CN113527655A - Fluorine-containing nonionic macromolecular surfactant and preparation method thereof - Google Patents
Fluorine-containing nonionic macromolecular surfactant and preparation method thereof Download PDFInfo
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- CN113527655A CN113527655A CN202110888786.5A CN202110888786A CN113527655A CN 113527655 A CN113527655 A CN 113527655A CN 202110888786 A CN202110888786 A CN 202110888786A CN 113527655 A CN113527655 A CN 113527655A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/26—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 from cyclic ethers and other compounds
- C08G65/2603—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 from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/26—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 from cyclic ethers and other compounds
- C08G65/2696—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 from cyclic ethers and other compounds characterised by the process or apparatus used
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Abstract
The invention discloses a fluorine-containing nonionic macromolecular surfactant and a preparation method thereof, wherein the preparation method comprises the following steps: weighing 100 parts of alcohol macroinitiator and 100 parts of solvent according to the mass parts, and mixing and dissolving to obtain an alcohol macroinitiator solution; then, weighing 10-50 parts of catalyst at the temperature of 0 ℃, adding the catalyst into the alcohol macroinitiator solution, and reacting for 1 hour to obtain a reaction solution A; weighing 50-500 parts of fluorine-containing monomer and 400 parts of solvent by mass, mixing and dissolving to obtain fluorine-containing monomer solution; dropwise adding the fluorine-containing monomer solution into the reaction solution A at the temperature of-10 ℃, and continuing to react for 8 hours after the dropwise adding is finished; cooling the reaction system to room temperature, and adding a proper amount of 2 wt% sodium bicarbonate water solution to adjust the reaction system to be neutral; standing and layering to obtain white transparent liquid on the lower layer; and (3) carrying out rotary evaporation on the white transparent liquid to obtain the fluorine-containing non-ionic macromolecular surfactant. The invention can improve the surface activity of the surfactant and reduce the critical micelle concentration of the surfactant.
Description
Technical Field
The invention relates to the field of surfactant preparation, in particular to a fluorine-containing nonionic macromolecular surfactant and a preparation method thereof.
Background
Surfactants have been used as cleaning aids for many years before they have been systematically recognized in the scientific community. With the establishment of surface science, the development of surfactants is formally on the way. Surfactants can be classified as ionic or nonionic surfactants, with the common surfactants being either soaps, quaternaries or sodium lauryl sulfate. However, with the development of the application of surfactants in non-cleaning fields, the above small molecular surfactants all face some problems, such as poor weather resistance, poor stability or molecular migration, and the research field of the large molecular surfactants is in the process of operation.
The development of artificial macromolecular surfactants has been in the last 50 s, before which natural macromolecular surfactants were mainly widely used. However, Strass synthesized the first artificial macromolecular surfactant in 1951, which was used in the industrial field in 1954 and was named as
Due to excellent weather resistance, lower critical micelle concentration and excellent rheological property of macromolecules, the macromolecules are widely applied to the fields of emulsion polymerization, special coatings, biotechnology, nanotechnology, medicine, daily chemical industry, wastewater treatment, photoelectricity and the like. With the development of fluorine chemistry, fluorocarbon surfactants gradually come into the visual field of people, and due to the strong electronegativity and excellent hydrophobic property of fluorine atoms, the fluorocarbon surfactants have extremely high surface activity and excellent chemical stability.
The present invention aims to obtain fluorinated nonionic macromolecular surfactants by using a mechanism of living cationic polymerization, thereby improving the yield of the fluorinated nonionic macromolecular surfactants and simplifying the preparation process thereof.
Disclosure of Invention
The invention provides a preparation method of a fluorine-containing nonionic macromolecular surfactant, which has the following technical scheme:
a method for preparing a fluorine-containing nonionic macromolecular surfactant, comprising:
weighing 100 parts of alcohol macroinitiator and 100 parts of solvent according to the mass parts, and fully mixing and dissolving to obtain an alcohol macroinitiator solution; then, weighing 10-50 parts of catalyst at the temperature of 0 ℃, putting into the alcohol macroinitiator solution, and reacting for 1h to obtain a reaction solution A;
weighing 50-500 parts of fluorine-containing monomer and 400 parts of solvent by mass, and fully mixing and dissolving to obtain fluorine-containing monomer solution;
slowly dripping the fluorine-containing monomer solution into the reaction solution A at the temperature of-10 ℃, and continuing to react for 8 hours after the dripping is finished;
after cooling the reaction system to room temperature, adding a proper amount of 2 wt% sodium bicarbonate water solution to adjust the reaction system to be neutral;
standing and layering, and taking out the white transparent liquid at the lower layer;
and (3) carrying out rotary evaporation on the taken white transparent liquid to obtain the fluorine-containing nonionic macromolecular surfactant.
In some embodiments, the addition time of the fluorine-containing monomer solution to the solution A is controlled to be 6 to 8 hours.
In some embodiments, the alcoholic macroinitiator is polyethylene glycol, polyvinyl alcohol, or polyethylene glycol monomethyl ether.
In some embodiments, the solvent is dichloromethane or ethyl acetate.
In some embodiments, the fluoromonomer is fluorinated epichlorohydrin.
In some embodiments, the initiator comprises a boron trifluoride etherate complex, a boron trifluoride tetrahydrofuran complex, or a tin hydroxide.
The invention provides a fluorine-containing nonionic macromolecular surfactant, which is prepared by the preparation method of any one of the fluorine-containing nonionic macromolecular surfactants.
The invention prepares the novel fluorine-containing nonionic surfactant by using an active cation polymerization mechanism between fluorinated epichlorohydrin and an alcohol macroinitiator as a principle, and the prepared fluorine-containing nonionic surfactant can greatly improve the surface activity of the surfactant and reduce the critical micelle concentration of the surfactant.
Drawings
FIG. 1 is a graph showing an infrared absorption spectrum of a fluorinated nonionic macromolecular surfactant prepared in example 1 of the present invention.
FIG. 2 is a NMR spectrum of a fluorinated nonionic macromolecular surfactant prepared in example 1 of the present invention.
FIG. 3 is a NMR fluorine spectrum of the fluorinated nonionic macromolecular surfactant prepared in example 1 of the present invention.
FIG. 4 is a gel permeation chromatogram of the fluorinated nonionic macromolecular surfactant prepared in example 1 of the present invention.
FIG. 5 is a digital photograph of a fluorinated nonionic macromolecular surfactant prepared according to example 1 of the present invention.
FIG. 6 is a graph showing the relationship between the critical micelle concentration and the surface tension of the fluorinated nonionic macromolecular surfactant prepared in example 1 of the present invention.
Detailed Description
The description is further elucidated with reference to specific examples. The description is to be regarded as illustrative and explanatory only and should not be taken as limiting the scope of the invention in any way.
First, in the embodiments of the present invention, an alcohol macroinitiator is used as an initiator for living cationic polymerization, and before use, the alcohol macroinitiator needs to be azeotropically removed with toluene to remove water absorbed by the alcohol macroinitiator in air, thereby reducing its polymerization inhibition effect on living cationic polymerization.
Example 1
The preparation of the fluorinated nonionic macromolecular surfactant by using the fluorinated epichlorohydrin initiated by the polyethylene glycol-2000 concretely comprises the following steps:
100g of polyethylene glycol-2000 and 100g of dichloromethane are weighed and put into a 1000mL four-neck flask to be uniformly stirred, so as to obtain an alcohol macroinitiator solution.
Weighing 50g of trifluoro-substituted fluorinated epichlorohydrin and 100g of dichloromethane solvent, putting into an isopiestic dropping funnel, assembling the isopiestic dropping funnel and a four-neck flask, checking the airtightness, introducing N2 into the whole device for about 30min, removing air and water vapor, and placing the whole device in an ice bath at 0 ℃.
10g of boron trifluoride etherate as a catalyst is added into a four-neck flask group through anhydrous and oxygen-free operation, so that the boron trifluoride etherate and the macromolecular alcohol initiator are fully complexed.
And (3) after 1h, placing the whole device in an ice bath at the temperature of-10 ℃, starting a constant-pressure dropping funnel, beginning to drop the fluorinated epichlorohydrin solution, controlling the dropping rate to be between 30mg/min and 80mg/min, and after the dropping is finished, continuing to react for 8h in the ice bath to improve the conversion rate of the fluorinated monomer.
After the reaction is finished, adding a proper amount of deionized water into the system to terminate the reaction and restore the temperature of the reaction system to room temperature, and adding a proper amount of 2 wt% sodium bicarbonate aqueous solution to adjust the whole system to be neutral. Then, the mixture was poured into a separatory funnel, and after standing and layering, a white transparent liquid was taken out from the lower layer.
And (3) carrying out rotary evaporation on the obtained white transparent liquid, discarding fractions evaporated at 45 ℃ and 50mm/Hg, taking the residual light yellow liquid in a rotary evaporation bottle, placing the liquid in an oven at 80 ℃ for 2h, and further removing the monomers to obtain the product.
Example 2
The preparation of the fluorinated nonionic macromolecular surfactant by using the fluorinated epichlorohydrin initiated by the polyethylene glycol-4000 comprises the following steps:
100g of polyethylene glycol-4000 and 100g of dichloromethane are weighed and put into a 1000mL four-neck flask to be uniformly stirred, so as to obtain an alcohol macroinitiator solution.
275g of trifluoro-substituted epichlorohydrin and 200g of dichloromethane solvent were weighed, and the weighed materials were put into an isopiestic dropping funnel, after the isopiestic dropping funnel and a four-neck flask were assembled, the airtightness was checked, N2 was introduced into the whole apparatus for about 30min, air and water vapor were removed, and the whole apparatus was placed in an ice bath at 0 ℃.
30g of boron trifluoride etherate as a catalyst is added into the system through anhydrous and oxygen-free operation, so that the boron trifluoride etherate and the macromolecular alcohol initiator are fully complexed.
And (3) after 1h, placing the whole device in an ice bath at the temperature of-10 ℃, starting a constant-pressure dropping funnel, beginning to drop the fluorinated epichlorohydrin solution, controlling the dropping rate to be between 60mg/min and 160mg/min, and after the dropping is finished, continuing to react for 8h in the ice bath to improve the conversion rate of the fluorinated monomer.
After the reaction is finished, adding a proper amount of deionized water into the system to terminate the reaction and restore the temperature of the reaction system to room temperature, and adding a proper amount of 2 wt% sodium bicarbonate aqueous solution to adjust the whole system to be neutral. Then, the mixture was poured into a separatory funnel, and after standing and layering, a white transparent liquid was taken out from the lower layer.
And (3) carrying out rotary evaporation on the obtained white transparent liquid, discarding fractions evaporated at 45 ℃ and 50mm/Hg, taking the residual light yellow liquid in a rotary evaporation bottle, placing the liquid in an oven at 80 ℃ for 2h, and further removing the monomers to obtain the product.
Example 3
The preparation of the fluorinated nonionic macromolecular surfactant by initiating fluorinated epichlorohydrin with polyethylene glycol monomethyl ether-2000 specifically comprises the following steps:
100g of polyethylene glycol monomethyl ether-2000 and 100g of dichloromethane are weighed and put into a 1000mL four-neck flask to be uniformly stirred, so as to obtain an alcohol macroinitiator solution.
Weighing 500g of trifluoro-substituted fluorinated epichlorohydrin and 400g of dichloromethane solvent, putting into an isopiestic dropping funnel, assembling the isopiestic dropping funnel and a four-neck flask, checking the air tightness, introducing N2 into the whole device for about 30min, removing air and water vapor, and placing the whole device in an ice bath at 0 ℃.
50g of boron trifluoride etherate as a catalyst is added into the system through anhydrous and oxygen-free operation, so that the boron trifluoride etherate and the macromolecular alcohol initiator are fully complexed.
And (3) after 1h, placing the whole device in an ice bath at the temperature of-10 ℃, starting a constant-pressure dropping funnel, beginning to drop the fluorinated epichlorohydrin solution, controlling the dropping rate to be between 120mg/min and 320mg/min, and after the dropping is finished, continuing to react for 8h in the ice bath to improve the conversion rate of the fluorinated monomer.
After the reaction is finished, adding a proper amount of deionized water into the system to terminate the reaction and restore the temperature of the reaction system to room temperature, and adding a proper amount of 2 wt% sodium bicarbonate aqueous solution to adjust the whole system to be neutral. Then, the mixture was poured into a separatory funnel, and after standing and layering, a white transparent liquid was taken out from the lower layer.
And (3) carrying out rotary evaporation on the obtained white transparent liquid, discarding fractions evaporated at 45 ℃ and 50mm/Hg, taking the residual light yellow liquid in a rotary evaporation bottle, placing the liquid in an oven at 80 ℃ for 2h, and further removing the monomers to obtain the product.
The following is an assay for the fluorinated nonionic macromolecular surfactant prepared in example 1:
and (3) structure determination: the molecular structure of the fluorinated nonionic macromolecular surfactant is determined by Fourier-infrared transform spectroscopy and nuclear magnetic resonance, and the molecular weight distribution of the synthesized fluorinated nonionic macromolecular surfactant are determined by gel permeation chromatography.
And (3) performance measurement: the curve of the surfactant concentration as a function of the water surface tension and its critical micelle concentration were measured using a tensiometer.
Fig. 1, 2 and 3 are an infrared absorption spectrum, a nuclear magnetic resonance hydrogen spectrum and a nuclear magnetic resonance fluorine spectrum of the fluorinated nonionic macromolecular surfactant prepared in example 1 of the present invention, respectively.
Fig. 4, 5 and 6 are graphs showing the relationship between the gel permeation chromatogram, the digital photograph, the critical micelle concentration and the surface tension of the fluorinated nonionic macromolecular surfactant prepared in example 1 of the present invention.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of a fluorine-containing nonionic macromolecular surfactant is characterized by comprising the following steps:
weighing 100 parts of alcohol macroinitiator and 100 parts of solvent according to the mass parts, and fully mixing and dissolving to obtain an alcohol macroinitiator solution; then, weighing 10-50 parts of catalyst at the temperature of 0 ℃, putting into the alcohol macroinitiator solution, and reacting for 1h to obtain a reaction solution A;
weighing 50-500 parts of fluorine-containing monomer and 400 parts of solvent by mass, and fully mixing and dissolving to obtain fluorine-containing monomer solution;
slowly dripping the fluorine-containing monomer solution into the reaction solution A at the temperature of-10 ℃, and continuing to react for 8 hours after the dripping is finished;
after cooling the reaction system to room temperature, adding a proper amount of 2 wt% sodium bicarbonate water solution to adjust the reaction system to be neutral;
standing and layering, and taking out the white transparent liquid at the lower layer;
and (3) carrying out rotary evaporation on the taken white transparent liquid to obtain the fluorine-containing nonionic macromolecular surfactant.
2. The method for producing a fluorinated nonionic macromolecular surfactant according to claim 1, wherein the dropping time of the solution of the fluorinated monomer into the solution A is controlled to 6 to 8 hours.
3. The method for preparing a fluorine-containing nonionic macromolecular surfactant according to claim 1, wherein the alcohol macroinitiator is in polyethylene glycol, polyvinyl alcohol or polyethylene glycol monomethyl ether.
4. The method for producing a fluorine-containing nonionic macromolecular surfactant according to claim 1, wherein the solvent is dichloromethane or ethyl acetate.
5. The method for producing a fluorine-containing nonionic macromolecular surfactant according to claim 1, wherein said fluorine-containing monomer is fluorinated epichlorohydrin.
6. The method of claim 1, wherein the initiator comprises boron trifluoride etherate complex, boron trifluoride tetrahydrofuran complex, or tin hydroxide.
7. A fluorine-containing nonionic macromolecular surfactant, characterized in that the fluorine-containing nonionic macromolecular surfactant is prepared by the preparation method of any one of claims 1 to 6.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850695A (en) * | 2022-11-21 | 2023-03-28 | 广州振清环保技术有限公司 | Bio-based water-based polyether amine high-molecular polymer and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0010523A1 (en) * | 1978-10-20 | 1980-04-30 | Ciba-Geigy Ag | Perfluoroalkylalkylenemercapto group containing non-ionic surfactants, process for their manufacture and their use |
| JP2015120861A (en) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | Surfactant composition, coating composition, and resist composition |
| CN106117413A (en) * | 2016-06-27 | 2016-11-16 | 南京信息工程大学 | Fluorine carbon emulsion without soap prepared by a kind of perfluoroalkyl acrylate copolymerization and preparation method thereof |
| US20170217863A1 (en) * | 2014-07-28 | 2017-08-03 | Merck Patent Gmbh | Fluorinated tensides |
| CN110156594A (en) * | 2019-05-21 | 2019-08-23 | 淮海工学院 | Polyoxyethylene ether carboxylic acid Gemini surface active agent class drag reducer and its preparation method and application |
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2021
- 2021-08-03 CN CN202110888786.5A patent/CN113527655B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0010523A1 (en) * | 1978-10-20 | 1980-04-30 | Ciba-Geigy Ag | Perfluoroalkylalkylenemercapto group containing non-ionic surfactants, process for their manufacture and their use |
| JP2015120861A (en) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | Surfactant composition, coating composition, and resist composition |
| US20170217863A1 (en) * | 2014-07-28 | 2017-08-03 | Merck Patent Gmbh | Fluorinated tensides |
| CN106117413A (en) * | 2016-06-27 | 2016-11-16 | 南京信息工程大学 | Fluorine carbon emulsion without soap prepared by a kind of perfluoroalkyl acrylate copolymerization and preparation method thereof |
| CN110156594A (en) * | 2019-05-21 | 2019-08-23 | 淮海工学院 | Polyoxyethylene ether carboxylic acid Gemini surface active agent class drag reducer and its preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850695A (en) * | 2022-11-21 | 2023-03-28 | 广州振清环保技术有限公司 | Bio-based water-based polyether amine high-molecular polymer and preparation method and application thereof |
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