CN103435520A - Preparation method of 1,4-butanediol gemini dioctyl sodium sulfosuccinate - Google Patents
Preparation method of 1,4-butanediol gemini dioctyl sodium sulfosuccinate Download PDFInfo
- Publication number
- CN103435520A CN103435520A CN2013103775642A CN201310377564A CN103435520A CN 103435520 A CN103435520 A CN 103435520A CN 2013103775642 A CN2013103775642 A CN 2013103775642A CN 201310377564 A CN201310377564 A CN 201310377564A CN 103435520 A CN103435520 A CN 103435520A
- Authority
- CN
- China
- Prior art keywords
- preparation
- bdo
- butanediol
- butyleneglycol
- shuangzi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of 1,4-butanediol gemini dioctyl sodium sulfosuccinate. The preparation method is characterized in that maleic anhydride and two hydroxide radicals on 1,4-butanediol are combined and subjected to mono-esterification reaction so as to generate 1,4-butanediol dual-maleic monoester, then the 1,4-butanediol dual-maleic monoester and iso-octyl alcohol are subjected to dual-esterification reaction so as to obtain 1,4-butanediol dual-diisooctyl maleate, and finally the 1,4-butanediol dual-diisooctyl maleate and sodium bisulfite are subjected to conjugate addition sulfonation reaction so as to obtain the product, wherein a catalyst for the dual-esterification reaction is a carbon-based solid acid catalyst. The preparation method is easy to operate and simple in synthetic method and has good environmental friendliness.
Description
Technical field
The present invention relates to a kind of preparation method of BDO Shuangzi Aerosol OT.
Background technology
1,4-butyleneglycol Shuangzi Aerosol OT is the ion head of design using the different monooctyl ester sodium salt of single linked list surface-active agent sulfo-succinic acid as parents' molecule in molecule, connect the Gemini surface active agent formed by chemical bond through the linking group BDO.Its surfactivity, except all advantages with single linked list surface-active agent, also has the i.e. higher surfactivity of lower surface tension.Because its special structural table reveals unique performance, thereby application is more extensive.Take BDO, MALEIC ANHYDRIDE and isooctyl alcohol prepares BDO Shuangzi Aerosol OT as raw material, and this product is at present without bibliographical information.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of easy to operate, synthetic method is simple, the feature of environmental protection is good BDO Shuangzi Aerosol OT.
Technical solution of the present invention is:
A kind of 1, the preparation method of 4-butyleneglycol Shuangzi Aerosol OT, it is characterized in that: comprise the following steps: maleic anhydride and 1, two hydroxy combinings on the 4-butyleneglycol carry out single-esterification and generate 1,4-butyleneglycol span carrys out acid monoester, 1,4-butyleneglycol span comes acid monoester to carry out double esterification reaction with isooctyl alcohol again to obtain 1, the two diisooctyl maleates of 4-butyleneglycol, the two diisooctyl maleates of last BDO carry out the conjugate addition sulfonation reaction with sodium bisulfite again and make product; Wherein, the catalyzer of double esterification reaction is carbon-based solid acid catalyst.
During single-esterification, by maleic anhydride and BDO mol ratio, be 2.15:1.0.
During double esterification reaction, the isooctyl alcohol add-on is 1.00 ﹕ 1.05 by the mol ratio of maleic anhydride and isooctyl alcohol; The carbon-based solid acid catalyst consumption is cis-butenedioic anhydride quality 1%.
During sulfonation reaction, the sodium bisulfite consumption is pressed maleic anhydride and NaHSO
3mol ratio be 1.00 ﹕ 1.05.
Reaction formula:
Synthetic method of the present invention is simple, easy to operate, and the feature of environmental protection is good.
1, BDO Shuangzi Aerosol OT is a kind of new Gemini surface active agent, there is no at present directly related bibliographical information mistake.
2, the present invention adopts carbon-based solid acid (the immobilized tosic acid of starch) to make catalyst for esterification reaction, and the catalyzer manufacture is simple, cheap, and only need carry out just energy separating catalyst of simple filtration to esterification products, and the catalyzer of separation is reusable.Avoided liquid acid catalyst and product to be difficult to separate, etching apparatus, metal solid acid waits catalyzer to make trouble and the shortcoming such as price height.
3, this technique does not need additionally to make the band aqua and double esterification reaction carries out the esterification dehydration reaction under normal pressure as the toluene equal solvent when double esterification reaction.Avoided the existing Shuangzi sulphosuccinates for preparing to need the additional method that maybe needs to adopt decompression dehydration with aqua, reduced decompression and the requirement of equipment, the consumption that has reduced raw material and distillation have been removed to the operation of toluene.
4, this technique is when esterification, directly by the reaction of ethylene glycol and cis-butenedioic anhydride, do not need additional acetone etc. to make solubility promoter, avoided original technique to need additional acetone make solubility promoter, reduced the consumption of raw material and reacted while finishing and need distill the operation except acetone, also having avoided environmental pollution.
5, the single, double reaction time of esterification of the present invention is short, has effectively contained the hydrolysis of dibasic acid esters and the phenomenon that the product color and luster is deepened.
6, the not additional phase-transfer catalyst of sulfonation reaction, utilize to control the double esterification reaction esterification yield, using in the monoesters in double esterification reaction and salify as phase-transfer catalyst.Reduced the utilization ratio of impurity and the equipment of product.
The accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is the infrared spectrogram of BDO Shuangzi Aerosol OT.
Fig. 2 is the mass spectrum of BDO Shuangzi Aerosol OT.
Embodiment
A kind of 1, the preparation method of 4-butyleneglycol Shuangzi Aerosol OT, comprise the following steps: the first step single-esterification (I), the ratio that is 2.15:1.0 in maleic anhydride and BDO mol ratio take BDO and maleic anhydride add be furnished with agitator, in the reactor of thermometer and reflux condensing tube, pass into nitrogen, stir and be warming up to 110 ℃ and timing in 10min, maintain the temperature at 110 ℃ ± 2 ℃ reaction 2.0h, single-esterification finishes.Second step double esterification reaction (II), add isooctyl alcohol on same table apparatus, the ratio that add-on is 1.00 ﹕ 1.05 in the mol ratio of maleic anhydride and isooctyl alcohol takes, (add Zulkovsky starch and tosic acid by m (tosic acid): m (starch)=1 ﹕ 2 in beaker, heating is dissolved with distilled water to add the carbon-based solid acid catalyst that accounts for cis-butenedioic anhydride quality 1% again.Treat the solution clear, be cooled to room temperature, with Rotary Evaporators, flash to sticky shape colloid, insert in retort furnace in 200 ℃ of lower charing 8h.Grind, cross 80 mesh sieves, obtain carbon-based solid acid catalyst), load onto water trap, continue to pass into nitrogen, be warming up to 170 ± 2 ℃ and timing in 10min, during constantly separate the water of generation, reaction 2.5h, double esterification reaction finishes (esterification yield is 94%～96%).Product is cooled to 50 ± 10 ℃, filtering recovering catalyst, reusable after reclaiming.Filtrate is neutralized to pH=7 ± 0.5 with 30% the NaOH aqueous solution.The 3rd step sulfonation reaction (III) adds aqueous solution of sodium bisulfite on same table apparatus, and the amount of sodium bisulfite is pressed maleic anhydride and NaHSO
3mol ratio be 1.00 ﹕ 1.05 ratio takes, the aqueous solution of sodium bisulfite quality adds by 1.0 times of double esterification product theoretical yield.Pass into nitrogen, stir oil bath in lower 10min and be warmed up to 120 ± 2 ℃ of insulations, vigorous stirring, system, at 104 ℃ of lower azeotropic reaction 3.0h, obtains product.Sulfonated tail gas SO
2with sig water, absorb.
Survey surface tension γ with Zibo CL-3 of Zi Fen Instrument Ltd. type automatic tension determinator
cMCwith micelle-forming concentration CMC; The U.S. AVATAR-370 of Nicolet company Fourier transformation infrared spectrometer is surveyed infrared spectra; U.S. Thermo company's T race DSQ-GC/MS type list quadrupole gas chromatograph-mass spectrometer is surveyed mass spectrum.
The product structure checking
1) infrared analysis
2960.18cm
-1for-CH
3antisymmetric stretching vibration, 2931.64cm
-1for-CH
2antisymmetric stretching vibration 2873.92cm
-1for-CH
3symmetrical stretching vibration, 1734.71cm
-1for the stretching vibration of C=O, 1465.08cm
-1, 1396.00cm
-1left and right is C-CH
3formation vibration, 1224.20cm
-1asymmetric stretching vibration 1047.99cm for C-O-C
-1for the symmetrical stretching vibration of C-O-C, 500～600cm
-1stretching vibration for C-S.Prove the functional group that the target product structure is arranged in synthetic product.
2) mass spectroscopy
In figure, m/z336.08 is that target product is sloughed two Na
+the fragment ion formed; M/z256.39 is that target product is sloughed two-SO
3the formed fragment ion of Na; M/z81.03 is that target product is sloughed functional group's fragment ion.
Above data, whichsoever spectrogram all can verify that the product of synthesized is BDO Shuangzi Aerosol OT, according to above characterization result, synthetic product is target product.
The surface property of product and application performance
Table 1:1,4-butyleneglycol Shuangzi Aerosol OT surface property and application performance
The toxicity detected result of product
Table 2:1, the toxicity detected result of 4-butyleneglycol Shuangzi Aerosol OT
As can be seen from Table 2: BDO Shuangzi Aerosol OT belongs to that low toxicity, pungency are little, the material of weak sensitization.
Claims (4)
1. one kind 1, the preparation method of 4-butyleneglycol Shuangzi Aerosol OT, it is characterized in that: comprise the following steps: maleic anhydride and 1, two hydroxy combinings on the 4-butyleneglycol carry out single-esterification and generate 1,4-butyleneglycol span carrys out acid monoester, 1,4-butyleneglycol span comes acid monoester to carry out double esterification reaction with isooctyl alcohol again to obtain 1, the two diisooctyl maleates of 4-butyleneglycol, the two diisooctyl maleates of last BDO carry out the conjugate addition sulfonation reaction with sodium bisulfite again and make product; Wherein, the catalyzer of double esterification reaction is carbon-based solid acid catalyst.
2. the preparation method of BDO Shuangzi Aerosol OT according to claim 1, is characterized in that: during single-esterification, by maleic anhydride and BDO mol ratio, be 2.15:1.0.
3. the preparation method of BDO Shuangzi Aerosol OT according to claim 1 and 2, it is characterized in that: during double esterification reaction, the isooctyl alcohol add-on is 1.00 ﹕ 1.05 by the mol ratio of maleic anhydride and isooctyl alcohol; The carbon-based solid acid catalyst consumption is cis-butenedioic anhydride quality 1%.
4. the preparation method of BDO Shuangzi Aerosol OT according to claim 1 and 2, it is characterized in that: during sulfonation reaction, the sodium bisulfite consumption is pressed maleic anhydride and NaHSO
3mol ratio be 1.00 ﹕ 1.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103775642A CN103435520A (en) | 2013-08-26 | 2013-08-26 | Preparation method of 1,4-butanediol gemini dioctyl sodium sulfosuccinate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103775642A CN103435520A (en) | 2013-08-26 | 2013-08-26 | Preparation method of 1,4-butanediol gemini dioctyl sodium sulfosuccinate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103435520A true CN103435520A (en) | 2013-12-11 |
Family
ID=49689268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103775642A Pending CN103435520A (en) | 2013-08-26 | 2013-08-26 | Preparation method of 1,4-butanediol gemini dioctyl sodium sulfosuccinate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103435520A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300032A (en) * | 2020-11-20 | 2021-02-02 | 太原理工大学 | Branched alkyl sulfonate anionic surfactant and preparation process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0295535A1 (en) * | 1987-06-15 | 1988-12-21 | Henkel Kommanditgesellschaft auf Aktien | Sulfonates of polyoxyalkyl esters of fatty acids, process for their preparation and their use as tensides |
| JPH10245370A (en) * | 1997-03-04 | 1998-09-14 | Daikin Ind Ltd | Fluorine-containing polymerizable surfactant and its production |
| CN102001975A (en) * | 2010-10-29 | 2011-04-06 | 南通大学 | Ethylene glycol bi-sulpho succinic acid bi(2-methyl amyl) artesunate and production method thereof |
| CN102351747A (en) * | 2011-09-08 | 2012-02-15 | 南通大学 | Method for preparing disodium ethylene glycol dihexyl sulfosuccinate |
| CN102351745A (en) * | 2011-09-08 | 2012-02-15 | 南通大学 | Method for preparing disodium ethylene glycol bis(2-ethyl-1-butyl)sulfosuccinate |
| CN102351746A (en) * | 2011-09-08 | 2012-02-15 | 南通大学 | Method for preparing glycol sodium di-sulpho succinate di(2-methyl1-amyl) ester |
-
2013
- 2013-08-26 CN CN2013103775642A patent/CN103435520A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0295535A1 (en) * | 1987-06-15 | 1988-12-21 | Henkel Kommanditgesellschaft auf Aktien | Sulfonates of polyoxyalkyl esters of fatty acids, process for their preparation and their use as tensides |
| JPH10245370A (en) * | 1997-03-04 | 1998-09-14 | Daikin Ind Ltd | Fluorine-containing polymerizable surfactant and its production |
| CN102001975A (en) * | 2010-10-29 | 2011-04-06 | 南通大学 | Ethylene glycol bi-sulpho succinic acid bi(2-methyl amyl) artesunate and production method thereof |
| CN102351747A (en) * | 2011-09-08 | 2012-02-15 | 南通大学 | Method for preparing disodium ethylene glycol dihexyl sulfosuccinate |
| CN102351745A (en) * | 2011-09-08 | 2012-02-15 | 南通大学 | Method for preparing disodium ethylene glycol bis(2-ethyl-1-butyl)sulfosuccinate |
| CN102351746A (en) * | 2011-09-08 | 2012-02-15 | 南通大学 | Method for preparing glycol sodium di-sulpho succinate di(2-methyl1-amyl) ester |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300032A (en) * | 2020-11-20 | 2021-02-02 | 太原理工大学 | Branched alkyl sulfonate anionic surfactant and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102351745B (en) | Method for preparing disodium ethylene glycol bis(2-ethyl-1-butyl)sulfosuccinate | |
| CN103450054A (en) | Preparation method of 1,4-butylene glycol gemini di-sec-octyl succinate sodium sulfonate | |
| CN102351747B (en) | Method for preparing disodium ethylene glycol dihexyl sulfosuccinate | |
| CN103086928A (en) | Sodium 1,4-butanediol bissulfosuccinate laurylpolyoxyethene (3) isooctyl sulfonate and its preparation method | |
| CN104262200B (en) | One recycles waste water and prepares N, N ' production method of-dicyclohexylcarbodiimide | |
| CN102351746A (en) | Method for preparing glycol sodium di-sulpho succinate di(2-methyl1-amyl) ester | |
| CN104250232A (en) | Preparation method of parecoxib sodium | |
| CN103435519A (en) | Preparation method of ethylene glycol gemini di-sec-octyl phthalate sodium sulfosuccinate | |
| CN103435520A (en) | Preparation method of 1,4-butanediol gemini dioctyl sodium sulfosuccinate | |
| CN103450053A (en) | Preparation method of ethylene glycol gemini di-isooctyl succinate sodium sulfonate | |
| CN103435521A (en) | Preparation method of ethylene glycol gemini di-n-octyl phthalate sodium sulfosuccinate | |
| CN102199073A (en) | Method for preparing 4,4'-dihydroxydiphenylmethane | |
| CN103435522A (en) | Preparation method of 1,3-propanediol gemini dioctyl sodium sulfosuccinate | |
| CN103450052A (en) | Preparation method of 1,3-propylene glycol gemini di-sec-octyl succinate sodium sulfonate | |
| CN103450051A (en) | Preparation method of 1,4-butylene glycol gemini di-n-octyl succinate sodium sulfonate | |
| CN103450049A (en) | Preparation method of 1,3-propylene glycol gemini di-n-octyl succinate sodium sulfonate | |
| CN103450157A (en) | Preparation method for high-purity hydroxyfasudil semihydrate | |
| CN103965020A (en) | Method for preparing 5-iodine-2-bromobenzylalcohol | |
| CN107840811A (en) | A kind of preparation method of dicyandiamide | |
| CN114262320A (en) | Synthesis method for preparing anilinopiperidine drugs by using continuous flow microchannel reactor | |
| CN103288822B (en) | Preparation method of vinpocetine | |
| CN103694267B (en) | The purification process of the two tetraethyl ammoniums of a kind of decahydro ten boric acid | |
| CN109289930A (en) | A method of efficiently separating and purify 1- methyl naphthalene | |
| CN101270109B (en) | Method for preparing 3,5,7,3',4'-pentamethyl meletin by using meletin | |
| JP7454498B2 (en) | Method for producing salicylamide acetate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20131211 |
|
| RJ01 | Rejection of invention patent application after publication |