthetic method of oleic acid disodium salt |
| CN116041229A (en) * | 2023-02-21 | 2023-05-02 | 太原理工大学 | Castor oil-based sulfonate anionic surfactant and preparation method thereof |
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| CN103086927A (en) * | 2012-12-06 | 2013-05-08 | 广西民族大学 | Tertiary amine oxide with rosinyl three-membered phenanthrene ring structure and preparation method of tertiary amine oxide |
| CN103201359A (en) * | 2010-10-25 | 2013-07-10 | 斯特潘公司 | Alkoxylated fatty esters and derivatives from natural oil metathesis |
| CN104356030A (en) * | 2014-10-22 | 2015-02-18 | 中国日用化学工业研究院 | Preparation method of castor oil methyl ester ethoxylate sulphonate or castor oil methyl ester ethoxylate sulfate |
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| JPS63179940A (en) * | 1987-01-21 | 1988-07-23 | Showa Highpolymer Co Ltd | Foamed phenolic resin composition |
| CN103623740B (en) * | 2013-10-23 | 2015-03-18 | 长江大学 | Gemini surfactant containing sulfo group and sulfate group anions |
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| CN103201359A (en) * | 2010-10-25 | 2013-07-10 | 斯特潘公司 | Alkoxylated fatty esters and derivatives from natural oil metathesis |
| CN103086927A (en) * | 2012-12-06 | 2013-05-08 | 广西民族大学 | Tertiary amine oxide with rosinyl three-membered phenanthrene ring structure and preparation method of tertiary amine oxide |
| CN104356030A (en) * | 2014-10-22 | 2015-02-18 | 中国日用化学工业研究院 | Preparation method of castor oil methyl ester ethoxylate sulphonate or castor oil methyl ester ethoxylate sulfate |
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