CN107915664A - A kind of amphiphilic compound and preparation method thereof - Google Patents
A kind of amphiphilic compound and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of amphiphilic compound and preparation method thereof, the structure of the amphiphilic compound is as follows；Wherein：X is H, SO3H or SO3M；Y is H, SO3H or SO3M；M is Na, K or NH4；M, n, z are positive integer, and 5≤m≤10；5≤n≤10；2≤z≤20.The amphiphilic compound of an embodiment of the present invention, contains anion and ion inactive group in molecular structure at the same time, and the aqueous solution of the compound does not have gelatin phenomenon, makes it have excellent unique some surface active property.
Description
Technical field
The present invention relates to a kind of amphiphilic compound and preparation method thereof, is specially to contain anion in a kind of molecular structure
With the amphiphilic compound that can be used as surfactant of ion inactive group and preparation method thereof.
Background technology
Surfactant refers to add the material for the interface state that can make its solution system being occurred on a small quantity to significant change.Table
Face activating agent is mostly the amphiphilic compound containing hydrophilic radical and hydrophobic grouping in molecular structure, and hydrophilic radical is often polar group
Group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amido and its salt, hydroxyl, amide groups, ehter bond etc. can also be used as polar hydrophilic group.
And hydrophobic grouping is often nonpolar hydrocarbon chain, such as 8 carbon atom above hydrocarbon chains.Surfactant according to molecular structure can be divided into sun from
Sub- surfactant, anion surfactant, nonionic surface active agent, amphoteric surfactant etc..
Sodium alkyl sulfate, it is insensitive to alkali and hard water such as lauryl sodium sulfate (K12), there is decontamination, emulsification and excellent
Different foaming power, is a kind of nontoxic anion surfactant, its biological degradability>90%, it can be used as emulsifying agent, fire extinguishing
Agent, foaming agent and textile auxiliary；Toothpaste and paste, powdery, shampoo are also served as, is industrially usually used in detergent and weaving work
Industry.
Fatty acid methyl ester ethoxylate (FMEE) is a kind of Etheric ester type nonionic surfactant, is with fatty acid methyl ester
Under special special-purpose catalyst effect, addition directly occurs with ethylene oxide (EO) and is made, with traditional alcohol ethoxy
Compound (AEO) is compared, and has low foam, high cloud point, and cold water-soluble speed is fast, and removing oil-removing wax effect is good, is still had in the winter time fine
Mobility.The characteristics of its gel phase narrow range, makes it have unique advantage in liquid detergent application aspect.
Now widely used Fatty Alcohol Ether Carboxylate and fatty alcohol ether sulphate are exactly in two class formations while have non-
The surfactant of ion and anion active group, has a good application performance, but the nonionic base in this class formation
Group is closely coupled with anionic group, can strengthen the hydrophilic sexual function for improving surfactant molecule.For Long carbon chain
Surfactant, introduce certain hydrophilic functional group in oil loving Long carbon chain part, can also realize that enhancing improves point
The hydrophilic sexual function of son, and the arrangement mode of modulation surfactant molecule in the solution, so as to influence the gel of surfactant
The performances such as concentration range, critical micelle concentration size.
The content of the invention
A primary object of the present invention is to provide a kind of amphiphilic compound that can be used as surfactant, the chemical combination
The non-ionic group of thing is separated with anionic group, and concrete structure is as follows：
Wherein：X is H, SO3H or SO3M；Y is H, SO3H or SO3M；M is Na, K or NH4；M, n, z are positive integer, and 5≤
m≤10；5≤n≤10；2≤z≤20.
Present invention also offers a kind of preparation method of amphiphilic compound, including：
By unsaturated fatty acid methyl ester by epoxidation reaction, epoxy aliphatic acid methyl ester is made；
By the epoxy aliphatic acid methyl ester by ethoxylation, epoxy aliphatic acid methyl ester ethoxylate is made；With
And
The epoxy aliphatic acid methyl ester ethoxylate is reacted by ring opening hydrolysis, double hydroxy fatty acid methyl esters second are made
Epoxide compound；
Wherein, the structural formula of the unsaturated fatty acid methyl ester is as follows：
CH3(CH2)mCH=CH (CH2)nCOOCH3
M, n is positive integer, and 5≤m≤10；5≤n≤10.
According to an embodiment of the present invention, wherein the method is further included double hydroxy fatty acid methyl esters ethyoxyls
Compound carries out sulfating reaction or sulfating reaction and neutralization reaction.
According to an embodiment of the present invention, wherein the sulfur acidizing reagent of the sulfating reaction is oleum, dense sulphur
Acid or sulfur trioxide；The reaction reagent of the neutralization reaction is sodium hydroxide, potassium hydroxide or ammonium hydroxide.
According to an embodiment of the present invention, wherein the epoxidation reaction includes, by the unsaturated fatty acid methyl ester
Mixed with acetic acid, mixeding liquid temperature is controlled in 45~55 DEG C, and hydrogen peroxide is added dropwise thereto, and hydrogen peroxide time for adding is small for 2~3
When, after hydrogen peroxide completion of dropwise addition, by reaction solution insulation reflux 2~3 it is small when, obtain the epoxy aliphatic acid methyl ester.
Another embodiment according to the present invention, wherein the epoxidation reaction includes：
The unsaturated fatty acid methyl ester is mixed with catalyst, organic solvent, a mixed liquor is formed, by the mixed liquor
It is heated to 50~70 DEG C；
Hydrogen peroxide is added dropwise into the mixed liquor, and makes hydrogen peroxide is interior when 2~2.5 is small to drip off, after being added dropwise
Be further continued for insulation 2~6 it is small when；
Mixed liquor after reaction is placed in 5~10 DEG C of environment 3~5 it is small when, after catalyst precipitation, by mixed liquor
Filter to remove catalyst；And
By the mixed liquor stratification after removing catalyst, vacuum distillation removes organic layer, obtains the epoxyfatty acid
Methyl esters；
Wherein, the hydrogen peroxide and the unsaturated fatty acid methyl ester mass ratio are (1~2):1, the organic solvent
Mass ratio with the unsaturated fatty acid methyl ester is (2.0~5.0):1, the catalyst and the unsaturated fatty acid methyl ester
Mass ratio be (5~25):1000.
According to an embodiment of the present invention, wherein the epoxy aliphatic acid methyl ester in Mg-Al composite oxide catalyst or
Ethoxylation is carried out under the catalytic action of alkoxy calcium class catalyst, the epoxy aliphatic acid methyl ester ethoxylation is made
Thing.
According to an embodiment of the present invention, wherein the catalyst amount of the ethoxylation for product 0.3~
1.0wt%；The reaction temperature of the ethoxylation is 140~180 DEG C, and reaction pressure is 0.3~0.6MPa.
According to an embodiment of the present invention, wherein the epoxy aliphatic acid methyl ester ethoxylate is made in acidic catalyst
Ring opening hydrolysis reaction is carried out under, double hydroxy fatty acid methyl ester ethoxylates are made；The acidic catalyst is selected from sulphur
One or more in acid, nitric acid, hydrochloric acid, phosphoric acid and solid acid；The reaction temperature of the ring opening hydrolysis reaction is 60~90 DEG C.
Invention further provides a kind of preparation method of amphiphilic compound, including：By unsaturated fatty acid methyl ester
By ethoxylation, unsaturated fatty acid methyl ester ethoxylate is made；
By the unsaturated fatty acid methyl ester ethoxylate by epoxidation reaction, epoxy aliphatic acid methyl ester is made；With
And
The epoxy aliphatic acid methyl ester ethoxylate is subjected to ring opening hydrolysis reaction, double hydroxy fatty acid methyl esters second are made
Epoxide compound；
Wherein, the structural formula of the unsaturated fatty acid methyl ester is as follows：
CH3(CH2)mCH=CH (CH2)nCOOCH3
M, n is positive integer, and 5≤m≤10；5≤n≤10.
The amphiphilic compound of an embodiment of the present invention, contains anion and ion inactive base in molecular structure at the same time
Group, and the aqueous solution of the compound does not have gelatin phenomenon, makes it have excellent unique some surface active property.
Embodiment
Embodying the exemplary embodiments of inventive features and advantage will describe in detail in the following description.It should be understood that this hair
Bright to have various changes in different embodiments, it is neither departed from the scope of the present invention, and description therein is at this
It is to be illustrated as being used in matter, and is not used to the limitation present invention.
The present invention provides a kind of amphiphilic compound, has such as lower structure：
Wherein：X is H, SO3H or SO3M；Y is H, SO3H or SO3M；M is Na, K or NH4.In the present invention, X, Y can be identical,
Such as it is SO3H is SO3M；X, Y can not also be same, such as one of them is SO3H, another is SO3M；Or its
In one be SO3H, another is H.
In said structure, m, n, z are positive integer, and 5≤m≤10；5≤n≤10；2≤z≤20.Such as m can be 5,
6th, 7,8,9,10, n can be 5,6,7,8,9,10, z can be 5,10,15 etc..
The amphiphilic compound of an embodiment of the present invention, has fatty alkyd or salt and fatty acid methyl at the same time in structure
The active group of ester ethoxylate, and this two classes active group is disconnected from each other so that its had concurrently in performance it is cloudy from
The performance characteristics of son and nonionic surfactant, can be used as surfactant, have extensive use in its application field.
Invention further provides a kind of preparation method of above-claimed cpd, including：
By unsaturated fatty acid methyl ester by epoxidation reaction, epoxy aliphatic acid methyl ester is made；
By the epoxy aliphatic acid methyl ester by ethoxylation, epoxy aliphatic acid methyl ester ethoxylate is made；With
And
The epoxy aliphatic acid methyl ester ethoxylate is reacted by ring opening hydrolysis, an embodiment of the present invention is made
Amphiphilic compound --- double hydroxy fatty acid methyl ester ethoxylates.
Wherein, shown in the structure of unsaturated fatty acid methyl ester such as formula (1)：
CH3(CH2)mCH=CH (CH2)nCOOCH3Formula (1)
Shown in the structure of epoxy aliphatic acid methyl ester such as formula (2)：
Shown in the structure of epoxy aliphatic acid methyl ester ethoxylate such as formula (3)：
Shown in the structure such as formula (4) of double hydroxy fatty acid methyl ester ethoxylates：
Further, can be by the way that double hydroxy fatty acid methyl ester ethoxylates be passed through sulfating reaction, or sulphation
Reaction and neutralization reaction obtain the amphiphilic compound as shown in formula (5).
Wherein, X SO3H or SO3M；Y is SO3H or SO3M；M is Na, K or NH4。
In one embodiment of the present invention, the method for organic peroxy acid oxidase or catalysis oxidation can be used to realize unsaturated
Epoxy aliphatic acid methyl ester is prepared in the epoxidation reaction of double bond in fatty acid methyl ester molecular structure.
Specifically, organic peroxide acid oxidizing process can be：Unsaturated fatty acid methyl ester is used as raw material, hydrogen peroxide be to
Oxygen agent, acetic acid make oxygen carrier.Unsaturated fatty acid methyl ester is mixed with acetic acid, mixeding liquid temperature is controlled in 45~60 DEG C, Xiang Qi
Middle dropwise addition hydrogen peroxide is small by reaction solution insulation reflux 2~3 after hydrogen peroxide completion of dropwise addition when hydrogen peroxide time for adding is 2~3 small
When, it is ensured that epoxidation reaction is abundant, and then hot water cleaning, neutralization, vacuum distillation dehydration obtains epoxy aliphatic acid methyl ester.
The process that catalysis oxidation prepares epoxy aliphatic acid methyl ester can be：
(i) unsaturated fatty acid methyl ester is added in reactor by, adds catalyst and organic solvent, is heated to required
50~70 DEG C of reaction temperature, and keep the constant temperature, the hydrogen peroxide that concentration is 30wt%, the quality of hydrogen peroxide be added dropwise
It is (1~2) with unsaturated fatty acid methyl ester mass ratio:1, and make hydrogen peroxide is interior when 2~2.5 is small to drip off, after being added dropwise
Be further continued for insulation 2~6 it is small when；
Wherein, above-mentioned catalyst can be phosphotungstic acid quaternary or phosphomolybdic acid quaternary ammonium salt, such as phosphotungstic acid double octadecyl seasons
Ammonium salt, phosphomolybdic acid hexadecanyl trimethyl quaternary ammonium salt etc.；Organic solvent can be such as dichloroethanes or chloroform；Organic solvent
Mass ratio with unsaturated fatty acid methyl ester can be (2.0~5.0):1, the quality of catalyst and unsaturated fatty acid methyl ester
Mass ratio can be (5~25):1000；
(ii) the mixed liquor after reaction is placed in 5~10 DEG C of environment 3~5 it is small when, at this moment catalyst can be analysed slowly
Go out, mixed liquor is filtered to remove catalyst；
(iii) organic layer is evaporated under reduced pressure and removes organic solvent, obtained product is epoxy by by filtrate stratification
Fatty acid methyl ester.
, can be by epoxy aliphatic acid methyl ester in Mg-Al composite oxide catalyst or alcoxyl in one embodiment of the present invention
Ethoxylation is carried out under the catalytic action of base calcium class catalyst, epoxy aliphatic acid methyl ester ethoxylate is made.
The catalyst amount of ethoxylation can be 0.3~1.0wt% of product, and ethoxylation temperature can be with
For 140~180 DEG C, preferably 160~180 DEG C, reaction pressure can be 0.3~0.6MPa, and the addition of ethylene oxide can basis
The requirement of target product is calculated.
In one embodiment of the present invention, epoxy aliphatic acid methyl ester ethoxylate can under acidic catalyst effect into
Row ring opening hydrolysis reacts, and double hydroxy fatty acid methyl ester ethoxylates are prepared.
Acidic catalyst used can be one kind or more in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and solid acid such as heteropoly acid
Kind, reaction temperature can be 60~90 DEG C.
In one embodiment of the present invention, double hydroxy fatty acid methyl ester ethoxylates can pass through sulfating reaction, in
The amphiphilic compound of another structure is obtained with reaction.
Sulfur acidizing reagent used is oleum, the concentrated sulfuric acid, sulfur trioxide, and membrane type can be used with SO 3 sulfonated
Sulfonation reactor.Neutralization reaction reagent can be sodium hydroxide, potassium hydroxide, ammonium hydroxide etc..
In the present invention, the sequencing of epoxidation reaction and ethoxylation to above-mentioned steps does not limit, can be with
It is that raw material unsaturated fatty acid methyl ester is first first subjected to epoxidation reaction, obtained product carries out ethoxylation again；Also may be used
To be that raw material unsaturated fatty acid methyl ester is first first carried out ethoxylation, obtained product carries out epoxidation reaction again.
For example, in one embodiment of the present invention, the preparation method of the amphiphilic compound includes：
By unsaturated fatty acid methyl ester by ethoxylation, unsaturated fatty acid methyl ester ethoxylate is made；Should
The catalyst of ethoxylation can be Mg-Al composite oxide catalyst, alkoxy calcium class catalyst or other applicable catalysis
Agent；
By unsaturated fatty acid methyl ester ethoxylate by epoxidation reaction, epoxy aliphatic acid methyl ester is made；Can be
Epoxy is prepared in the epoxidation reaction for realizing double bond in molecular structure by the method for organic peroxy acid oxidase or catalysis oxidation
Fatty acid methyl ester ethoxylate；And
Epoxy aliphatic acid methyl ester ethoxylate is subjected to ring opening hydrolysis reaction, an embodiment of the present invention is prepared
Amphiphilic compound -- double hydroxyl unsaturated fatty acid methyl ester ethoxylates；Ring opening hydrolysis reaction can be in acidic catalyst
Agent effect is lower to be carried out, and acidic catalyst used can be sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and solid acid such as heteropoly acid etc..
Further, can be by the way that double hydroxy fatty acid methyl ester ethoxylates be passed through sulfating reaction, or sulphation
Reaction and neutralization reaction obtain the amphiphilic compound as shown in formula (5).
In the following, amphiphilic compound of the present invention and preparation method thereof is described further by specific embodiment, its
In involved source chemicals can pass through commercially available acquisition.The test condition and method of involved dependence test are as follows：
The measure of iodine number according to《The measure of GB/T 5532-2008 animal and plant fat iodine numbers》Carry out；The measure of epoxide number is pressed
According to《The measure of GB/T1677-2008 plasticizer epoxide numbers》Carry out；Surface tension according to《GB/T 22237-2008 surface-actives
The measure of agent surface tension》Carry out；Gel strength scope measure is measured with 25 DEG C of aqueous solution.
Embodiment 1
The preparation of epoxyoleic acid methyl esters
(i) 50g methyl oleates are added in reactor, add the double octadecyl quaternary ammonium salts of phosphate-tungstic acid and dichloro
The mass ratio of ethane, dichloroethanes and methyl oleate is 3.0:1, the mass ratio of catalyst and methyl oleate is 0.025:1.Will be upper
State mixed liquor and be heated to 60 DEG C of required reaction temperature, and keep the constant temperature, the hydrogen peroxide that concentration is 30wt% is added dropwise,
Hydrogen peroxide is 1.5 with methyl oleate mass ratio:1, and make hydrogen peroxide is interior when 2.5 is small to drip off, it is further continued for after being added dropwise
Keep the temperature 3 it is small when；
(ii) mixed liquor after reaction is placed in 5~10 DEG C of environment 4 it is small when, at this moment catalyst can be separated out slowly,
Mixed liquor is filtered to remove catalyst；
(iii) by filtrate stratification, organic layer is evaporated under reduced pressure and removes organic solvent, obtained product is Epoxy oil
Sour methyl esters, it is 2.6g I to measure its iodine number2/ 100g, epoxide number 3.9g/100g.
The preparation of epoxyoleic acid methyl ester ethoxylates
The above-mentioned epoxyoleic acid methyl esters of 50g and 1g catalyst Al are added in autoclave2O3/ MgO, nitrogen displacement three times, heating
To 145~150 DEG C, 63.5gEO is slowly added to, control temperature is between 165~175 DEG C, pressure≤0.5MPa.Add aging after EO
Untill pressure no longer reduces, 80 DEG C are cooled to, kettle discharging is opened, filters out catalyst and obtain final products ethoxymer distribution
Z is 9 epoxyoleic acid methyl ester ethoxylates.
The preparation of double hydroxy oleate methyl ester ethoxylates
The above-mentioned epoxyoleic acid methyl ester ethoxylates of 30g is dissolved in 60g water, pH is adjusted with the dilute sulfuric acid of 0.1mol/L
It is worth for 5, is then stirred at reflux reaction 4h, double hydroxy oleate methyl ester ethoxylates are obtained after removed under reduced pressure moisture, measure epoxy
It is worth for 0, shows epoxide group whole open loop.
The preparation of amphiphilic compound
By the above-mentioned double hydroxy oleate methyl ester ethoxylates of 30g and the SO of equimolar amounts3Gas is anti-in 50 DEG C of progress membrane types
Should, reaction product reacts 0.5h with 30% sodium hydroxide solution again, and control final ph is after 10 or so, removed under reduced pressure moisture
Target product amphiphilic compound is obtained, it is 29.5mN/m to measure its surface tension.
Embodiment 2
The preparation of epoxy 12- alkene tetracosanoic acid methyl esters
(i) 12- alkene tetracosanoic acid methyl esters is added in reactor, adds acetic acid and dichloroethanes, form mixed liquor, will
The mixed liquor is heated to 60 DEG C of required reaction temperature, and keeps the constant temperature, and the hydrogen peroxide that concentration is 30wt% is added dropwise,
Hydrogen peroxide is 1.3 with 12- alkene tetracosanoic acid methyl esters mass ratio:1, and make hydrogen peroxide is interior when 1~1.5 is small to drip off, it is added dropwise
After be further continued for insulation 2.5 it is small when, the mass ratio of wherein dichloroethanes and 12- alkene tetracosanoic acid methyl esters is 3.0:1, acetic acid with
The mass ratio of 12- alkene tetracosanoic acid methyl esters is 1:5；
(ii) vacuum distillation removes organic solvent, and obtained product is epoxy 12- alkene tetracosanoic acid methyl esters, its iodine number is
2.7g I2/ 100g, epoxide number 4.1g/100g.
The preparation of epoxy 12- alkene tetracosanoic acid methyl ester ethoxylates
The above-mentioned epoxy 12- alkene tetracosanoic acid methyl esters of 50g and 1g catalyst calcium butoxides, nitrogen displacement three are added in autoclave
Time, it is warming up to 145~150 DEG C.It is slowly added to 127gEO, controls 165~175 DEG C of temperature, pressure≤0.5Mpa, adds old after EO
Change untill pressure no longer reduces.80 DEG C are cooled to, kettle discharging is opened, filters out catalyst and obtain final products ethyleneoxide addition
The epoxy 12- alkene tetracosanoic acid methyl ester ethoxylates that number z is 18.
The preparation of double hydroxyl 12- alkene tetracosanoic acid methyl ester ethoxylates
The above-mentioned epoxy 12- alkene tetracosanoic acid methyl ester ethoxylates of 30g is dissolved in 60g water, it is dilute with 0.1mol/L
Phosphorus acid for adjusting pH value is 5, is then stirred at reflux reaction 4h, double hydroxyl 12- alkene tetracosanoic acid methyl esters are obtained after removed under reduced pressure moisture
Ethoxylate, measure epoxide number is 0, shows epoxide group whole open loop.
The preparation of amphiphilic compound
The above-mentioned double hydroxyl 12- alkene tetracosanoic acid methyl ester ethoxylates of 30g are dissolved in 60g ethyl acetate, at 35 DEG C
The equimolar concentrated sulfuric acid of agitation and dropping, after reacting 2h, is added dropwise 30% sodium hydroxide solution, control temperature is less than 45 DEG C, charging
PH value of solution=8~9 are finished, target product novel surfactant is obtained after removed under reduced pressure organic solvent and moisture, measure its table
Face tension force is 28.4mN/m.
Embodiment 3
The preparation of methyl oleate ethoxylate
50g methyl oleates and 1g catalyst calcium ethoxides are added in autoclave, nitrogen displacement three times, is warming up to 145~150
℃.Be slowly added to 21gEO, control 165~175 DEG C of temperature, pressure≤0.5MPa, after adding EO aging be no longer reduced to pressure
Only.80 DEG C are cooled to, opens kettle discharging, catalyst is filtered out and obtains the methyl oleate second that final products ethoxymer distribution z is 3
Epoxide compound.
The preparation of epoxyoleic acid methyl ester ethoxylates
(i) above-mentioned methyl oleate ethoxylate is added in reactor, adds acetic acid and chloroform, be heated to required
60 DEG C of reaction temperature, and keep the constant temperature, dropwise addition concentration are 30wt% hydrogen peroxide, quality and the oleic acid first of hydrogen peroxide
Ester mass ratio is 1.3:1, and make hydrogen peroxide is interior when 1.5 is small to drip off, be further continued for after being added dropwise insulation 3 it is small when, wherein chlorine
The imitative mass ratio with methyl oleate ethoxylate is 3.0:1, the mass ratio of acetic acid and methyl oleate is 1:5.5；
(ii) vacuum distillation removes organic solvent, and obtained product is epoxyoleic acid methyl esters, its iodine number is 2.9g I2/
100g, epoxide number 4.2g/100g.
The preparation of double hydroxy oleate methyl ester ethoxylates
The above-mentioned epoxyoleic acid methyl ester ethoxylates of 30g is dissolved in 60g water, pH is adjusted with the phosphoric acid,diluted of 0.1mol/L
It is worth for 5, is then stirred at reflux reaction 4h, double hydroxy oleate methyl ester ethoxylates are obtained after removed under reduced pressure moisture, measure epoxy
It is worth for 0, shows epoxide group whole open loop.
The preparation of amphiphilic compound
The above-mentioned double hydroxy oleate methyl ester ethoxylates of 30g are dissolved in 60g ethyl acetate, in 35 DEG C of agitation and droppings etc.
Mole oleum, react 2h after, be added dropwise 30% potassium hydroxide solution, control temperature be less than 45 DEG C, charging finish solution
PH=8~9, obtain target product novel surfactant after removed under reduced pressure organic solvent and moisture, measuring its surface tension is
28.8mN/m。
Embodiment 4
The preparation of methyl oleate ethoxylate
50g methyl oleates and 1g catalyst Al are added in autoclave2O3/ MgO, nitrogen displacement three times, it is warming up to 145~
150℃.Be slowly added to 84gEO, control 165~175 DEG C of temperature, pressure≤0.5MPa, after adding EO aging no longer dropped to pressure
Untill low.80 DEG C are cooled to, opens kettle discharging, catalyst is filtered out and obtains the oleic acid that final products ethoxymer distribution z is 12
Methyl ester ethoxylates.
The preparation of epoxyoleic acid methyl ester ethoxylates
(i) the above-mentioned methyl oleate ethoxylates of 50g are added in reactor, add the double octadecanes of phosphate-tungstic acid
The mass ratio of based quaternary ammonium salt and dichloroethanes, dichloroethanes and methyl oleate is 3.0:1, quality and the methyl oleate second of catalyst
The mass ratio of epoxide compound is 0.03:1,65 DEG C of required reaction temperature is heated to, and the constant temperature is kept, concentration, which is added dropwise, is
30wt% hydrogen peroxide, the quality of hydrogen peroxide are 1.5 with the mass ratio of methyl oleate ethoxylate:1, and make hydrogen peroxide
It is interior when 2.5 is small to drip off, be further continued for after being added dropwise insulation 3 it is small when；
(ii) by the mixed liquor after reaction be placed in 5~10 DEG C of environment place 4 it is small when, at this moment catalyst can be analysed slowly
Go out, mixed liquor is filtered to remove catalyst；
(iii) by filtrate stratification, organic layer is evaporated under reduced pressure and removes organic solvent, obtained product is Epoxy oil
Sour methyl ester ethoxylates, its iodine number are 2.4g I2/ 100g, epoxide number 3.8g/100g.
The preparation of double hydroxy oleate methyl ester ethoxylates
The above-mentioned epoxyoleic acid methyl ester ethoxylates of 30g is dissolved in 60g water, pH is adjusted with the dilute hydrochloric acid of 0.1mol/L
It is worth for 4.5, is then stirred at reflux reaction 3h, double hydroxy oleate methyl ester ethoxylates are obtained after removed under reduced pressure moisture, measure ring
Oxygen value is 0, shows epoxide group whole open loop.
The preparation of amphiphilic compound
By the above-mentioned double hydroxy oleate methyl ester ethoxylates of 30g and the SO of equimolar amounts3Gas is anti-in 45 DEG C of progress membrane types
Should, reaction product reacts 0.5h with 30% ammonium hydroxide again, and control final ph obtains mesh after 9.5 or so, removed under reduced pressure moisture
Product novel surfactant is marked, it is 29.8mN/m to measure its surface tension.
Amphiphilic compound made from the embodiment of the present invention 1 to 4 and comparative example 1, the surface of comparative example 2 are listed in table 1
The test data of tension force, gel strength scope.Wherein, the product of comparative example 1 is methyl oleate ethoxy obtained in embodiment 4
Glycolylate；The product of comparative example 2 is methyl stearate ethoxylate, is substituted except with methyl stearate outside methyl oleate, firmly
Other preparation processes and raw material dosage of resin acid methyl ester ethoxylates are identical with the methyl oleate ethoxylate of comparative example 1.
Table 1
| Name of product | Surface tension (mN/m) | Gel strength scope % |
| Comparative example 1 | 35.6 | 40-60 |
| Comparative example 2 | 36.7 | 35-70 |
| Embodiment 1 | 29.5 | Without gelatin phenomenon |
| Embodiment 2 | 28.4 | Without gelatin phenomenon |
| Embodiment 3 | 28.8 | Without gelatin phenomenon |
| Embodiment 4 | 29.8 | Without gelatin phenomenon |
| Water | 72.0 |
As shown by data listed by table 1, compared to the methyl oleate ethoxylate and tristearin of same ethoxymer distribution
Sour methyl ester ethoxylates, the amphiphilic compound of the embodiment of the present application are hydrophilic since oil loving Long carbon chain part introduces
Functional group, its surface tension are further reduced, while its aqueous solution does not have gelatin phenomenon.
Unless limited otherwise, term used herein is the normally understood implication of those skilled in the art.
Embodiment described in the invention is not used to limit the scope of the invention merely for exemplary purpose,
Those skilled in the art can be made within the scope of the invention various other replacements, changes and improvements, thus, the invention is not restricted to
The above embodiment, and be only defined by the claims.
Claims (10)
1. a kind of amphiphilic compound, has such as lower structure：
Wherein：X is H, SO3H or SO3M；Y is H, SO3H or SO3M；M is Na, K or NH4；M, n, z are positive integer, and 5≤m≤
10；5≤n≤10；2≤z≤20.
2. a kind of preparation method of amphiphilic compound, including：
By unsaturated fatty acid methyl ester by epoxidation reaction, epoxy aliphatic acid methyl ester is made；
By the epoxy aliphatic acid methyl ester by ethoxylation, epoxy aliphatic acid methyl ester ethoxylate is made；And
The epoxy aliphatic acid methyl ester ethoxylate is reacted by ring opening hydrolysis, double hydroxy fatty acid methyl esters ethyoxyls are made
Compound；
Wherein, the structural formula of the unsaturated fatty acid methyl ester is as follows：
CH3(CH2)mCH=CH (CH2)nCOOCH3
M, n is positive integer, and 5≤m≤10；5≤n≤10.
3. double hydroxy fatty acid methyl ester ethoxylates are carried out according to the method described in claim 2, wherein further including
Sulfating reaction or sulfating reaction and neutralization reaction.
4. according to the method described in claim 3, the sulfur acidizing reagent of wherein described sulfating reaction is oleum, the concentrated sulfuric acid
Or sulfur trioxide；The reaction reagent of the neutralization reaction is sodium hydroxide, potassium hydroxide or ammonium hydroxide.
5. according to the method described in claim 2, wherein described epoxidation reaction includes, by the unsaturated fatty acid methyl ester with
Acetic acid mixes, and mixeding liquid temperature is controlled in 45~55 DEG C, and hydrogen peroxide is added dropwise thereto, when hydrogen peroxide time for adding is 2~3 small,
After hydrogen peroxide completion of dropwise addition, by reaction solution insulation reflux 2~3 it is small when, obtain the epoxy aliphatic acid methyl ester.
6. according to the method described in claim 2, wherein described epoxidation reaction includes：
The unsaturated fatty acid methyl ester is mixed with catalyst, organic solvent, a mixed liquor is formed, the mixed liquor is heated
To 50~70 DEG C；
Hydrogen peroxide is added dropwise into the mixed liquor, and makes hydrogen peroxide is interior when 2~2.5 is small to drip off, after being added dropwise followed by
When continuation of insurance temperature 2~6 is small；
Mixed liquor after reaction is placed in 5~10 DEG C of environment 3~5 it is small when, after catalyst precipitation, mixed liquor is filtered
To remove catalyst；And
By the mixed liquor stratification after removing catalyst, vacuum distillation removes organic layer, obtains the epoxy aliphatic acid methyl ester；
Wherein, the hydrogen peroxide and the unsaturated fatty acid methyl ester mass ratio are (1~2):1, the organic solvent and institute
The mass ratio for stating unsaturated fatty acid methyl ester is (2.0~5.0):1, the matter of the catalyst and the unsaturated fatty acid methyl ester
It is (5~25) to measure ratio:1000.
7. according to the method described in claim 2, wherein described epoxy aliphatic acid methyl ester in Mg-Al composite oxide catalyst or
Ethoxylation is carried out under the catalytic action of alkoxy calcium class catalyst, the epoxy aliphatic acid methyl ester ethoxylation is made
Thing.
8. according to the method described in claim 7, the catalyst amount of wherein described ethoxylation for product 0.3~
1.0wt%；The reaction temperature of the ethoxylation is 140~180 DEG C, and reaction pressure is 0.3~0.6MPa.
9. according to the method described in claim 2, wherein described epoxy aliphatic acid methyl ester ethoxylate is made in acidic catalyst
Ring opening hydrolysis reaction is carried out under, double hydroxy fatty acid methyl ester ethoxylates are made；The acidic catalyst is selected from sulphur
One or more in acid, nitric acid, hydrochloric acid, phosphoric acid and solid acid；The reaction temperature of the ring opening hydrolysis reaction is 60~90 DEG C.
10. a kind of preparation method of amphiphilic compound, including：Unsaturated fatty acid methyl ester is passed through into ethoxylation, system
Obtain unsaturated fatty acid methyl ester ethoxylate；
By the unsaturated fatty acid methyl ester ethoxylate by epoxidation reaction, epoxy aliphatic acid methyl ester is made；And
The epoxy aliphatic acid methyl ester ethoxylate is subjected to ring opening hydrolysis reaction, double hydroxy fatty acid methyl esters ethyoxyls are made
Compound；
Wherein, the structural formula of the unsaturated fatty acid methyl ester is as follows：
CH3(CH2)mCH=CH (CH2)nCOOCH3
M, n is positive integer, and 5≤m≤10；5≤n≤10.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948342A (en) * | 2018-08-07 | 2018-12-07 | 江苏四新界面剂科技有限公司 | A kind of preparation method of the chain of oxyethylene group containing poly amphoteric surfactant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2729612A (en) * | 1950-01-13 | 1956-01-03 | Hogan B Knight | Esters of 9,10-dihydroxystearic acid with ether alcohols |
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2016
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2729612A (en) * | 1950-01-13 | 1956-01-03 | Hogan B Knight | Esters of 9,10-dihydroxystearic acid with ether alcohols |
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| Title |
|---|
| H.B.KNIGHT ET AL.: "Compatibility of Derivatives of 9，10-Dihydroxystearic Acid and 9，10-Dihydroxyoctadecanol With Some Commercial Polymers", 《THE JOURNAL OF THE AMERICAN OIL CHEMISTS’ SOCIETY》 * |
| MARKUS DIERKER ET AL.: "Surfactants from oleic，erucic and petroselinic acid：Synthesis and properties", 《EUROPEAN JOURNAL OF LIPID AND SCIENCE AND TECHNOLOGY》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108948342A (en) * | 2018-08-07 | 2018-12-07 | 江苏四新界面剂科技有限公司 | A kind of preparation method of the chain of oxyethylene group containing poly amphoteric surfactant |
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