CN107522619A - A kind of Guerbet alcohol nonionic surfactant and preparation method thereof - Google Patents
A kind of Guerbet alcohol nonionic surfactant and preparation method thereof Download PDFInfo
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- CN107522619A CN107522619A CN201710707655.6A CN201710707655A CN107522619A CN 107522619 A CN107522619 A CN 107522619A CN 201710707655 A CN201710707655 A CN 201710707655A CN 107522619 A CN107522619 A CN 107522619A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
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Abstract
The present invention relates to a kind of Guerbet alcohol nonionic surfactant and preparation method thereof, the preparation method comprises the following steps：1）The double hydroxyl polyethylene glycol of single dispersing and metal base are dissolved in the first organic solvent, instill tert-butyl acrylate, reaction obtains polyethylene glycol dipropyl tert-butyl acrylate；2）Polyethylene glycol dipropyl tert-butyl acrylate is dissolved in the first organic solvent, adds trifluoroacetic acid, reaction obtains polyethylene glycol dipropionic acid；3）Polyethylene glycol dipropionic acid is dissolved in thionyl chloride and reacted, is re-dissolved in the second organic solvent, under base catalysis, single-esterification is carried out with Guerbet alcohol and obtains mono-esterification product；4）Mono-esterification product is dissolved in the second organic solvent, PEG is added and alkali carries out being condensed to yield end-product；The present invention is without separating-purifying, and simple to operate, range of reaction temperature is small, and course of reaction controllability is strong, and cost is cheap, and yield is high.
Description
Technical field
The invention belongs to nonionic surfactant chemical field, and in particular to a kind of Guerbet alcohol non-ionic surface is lived
Property agent and preparation method thereof.
Background technology
Traditional organic reaction occurs in organic solvent mostly, and there is the problems such as organic solvent recovery difficulty for it.This
The increase of cost is not only caused, while also brings serious problem of environmental pollution.It is micro especially to some pharmaceutical synthesis
Dissolvent residual can cause the activity reduction of medicine, or even produce physiological-toxicity.The Green Chemistry concept that American Chemical Society proposes, drum
Encourage scholars and inquire into more green chemical solvent, water has the bright outlook as rich reserves, green and the low solvent of cost.So
And most of organic reagent is insoluble in water, this directly hinders the progress of reaction.For problem above, lived by adding surface
Property material, chemical reaction generation rate in the solution can be improved, may finally realize some perspire with organic reactions exist
Carried out in water.
Guerbet alcohol be by chemist Marcel Guerbet the nineties in 19th century find, be one kind in second carbon
On be connected with the fatty alcohol of side chain, also known as 2- alkyl -1- alkanols, it is a kind of saturation primary alconol, but it have it is different from straight chain alcohol
Peculiar property, such as：It is in liquid condition at room temperature, lipophile is stronger than the straight chain alcohol of equal carbon number；It is oxidation-stabilized under high temperature
Property is good, while has good wettability, greasy property and permeance property, also good biodegradability, as
The surfactant of lipophilic group synthesis has some unique performances.Therefore, the friendly new Ge Er of synthetic environment is developed
Bert alcohols nonionic surfactant, furthers investigate its relevant physical properties, realizes some non-water soluble substances in room temperature, water
Reacted in phase, and expand application field, further investigate its catalytic mechanism, the surfactant is closed in medicine, natural products etc.
More, wider application is obtained in, the research of this respect has highly important theory significance and very bright application
Prospect.(13 carbon Ge Er baud spring APEOs of collateralization, structural formula are the Lutensol TO developed such as BASF Corp. of Germany
RO (CH2CH2O) XH, wherein R=iso-C13H27, x=2,3,4,5,6,7,8,10,11,12,15,20) series of products, have
Good emulsifiability, with dyestuff, pigment, protecting colloid, the material of thickener and other molecular weight in the above range
Compatibility is very good, can also be made into acid, alkaline, neutral detergent to adapt to different requirements.At present, this surface-active
Agent is widely used in lubricant, cosmetics and prevents the every field such as product.
Nonionic surfactant is the surfactant for not producing ion in aqueous, and it is not solved when being dissolved in water
From the lipophilic group in its molecule is roughly the same with the lipophilic group of ionic surfactant, and its hydrophilic radical mainly has
There is a number of oxy radical (such as hydroxyl and polyoxyethylene chain) composition.Because nonionic surfactant is not in the solution
Exist with ionic condition, so its stability is high, be not easy to be influenceed by existing for strong dielectric, be not easy to be influenceed by acid, alkali, with
You can be used in mixed way other types surfactant, and compatibility is good, by good dissolubility in various solvents, in solid table
Strong adsorption does not occur on face, it in water solubility with temperature rise and reduce.Nonionic surfactant has good
The multiple performance such as scattered, emulsification, wetting and increase-volume, be widely used in the various aspects of life.Nonionic surfactant
Classify by hydrophilic radical, there is oxirane and the class of polyol type two.
The surfactant of polyoxyethylene-type is also known as polyethylene glycol type, is oxirane and the compound containing active hydrogen
The product of the addition reaction of progress.Polyethylene glycol (PEG) is the compound formed by epoxyethane ring-expansion polymerization, with the degree of polymerization
Difference, polyethylene glycol has different physics and chemical property.But all nontoxic, nonirritant, it has good water solubility,
And there is good intermiscibility in many organic constituentses.They are respectively provided with excellent lubricity, moisture retention, dispersiveness etc., are making
There is extremely wide application in the industries such as medicine, chemical fibre, bioengineering and food processing.In addition PEG is also widely used in
Nonionic surfactant industry, cosmetics etc., polyethylene glycol series of products can as the raw material of ester type surfactant,
For improving the water dispersible of product, improve water-soluble.
The content of the invention
The invention provides a kind of Guerbet alcohol nonionic surfactant and preparation method thereof, the Guerbet alcohol are non-
Ionic surface active agent, it is by Guerbet alcohol, monodisperse small molecules PEG and the PEG reaction formings that molecular weight is 500-20000
Form, its general structure is：
Wherein R is the primary alkyl of 2 collateralizations, and carbochain total length is in C12-C24Between, n=1-12, PEG molecular weight is
500-20000。
Preferably, the preferred Guerbet hexadecanol of the Guerbet alcohol.
A kind of preparation method of Guerbet alcohol nonionic surfactant, the preparation method comprise the following steps：1)
The double hydroxyl polyethylene glycol of single dispersing and metal base are dissolved in the first organic solvent, instill tert-butyl acrylate, reaction is gathered
Ethylene glycol dipropyl tert-butyl acrylate；2) polyethylene glycol dipropyl tert-butyl acrylate is dissolved in the first organic solvent, adds trifluoroacetic acid, instead
Polyethylene glycol dipropionic acid should be obtained；3) polyethylene glycol dipropionic acid is dissolved in thionyl chloride and reacted, be re-dissolved in the second organic solvent,
Under base catalysis, carry out single-esterification with Guerbet alcohol and obtain mono-esterification product；4) mono-esterification product is dissolved in into second has
Solvent, adds PEG and alkali carries out being condensed to yield end-product, and the molecular formula of the wherein double hydroxyl polyethylene glycol of single dispersing isWherein n=1-12.
Preferably, the first described organic solvent is one kind in tetrahydrofuran, dichloromethane, dioxane；Second has
Solvent is one kind in tetrahydrofuran, benzene, toluene.
Preferably, described metal base is one kind in sodium, potassium, lithium.
Preferably, mole of the double hydroxyl polyethylene glycol of the single dispersing in the step 1), tert-butyl acrylate and metal base
Than for 1：2.2~2.5：0.03~0.05.
Preferably, the mol ratio of Guerbet alcohol and polyethylene glycol dipropionic acid is in the step 3)：1：1~1.3, reaction
Temperature is 30~50 DEG C, and the reaction time is 1~5h.
Preferably, the alkali in the step 3) is one kind in triethylamine, pyridine, sodium hydroxide.
Preferably, the alkali in the step 4) is one kind in triethylamine, pyridine, sodium hydroxide.
Preferably, the mol ratio of the alkali in the step 3) and Guerbet alcohol is：1：1.4~1.7, reaction temperature 20
~30 DEG C, the reaction time is 30~60min.
The process route of the preparation method is as follows：
The invention has the advantages that：
1. monodisperse small molecules PEG and molecular weight that the present invention is determined by Guerbet alcohol, molecular weight are 500-20000's
PEG reaction formings are prepared for a kind of new non-ionic surfactants, and the surfactant has that oxidation stability under high temperature is good,
There is the characteristics of nontoxic, good water solubility simultaneously, additionally with good biodegradability.
2. the present invention is without separating-purifying, simple to operate, range of reaction temperature is small, and course of reaction controllability is strong, and cost is low
Honest and clean, yield is high.
Specific implementation step
Embodiment 1
The polyethylene glycol diester malonates of Guerbet hexadecanol PEG500 tetra-
(1) 20g tetraethylene glycols are added into 150ml tetrahydrofurans, weighs the broken metallic sodiums of 0.12g and add above-mentioned solution
In, and 1h is stirred at room temperature.Weigh 33g tert-butyl acrylates to be added drop-wise in above-mentioned reaction solution, 12h is stirred at room temperature.TLC display reactions
Terminate, add 20ml water quenchings to go out reaction, rotation removes solvents tetrahydrofurane, adds 150ml water, then with 200ml dichloromethane extraction 3
It is secondary.Anhydrous sodium sulfate drying dichloromethane phase, is spin-dried for, and post purifies to obtain about 42g polyethylene glycol dipropyl tert-butyl acrylates, yield：
92%.Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.724 (t, J=6.4Hz, 4H)；3.672~3.638 (m,
12H)；3.530 (t, J=4.8Hz, 4H)；2.893 (t, J=6.8Hz, 4H)；1.460 (s, 18H).
(2) step (1) products therefrom 42g is dissolved in 200ml dichloromethane, added to 200ml trifluoroacetic acids, and room temperature
Stir 8h.After having reacted, rotation removes trifluoroacetic acid, and with Diethyl ether recrystallization, obtains 30g polyethylene glycol dipropionic acids, yield：95%.
Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.755 (t, J=6.4Hz, 4H)；3.683~3.665 (m, 12H)；
3.510 (t, J=4.8Hz, 4H)；2.889 (t, J=6.8Hz, 4H).
(3) polyethylene glycol dipropionic acid 30g obtained by step (2) is mixed with 54g thionyl chlorides, is warming up to 50 DEG C of reaction 1h.
Rotation removes excessive thionyl chloride, obtains weak yellow liquid 33g polyethylene glycol diacid chlorides.By Guerbet hexadecanol 18g and triethylamine
13g is dissolved in 20ml toluene, is added dropwise in the above-mentioned product of 200ml toluene dissolving, 20 DEG C of stirring 30min.Then it is added dropwise
The 50ml toluene solutions of 44gPEG500 and 13g triethylamines.It is added dropwise, 28 DEG C of stirring 1h.100ml saturated common salts are washed, and are done
Dry, concentration, Diethyl ether recrystallization obtains product 80g, yield：90%.White solid.Nuclear magnetic data is as follows：1HNMR (400MHz,
CDCl3)：δ：3.755 (t, J=6.4Hz, 4H)；3.683~3.625 (m, 34H)；3.510 (t, J=4.8Hz, 6H)；1.560
(t, J=4.8Hz, 1H)；1.335~1.304 (m, 28H)；1.010 (s, 6H).
Embodiment 2
The polyethylene glycol diester malonates of Guerbet hexadecanol PEG2000 tetra-
(1) 20g tetraethylene glycols are added into 150ml dioxane, weighs the broken metallic potassiums of 0.15g and add above-mentioned solution
In, and 1h is stirred at room temperature.Weigh 33g tert-butyl acrylates to be added drop-wise in above-mentioned reaction solution, 12h is stirred at room temperature.TLC display reactions
Terminate, add 20ml water quenchings to go out reaction, rotation removes solvent dioxane, adds 150ml water, then with 200ml dichloromethane extraction 3
It is secondary.Anhydrous sodium sulfate drying dichloromethane phase, is spin-dried for, and post purifies to obtain 42g products, yield：92%.Nuclear magnetic data is as follows：
1HNMR (400MHz, CDCl3)：δ：3.733 (t, J=6.4Hz, 4H)；3.652~3.622 (m, 12H)；3.520 (t, J=
4.8Hz, 4H)；2.890 (t, J=6.8Hz, 4H)；1.458 (s, 18H).
(2) step (1) products therefrom 42g is dissolved in 200ml dichloromethane, added to 200ml trifluoroacetic acids, and room temperature
Stir 8h.After having reacted, rotation removes trifluoroacetic acid, and with Diethyl ether recrystallization, obtains 30g products, yield：95%.Nuclear magnetic data is such as
Under：1HNMR (400MHz, CDCl3)：δ：3.753 (t, J=6.4Hz, 4H)；3.683~3.661 (m, 12H)；3.520 (t, J=
4.8Hz, 4H)；2.893 (t, J=6.8Hz, 4H).
(3) step (2) products therefrom 30g is mixed with 54g thionyl chlorides, is warming up to 30 DEG C of reaction 5h.Rotation is except excessive two
Chlorine sulfoxide, obtain weak yellow liquid 33g.Guerbet hexadecanol 18g and pyridine 10g are dissolved in 20ml benzene, are added dropwise to 200ml
In the above-mentioned product of toluene dissolving, 30 DEG C of stirring 45min.Then the 50ml benzole solns of 174gPEG2000 and 10g pyridines are added dropwise.
It is added dropwise, 25 DEG C of stirring 1h.100ml saturated common salts are washed, and are dried, and concentration, Diethyl ether recrystallization obtains product 202g, yield：
87%.White solid.Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.735 (t, J=6.4Hz, 4H)；3.643~
3.605 (m, 102H)；3.501 (t, J=4.8Hz, 6H)；1.544 (t, J=4.8Hz, 1H)；1.315~1.304 (m, 28H)；
0.998 (s, 6H).
Embodiment 3
The polyethylene glycol diester malonates of Guerbet hexadecanol PEG2000 tetra-
(1) 20g tetraethylene glycols are added into 150ml dioxane, weighs the broken metallic potassiums of 0.15g and add above-mentioned solution
In, and 1h is stirred at room temperature.Weigh 33g tert-butyl acrylates to be added drop-wise in above-mentioned reaction solution, 12h is stirred at room temperature.TLC display reactions
Terminate, add 20ml water quenchings to go out reaction, rotation removes solvent dioxane, adds 150ml water, then with 200ml dichloromethane extraction 3
It is secondary.Anhydrous sodium sulfate drying dichloromethane phase, is spin-dried for, and post purifies to obtain 42g products, yield：92%.Nuclear magnetic data is as follows：
1HNMR (400MHz, CDCl3)：δ：3.733 (t, J=6.4Hz, 4H)；3.652~3.622 (m, 12H)；3.520 (t, J=
4.8Hz, 4H)；2.890 (t, J=6.8Hz, 4H)；1.458 (s, 18H).
(2) step (1) products therefrom 42g is dissolved in 200ml dichloromethane, added to 200ml trifluoroacetic acids, and room temperature
Stir 8h.After having reacted, rotation removes trifluoroacetic acid, and with Diethyl ether recrystallization, obtains 30g products, yield：95%.Nuclear magnetic data is such as
Under：1HNMR (400MHz, CDCl3)：δ：3.753 (t, J=6.4Hz, 4H)；3.683~3.661 (m, 12H)；3.520 (t, J=
4.8Hz, 4H)；2.893 (t, J=6.8Hz, 4H).
(3) step (2) products therefrom 30g is mixed with 54g thionyl chlorides, is warming up to 40 DEG C of reaction 3h.Rotation is except excessive two
Chlorine sulfoxide, obtain weak yellow liquid 33g.Guerbet hexadecanol 18g and pyridine 10g are dissolved in 20ml benzene, are added dropwise to 200ml
In the above-mentioned product of benzene dissolving, 25 DEG C of stirring 30min.Then the 50ml benzole solns of 174gPEG2000 and 10g pyridines are added dropwise.Drop
Add complete, 30 DEG C of stirring 1h.100ml saturated common salts are washed, and are dried, and concentration, Diethyl ether recrystallization obtains product 202g, yield：
87%.White solid.Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.735 (t, J=6.4Hz, 4H)；3.643~
3.605 (m, 192H)；3.501 (t, J=4.8Hz, 6H)；1.544 (t, J=4.8Hz, 1H)；1.315~1.304 (m, 28H)；
0.998 (s, 6H).
Embodiment 4
The polyethylene glycol diester malonates of Guerbet hexadecanol PEG20000 tetra-
(1) 20g tetraethylene glycols are added into 150ml dioxane, weighs the broken metallic potassiums of 0.15g and add above-mentioned solution
In, and 1h is stirred at room temperature.Weigh 33g tert-butyl acrylates to be added drop-wise in above-mentioned reaction solution, 12h is stirred at room temperature.TLC display reactions
Terminate, add 20ml water quenchings to go out reaction, rotation removes solvent dioxane, adds 150ml water, then with 200ml dichloromethane extraction 3
It is secondary.Anhydrous sodium sulfate drying dichloromethane phase, is spin-dried for, and post purifies to obtain 43g products, yield：92%.Nuclear magnetic data is as follows：
1HNMR (400MHz, CDCl3)：δ：3.733 (t, J=6.4Hz, 4H)；3.652~3.622 (m, 12H)；3.520 (t, J=
4.8Hz, 4H)；2.890 (t, J=6.8Hz, 4H)；1.458 (s, 18H).
(2) step (1) products therefrom 42g is dissolved in 200ml dichloromethane, added to 200ml trifluoroacetic acids, and room temperature
Stir 8h.After having reacted, rotation removes trifluoroacetic acid, and with Diethyl ether recrystallization, obtains 30g products, yield：95%.Nuclear magnetic data is such as
Under：1HNMR (400MHz, CDCl3)：δ：3.753 (t, J=6.4Hz, 4H)；3.683~3.661 (m, 12H)；3.520 (t, J=
4.8Hz, 4H)；2.893 (t, J=6.8Hz, 4H).
(3) step (2) products therefrom 3g is mixed with 5.4g thionyl chlorides, is warming up to 35 DEG C of reaction 4h.Rotation is except excessive two
Chlorine sulfoxide, obtain weak yellow liquid 3g.Guerbet hexadecanol 1.8g and pyridine 1.0g are dissolved in 5ml tetrahydrofurans, are added dropwise
In the above-mentioned product for entering the dissolving of 50ml tetrahydrofurans, 20 DEG C of stirring 30min.Then 174gPEG20000 and 1.0g pyridines are added dropwise
150ml tetrahydrofuran solutions.It is added dropwise, 30 DEG C of stirring 1h.200ml saturated common salts are washed, and are dried, concentration, Diethyl ether recrystallization
Obtain product 160g, yield：91%.White solid.Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.663~
3.605 (m, 1834H)；3.496 (t, J=4.8Hz, 6H)；1.521 (t, J=4.8Hz, 1H)；1.305~1.308 (m, 28H)；
0.997 (s, 6H).
Embodiment 4
The polyethylene glycol diester malonates of Guerbet hexadecanol PEG1000 eight
(1) glycol of 20g eight is added into 150ml dichloromethane, weighs the broken metallic sodiums of 0.06g and add above-mentioned solution
In, and 1h is stirred at room temperature.Weigh 16.5g tert-butyl acrylates to be added drop-wise in above-mentioned reaction solution, 12h is stirred at room temperature.TLC is shown instead
It should terminate, add 20ml water quenchings to go out reaction, rotation remove solvents tetrahydrofurane, adds 150ml water, then with 200ml dichloromethane extraction
Take 3 times.Anhydrous sodium sulfate drying dichloromethane phase, is spin-dried for, and post purifies to obtain 33g products, yield：93%.Nuclear magnetic data is as follows：
1HNMR (400MHz, CDCl3)：δ：3.744 (t, J=6.4Hz, 4H)；3.671~3.635 (m, 28H)；3.534 (t, J=
4.8Hz, 4H)；2.895 (t, J=6.8Hz, 4H)；1.450 (s, 18H).
(2) step (1) products therefrom 33g is dissolved in 200ml dichloromethane, added to 200ml trifluoroacetic acids, and room temperature
Stir 8h.After having reacted, rotation removes trifluoroacetic acid, and with Diethyl ether recrystallization, obtains 30g products, yield：96%.Nuclear magnetic data is such as
Under：1HNMR (400MHz, CDCl3)：δ：3.755 (t, J=6.4Hz, 4H)；3.683~3.665 (m, 12H)；3.510 (t, J=
4.8Hz, 4H)；2.889 (t, J=6.8Hz, 4H).
(3) step (2) products therefrom 30g is mixed with 54g thionyl chlorides, is warming up to 50 DEG C of reaction 3h.Rotation is except excessive two
Chlorine sulfoxide, obtain weak yellow liquid 28g.Guerbet hexadecanol 9.5g and triethylamine 7.0g are dissolved in 20ml tetrahydrofurans,
It is added dropwise in the above-mentioned product of 200ml tetrahydrofurans dissolving, 30 DEG C of stirring 30min.Then 51gPEG1000 and the second of 7g tri- is added dropwise
The 70ml tetrahydrofuran solutions of amine.It is added dropwise, 25 DEG C of stirring 1h.100ml saturated common salts are washed, and are dried, and concentration, ether is tied again
Crystalline substance obtains product 83g, yield：95%.White solid.Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.755 (t, J
=6.4Hz, 4H)；3.683~3.629 (m, 118H)；3.511 (t, J=4.8Hz, 6H)；1.550 (t, J=4.8Hz, 1H)；
1.331~1.314 (m, 28H)；1.005 (s, 6H).
Embodiment 5
The polyethylene glycol diester malonates of Guerbet hexadecanol PEG5000 eight
(1) glycol of 20g eight is added into 150ml tetrahydrofurans, weighs the broken metallic sodiums of 0.06g and add above-mentioned solution
In, and 1h is stirred at room temperature.Weigh 16.5g tert-butyl acrylates to be added drop-wise in above-mentioned reaction solution, 12h is stirred at room temperature.TLC is shown instead
It should terminate, add 20ml water quenchings to go out reaction, rotation remove solvents tetrahydrofurane, adds 150ml water, then with 200ml dichloromethane extraction
Take 3 times.Anhydrous sodium sulfate drying dichloromethane phase, is spin-dried for, and post purifies to obtain 33g products, yield：93%.Nuclear magnetic data is as follows：
1HNMR (400MHz, CDCl3)：δ：3.744 (t, J=6.4Hz, 4H)；3.671~3.635 (m, 28H)；3.534 (t, J=
4.8Hz, 4H)；2.895 (t, J=6.8Hz, 4H)；1.450 (s, 18H).
(2) step (1) products therefrom 33g is dissolved in 200ml dichloromethane, added to 200ml trifluoroacetic acids, and room temperature
Stir 8h.After having reacted, rotation removes trifluoroacetic acid, and with Diethyl ether recrystallization, obtains 30g products, yield：96%.Nuclear magnetic data is such as
Under：1HNMR (400MHz, CDCl3)：δ：3.755 (t, J=6.4Hz, 4H)；3.683~3.665 (m, 12H)；3.510 (t, J=
4.8Hz, 4H)；2.889 (t, J=6.8Hz, 4H).
(3) step (2) products therefrom 6g is mixed with 11g thionyl chlorides, is warming up to 30 DEG C of reaction 4h.Rotation removes excessive dichloro
Sulfoxide, obtain weak yellow liquid 5.5g.Guerbet hexadecanol 1.9g and triethylamine 1.4g are dissolved in 20ml toluene, are added dropwise to
In the above-mentioned product of 100ml toluene dissolving, 30 DEG C of stirring 1h.Then the 70ml toluene of 51gPEG5000 and 1.4g triethylamines is added dropwise
Solution.It is added dropwise, 25 DEG C of stirring 1h.100ml saturated common salts are washed, and are dried, and concentration, Diethyl ether recrystallization obtains product 57g, are produced
Rate：95%.White solid.Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.765 (t, J=6.4Hz, 4H)；
3.681~3.609 (m, 481H)；3.500 (t, J=4.8Hz, 6H)；1.545 (t, J=4.8Hz, 1H)；1.321~1.314
(m, 28H)；0.998 (s, 6H).
Embodiment 6
The polyethylene glycol diester malonates of Guerbet hexadecanol PEG10000 eight
(1) glycol of 20g eight is added into 150ml tetrahydrofurans, weighs the broken metallic sodiums of 0.06g and add above-mentioned solution
In, and 1h is stirred at room temperature.Weigh 16.5g tert-butyl acrylates to be added drop-wise in above-mentioned reaction solution, 12h is stirred at room temperature.TLC is shown instead
It should terminate, add 20ml water quenchings to go out reaction, rotation remove solvents tetrahydrofurane, adds 150ml water, then with 200ml dichloromethane extraction
Take 3 times.Anhydrous sodium sulfate drying dichloromethane phase, is spin-dried for, and post purifies to obtain 33g products, yield：93%.Nuclear magnetic data is as follows：
1HNMR (400MHz, CDCl3)：δ：3.744 (t, J=6.4Hz, 4H)；3.671~3.635 (m, 28H)；3.534 (t, J=
4.8Hz, 4H)；2.895 (t, J=6.8Hz, 4H)；1.450 (s, 18H).
(2) step (1) products therefrom 33g is dissolved in 200ml dichloromethane, added to 200ml trifluoroacetic acids, and room temperature
Stir 8h.After having reacted, rotation removes trifluoroacetic acid, and with Diethyl ether recrystallization, obtains 30g products, yield：96%.Nuclear magnetic data is such as
Under：1HNMR (400MHz, CDCl3)：δ：3.755 (t, J=6.4Hz, 4H)；3.683~3.665 (m, 12H)；3.510 (t, J=
4.8Hz, 4H)；2.889 (t, J=6.8Hz, 4H).
(3) step (2) products therefrom 6g is mixed with 11g thionyl chlorides, is warming up to 50 DEG C of reaction 3h.Rotation removes excessive dichloro
Sulfoxide, obtain weak yellow liquid 5.5g.Guerbet hexadecanol 1.9g and triethylamine 1.4g are dissolved in 20ml toluene, are added dropwise to
In the above-mentioned product of 100ml toluene dissolving, 20 DEG C of stirring 30min.Then the 70ml of 51gPEG5000 and 1.4g triethylamines is added dropwise
Toluene solution.It is added dropwise, 20 DEG C of stirring 1h.100ml saturated common salts are washed, and are dried, and concentration, Diethyl ether recrystallization obtains product
57g, yield：95%.White solid.Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.765 (t, J=6.4Hz,
4H)；3.681~3.609 (m, 481H)；3.500 (t, J=4.8Hz, 6H)；1.545 (t, J=4.8Hz, 1H)；1.321~
1.314 (m, 28H)；0.998 (s, 6H).
Embodiment 7
The polyethylene glycol diester malonates of Guerbet hexadecanol PEG1000 12
(1) diethylene glycol (DEG)s of 60g ten are added into 150ml tetrahydrofurans, weighs the broken metallic sodiums of 0.12g and add above-mentioned solution
In, and 1h is stirred at room temperature.Weigh 33g tert-butyl acrylates to be added drop-wise in above-mentioned reaction solution, 12h is stirred at room temperature.TLC display reactions
Terminate, add 20ml water quenchings to go out reaction, rotation removes solvents tetrahydrofurane, adds 150ml water, then with 200ml dichloromethane extraction 3
It is secondary.Anhydrous sodium sulfate drying dichloromethane phase, is spin-dried for, and post purifies to obtain about 42g products, yield：92%.Nuclear magnetic data is as follows：
1HNMR (400MHz, CDCl3)：δ：3.724 (t, J=6.4Hz, 4H)；3.672~3.638 (m, 44H)；3.530 (t, J=
4.8Hz, 4H)；2.893 (t, J=6.8Hz, 4H)；1.460 (s, 18H).
(2) step (1) products therefrom 60g is dissolved in 200ml dichloromethane, added to 200ml trifluoroacetic acids, and room temperature
Stir 8h.After having reacted, rotation removes trifluoroacetic acid, and with Diethyl ether recrystallization, obtains 50g products, yield：95%.Nuclear magnetic data is such as
Under：1HNMR (400MHz, CDCl3)：δ：3.755 (t, J=6.4Hz, 4H)；3.683~3.665 (m, 12H)；3.510 (t, J=
4.8Hz, 4H)；2.889 (t, J=6.8Hz, 4H).
(3) step (2) products therefrom 30g is mixed with 54g thionyl chlorides, is warming up to 50 DEG C of reaction 3h.Rotation is except excessive two
Chlorine sulfoxide, obtain weak yellow liquid 33g.Guerbet hexadecanol 11g and triethylamine 7g are dissolved in 20ml toluene, are added dropwise to
In the above-mentioned product of 100ml toluene dissolving, 30 DEG C of stirring 30min.Then the 50ml first of 46gPEG1000 and 7g triethylamines is added dropwise
Benzole soln.It is added dropwise, 20 DEG C of stirring 30min.100ml saturated common salts are washed, and are dried, and concentration, Diethyl ether recrystallization obtains product
82g, yield：94%.White solid.Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.682~3.635 (m,
84H)；3.511 (t, J=4.8Hz, 6H)；1.550 (t, J=4.8Hz, 1H)；1.312~1.290 (m, 28H)；0.998 (s,
6H)。
Embodiment 8
The polyethylene glycol diester malonates of Guerbet hexadecanol PEG5000 12
(1) diethylene glycol (DEG)s of 60g ten are added into 150ml tetrahydrofurans, weighs the broken metallic sodiums of 0.12g and add above-mentioned solution
In, and 1h is stirred at room temperature.Weigh 33g tert-butyl acrylates to be added drop-wise in above-mentioned reaction solution, 12h is stirred at room temperature.TLC display reactions
Terminate, add 20ml water quenchings to go out reaction, rotation removes solvents tetrahydrofurane, adds 150ml water, then with 200ml dichloromethane extraction 3
It is secondary.Anhydrous sodium sulfate drying dichloromethane phase, is spin-dried for, and post purifies to obtain about 42g products, yield：92%.Nuclear magnetic data is as follows：
1HNMR (400MHz, CDCl3)：δ：3.724 (t, J=6.4Hz, 4H)；3.672~3.638 (m, 44H)；3.530 (t, J=
4.8Hz, 4H)；2.893 (t, J=6.8Hz, 4H)；1.460 (s, 18H).
(2) step (1) products therefrom 60g is dissolved in 200ml dichloromethane, added to 200ml trifluoroacetic acids, and room temperature
Stir 8h.After having reacted, rotation removes trifluoroacetic acid, and with Diethyl ether recrystallization, obtains 50g products, yield：95%.Nuclear magnetic data is such as
Under：1HNMR (400MHz, CDCl3)：δ：3.755 (t, J=6.4Hz, 4H)；3.683~3.665 (m, 12H)；3.510 (t, J=
4.8Hz, 4H)；2.889 (t, J=6.8Hz, 4H).
(3) step (2) products therefrom 3.0g is mixed with 5.4g thionyl chlorides, is warming up to 50 DEG C of reaction 3h.Rotation is except excessive
Thionyl chloride, obtain weak yellow liquid 3.3g.Guerbet hexadecanol 1.1g and triethylamine 0.7g are dissolved in 20ml toluene, dripped
Add in the above-mentioned product of 100ml toluene dissolving, 20 DEG C of stirring 30min.Then 23gPEG5000 and 0.7g triethylamines are added dropwise
50ml toluene solutions.It is added dropwise, 30 DEG C of stirring 1h.100ml saturated common salts are washed, and are dried, and concentration, Diethyl ether recrystallization is produced
Product 80g, yield：90%.White solid.Nuclear magnetic data is as follows：1HNMR (400MHz, CDCl3)：δ：3.712~3.645 (m,
446H)；3.520 (t, J=4.8Hz, 6H)；1.554 (t, J=4.8Hz, 1H)；1.315~1.294 (m, 28H)；0.997 (s,
6H)。
Claims (9)
1. a kind of Guerbet alcohol nonionic surfactant, its general structure are：
Wherein R is the primary alkyl of 2 collateralizations, and carbochain total length is in C12-C24Between, n=1-12, PEG molecular weight is 500-
20000。
A kind of 2. Guerbet alcohol nonionic surfactant according to claim 1, it is characterised in that the gerber
Extra Old is Guerbet hexadecanol.
3. preparing the method for Guerbet alcohol nonionic surfactant as claimed in claim 1, mainly include the following steps that：
1) the double hydroxyl polyethylene glycol of single dispersing and metal base are dissolved in the first organic solvent, instill tert-butyl acrylate, reaction obtains
Polyethylene glycol dipropyl tert-butyl acrylate；2) polyethylene glycol dipropyl tert-butyl acrylate is dissolved in the first organic solvent, adds trifluoroacetic acid,
Reaction obtains polyethylene glycol dipropionic acid；3) polyethylene glycol dipropionic acid is dissolved in thionyl chloride and reacted, it is organic molten to be re-dissolved in second
Agent, under base catalysis, carry out single-esterification with Guerbet alcohol and obtain mono-esterification product；4) mono-esterification product is dissolved in second
Organic solvent, adds PEG and alkali carries out being condensed to yield end-product, and the molecular formula of the wherein double hydroxyl polyethylene glycol of single dispersing isWherein n=1-12.
4. a kind of preparation method of described Guerbet alcohol nonionic surfactant according to claim 3, it is special
Sign is that the first described organic solvent is one kind in tetrahydrofuran, dichloromethane, dioxane；Second organic solvent is
One kind in tetrahydrofuran, benzene, toluene.
5. a kind of preparation method of described Guerbet alcohol nonionic surfactant according to claim 3 or 4, its
It is characterised by, the metal base in the step 1) is one kind in sodium, potassium, lithium.
6. a kind of preparation method of described Guerbet alcohol nonionic surfactant according to claim 5, it is special
Sign is that the mol ratio of the double hydroxyl polyethylene glycol of the single dispersing in the step 1), tert-butyl acrylate and metal base is 1：2.2
~2.5：0.03~0.05.
7. a kind of preparation method of described Guerbet alcohol nonionic surfactant according to claim 6, it is special
Sign is that the mol ratio of Guerbet alcohol and polyethylene glycol dipropionic acid is in the step 3)：1：1~1.3, reaction temperature 30
~50 DEG C, the reaction time is 1~5h.
8. a kind of preparation method of described Guerbet alcohol nonionic surfactant according to claim 7, it is special
Sign is that the alkali in the step 3) is one kind in triethylamine, pyridine, sodium hydroxide.
9. a kind of preparation method of described Guerbet alcohol nonionic surfactant according to claim 8, it is special
Sign is, the mol ratio of alkali and Guerbet alcohol in the step 3)：1：1.4~1.7, reaction temperature is 20~30 DEG C, instead
It is 30~60min between seasonable.
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Cited By (3)
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| CN109337064A (en) * | 2018-09-17 | 2019-02-15 | 辽宁科隆精细化工股份有限公司 | A kind of method of synthesizing methoxy polyethylene glycol methacrylate-styrene polymer |
| CN111036136A (en) * | 2019-12-25 | 2020-04-21 | 湖南华腾制药有限公司 | Novel cationic surfactant and preparation method thereof |
| DE102019217963A1 (en) * | 2019-11-21 | 2021-05-27 | Henkel Ag & Co. Kgaa | Polymeric surface-active ingredients and detergents and cleaning agents containing them |
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| WO2012054110A2 (en) * | 2010-07-07 | 2012-04-26 | Ardelyx, Inc. | Compounds and methods for inhibiting phosphate transport |
| CN103642033A (en) * | 2013-11-18 | 2014-03-19 | 南京理工大学 | Guerbet alcohol nonionic surfactant |
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2017
- 2017-08-17 CN CN201710707655.6A patent/CN107522619A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012054110A2 (en) * | 2010-07-07 | 2012-04-26 | Ardelyx, Inc. | Compounds and methods for inhibiting phosphate transport |
| CN103642033A (en) * | 2013-11-18 | 2014-03-19 | 南京理工大学 | Guerbet alcohol nonionic surfactant |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337064A (en) * | 2018-09-17 | 2019-02-15 | 辽宁科隆精细化工股份有限公司 | A kind of method of synthesizing methoxy polyethylene glycol methacrylate-styrene polymer |
| DE102019217963A1 (en) * | 2019-11-21 | 2021-05-27 | Henkel Ag & Co. Kgaa | Polymeric surface-active ingredients and detergents and cleaning agents containing them |
| CN111036136A (en) * | 2019-12-25 | 2020-04-21 | 湖南华腾制药有限公司 | Novel cationic surfactant and preparation method thereof |
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