Gemini type perfluoroether surfactant and preparation method thereof
阅读说明：本技术 一种双子型全氟醚类表面活性剂及其制备方法 (Gemini type perfluoroether surfactant and preparation method thereof ) 是由 谢伟东 郭勇 杜芳琼 吴成英 陈庆云 黄美薇 王孟英 于 2020-03-03 设计创作，主要内容包括：本发明提供了一种双子型全氟醚类表面活性剂,包括以下结构:<Image he="246" wi="700" file="DDA0002398706720000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,R<Sub>1</Sub>和R<Sub>3</Sub>各自独立地选自碳原子数2-7的直链或支链的全氟醚链和全氟多醚链；R<Sub>2</Sub>选自碳原子数2～12的直链或支链的烃基或醚基以及邻位、间位或对位的芳香基团；R<Sub>4</Sub>和R<Sub>5</Sub>各自独立地选自碳原子数2～5的直链或支链的烃基或芳香基团；R<Sub>6</Sub>和R<Sub>7</Sub>各自独立地选自O或NR<Sub>8</Sub>,R<Sub>8</Sub>选自H或碳原子数1～3的烃基,X选自卤素。同时,本发明还公开了上述双子型全氟醚类表面活性剂的制备方法。本发明提供的双子型全氟醚类表面活性剂具有良好的可降解性能和较低的毒性,能够有效解决现有碳氟表面活性剂存在的生物蓄积性和毒性高的问题。(The invention provides a Gemini type perfluoroether surfactant, which comprises the following structures: wherein R is 1 And R 3 Each independently selected from linear or branched perfluoroether chains and perfluoropolyether chains having 2 to 7 carbon atoms; r 2 The aromatic functional group is selected from a straight chain or branched chain alkyl group or ether group with 2-12 carbon atoms and an ortho-position, meta-position or para-position aromatic group; r 4 And R 5 Each independently selected from linear chain with 2-5 carbon atomsOr a branched hydrocarbon or aromatic group; r 6 And R 7 Each independently selected from O or NR 8 ，R 8 Selected from H or alkyl with 1-3 carbon atoms, and X is selected from halogen. Meanwhile, the invention also discloses a preparation method of the gemini perfluoroether surfactant. The gemini perfluoroether surfactant provided by the invention has good degradability and low toxicity, and can effectively solve the problems of high bioaccumulation and toxicity of the existing fluorocarbon surfactant.)
1. A gemini perfluoroether surfactant is characterized by comprising the following structure:
wherein R is1And R3Each independently selected from linear or branched perfluoroether chains and perfluoropolyether chains having 2 to 7 carbon atoms; r2Selected from linear chain or branched chain alkyl with 2-12 carbon atomsOr ether groups and ortho-, meta-or para-aromatic groups; r4And R5Each independently selected from a linear chain or branched chain alkyl or aromatic group with 2-5 carbon atoms; r6And R7Each independently selected from O or NR8，R8Selected from H or alkyl with 1-3 carbon atoms, and X is selected from halogen.
2. The gemini perfluoroether surfactant according to claim 1, wherein R is R1And R3Each independently selected from the following general formula:
R9(OCF2)m(OCF(CF3))n(CF2)p
wherein R is9Selected from CF3、C2F5、C3F7Or C4F9；m＝0～6；n＝0～3；p＝0～2。
3. The gemini perfluoroether surfactant according to claim 1, wherein R is R1And R3Each independently selected from CF3OCF2OCF2CF2OCF(CF3)-、CF3CF2CF2OCF(CF3)-、CF3OCF2CF2OCF(CF3)-、CF3OCF(CF3)CF2OCF(CF3)-、CF3CF2OCF(CF3)CF2OCF(CF3)-、CF3OCF2-、CF3O(CF2)2-、CF3(OCF2)3-、CF3(OCF2)4-or CF3(OCF2)5-。
4. The gemini perfluoroether surfactant according to claim 1, wherein R is R2Selected from linear alkyl group with 2-6 carbon atoms, -CH2CH2OCH2CH2-、
5. The gemini perfluoroether surfactant according to claim 1, wherein R is R4And R5Is selected from-CH2CH2CH2-。
6. The gemini perfluoroether surfactant according to claim 1, wherein R is R8Selected from H or methyl.
7. A gemini perfluoroether type surfactant according to claim 1, wherein said gemini perfluoroether type surfactant is selected from the following structures:
8. a gemini perfluoroether type surfactant according to claim 1, wherein said gemini perfluoroether type surfactant is selected from the following structures:
9. the method for preparing a Gemini perfluoroether surfactant according to any one of claims 1 to 8, comprising the following steps:
obtaining compounds shown as structural formulas 2, 3 and 4, mixing the compound shown as the structural formula 2, the compound shown as the structural formula 3 and the compound shown as the structural formula 4 in a solvent, heating until the solvent refluxes, and removing the solvent after reaction to obtain the compound shown as the structural formula 1;
wherein R is1And R3Each independently selected from linear or branched perfluoroether chains and perfluoropolyether chains having 2 to 7 carbon atoms; r2The aromatic functional group is selected from a straight chain or branched chain alkyl group or ether group with 2-12 carbon atoms and an ortho-position, meta-position or para-position aromatic group; r4And R5Each independently selected from a linear chain or branched chain alkyl or aromatic group with 2-5 carbon atoms; r6And R7Each independently selected from O or NR8，R8Selected from H or alkyl with 1-3 carbon atoms, and X is selected from halogen.
10. The method for producing a gemini perfluoroether surfactant according to claim 9, wherein the total amount of the substances of the compound represented by the structural formula 2 and the compound represented by the structural formula 3 is 1.5 to 3 times the amount of the substance of the compound represented by the structural formula 4.
11. The method for preparing a Gemini perfluoroether surfactant according to claim 9, wherein the reaction temperature is 70-90 ℃ and the reaction time is 8-16 hours.
12. The method of preparing a gemini perfluoro ether type surfactant according to claim 9, wherein the solvent comprises one or more of acetonitrile, ethanol, acetone, ethyl acetate, DMF, DMSO and methanol.
13. The method for preparing a Gemini perfluoroether surfactant according to claim 9, wherein the solvent is removed by the reaction, and the product is recrystallized or washed to obtain the compound represented by formula 1.
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to a Gemini type perfluoroether surfactant and a preparation method thereof.
Background
The fluorocarbon surfactant as a new special surfactant begins to become a hotspot of research in the field of chemical surfactants, the traditional fluorocarbon surfactant means that hydrogen atoms on a hydrophobic chain are partially or completely replaced by fluorine atoms, and the compound has the functions of hydrophobicity and lipophobicity, so that the fluorine-containing surfactant is mainly applied to the fields of fire-fighting foam fire extinguishing, industry, agriculture, machinery, textile, medicine and the like, has irreplaceable effects and is entitled to industrial monosodium glutamate.
Traditional surfactants consist of a terminal hydrophilic group and a hydrophobic group, while Gemini surfactants (Gemini surfactants or Gemini) are formed by covalently linking two or more hydrophilic tail groups, two or more hydrophobic head groups and a bridging group, also known as Gemini surfactants. Compared with the traditional hydrocarbon surfactant, the gemini surfactant has lower Critical Micelle Concentration (CMC) and C20Small values, various aggregate structures, etc., which exhibit better wetting, lower surface tension, due to these unique propertiesThe aqueous solution thereof also has special phase behavior and rheological property, and the formed molecular ordered assembly thereof has some special properties and functions, which has attracted the extensive interest and attention of academia and industry.
The Gemini type fluorocarbon cationic surfactant has attracted much attention as a new surfactant. These surfactants not only have less repulsion between hydrophilic head groups, but also are more tightly aligned at the interface, greatly reducing surface and interfacial tension. However, the Gemini type fluorocarbon cationic surfactant is easy to generate long-chain perfluoroalkyl compounds in the degradation process, is difficult to further degrade and accumulate in organisms, and has certain biological toxicity.
Until the last decade, humans have not recognized the widespread presence of perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), and other perfluoroalkyl chain (C >8) fluorosurfactants like PFAAs in the global environment, and have raised enormous environmental and toxicity concerns due to their persistence in the environment and high tendency to accumulate in animals and humans. Thus, 3M company announced a global phase-out of long-chain PFAAs in 2000, which was listed on the stockholm convention permanent organic pollutants (pop) list in 2009 at 5 months, leading to global restrictions on their production. PFOA was banned by listing in 2019, annex a of stockholm convention, 5 months. Because perfluoroalkyl surfactants have a range of unique properties, extremely low surface tension and high hydrophobicity/oiliness, making them difficult to replace in advanced technology applications, there is an urgent need to replace these fluorocarbon surfactants to meet higher environmental sustainability standards and increasingly stringent legal regulations, and it is imperative to design a greener, more efficient, longer-lasting, more sustainable strategy for new fluorosurfactants.
Disclosure of Invention
Aiming at the problems of high bioaccumulation and toxicity of the existing perfluoroalkyl chain surfactant, the invention provides a preparation method of a gemini perfluoroether surfactant.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a gemini type perfluoroether surfactant, which comprises the following structure:
wherein R is1And R3Each independently selected from linear or branched perfluoroether chains and perfluoropolyether chains having 2 to 7 carbon atoms; r2The aromatic functional group is selected from a straight chain or branched chain alkyl group or ether group with 2-12 carbon atoms and an ortho-position, meta-position or para-position aromatic group; r4And R5Each independently selected from a linear chain or branched chain alkyl or aromatic group with 2-5 carbon atoms; r6And R7Each independently selected from O or NR8，R8Selected from H or alkyl with 1-3 carbon atoms, and X is selected from halogen.
Optionally, R1And R3Each independently selected from the following general formula:
R9(OCF2)m(OCF(CF3))n(CF2)p
wherein R is9Selected from CF3、C2F5、C3F7Or C4F9；m＝0～6；n＝0～3；p＝0～2。
Optionally, R1And R3Each independently selected from CF3OCF2OCF2CF2OCF(CF3)-、CF3CF2CF2OCF(CF3)-、CF3OCF2CF2OCF(CF3)-、CF3OCF(CF3)CF2OCF(CF3)-、CF3CF2OCF(CF3)CF2OCF(CF3)-、CF3OCF2-、CF3(OCF2)2-、CF3(OCF2)3-、CF3(OCF2)4-or CF3(OCF2)5-。
Optionally, R2Selected from linear alkyl group with 2-6 carbon atoms, -CH2CH2OCH2CH2-、
Optionally, R4And R5Is selected from-CH2CH2CH2-。
Optionally, R8Selected from H or methyl.
Optionally, the gemini perfluoroether surfactant is selected from the following structures:
optionally, the gemini perfluoroether surfactant is selected from the following structures:
in another aspect, the present invention provides a method for preparing the gemini type perfluoroether surfactant, comprising the following steps:
obtaining compounds shown as structural formulas 2, 3 and 4, mixing the compound shown as the structural formula 2, the compound shown as the structural formula 3 and the compound shown as the structural formula 4 in a solvent, heating until the solvent refluxes, and removing the solvent after reaction to obtain the compound shown as the structural formula 1;
wherein R is1And R3Each independently selected from linear or branched perfluoroether chains and perfluoropolyether chains having 2 to 7 carbon atoms; r2The aromatic functional group is selected from a straight chain or branched chain alkyl group or ether group with 2-12 carbon atoms and an ortho-position, meta-position or para-position aromatic group; r4And R5Each independently selected from a linear chain or branched chain alkyl or aromatic group with 2-5 carbon atoms; r6And R7Each independently selected from O or NR8，R8Selected from H or alkyl with 1-3 carbon atoms, and X is selected from halogen.
Optionally, the total amount of the substances of the compound shown in the structural formula 2 and the compound shown in the structural formula 3 is 1.5-3 times of the amount of the substance of the compound shown in the structural formula 4.
Optionally, the reaction temperature is 70-90 ℃, and the reaction time is 8-16 h.
Optionally, the solvent comprises one or more of acetonitrile, ethanol, acetone, ethyl acetate, DMF, DMSO, and methanol.
Optionally, after the solvent is removed in the reaction, the product is recrystallized or washed to obtain the compound shown in the structural formula 1.
The degradation products of the common fluorine-containing surfactant in nature are fluorine-containing carboxylate and sulfonate, so the judgment of the bioaccumulation and toxicity of the degradation products can prove the bioaccumulation and toxicity of the original surfactant. The inventors have found in the article a perfluoropolyether carboxylate CF3(OCF2)nCO2M(n<4) has a significant reduction in both toxicity and bioaccumulation compared to PFOA ("comprehensive Hepatotoxicity of Novel PFOA identities) on Male rice", environ, sci, technol.2019,53, 3929-3937 "). The inventors have also found that long-chain perfluoroether-derived structures have greater bioaccumulation and toxicity than PFOA, such as hexafluoropropylene Oxide Trimer Acid (HFPO-TA) ("Heptotoxin Effects of Hexafluoroxypropylene Oxide Trimer Acid (HFPO-TA), A Novel Perfluorooctanoic Acid (PFOA) Alternative, on Mice," environ. Sci. Technol.2018,52, 8005-. Thus, derivatization of short-chain perfluoroethers and polyethersThe compound has lower bioaccumulation and toxicity than PFOA, and can be used for developing fluorine-containing gemini surfactants.
Compared with the existing fluorocarbon surfactant, the Gemini perfluoroether surfactant provided by the invention has the advantages that two hydrophilic groups are bridged, two perfluoroether chains or two perfluoropolyether chains are used as hydrophobic groups, better surface tension, good wettability and excellent surface activity are shown, the raw materials are easily available, the synthesis process is simple, the traditional fluorocarbon surfactant can be replaced, and the combination of functions of the traditional fluorocarbon surfactant is realized. Meanwhile, the gemini perfluoroether surfactant has low bioaccumulation and low toxicity, and can effectively solve the problems of high bioaccumulation and toxicity of the existing fluorocarbon surfactant.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
An embodiment of the present invention provides a gemini perfluoroether surfactant, which comprises the following structure:
wherein R is1And R3Each independently selected from linear or branched perfluoroether chains and perfluoropolyether chains having 2 to 7 carbon atoms; r2The aromatic functional group is selected from a straight chain or branched chain alkyl group or ether group with 2-12 carbon atoms and an ortho-position, meta-position or para-position aromatic group; r4And R5Each independently selected from a linear chain or branched chain alkyl or aromatic group with 2-5 carbon atoms; r6And R7Each independently selected from O or NR8，R8Selected from H or alkyl with 1-3 carbon atoms, and X is selected from halogen.
Compared with the existing fluorocarbon surfactant, the gemini perfluoroether surfactant has better surface tension, good wettability and excellent surface activity by bridging two hydrophilic groups and adopting two perfluoroether chains or two perfluoropolyether chains as hydrophobic groups, has easily obtained raw materials and simple synthesis process, can replace the traditional fluorocarbon surfactant and realizes the combination of functions. Meanwhile, the gemini perfluoroether surfactant has good degradability and low toxicity, and can effectively solve the problems of difficult degradation and high toxicity existing in the existing fluorocarbon surfactant.
In some embodiments, R1And R3Each independently selected from the following general formula:
R9(OCF2)m(OCF(CF3))n(CF2)p
wherein R is9Selected from CF3、C2F5、C3F7Or C4F9；m＝0～6；n＝0～3；p＝0～2。
In a more preferred embodiment, R1And R3Each independently selected from CF3OCF2OCF2CF2OCF(CF3)-、CF3CF2CF2OCF(CF3)-、CF3OCF2CF2OCF(CF3)-、CF3OCF(CF3)CF2OCF(CF3)-、CF3CF2OCF(CF3)CF2OCF(CF3)-、CF3OCF2-、CF3(OCF2)2-、CF3(OCF2)3-、CF3(OCF2)4-or CF3(OCF2)5-。
It should be noted that the above are only some of the claimed embodiments of the present invention, and should not be construed as limiting the present invention.
In some embodiments, R2Selected from linear alkyl group with 2-6 carbon atoms, -CH2CH2OCH2CH2-、
In some embodiments, R4And R5Is selected from-CH2CH2CH2-。
In some embodiments, R8Selected from H or methyl.
In some embodiments, the gemini perfluoroether surfactants are selected from the following structures:
in a more preferred embodiment, the gemini perfluoroether surfactant is selected from the following structures:
another embodiment of the present invention provides a method for preparing the gemini type perfluoroether surfactant, which comprises the following steps:
obtaining compounds shown as structural formulas 2, 3 and 4, mixing the compound shown as the structural formula 2, the compound shown as the structural formula 3 and the compound shown as the structural formula 4 in a solvent, heating until the solvent refluxes, and removing the solvent after reaction to obtain the compound shown as the structural formula 1;
wherein R is1And R3Each independently selected from linear or branched perfluoroether chains and perfluoropolyether chains having 2 to 7 carbon atoms; r2The aromatic functional group is selected from a straight chain or branched chain alkyl group or ether group with 2-12 carbon atoms and an ortho-position, meta-position or para-position aromatic group; r4And R5Each independentlySelected from linear chain or branched chain alkyl or aromatic group with 2-5 carbon atoms; r6And R7Each independently selected from O or NR8，R8Selected from H or alkyl with 1-3 carbon atoms, and X is selected from halogen.
In some embodiments, the sum of the amounts of the substance of the compound of formula 2 and the compound of formula 3 is 1.5 to 3 times the amount of the substance of the compound of formula 4.
In a more preferred embodiment, the sum of the amounts of the substances of the compound represented by structural formula 2 and the compound represented by structural formula 3 is 2 times the amount of the substance of the compound represented by structural formula 4.
In some embodiments, the reaction temperature is 70-90 ℃ and the reaction time is 8-16 hours.
In some embodiments, the solvent comprises one or more of acetonitrile, ethanol, acetone, ethyl acetate, DMF, DMSO, and methanol.
In some embodiments, the reaction is performed to remove the solvent and then the product is recrystallized or washed to obtain the compound of formula 1.
The compound shown in the structural formula 2 and the compound shown in the structural formula 3 can be prepared by the existing method, for example, the compound shown in the structural formula 2 and the compound shown in the structural formula 3 are selected fromFor example, wherein RFIs the above-mentioned R1Or R3The preparation method can be used for preparing the following components:
the first method comprises the steps of adding 2.04g (20mmol, 1.0eq.) of 3-dimethylaminopropylamine, 3.03g (30mmol, 1.5eq.) of triethylamine, 10m of methanol L into a 100m L round-bottom flask, stirring to uniformly mix the system, dropwise adding the compound A (20mmol, 1.0eq.) into a constant-pressure dropping funnel, reacting at room temperature for 20 hours, washing with saturated saline after the reaction is finished, extracting with dichloromethane for three times, combining organic layers, drying with anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain a light yellow liquid C, wherein the yield is 90-92%.
The specific reaction formula is as follows:
the second method comprises the steps of adding 2.04g (20mmol, 2.0eq.) of 3-dimethylaminopropylamine, 10m L of methyl tert-butyl ether and 3.03g (30mmol, 1.5eq.) of triethylamine into a 100m L round-bottom flask, stirring to uniformly mix a reaction system, then dropwise adding the compound B (10mmol, 1.0eq.) for reacting at room temperature for 2 hours, washing with saturated saline after the reaction is finished, extracting with dichloromethane for three times, combining organic layers, drying with anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain a light yellow liquid compound C, wherein the yield is 84-90%.
The specific reaction formula is as follows:
the present invention will be further illustrated by the following examples.
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