CN105218511B - A kind of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er and its preparation technology - Google Patents
A kind of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er and its preparation technology Download PDFInfo
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Abstract
The invention discloses a kind of anion surfactant fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er and its preparation technology, belong to fine chemistry industry technical field of surfactant.This technique comprises the following steps：1. acetalation：Using water as solvent, using organic acid as catalyst, catalyzing glycerol occurs acetalation with saturated aliphatic aldehyde and prepares fatty aldehyde contracting glycerine；2. esterification：Using organic base as catalyst, catalysis fatty aldehyde contracting glycerine and maleic anhydride occur esterification and prepare fatty aldehyde contracting glyceryl maleate monoesters；3. sulfonating reaction：Sodium, potassium or ammonium salt using sulfurous acid occurs sulfonating reaction as sulfonating agent, with fatty aldehyde contracting glyceryl maleate monoesters and prepares fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er.The product purity that the present invention is synthesized is high, and anionic Active content is high, and the ability for reducing aqueous solution surface tension is strong, and foaming abundancy is degradable, has the advantages that technological operation simplicity, energy-conserving and environment-protective, is easy to industrializing implementation.
Description
Technical field
The present invention relates to a kind of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er and its preparation technology, belong to fine chemistry industry table
Face activating agent technical field.
Background technology
By raw material of renewable resource, multi-functional and efficient green receive people for the novel surfactant of target developing
Increasing concern.Glycerine as green reproducible material be synthesize renewable surfactant important source material it
One.As biodiesel is used as a large amount of of alternative energy source, glycerin by-product is superfluous, price drops.Using glycerine as plateform molecules,
Exploitation is adapted to industrial production and cheap glycerols surfactant is significantly.
Glycerine contains three hydroxyls, and its own can be as NMF and additive application in daily chemical products.Polyglycereol, fat
The glycerine analog derivatives such as fatty acid glyceride, fatty alcohol glycerin ether, fatty aldehyde contracting glycerine can also be used as surfactant or surface
The presoma of activating agent synthesis is used, therefore also receives the extensive concern of people.
Fatty aldehyde contracting glycerine is that glycerine and fatty aldehyde have dioxolane and dioxane by what acetalation was synthesized
Material.Because glycerine and carbon number are C8~C16Fatty aldehyde both can not dissolve each other, existing literature introduce fatty aldehyde contracting glycerine
Synthesis more carried out under the conditions of the organic solvents such as benzene, toluene or N,N-dimethylformamide.
C8~C16Fatty aldehyde contracting glycerine is hydrophobic, by regulation and control, introduces the C that hydrophilic radical is obtained8~C16Fatty aldehyde contracts
Glycerol derivatives have good application in terms of soaking, washing, foaming and disperseing, simultaneously as C8~C16Fatty aldehyde contracting is sweet
Make it that product is degradable containing acetal groups in oily derivative, therefore C8~C16Fatty aldehyde contracting glycerol derivatives would is that a class
Green surfactant new, with potential industrial prospect.
Fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er is the derivative of fatty aldehyde contracting glycerine, at present on its synthesis and
Using having not been reported, it is a kind of new anion surfactant, and water-soluble, foaming power and foam stability are good,
The advantage of fatty aldehyde contracting glycerine acetal group degradability is not only remained, while by introducing hydrophilic radical so that fatty aldehyde contracts
The shortcoming of glycerine has obvious improvement.
The content of the invention
The present invention is intended to provide a kind of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er and its preparation technology, the present invention are made
Product have purity high, anionic Active content is high, and the ability for reducing aqueous solution surface tension is strong, and foaming abundancy can drop
Solution, technological operation is easy, the advantage of energy-conserving and environment-protective.
The present invention is achieved by the following technical solutions：
The invention provides a kind of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er, with shown in following (I) or (II)
Formula：
In formula, R is C7~C15Straight chained alkyl, M be-Na ,-K ,-NH4。
The invention provides a kind of preparation technology of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er, comprise the following steps：
(1) acetalation：
Using saturated aliphatic aldehyde and glycerine as raw material, by saturated aliphatic aldehyde：The mol ratio of glycerine is 1:0.5~6, saturated fat
Aldehyde：The mass ratio of solvent is 1:1~6, add organic acid catalyst, catalyst after saturated aliphatic aldehyde, glycerine and solvent are mixed
Addition be saturated aliphatic aldehyde quality 0.5%~5%, in stirring reaction 2~12 hours at 80~150 DEG C, reaction terminates
Afterwards, fatty aldehyde contracting glycerine is obtained through extraction, washing, dry, vacuum concentration；
Acetalation equation is：
In formula, R is C7~C15Straight chained alkyl.
(2) esterification：
The fatty aldehyde contracting glycerine obtained using acetalation is raw material, by fatty aldehyde contracting glycerine：The mol ratio of maleic anhydride
For 1：0.5~2, fatty aldehyde contracting glycerine, maleic anhydride and catalyst are added in reactor, catalyst is organic base, wherein urging
The addition of agent is the 1%~20% of maleic anhydride quality, and in stirring reaction 1~6 hour at 50~130 DEG C, reaction is completed
After obtain intermediate fatty aldehyde contracting glyceryl maleate monoesters；
Esterification equation is：
In formula, R is C7~C15Straight chained alkyl.
(3) sulfonating reaction：
It is 10 that mass concentration is added in the intermediate fatty aldehyde contracting glyceryl maleate monoesters that step (2) esterification is obtained
~25% sulfonating agent aqueous solution, the wherein mol ratio of sulfonating agent and maleic anhydride are 1~1.5:1, stirred at 60~120 DEG C
1~4h of reaction obtains fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er；
Sulfonating reaction equation is：
In formula, R is C7~C15Straight chained alkyl, M be-Na ,-K ,-NH4。
In such scheme, described fatty aldehyde contracting glycerine has the formula shown in following (i) or (ii)：
In formula, R is C7~C15Straight chained alkyl.
Further, saturated aliphatic aldehyde used in step (1) acetalation is C8~C16Straight long-chain saturation
Any of fatty aldehyde.
Further, solvent used in step (1) acetalation is water.It is in existing acetalation to use more
Organic solvent, the present invention replaces organic solvent, environment-protecting clean with water.
Further, organic acid used in step (1) acetalation is p-methyl benzenesulfonic acid or detergent alkylate
Sulfonic acid.
Further, after step (1) acetalation terminates, gained fatty aldehyde contracting glycerine is extracted using ethyl acetate
Take, saturated sodium bicarbonate solution is washed, anhydrous sodium sulfate drying.
Further, organic base used in step (2) esterification is sodium formate, sodium acetate or 4- dimethylaminos
Pyridine.
Further, sulfonating agent used in step (3) sulfonating reaction is sodium sulfite, potassium sulfite or sulfurous acid
One kind in ammonium.
Beneficial effects of the present invention：
1) acetalation is prepared during fatty aldehyde contracting glycerine for green solvent, to instead of organic solvent, technique
Clean environment firendly, while product yield, reduction production cost can be improved, improve product quality.
2) using glycerine as plateform molecules, the utilization ways of glycerine, prepared fatty aldehyde contracting glycerine sulfosuccinic have been expanded
Acid monoester product salt has purity high, and anionic Active content is high, and the ability for reducing aqueous solution surface tension is strong, and foam is rich
Richness, is the new green surfactant of a class the features such as degradable.
3) present invention process is easy to operate, energy-conserving and environment-protective, and production efficiency is high, is easy to industrializing implementation.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1：
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
5.07g (0.055mol), by positive lauric aldehyde：Glycerine=1:1.1 (mol ratios) add positive lauric aldehyde 9.22g (0.050mol), press
Catalyst DBSA 0.09g is added according to the 1.0% of positive lauric aldehyde quality, according to positive lauric aldehyde：Water=1:1 (quality
Than) water 9.22g is added, under nitrogen atmosphere, stirring is warming up to 120 DEG C, and reaction is cooled to room temperature, gained reaction solution after 4 hours
Extracted through ethyl acetate, saturated sodium bicarbonate solution is washed, anhydrous sodium sulfate drying, be concentrated in vacuo to obtain lauric aldehyde contracting glycerol production
12.26g, it is 99.0% to measure product purity through gas-chromatography, and yield is 94.1%, and it is 258 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The positive lauric aldehyde contracting glycerol production 11.61g (0.045mol) obtained by above-mentioned reaction is taken to be added to equipped with electric mixing
In the three neck round bottom flask for mixing device, water knockout drum, condenser pipe, nitrogen ingress pipe, according to positive lauric aldehyde contracting glycerine：Maleic anhydride=1:
1.5 (mol ratios) add maleic anhydride 6.62g (0.068mol), and catalyst acetic acid is added according to the 5.0% of maleic anhydride quality
Sodium 0.33g, under nitrogen atmosphere, stirring are warming up to 100 DEG C, and reaction is cooled to room temperature after 3 hours.Adding 74.26g concentration is
15wt.% sodium sulfite aqueous solution, is warming up to 100 DEG C and reacts 1.5 hours, obtain the positive lauric aldehyde contracting glycerine sulfosuccinic of product
Acid monoester disodium salt.Esterification yield is 89.7% after measured, and sulphonation rate is 93.1%, and anionic Active content is 70.4%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
Lauric aldehyde contracting glycerine mono sulfosuccinates positive to product carry out infrared spectrum characterization：
FTIR (KBr, cm-1)：2928,2849(-C-H)；1727(-COO-)；1601(-COO-)；1037(-SO3 -)。
Embodiment 2
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
5.53g (0.060mol), by n-undecylic aldehyde：Glycerine=1:1.5 (mol ratios) add n-undecylic aldehyde 6.81g (0.040mol), press
Catalyst p-methyl benzenesulfonic acid 0.04g is added according to the 0.5% of n-undecylic aldehyde quality, according to n-undecylic aldehyde：Water=1:1.5 (mass ratioes)
Water 10.22g is added, under nitrogen atmosphere, stirring is warming up to 100 DEG C, and reaction is cooled to room temperature, gained reaction solution warp after 6 hours
Ethyl acetate extraction, saturated sodium bicarbonate solution are washed, anhydrous sodium sulfate drying, are concentrated in vacuo to obtain n-undecylic aldehyde contracting glycerol production
9.43g, it is 98.2% to measure product purity through gas-chromatography, and yield is 94.9%, and it is 244 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The n-undecylic aldehyde contracting glycerol production 8.54g (0.035mol) obtained by above-mentioned reaction is taken to be added to equipped with electric stirring
In device, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe, according to n-undecylic aldehyde contracting glycerine：Maleic anhydride=1:
1.4 (mol ratios) add maleic anhydride 4.80g (0.049mol), and catalyst formic acid is added according to the 3.0% of maleic anhydride quality
Sodium 0.14g, under nitrogen atmosphere, stirring are warming up to 90 DEG C, and reaction is cooled to room temperature after 4 hours.Adding 92.90g concentration is
The 10wt.% potassium sulfite aqueous solution, is warming up to 90 DEG C and reacts 2 hours, obtain product n-undecylic aldehyde contracting glycerine sulfosuccinic acid
Monoesters di-potassium.Esterification yield is 84.3% after measured, and sulphonation rate is 92.5%, and anionic Active content is 69.5%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
Infrared spectrum characterization is carried out to product n-undecylic aldehyde contracting glycerine sulfosuccinic acid monoesters di-potassium：
FTIR (KBr, cm-1)：2930,2855(-C-H)；1730(-COO-)；1603(-COO-)；1039(-SO3 -)。
Embodiment 3
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
4.60g (0.050mol), by n-capric aldehyde：Glycerine=1:1 (mol ratio) adds n-capric aldehyde 7.81g (0.050mol), according to the positive last of the ten Heavenly stems
The 4.0% of aldehyde quality adds catalyst p-methyl benzenesulfonic acid 0.31g, according to n-capric aldehyde：Water=1:4 (mass ratioes) add water
31.24g, under nitrogen atmosphere, stirring are warming up to 110 DEG C, and reaction is cooled to room temperature after 5 hours, and gained reaction solution is through acetic acid second
Ester extraction, saturated sodium bicarbonate solution are washed, anhydrous sodium sulfate drying, are concentrated in vacuo to obtain n-capric aldehyde contracting glycerol production 10.95g, warp
It is 97.6% that gas-chromatography, which measures product purity, and yield is 92.9%, and it is 230 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The n-capric aldehyde contracting glycerol production 10.35g (0.045mol) obtained by above-mentioned reaction is taken to be added to equipped with electric stirring
In device, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe, according to n-capric aldehyde contracting glycerine：Maleic anhydride=1:1.3
(mol ratio) adds maleic anhydride 5.79g (0.059mol), and catalyst acetic acid sodium is added according to the 10.0% of maleic anhydride quality
0.58g, under nitrogen atmosphere, stirring are warming up to 80 DEG C, and reaction is cooled to room temperature after 6 hours.Adding 37.64g concentration is
The 20wt.% ammonium sulfite aqueous solution, is warming up to 60 DEG C and reacts 3 hours, obtain product n-capric aldehyde contracting glycerine sulfosuccinic acid list
Ester di-ammonium salts.Esterification yield is 83.3% after measured, and sulphonation rate is 90.7%, and anionic Active content is 66.5%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
Infrared spectrum characterization is carried out to product n-capric aldehyde contracting glycerine sulfosuccinic acid monoesters di-ammonium salts：
FTIR (KBr, cm-1)：2931,2850(-C-H)；1729(-COO-)；1600(-COO-)；1038(-SO3 -)。
Embodiment 4
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
7.37g (0.080mol), by n-nonyl aldehyde：Glycerine=1:2 (mol ratios) add n-nonyl aldehyde 5.69g (0.040mol), according to positive nonyl
The 2.0% of aldehyde quality adds catalyst DBSA 0.11g, according to n-nonyl aldehyde：Water=1:2 (mass ratioes) add water
11.38g, under nitrogen atmosphere, stirring are warming up to 105 DEG C, and reaction is cooled to room temperature after 2 hours, and gained reaction solution is through acetic acid second
Ester extraction, saturated sodium bicarbonate solution are washed, anhydrous sodium sulfate drying, n-nonyl aldehyde contracting glycerol production 8.44g are concentrated in vacuo to obtain, through gas
It is 96.9% that phase chromatogram, which measures product purity, and yield is 94.7%, and it is 216 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The n-nonyl aldehyde contracting glycerol production 7.56g (0.035mol) obtained by above-mentioned reaction is taken to be added to equipped with electric stirring
In device, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe, according to n-nonyl aldehyde contracting glycerine：Maleic anhydride=1:1.2
(mol ratio) adds maleic anhydride 4.12g (0.042mol), and catalyst 4- diformazan ammonia is added according to the 1.0% of maleic anhydride quality
Yl pyridines (DMAP) 0.04g, under nitrogen atmosphere, stirring are warming up to 70 DEG C, and reaction is cooled to room temperature after 2 hours.Add
29.64g concentration is 25wt.% sodium sulfite aqueous solution, is warming up to 80 DEG C and reacts 2.5 hours, obtains the contracting of product n-nonyl aldehyde sweet
Oily mono sulfosuccinates.Esterification yield is 82.2% after measured, and sulphonation rate is 93.1%, and anionic Active content is
68.4%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
Infrared spectrum characterization is carried out to product n-nonyl aldehyde contracting glycerine mono sulfosuccinates：
FTIR (KBr, cm-1)：2933,2854(-C-H)；1728(-COO-)；1601(-COO-)；1040(-SO3 -)。
Embodiment 5
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
14.74g (0.160mol), by n-octaldehyde：Glycerine=1:2.5 (mol ratios) add n-octaldehyde 8.21g (0.064mol), according to just
The 5.0% of octanal quality adds catalyst DBSA 0.41g, according to n-octaldehyde：Water=1:1 (mass ratio) adds water
8.21g, under nitrogen atmosphere, stirring are warming up to 80 DEG C, and reaction is cooled to room temperature after 12 hours, and gained reaction solution is through ethyl acetate
Extraction, saturated sodium bicarbonate solution wash, anhydrous sodium sulfate drying, n-octaldehyde contracting glycerol production 7.84g are concentrated in vacuo to obtain, through gas phase
It is 97.2% that chromatogram, which measures product purity, and yield is 94.3%, and it is 202 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The n-octaldehyde contracting glycerol production 7.27g (0.036mol) obtained by above-mentioned reaction is taken to be added to equipped with electric stirring
In device, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe, according to n-octaldehyde contracting glycerine：Maleic anhydride=1:0.5
(mol ratio) adds maleic anhydride 1.77g (0.018mol), and catalyst sodium formate is added according to the 8.0% of maleic anhydride quality
0.14g, under nitrogen atmosphere, stirring are warming up to 50 DEG C, and reaction is cooled to room temperature after 6 hours.Adding 21.33g concentration is
The 20wt.% potassium sulfite aqueous solution, is warming up to 70 DEG C and reacts 4 hours, obtain product n-octaldehyde contracting glycerine sulfosuccinic acid list
Ester di-potassium.Esterification yield is 86.5% after measured, and sulphonation rate is 97.1%, and anionic Active content is 72.7%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
Infrared spectrum characterization is carried out to product n-octaldehyde contracting glycerine sulfosuccinic acid monoesters di-potassium：
FTIR (KBr, cm-1)：2927,2845(-C-H)；1726(-COO-)；1602(-COO-)；1041(-SO3 -)。
Embodiment 6
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
11.05g (0.120mol), by positive tridecylic aldehyde：Glycerine=1:3 (mol ratios) add positive tridecylic aldehyde 7.93g (0.040mol), according to
The 3.0% of positive tridecylic aldehyde quality adds catalyst p-methyl benzenesulfonic acid 0.24g, according to positive tridecylic aldehyde：Water=1:3 (mass ratioes) are added
Water 23.79g, under nitrogen atmosphere, stirring are warming up to 130 DEG C, and reaction is cooled to room temperature after 8 hours, and gained reaction solution is through acetic acid
Ethyl ester extraction, saturated sodium bicarbonate solution are washed, anhydrous sodium sulfate drying, be concentrated in vacuo to obtain positive tridecylic aldehyde contracting glycerol production 9.97g,
It is 97.3% to measure product purity through gas-chromatography, and yield is 89.2%, and it is 272 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The positive tridecylic aldehyde contracting glycerol production 9.52g (0.035mol) obtained by above-mentioned reaction is taken to be added to equipped with electric stirring
In device, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe, according to positive tridecylic aldehyde contracting glycerine：Maleic anhydride=1:
1.6 (mol ratios) add maleic anhydride 5.49g (0.056mol), and catalyst 4- bis- is added according to the 2.0% of maleic anhydride quality
Methylamino pyridine (DMAP) 0.11g, under nitrogen atmosphere, stirring are warming up to 110 DEG C, and reaction is cooled to room temperature after 1 hour.Add
70.56g concentration is 10wt.% sodium sulfite aqueous solution, is warming up to 120 DEG C and reacts 1 hour, obtains the positive tridecylic aldehyde contracting of product sweet
Oily mono sulfosuccinates.Esterification yield is 85.2% after measured, and sulphonation rate is 95.9%, and anionic Active content is
73.3%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
Tridecylic aldehyde contracting glycerine mono sulfosuccinates positive to product carry out infrared spectrum characterization：
FTIR (KBr, cm-1)：2934,2857(-C-H)；1733(-COO-)；1610(-COO-)；1043(-SO3 -)。
Embodiment 7
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
13.81g (0.150mol), by positive undecalactone：Glycerine=1:5 (mol ratios) add positive undecalactone 6.37g (0.030mol), according to
The 2.5% of positive undecalactone quality adds catalyst DBSA 0.16g, according to positive undecalactone：Water=1:5 (mass ratioes)
Water 31.85g is added, under nitrogen atmosphere, stirring is warming up to 140 DEG C, and reaction is cooled to room temperature, gained reaction solution warp after 7 hours
Ethyl acetate extraction, saturated sodium bicarbonate solution are washed, anhydrous sodium sulfate drying, be concentrated in vacuo to obtain positive undecalactone contracting glycerol production
8.37g, it is 97.9% to measure product purity through gas-chromatography, and yield is 95.5%, and it is 286 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The undecalactone contracting glycerol production 7.15g (0.025mol) obtained by above-mentioned reaction is taken to be added to equipped with electric stirring
In device, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe, according to positive undecalactone contracting glycerine：Maleic anhydride=1:
1.7 (mol ratios) add maleic anhydride 4.22g (0.043mol), and catalyst acetic acid is added according to the 20.0% of maleic anhydride quality
Sodium 0.84g, under nitrogen atmosphere, stirring are warming up to 120 DEG C, and reaction is cooled to room temperature after 2 hours.Adding 34.92g concentration is
The 15wt.% ammonium sulfite aqueous solution, is warming up to 110 DEG C and reacts 3 hours, obtain the positive undecalactone contracting glycerine sulfosuccinic acid of product
Monoesters di-ammonium salts.Esterification yield is 83.6% after measured, and sulphonation rate is 91.1%, and anionic Active content is 63.5%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
Undecalactone contracting glycerine sulfosuccinic acid monoesters di-ammonium salts positive to product carry out infrared spectrum characterization：
FTIR (KBr, cm-1)：2933,2852(-C-H)；1727(-COO-)；1601(-COO-)；1037(-SO3 -)。
Embodiment 8
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
4.60g (0.050mol), by n-octaldehyde：Glycerine=1:0.5 (mol ratio) adds n-octaldehyde 12.82g (0.100mol), according to just
The 2.0% of octanal quality adds catalyst p-methyl benzenesulfonic acid 0.26g, according to n-octaldehyde：Water=1:1.25 (mass ratioes) add water
16.03g, under nitrogen atmosphere, stirring are warming up to 130 DEG C, and reaction is cooled to room temperature after 3 hours, and gained reaction solution is through acetic acid second
Ester extraction, saturated sodium bicarbonate solution are washed, anhydrous sodium sulfate drying, n-octaldehyde contracting glycerol production 9.78g are concentrated in vacuo to obtain, through gas
It is 91.6% that phase chromatogram, which measures product purity, and yield is 88.7%, and it is 202 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The n-octaldehyde contracting glycerol production 9.09g (0.045mol) obtained by above-mentioned reaction is taken to be added to equipped with electric stirring
In device, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe, according to n-octaldehyde contracting glycerine：Maleic anhydride=1:1.1
(mol ratio) adds maleic anhydride 4.85g (0.0495mol), and catalyst acetic acid sodium is added according to the 12.0% of maleic anhydride quality
0.58g, under nitrogen atmosphere, stirring are warming up to 90 DEG C, and reaction is cooled to room temperature after 3 hours.Adding 49.90g concentration is
15wt.% sodium sulfite aqueous solution, is warming up to 80 DEG C and reacts 2 hours, obtain product n-octaldehyde contracting glycerine sulfosuccinic acid list
Ester disodium salt.Esterification yield is 83.0% after measured, and sulphonation rate is 94.2%, and anionic Active content is 70.9%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
Infrared spectrum characterization is carried out to product n-octaldehyde contracting glycerine mono sulfosuccinates：
FTIR (KBr, cm-1)：2927,2845(-C-H)；1726(-COO-)；1602(-COO-)；1041(-SO3 -)。
Embodiment 9
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
7.37g (0.080mol), by positive 15 aldehyde：Glycerine=1:4 (mol ratios) add positive 15 aldehyde 4.53g (0.020mol), according to
The 1.5% of positive 15 aldehyde quality adds catalyst p-methyl benzenesulfonic acid 0.07g, according to positive 15 aldehyde：Water=1:2 (mass ratioes) are added
Water 9.06g, under nitrogen atmosphere, stirring are warming up to 120 DEG C, and reaction is cooled to room temperature after 9 hours, and gained reaction solution is through acetic acid second
Ester extraction, saturated sodium bicarbonate solution are washed, anhydrous sodium sulfate drying, are concentrated in vacuo to obtain just 15 aldehyde contracting glycerol production 5.47g, warp
It is 92.1% that gas-chromatography, which measures product purity, and yield is 84.0%, and it is 300 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The positive 15 aldehyde contracting glycerol production 4.80g (0.016mol) obtained by above-mentioned reaction is taken to be added to equipped with electric stirring
In device, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe, according to positive 15 aldehyde contracting glycerine：Maleic anhydride=1:
1.8 (mol ratios) add maleic anhydride 2.82g (0.029mol), and catalyst formic acid is added according to the 5.0% of maleic anhydride quality
Sodium 0.14g, under nitrogen atmosphere, stirring are warming up to 120 DEG C, and reaction is cooled to room temperature after 5 hours.Adding 25.20g concentration is
The 20wt.% potassium sulfite aqueous solution, is warming up to 100 DEG C and reacts 2 hours, obtain the positive 15 aldehyde contracting glycerine sulfosuccinic acid of product
Monoesters di-potassium.Esterification yield is 80.2% after measured, and sulphonation rate is 90.6%, and anionic Active content is 66.1%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
15 aldehyde contracting glycerine sulfosuccinic acid monoesters di-potassium positive to product carries out infrared spectrum characterization：
FTIR (KBr, cm-1)：2931,2847(-C-H)；1731(-COO-)；1606(-COO-)；1035(-SO3 -)。
Embodiment 10
Glycerine is added in equipped with electric mixer, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe
11.05g (0.120mol), by positive hexadecanoyl：Glycerine=1:6 (mol ratios) add positive hexadecanoyl 4.81g (0.020mol), according to
The 3.5% of positive hexadecanoyl quality adds catalyst DBSA 0.17g, according to positive hexadecanoyl：Water=1:6 (mass ratioes)
Water 28.86g is added, under nitrogen atmosphere, stirring is warming up to 150 DEG C, and reaction is cooled to room temperature, gained reaction solution warp after 10 hours
Ethyl acetate extraction, saturated sodium bicarbonate solution are washed, anhydrous sodium sulfate drying, be concentrated in vacuo to obtain positive hexadecanoyl contracting glycerol production
6.07g, it is 94.6% to measure product purity through gas-chromatography, and yield is 91.4%, and it is 314 that mass spectrum, which measures molecular weight of product,.
The reaction equation of above-mentioned acetalation is as follows：
The positive hexadecanoyl contracting glycerol production 5.65g (0.018mol) obtained by above-mentioned reaction is taken to be added to equipped with electric stirring
In device, water knockout drum, condenser pipe, the three neck round bottom flask of nitrogen ingress pipe, according to positive hexadecanoyl contracting glycerine：Maleic anhydride=1:2
(mol ratio) adds maleic anhydride 3.53g (0.036mol), and catalyst acetic acid sodium is added according to the 10.0% of maleic anhydride quality
0.35g, under nitrogen atmosphere, stirring are warming up to 130 DEG C, and reaction is cooled to room temperature after 3 hours.Adding 22.68g concentration is
25wt.% sodium sulfite aqueous solution, is warming up to 110 DEG C and reacts 4 hours, obtain the positive hexadecanoyl contracting glycerine sulfosuccinic acid of product
Monoester disodium salt.Esterification yield is 82.0% after measured, and sulphonation rate is 94.3%, and anionic Active content is 70.0%.
The reaction equation of above-mentioned chemical reaction is as follows：
1) esterification equation：
2) sulfonating reaction equation：
Hexadecanoyl contracting glycerine mono sulfosuccinates positive to product carry out infrared spectrum characterization：
FTIR (KBr, cm-1)：2935,2850(-C-H)；1729(-COO-)；1605(-COO-)；1039(-SO3 -)。
Claims (9)
1. a kind of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er, it is characterised in that：With logical shown in following (I) or (II)
Formula：
In formula, R is C7~C15Straight chained alkyl, M be-Na ,-K ,-NH4。
2. a kind of preparation technology of the fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er described in claim 1, it is characterised in that：Bag
Include following steps：
(1) acetalation：
Using saturated aliphatic aldehyde and glycerine as raw material, by saturated aliphatic aldehyde：The mol ratio of glycerine is 1:0.5~6, saturated aliphatic aldehyde：
The mass ratio of solvent is 1:1~6, will saturated aliphatic aldehyde, glycerine and solvent mix after add organic acid catalyst, catalyst plus
It is the 0.5%~5% of saturated aliphatic aldehyde quality to enter amount, in stirring reaction 2~12 hours at 80~150 DEG C, after reaction terminates, warp
Extraction, washing, dry, vacuum concentration obtain fatty aldehyde contracting glycerine；
(2) esterification：
The fatty aldehyde contracting glycerine obtained using step (1) acetalation is raw material, by fatty aldehyde contracting glycerine：Mole of maleic anhydride
Than for 1：0.5~2, fatty aldehyde contracting glycerine, maleic anhydride and catalyst are added in reactor, catalyst is organic base, wherein
The addition of catalyst is the 1%~20% of maleic anhydride quality, in stirring reaction 1~6 hour at 50~130 DEG C, has been reacted
Intermediate fatty aldehyde contracting glyceryl maleate monoesters is obtained after；
(3) sulfonating reaction：
In the intermediate fatty aldehyde contracting glyceryl maleate monoesters that step (2) esterification is obtained add mass concentration be 10~
The 25% sulfonating agent aqueous solution, the wherein mol ratio of sulfonating agent and maleic anhydride are 1~1.5:1, stir anti-at 60~120 DEG C
1~4h is answered to obtain fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er.
3. the preparation technology of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er according to claim 2, it is characterised in that：Institute
The fatty aldehyde contracting glycerine stated has the formula shown in following (i) or (ii)：
In formula, R is C7~C15Straight chained alkyl.
4. the preparation technology of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er according to claim 2, it is characterised in that：Institute
It is C to state saturated aliphatic aldehyde used in step (1) acetalation8~C16Any of straight long-chain saturated aliphatic aldehyde.
5. the preparation technology of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er according to claim 2, it is characterised in that：Institute
It is water to state solvent used in step (1) acetalation.
6. the preparation technology of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er according to claim 2, it is characterised in that：Institute
It is p-methyl benzenesulfonic acid or DBSA to state organic acid used in step (1) acetalation.
7. the preparation technology of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er according to claim 2, it is characterised in that：Institute
State after step (1) acetalation terminates, gained fatty aldehyde contracting glycerine adopt be extracted with ethyl acetate, saturated sodium bicarbonate solution
Wash, anhydrous sodium sulfate drying.
8. the preparation technology of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er according to claim 2, it is characterised in that：Institute
It is sodium formate, sodium acetate or DMAP to state organic base used in step (2) esterification.
9. the preparation technology of fatty aldehyde contracting glycerine Di-sodium Sulfo-succinate Mono Est-er according to claim 2, it is characterised in that：Institute
It is one kind in sodium sulfite, potassium sulfite or ammonium sulfite to state sulfonating agent used in step (3) sulfonating reaction.
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