CN107118134A - One pot process AEO（3）Sodium sulfonate（AESO‑3）Method - Google Patents
One pot process AEO（3）Sodium sulfonate（AESO‑3）Method Download PDFInfo
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- CN107118134A CN107118134A CN201710325402.2A CN201710325402A CN107118134A CN 107118134 A CN107118134 A CN 107118134A CN 201710325402 A CN201710325402 A CN 201710325402A CN 107118134 A CN107118134 A CN 107118134A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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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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Abstract
The invention provides a kind of method of one pot process AEO (3) sodium sulfonate (AESO 3).The present invention is with AEO (AEO 3), 2 chloroethyl sodium sulfonate (C2H4ClSO3Na) and sodium hydroxide (NaOH) be raw material, the crude product for obtaining AEO (3) sodium sulfonate (AESO 3) is reacted in the mixed solvent, crude product is scrubbed, filters, concentrate, recrystallize and dries, finally obtain target product, AESO 3 yield is 75~85%, purity is 80~87%, and solvent is recyclable in reaction recycles.This method has following advantage relative to the technique reported：(1) reaction uses one kettle way, and reaction efficiency is higher and easy to operate, reduces waste of solvent and energy resource consumption because caused by changing solvent in building-up process；(2) reaction is carried out in the mixed solvent, and reaction temperature is relatively low, and mixed solvent is good to the selectivity of target product, and the conversion ratio that generation AESO 3 reacts is higher；(3) do not have to introduce the other materials in addition to raw material and mixed solvent in course of reaction, mixed solvent is not contaminated and is easily recycled.
Description
Technical field
The invention belongs to the synthesis technical field of organic monomer, it is related to AEO (3) sodium sulfonate (AESO-
3) preparation, more particularly to aliphatic alcohol polyethenoxy (3) ether sulfonic acid sodium (AESO-3) novel preparation method, enter in mixed solvent method
Row synthesis.The advantage of mixed solvent method is：One side reaction temperature is relatively low, and mixed solvent is good to the selectivity of target product；
On the other hand it can be achieved to react in dehydration, farthest improve the conversion ratio of reaction.
Background technology
AEO (3) sodium sulfonate (abbreviation AESO-3) is white or light yellow crystal.Fatty alcohol polyoxy second
Alkene ether sulfonic acid type surfactant designs alkoxy and sulfonic group in same surfactant molecule, it is had the moon concurrently
The two-fold advantage of ion high temperature resistance and nonionic salt tolerant, in addition, also making it have excellent foaming properties, chemical stability and width
The wide pH scope of applications.It is applied in tertiary oil recovery technology, the prospect in high temperature, high salinity, high calcium magnesium ion oil reservoir
It is wide.In recent years, with the continuous progress of oil exploitation, conventional oil reservoir is gradually decreased, and exploitation difficulty is increased, to fatty alcohol polyoxy
The development and application of vinethene Sulfonates salt resistance surfactant has important strategic importance.
According to domestic and foreign literature, the synthetic method of aliphatic alcohol polyoxyethylene sulfonate has following four：
(1) Stecker methods：AEO and thionyl chloride (SOCl2), in weakly acidic condition, given birth to through chlorination reaction
Into intermediate Alkylpolyethoxychloride, chloro intermediate is poly- through sulphite sulfonation synthetic fatty alcohol under the high temperature conditions
Oxygen ethene ether sulfonate, reaction equation is as follows：
R(OCH2CH2)nOH+SOCl2R(OCH2CH2)nCl+SO2+HCl (1-1)
R(OCH2CH2)nCl+Na2SO3R(OCH2CH2)nSO3Na+NaCl (1-2)
Reaction equation (1-1) in Stecker methods carries out chlorination reaction under the catalysis of aminated compounds, with reaction condition temperature
With, operating procedure is simple, high income the advantages of, but SO can be produced in course of reaction2With the sour gas such as HCl, etching apparatus is dirty
Contaminate environment；Reaction equation (1-2) needs to carry out at a higher pressure, high to equipment requirement, so that industrialization relatively difficult to achieve.
(2) AES sulfonation methods：Laboratory is with sodium sulfate of polyethenoxy ether of fatty alcohol (AES) for raw material, and water is solvent, uses Na2SO3
And NaHSO3Sulfonation is made polyoxyethylene fatty alkyl ether sulfonate (AESO), and yield reaches 84%, and product purity is up to 98%.In view of
This method AES costs are higher, and further synthesis is especially needed in laboratory, is lain on the table in this way.
(3) propane sultone method：Propane sultone is a kind of efficient fine chemical intermediate, and active sulfopropyl can be provided to acceptor
Intermediate, alcohol ether sulfonate can be prepared by sulfopropylization reaction, while can also make molecule have the characteristic of anion.Reaction
Formula such as (1-3) and (1-4)：
2R(OCH2CH2)nOH+2Na→2R(OCH2CH2)nONa+H2 (1-3)
R(OCH2CH2)nONa+SO2CH2CH2CH2O→R(OCH2CH2)n+1CH2SO3Na (1-4)
It can be seen from reaction equation (1-3) and (1-4) reaction be first in a solvent by AEO sodium,
Again under certain condition with propane sultone sulfonation synthetic fatty alcohol sodium sulfonate of ethoxylated.Have with propane sultone sulfonation
Certain advantage：Synthetic reaction speed is fast, yield is high, reaction condition is gentle, side reaction is few, is to introduce sulfonic acid group in compound
Important method, typically based on laboratory research.But PS industrial source is not wide, cost of material is high, and third
Sultones has carcinogenicity, is greatly limited its industrial applications and popularization.
(4) sulfoalkylation method：Sulfoalkylation method is main to generate alcohol ether sulfonate by raw material of alkyl alcohol ether, and the process will be by one
Fixed sulfoalkyl agent, sulfoalkyl agent is usually the organic sulfonate of 1~3 carbon atom, wherein also including an active official
It can roll into a ball, its purpose is to introduce sulfonic group on alkyl alcohol ether molecule.The sulfoalkyl agent that common laboratory is used to synthesize has
2- sodium isethionates, 2- chloroethyl sodium sulfonates, sodium vinyl sulfonate etc..
The content of the invention
The synthetic method to polyoxyethylene fatty alkyl ether sulfonate has carried out many experiments in the lab and industrialization can
Row Journal of Sex Research, find sulfoalkylation method prepare AESO-3 synthetic method other three kinds of methods that compare it is best.From the current country
Outer document report can be seen that this method still suffers from problems with：(1) building-up process is divided to sodium and substitution two steps, in sodium knot
Shu Houxu separates intermediate product, and two-step reaction solvent for use is different, and the recovery of solvent twice is not only time-consuming but also largely consumes the energy；
(2) dewatering efficiency of single solvent is not high；(3) second step reaction sulfoalkyl agent used contains the crystallization water, and this part water is the
It is difficult removing under the reaction condition of two steps reaction, causes the conversion ratio of reaction relatively low；(4) reaction temperature is higher, energy loss compared with
Greatly；(5) yield and purity of product be not high.To solve this contradiction, the present invention is by two-step reaction in same reactor and mixing
It is carried out continuously in solvent, it is not necessary to separate intermediate product.The use of mixed solvent not only ensures building-up process high-efficiency dehydration,
And the temperature of reaction is reduced, the generating rate of accessory substance is reduced, substantial amounts of energy, the purity and yield of product has been saved
Respectively reach 80% and more than 75%.
The present invention is AEO (AEO-3) with 2- chloroethyls sodium sulfonate and NaOH in the mixed of benzene and hexamethylene
Reacted in bonding solvent, be 74~76 DEG C, under normal pressure in temperature, one pot process polyoxyethylene fatty alkyl ether sulfonate (AESO-
3)。
Specific preparation method is comprised the following steps that：15g AEOs (AEO-3) are added equipped with stirring
In the three-necked flask of device and thermometer, measuring the mixed solvent of 30~45ml benzene and hexamethylene, (volume ratio is 2:1~4:1), control
AEO-3 processed is 1 with mixed solvent volume ratio:2~1:3, then 1.89~2.08g solid NaOH are added into three-necked flask, control
AEO-3 and NaOH mol ratio is 1:1~1:1.1, it is to be dehydrated 3~4h at 74~76 DEG C in temperature, waits after dehydration terminates, press
AEO-3 and C2H4ClSO3Na mol ratio is 1:0.8~1:1, weigh 8.19~10.24g solids C2H4ClSO3Na points 3~4 batches
Add, and every batch is spaced in 1~2h, and 4~6h is reacted in the case where temperature is 74~76 DEG C, reaction will be produced slightly after terminating with absolute ethyl alcohol
Thing is repeatedly washed, filters, concentrates, recrystallizes and dried, and finally obtains white or light yellow crystal, and its yield is 75~85%,
Purity is 80~87%.
Reaction equation is as follows.
R(OCH2CH2)3OH+NaOH→R(OCH2CH2)3ONa+H2O
R(OCH2CH2)3ONa+ClCH2CH2SO3Na→R(OCH2CH2)3OCH2CH2SO3Na+NaCl
It is an object of the invention to provide the preparation side of one pot process AEO (3) sodium sulfonate (AESO-3)
Method.
The innovative point of the present invention is to use mixed solvent method synthetic fatty alcohol APEO (3) sodium sulfonate (AESO-3).
AESO-3 infrared spectrum analysis (FTIR)：By dry product sample preparation, determine red on Fourier infrared spectrograph
External spectrum, resolution ratio is 4cm-1, 400~4000cm of wave-number range-1, scan 30 times.AESO-3 AEOs (3)
The FTIR collection of illustrative plates of sodium sulfonate is shown in Fig. 1, as can be seen from Figure 1 in 1636cm-1Place occurs in that strong C=O vibration absorption peaks,
2916cm-1For-CH2Characteristic absorption peak, 1465cm-1For-CH=CH- absorption, 3302~3573cm-1For O-H stretching vibrations
Absworption peak.
Brief description of the drawings
Fig. 1 is the FTIR collection of illustrative plates of AEO (3) sodium sulfonate (AESO-3).
Embodiment
Embodiment one
15g AEOs (AEO-3) are added in the three-necked flask equipped with agitator and thermometer, 30ml benzene is measured
With hexamethylene mixed solvent (volume ratio 4:1), wherein AEO-3 and mixed solvent volume ratio are 1:2, added into three-necked flask
1.89g solid NaOH, the mol ratio for controlling AEO-3 and NaOH is 1:1, the reflux dewatering 4h in the case where temperature is 76 DEG C.Deng dehydration knot
Shu Hou, by AEO-3 and C2H4ClSO3Na mol ratio is 1:1, weigh 8.19g solids C2H4ClSO3Na points 4 batches add, between every batch
1h is interposed between, the course of reaction continues 6h at the temperature disclosed above.Crude product washs, filtered after terminating by reaction with absolute ethyl alcohol, dense
Contract, recrystallize and dry, that is, obtain light yellow crystal, its yield is 75%, and purity is 80%.
Embodiment two
15g AEOs (AEO-3) are added in the three-necked flask equipped with agitator and thermometer, 30ml benzene is measured
With hexamethylene mixed solvent (volume ratio 2:1), wherein AEO-3 and mixed solvent volume ratio are 1:2, when bath temperature is 74 DEG C
Backflow, 1.89g solid NaOH are added into three-necked flask, and the mol ratio for controlling AEO-3 and NaOH is 1:1, at the temperature disclosed above
Reflux dewatering 4h.After dehydration terminates, by AEO-3 and C2H4ClSO3Na mol ratio is 1:1, weigh 8.19g solids
C2H4ClSO3Na points of 4 batches of additions, every batch is spaced in 1h, and the course of reaction continues 6h at the temperature disclosed above.Reaction uses nothing after terminating
Crude product is repeatedly washed, filtered, concentrated, recrystallize and dried by water-ethanol, that is, obtains light yellow crystal, and its yield is 76%,
Purity is 82%.
Embodiment three
15g AEOs (AEO-3) are added in the three-necked flask equipped with agitator and thermometer, 30ml benzene is measured
With hexamethylene mixed solvent (volume ratio 3:1), wherein AEO-3 and mixed solvent volume ratio are 1:2, when bath temperature is 75 DEG C
Backflow, 1.89g solid NaOH are added into three-necked flask, and the mol ratio for controlling AEO-3 and NaOH is 1:1, at the temperature disclosed above
Reflux dewatering 4h.After dehydration terminates, by AEO-3 and C2H4ClSO3Na mol ratio is 1:1, weigh 8.19g solids
C2H4ClSO3Na points of 4 batches of additions, every batch is spaced in 1h, and the course of reaction continues 6h at the temperature disclosed above.Reaction uses nothing after terminating
Crude product is repeatedly washed, filtered, concentrated, recrystallize and dried by water-ethanol, that is, obtains light yellow crystal, and its yield is 75%,
Purity is 81%.
Example IV
15g AEOs (AEO-3) are added in the three-necked flask equipped with agitator and thermometer, 30ml benzene is measured
With hexamethylene mixed solvent (volume ratio 4:1), wherein AEO-3 and mixed solvent volume ratio are 1:2, when bath temperature is 76 DEG C
Backflow, the mol ratio that NaOH 1.89g, wherein AEO-3 and NaOH are added into three-necked flask is 1:1, azeotropic at the temperature disclosed above
It is dehydrated 4h.After dehydration terminates, by AEO-3 and C2H4ClSO3Na mol ratio is 1:0.8, weigh 6.55g solids C2H4ClSO3Na
Divide 4 batches of additions, every batch is spaced in 1h, the course of reaction continues 6h at the temperature disclosed above.Reaction will be thick with absolute ethyl alcohol after terminating
Product is repeatedly washed, filters, concentrates, recrystallizes and dried, that is, obtains light yellow crystal, and its yield is 80%, and purity is 82%.
Embodiment five
15g AEOs (AEO-3) are added in the three-necked flask equipped with agitator and thermometer, 30ml benzene is measured
With hexamethylene mixed solvent (volume ratio 4:1), wherein AEO-3 and mixed solvent volume ratio are 1:2, when bath temperature is 76 DEG C
Backflow, the mol ratio that 1.89g solid NaOH, wherein AEO-3 and NaOH are added into three-necked flask is 1:1, at the temperature disclosed above
It is dehydrated 3h.After dehydration terminates, by AEO-3 and C2H4ClSO3Na mol ratio is 1:1, weigh 8.19g solids C2H4ClSO3Na points 4
Criticize and add, every batch is spaced in 1h, the course of reaction continues 4h at the temperature disclosed above.Reaction terminate after with absolute ethyl alcohol by crude product
Repeatedly wash, filter, concentrate, recrystallize and dry, that is, obtain light yellow crystal, its yield is 80%, and purity is 83%.
Claims (2)
1. one kind method of one pot process AEO (3) sulfonate (AESO-3), with fatty alcohol polyoxy second
Alkene ether (AEO-3), 2- chloroethyl sodium sulfonates (C2H4ClSO3Na·H2O) and sodium hydroxide (NaOH) be raw material, in benzene and hexamethylene
In the mixed solvent, the temperature of alkane composition be 74~76 DEG C, under normal pressure through sodium and substitution two-step reaction synthetic fatty alcohol polyoxy second
Alkene ether (3) sodium sulfonate (AESO-3).
2. a kind of method of one pot process AEO (3) sodium sulfonate (AESO-3) described in claim 1, it is special
Levy and be：(a) in the three-necked flask equipped with agitator and thermometer, add AEO (AEO-3) and benzene and
The volume ratio of the mixed solvent of hexamethylene composition, in the mixed solvent benzene and hexamethylene is 2:1~4:1, control AEO-3 is molten with mixing
Agent volume ratio is 1:2~1:3, NaOH is added, the mol ratio for controlling AEO-3 and NaOH is 1:1~1:1.1, at 74~76 DEG C
3~4h of lower dehydration；Etc. (b) after process (a) terminates, 2- chloroethyl sodium sulfonates (C is added2H4ClSO3Na·H2O), AEO-3 is controlled
With C2H4ClSO3Na·H2O mol ratio is 1:0.8~1:1, wherein C2H4ClSO3Na·H2O points of 3~4 additions, per minor tick
1~2h, reacts 4~6h at 74~76 DEG C, and reaction terminates rear recycling design and washed crude product with absolute ethyl alcohol, mistake
Filter, concentration, recrystallization and dry, finally obtain white or light yellow crystal, its yield be 75~85%, purity be 80~
87%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087995A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Low-tension polymer microemulsion, profile control and flooding system, preparation method and application thereof |
| CN115069199A (en) * | 2022-07-14 | 2022-09-20 | 山东大明精细化工有限公司 | Preparation process of sodium alkyl polyoxyethylene ether sulfonate |
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| US20160107134A1 (en) * | 2014-10-20 | 2016-04-21 | Eastman Chemical Company | Amphoteric ester sulfonates |
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2017
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| US20160107134A1 (en) * | 2014-10-20 | 2016-04-21 | Eastman Chemical Company | Amphoteric ester sulfonates |
| CN105461916A (en) * | 2015-10-29 | 2016-04-06 | 清华大学 | Preparation method of lignin-based polyether sulfonate surfactant |
Non-Patent Citations (2)
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| 汪学良: "脂肪醇聚氧乙烯醚磺酸盐的合成及性能研究", 《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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087995A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Low-tension polymer microemulsion, profile control and flooding system, preparation method and application thereof |
| CN115069199A (en) * | 2022-07-14 | 2022-09-20 | 山东大明精细化工有限公司 | Preparation process of sodium alkyl polyoxyethylene ether sulfonate |
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Application publication date: 20170901 |