CN111440085A - Gemini type perfluoroether surfactant and preparation method thereof - Google Patents

Gemini type perfluoroether surfactant and preparation method thereof Download PDF

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CN111440085A
CN111440085A CN202010139890.XA CN202010139890A CN111440085A CN 111440085 A CN111440085 A CN 111440085A CN 202010139890 A CN202010139890 A CN 202010139890A CN 111440085 A CN111440085 A CN 111440085A
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gemini
perfluoroether
ocf
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carbon atoms
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CN111440085B (en
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谢伟东
郭勇
杜芳琼
吴成英
陈庆云
黄美薇
王孟英
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Shanghai Institute of Organic Chemistry of CAS
Sanming Hexafluo Chemicals Co Ltd
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Sanming Hexafluo Chemicals Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

The invention provides a Gemini type perfluoroether surfactant, which comprises the following structures:
Figure DDA0002398706720000011
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 linear chain with 2-5 carbon atomsOr a branched hydrocarbon or aromatic group; r6And R7Each independently selected from O or NR8，R8Selected 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.

Description

Gemini type perfluoroether surfactant and preparation method thereof
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:
Figure BDA0002398706710000021
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-、
Figure BDA0002398706710000022
Figure BDA0002398706710000031
Optionally, R4And R5Is selected from-CH2CH2CH2-。
Optionally, R8Selected from H or methyl.
Optionally, the gemini perfluoroether surfactant is selected from the following structures:
Figure BDA0002398706710000032
optionally, the gemini perfluoroether surfactant is selected from the following structures:
Figure BDA0002398706710000041
in another aspect, the present invention provides a method for preparing the gemini type perfluoroether surfactant, comprising the following steps:
Figure BDA0002398706710000042
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;
Figure BDA0002398706710000043
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:
Figure BDA0002398706710000061
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-、
Figure BDA0002398706710000062
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:
Figure BDA0002398706710000071
in a more preferred embodiment, the gemini perfluoroether surfactant is selected from the following structures:
Figure BDA0002398706710000081
another embodiment of the present invention provides a method for preparing the gemini type perfluoroether surfactant, which comprises the following steps:
Figure BDA0002398706710000082
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;
Figure BDA0002398706710000083
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 from
Figure BDA0002398706710000091
For 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:
Figure BDA0002398706710000092
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:
Figure BDA0002398706710000101
the present invention will be further illustrated by the following examples.
Figure BDA0002398706710000102
The reaction processes of examples 1 to 18 are as described above.
Example 1
This example is used to illustrate a gemini perfluoroether surfactant and a preparation method thereof disclosed in the present invention, and includes the following steps:
adding a compound C (2mmol, 1.0eq.), (4mmol, 2.0eq.) and 5m L acetonitrile/ethanol into a 50m L round bottom three-neck flask, wherein the compound C is selected from a compound 10, bromide is selected from 1, 2-bis (bromomethyl) benzene, assembling a reflux device, raising the temperature to 70-90 ℃, refluxing the solvent, reacting for 8-16 hours, removing the solvent by rotary evaporation after the reaction is finished, obtaining a solid crude product, recrystallizing and obtaining the yield of 94%, and marking the obtained product as a compound 11.
The compound 10 was subjected to a hydrogen nuclear magnetic resonance spectroscopy, a fluorine nuclear magnetic resonance spectroscopy and an infrared absorption spectroscopy, and the obtained test results were as follows:
2-(2-(difluoro(trifluoromethoxy)methoxy)-1,1,2,2-tetrafluoroethoxy)-N-(3-(dimethylamino)propyl)-2,3,3,3-tetrafluoropropanamide(10):
Figure BDA0002398706710000111
white solid, yield 90%.1H NMR(400MHz,CD3OD):3.36–3.24(m,2H),2.31(t,J＝7Hz,2H),2.18(s,6H),1.74–1.64(m,2H).19F NMR(376MHz,CD3OD):-55.3–-55.4(m,2F),-58.9(t,J＝11Hz,3F),-84.2(s,3F),-86.8(dd,J＝146,18Hz,1F),-90.2(dd,J＝146,8Hz,1F),-91.6–-91.9(m,4F),-134.0(dd,J＝18,8Hz,1F).HRMS-ESI(m/z):calcd for C12H13F13N2O4[M+H]+:497.0741,found:497.0732.IR(film)v/cm-1:3347,2955,2831,2791,1714,1532,1470,1309,1219,1106,1010,989,963,916,869,794,765,720,647.
The compound 11 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results obtained were as follows:
N,N'-(1,2-phenylenebis(methylene))bis(1,1,1,3,3,5,5,6,6,8-decafluoro-N,N-dimethyl-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-azatridecan-13-aminium)bromide(11):
Figure BDA0002398706710000112
white solid, yield 93%.1H NMR(400MHz,CD3OD):7.86-7.83(m,2H),7.80–7.75(m,2H),5.02(s,4H),3.74–3.56(m,4H),3.53–3.40(m,4H),3.16(s,6H),3.12(s,6H),2.22–2.09(m,4H).19F NMR(376MHz,CD3OD):-55.1–-55.3(m,4F),-58.7(t,J＝9Hz,6F),-83.9(s,6F),-86.8(dd,J＝146,18Hz,2F),-89.9(ddd,J＝146,8Hz,2F),-91.5–-91.7(m,4F),-133.8(dd,J＝18,8Hz,2F).HRMS-ESI(m/z):calcd for C32H34Br2F26N4O8[M–H]－:1253.0255,found:1253.0255.IR(film)v/cm-1:3443,3041,1714,1539,1487,1311,1223,1106,654,868,788,651.
Example 2
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
the compound C is selected from a compound 10, and the bromide is selected from 1, 3-di (bromomethyl) benzene;
the resulting product was labeled compound 12;
the compound 12 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results were as follows:
N,N'-(1,3-phenylenebis(methylene))bis(1,1,1,3,3,5,5,6,6,8-decafluoro-N,N-dimethyl-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-azatridecan-13-aminium)bromide(12):
Figure BDA0002398706710000121
white solid, yield 93%.1H NMR(400MHz,CD3OD):8.04(s,1H),7.83(t,J＝8Hz,2H),7.72(t,J＝8Hz,1H),4.76(s,4H),3.54–3.40(m,8H),3.18(s,6H),3.17(s,6H),2.27–2.17(m,4H).19F NMR(376MHz,CD3OD):-55.1–-55.3(m,4F),-58.7(t,J＝9Hz,6F),-83.9(s,6F),-86.7(dd,J＝146,18Hz,2F),-89.9(ddd,J＝146,8,2Hz,2F),-91.5–-91.7(m,4F),-133.7(dd,J＝18,8Hz,2F).HRMS-ESI(m/z):calcd for C32H34Br2F26N4O8[M–Br]+:1175.1139,found:1175.1122.IR(film)v/cm-1:3396,3208,3021,2051,1711,1630,1537,1483,1387,1220,1108,1026,956,920,869,794,718,637.
Example 3
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
the compound C is selected from a compound 10, and the bromide is selected from 1, 3-dibromopropane;
the resulting product was labeled compound 14;
the compound 14 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results were as follows:
N1,N3-bis(1,1,1,3,3,5,5,6,6,8-decafluoro-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-azatridecan-13-yl)-N1,N1,N3,N3-tetramethylpropane-1,3-diaminiumbromide(14):
Figure BDA0002398706710000131
white solid, 88% yield, melting point 134.6-136.1 ℃.1H NMR(400MHz,CD3OD):3.59–3.39(m,12H),3.21(s,12H),2.47–2.34(m,2H),2.19–2.05(m,4H).19F NMR(376MHz,CD3OD):-55.1–-55.3(m,4F),-58.6–-58.7(m,6F),-84.0(s,6F),-86.5–-86.8(m,4F),-89.8–-90.3(m,4F),-91.6–-91.8(m,4F),-133.9–-134.0(m,2F).HRMS-ESI(m/z):calcd forC27H32Br2F26N4O8[M–H]－:1191.0099；found:1191.0095.IR(film)v/cm-1:3399,3048,2965,2050,1708,1632,1538,1485,1445,1395,1220,1107,1025,956,869,794,767,719.
Example 4
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
the compound C is selected from a compound 10, and the bromide is selected from 1, 4-dibromobutane;
the resulting product was labeled compound 15;
the compound 15 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results obtained were as follows:
N1,N4-bis(1,1,1,3,3,5,5,6,6,8-decafluoro-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-azatridecan-13-yl)-N1,N1,N4,N4-tetramethylbutane-1,4-diaminiumbromide(15)：
Figure BDA0002398706710000141
white solid, 92% yield, 143.8-144.5 ℃ melting point.1H NMR(400MHz,CD3OD):3.61–3.36(m,12H),3.17(s,12H),2.18–2.07(m,4H),1.94(m,4H).19F NMR(376MHz,CD3OD):-55.2–-55.4(m,4F),-58.7(t,J＝9Hz,6F),-84.0(s,6F),-86.6(dd,J＝146,18Hz,2F),-90.0(dd,J＝146,8Hz,2F),-91.5–-91.7(m,4F),-133.9(dd,J＝18,8Hz,2F).HRMS-ESI(m/z):calcdfor C28H34Br2F26N4O8[M–H]－:1205.0255；found:1205.0248.IR(film)v/cm-1:3418,3049,2960,2055,1712,1632,1538,1485,1196,1026,964,870,792,721,636.
Example 5
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
the compound C is selected from a compound 10, and the bromide is selected from 1, 5-dibromopentane;
the resulting product was labeled compound 16;
the compound 16 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results obtained were as follows:
N1,N5-bis(1,1,1,3,3,5,5,6,6,8-decafluoro-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-azatridecan-13-yl)-N1,N1,N5,N5-tetramethylpentane-1,5-diaminiumbromide(16):
Figure BDA0002398706710000142
white solid, 89% yield, melting point 165.7-166.8 ℃.1H NMR(400MHz,CD3OD):3.43(m,12H),3.13(s,12H),2.14–2.03(m,4H),1.91–1.87(m,4H),1.49(m,2H).19F NMR(376MHz,CD3OD):-55.1–-55.3(m,4F),-58.7(t,J＝9Hz,6F),-84.0(d,J＝1Hz,6F),-86.6(dd,J＝146,18Hz,2F),-90.1(dd,J＝146,8Hz,2F),-91.5–-91.7(m,4F),-133.9(dd,J＝18,8Hz,2F).HRMS-ESI(m/z):calcd for C29H36Br2F26N4O8[M–H]－:1219.0412；found:1219.0403.IR(film)v/cm-1:3521,3342,3221,3065,2972,2945,2868,1708,1633,1556,1497,1449,1319,1212,1108,1014,977,964,956,906,889,869,719,701,608.
Example 6
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
the compound C is selected from a compound 10, and the bromide is selected from 1, 6-dibromohexane;
the resulting product was labeled compound 17;
the compound 17 was subjected to a hydrogen nuclear magnetic resonance spectrum, a fluorine nuclear magnetic resonance spectrum, and an infrared absorption spectrum, and the obtained test results were as follows:
N1,N6-bis(1,1,1,3,3,5,5,6,6,8-decafluoro-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-azatridecan-13-yl)-N1,N1,N6,N6-tetramethylhexane-1,6-diaminiumbromide(17):
Figure BDA0002398706710000151
white solid, yield 95%, melting point 188.6-189.4 ℃.1H NMR(400MHz,CD3OD):3.49–3.36(m,12H),3.13(s,12H),2.12–2.02(m,4H),1.89-1.79(m,4H),1.58-1.45(m,4H).19F NMR(376MHz,CD3OD):-55.1–-55.3(m,4F),-58.7(t,J＝9Hz,6F),-84.0(s,6F),-86.6(dd,J＝146,18Hz,2F),-90.0(dd,J＝146,8Hz,2F),-91.5–-91.7(m,4F),-133.9(dd,J＝18,8Hz,2F).HRMS-ESI(m/z):calcd for C30H38Br2F26N4O8[M–Br]+:1155.1452；found:1155.1447.IR(film)v/cm-1:3418,2956,1713,1633,1539,1308,1107,1026,954,869,792.
Example 7
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
compound C is selected from compound 10, bromide is selected from 2,2' -dibromo diethyl ether;
the resulting product was labeled compound 18;
the compound 18 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results were as follows:
N,N'-(oxybis(ethane-2,1-diyl))bis(1,1,1,3,3,5,5,6,6,8-decafluoro-N,N-dimethyl-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-azatridecan-13-aminium)bromide(18):
Figure BDA0002398706710000161
white solid, yield 95%, melting point 169.5-171.8 ℃.1H NMR(400MHz,CD3OD):4.11–4.00(m,4H),3.79–3.71(m,4H),3.49–3.31(m,8H),3.19(s,12H),2.12–1.98(m,4H).19F NMR(376MHz,CD3OD):-55.1–-55.3(m,4F),-58.7(t,J＝9Hz,6F),-83.9(s,6F),-86.8(dd,J＝146,19Hz,2F),-89.8(dd,J＝146,8Hz,2F),-91.5–-91.7(m,4F),-133.8(m,2F).HRMS-ESI(m/z):calcd for C28H34Br2F26N4O9[M–H]－:1221.0205；found:1221.0205.IR(film)v/cm-1:1706,1653,1558,1540,1208,1104,956,869,717,637,418.
Example 8
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
the compound C is selected from a compound 19, and the bromide is selected from 1, 4-dibromobutane;
the resulting product was labeled compound 20;
the compound 19 was subjected to the following nuclear magnetic resonance hydrogen spectrum, nuclear magnetic resonance fluorine spectrum and infrared absorption spectrum tests, and the obtained test results were as follows:
N-(3-(dimethylamino)propyl)-2,2-difluoro-2-(trifluoromethoxy)acetamide(19):
Figure BDA0002398706710000171
white solid, yield 84%.1H NMR(400MHz,CD3OD):3.20(t,J＝7Hz,2H),2.24(t,J＝7Hz,2H),2.12(s,6H),1.67–1.57(m,2H).19F NMR(376MHz,CD3OD):-56.8(t,J＝9Hz,3F),-81.7(q,J＝9Hz,2F).HRMS-ESI(m/z):calcd for C8H13F5N2O2[M–H]－:263.0824,Found:263.0825.IR(film)v/cm-1:3312,2830,1716,1548,1465,1348,1239,1161,1059,1038,989,797,668.
N1,N4-bis(3-(2,2-difluoro-2-(trifluoromethoxy)acetamido)propyl)-N1,N1,N4,N4-tetramethylbutane-1,4-diaminium bromide(20):
Figure BDA0002398706710000172
The compound 20 was subjected to the following nuclear magnetic resonance hydrogen spectroscopy, nuclear magnetic resonance fluorine spectroscopy and infrared absorption spectroscopy tests, and the obtained test results were as follows:
yellow viscous liquid, yield 86%.1H NMR(400MHz,CD3OD):3.58–3.49(m,4H),3.49–3.36(m,8H),3.17(s,12H),2.18–2.05(m,4H),1.94(m,4H).19F NMR(376MHz,CD3OD):-55.6(t,J＝9Hz,6F),-80.5(q,J＝9Hz,4F).HRMS-ESI(m/z):calcd for C20H34Br2F10N4O4[M–Br]+:663.1598；found:663.1595.IR(film)v/cm-1:3419,3041,2360,1783,1693,1035,956,794,541.418.
Example 9
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
the compound C is selected from a compound 22, and the bromide is selected from 1, 4-dibromobutane;
the resulting product was labeled compound 23;
the compound 22 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results were as follows:
2-(difluoro(trifluoromethoxy)methoxy)-N-(3-(dimethylamino)propyl)-2,2-difluoroacetamide(22):
Figure BDA0002398706710000181
pale yellow liquid, yield 86%.1H NMR(400MHz,CD3OD):3.14(t,J＝7Hz,2H),2.18(t,J＝7Hz,2H),2.05(s,6H),1.61–1.51(m,2H).19F NMR(376MHz,CD3OD):-55.0–-55.2(m,2F),-58.6(t,J＝9Hz,3F),-81.5(t,J＝10Hz,2F).HRMS-ESI(m/z):calcd for C9H13F7N2O3[M–H]－:329.0742；found:329.0743.IR(film)v/cm-1:3316,2953,2789,1716,1544,1375,1301,1002,989,862,765,682.
The compound 23 was subjected to a hydrogen nuclear magnetic resonance spectroscopy, a fluorine nuclear magnetic resonance spectroscopy and an infrared absorption spectroscopy, and the obtained test results were as follows:
N1,N4-bis(3-(2-(difluoro(trifluoromethoxy)methoxy)-2,2-difluoroacetamido)propyl)-N1,N1,N4,N4-tetramethylbutane-1,4-diaminium bromide(23):
Figure BDA0002398706710000182
a pale yellow viscous liquid, yield 82%.1H NMR(400MHz,CD3OD):3.64–3.55(m,4H),3.54–3.46(m,8H),3.24(s,12H),2.25–2.13(m,4H),2.05–1.85(m,4H).19F NMR(376MHz,CD3OD):-54.9–-55.0(m,4F),-58.5(t,J＝9Hz,6F),-81.3(t,J＝11Hz,4F).HRMS-ESI(m/z):calcdfor C22H34Br2F14N4O6[M–Br]+:795.1433；found:795.1426.IR(film)v/cm-1:3418,3065,2066,1550,1236,1141,963,896,797,683.
Example 10
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
the compound C is selected from a compound 25, and the bromide is selected from 1, 4-dibromobutane;
the resulting product was labeled compound 26;
the compound 25 was subjected to a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance fluorine spectrum, and an infrared absorption spectrum, and the obtained test results were as follows:
2-((difluoro(trifluoromethoxy)methoxy)difluoromethoxy)-N-(3-(dimethylamino)propyl)-2,2-difluoroacetamide(25):
Figure BDA0002398706710000191
light yellow liquid, yield 90%.1H NMR(400MHz,CD3OD):3.19(t,J＝7Hz,2H),2.24(t,J＝7Hz,2H),2.11(s,6H),1.66–1.58(m,2H).19F NMR(376MHz,CD3OD):-54.5–-54.7(m,2F),-56.8–-57.0(m,2F),-58.7(t,J＝9Hz,3F),-81.6(t,J＝11Hz,2F).HRMS-ESI(m/z):calcdfor C10H13F9N2O4[M–H]－:395.0659；found:395.0659.IR(film)v/cm-1:3690,3319,2790,1716,1544,1375,1235,1073,860,795,764,688.
The compound 26 was subjected to the following nuclear magnetic resonance hydrogen spectrum, nuclear magnetic resonance fluorine spectrum and infrared absorption spectrum tests, and the obtained test results were as follows:
N1,N1,N4,N4-tetramethyl-N1,N4-bis(1,1,1,3,3,5,5,7,7-nonafluoro-8-oxo-2,4,6-trioxa-9-azadodecan-12-yl)butane-1,4-diaminium bromide(26):
Figure BDA0002398706710000192
a pale yellow viscous liquid, yield 90%.1H NMR(400MHz,CD3OD):3.60–3.51(m,4H),3.51–3.42(m,8H),3.20(s,12H),2.22–2.08(m,4H),1.97(m,4H).19F NMR(376MHz,CD3OD):-54.4–-54.6(m,4F),-56.7–-56.9(m,4F),-58.6(t,J＝9Hz,6F),-81.3(t,J＝11Hz,4F).HRMS-ESI(m/z):calcd for C24H34Br2F18N4O8[M–Br]+:927.1267；found:927.1258.IR(film)v/cm-1:3426,3071,2964,2069,1715,1552,1485,1231,1076,985,917,854,792,684.
Example 11
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 10, except that:
compound C is selected from compound 25, bromide is selected from 1, 4-di (bromomethyl) benzene;
the resulting product was labeled compound 27;
the compound 27 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results were as follows:
N,N'-(1,4-phenylenebis(methylene))bis(1,1,1,3,3,5,5,7,7-nonafluoro-N,N-dimethyl-8-oxo-2,4,6-trioxa-9-azadodecan-12-aminium)bromide(27)：
Figure BDA0002398706710000201
white solid, yield 91%. The melting point is 210.1-212.6 ℃.1H NMR(400MHz,CD3OD):7.77(s,4H),4.68(s,4H),3.49–3.40(m,8H),3.15(s,12H),2.24–2.15(m,4H).19F NMR(376MHz,CD3OD):-54.4–-54.6(m,4F),-56.7–-56.9(m,4F),-58.6(t,J＝9Hz,6F),-81.3(t,J＝11Hz,4F).HRMS-ESI(m/z):calcd for C28H34Br2F18N4O8[M–Br]+:975.1267；found:975.1257.IR(film)v/cm-1:3427,3056,2073,1713,1557,1481,1223,1003,960,834,689,457.
Example 12
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
compound C is selected from compound 28, bromide is selected from 1, 4-dibromobutane;
the resulting product was labeled compound 29;
the compound 28 was subjected to the following nuclear magnetic resonance hydrogen spectrum, nuclear magnetic resonance fluorine spectrum and infrared absorption spectrum tests, and the obtained test results were as follows:
N-(3-(dimethylamino)propyl)-1,1,1,3,3,5,5,7,7,9,9-undecafluoro-2,4,6,8-tetraoxadecan-10-amide(28):
Figure BDA0002398706710000211
pale yellow liquid, yield 86%.1H NMR(400MHz,CD3OD):3.23(t,J＝7Hz,2H),2.29(t,J＝7Hz,2H),2.15(s,6H),1.70–1.61(m,2H).19F NMR(376MHz,CD3OD):-54.5–-54.7(m,2F),-56.3–-56.5(m,2F),-56.9–-57.0(m,2F),-58.7–-58.8(m,3F),-81.6(t,J＝11Hz,2F).HRMS-ESI(m/z):calcd for C11H13F11N2O5[M–H]－:461.0576；found:461.0577.IR(film)v/cm-1:3649,3327,2870,2790,1717,1544,1465,1235,1065,997,944,846,796,689.
The compound 29 was subjected to the following tests of hydrogen nuclear magnetic resonance, fluorine nuclear magnetic resonance and infrared absorption spectrum, and the obtained test results were as follows:
N1,N1,N4,N4-tetramethyl-N1,N4-bis(1,1,1,3,3,5,5,7,7,9,9-undecafluoro-10-oxo-2,4,6,8-tetraoxa-11-azatetradecan-14-yl)butane-1,4-diaminium bromide(29):
Figure BDA0002398706710000212
a pale yellow viscous liquid, 88% yield.1H NMR(400MHz,CD3OD):3.58–3.49(m,4H),3.49–3.42(m,8H),3.18(s,12H),2.17–2.08(m,4H),1.95–1.85(m,4H).19F NMR(376MHz,CD3OD):-54.4–-54.5(m,4F),-56.2–-56.4(m,4F),-56.8–-56.9(m,4F),-58.7(t,J＝9Hz,6F),-81.3(t,J＝11Hz,4F).HRMS-ESI(m/z):calcd for C26H34Br2F22N4O10[M–Br]+:1059.1102；found:1059.1084.IR(film)v/cm-1:2849,1714,1557,1488,1255,1219,1111,1064,931,781.
Example 13
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 12, except that:
compound C is selected from compound 28, bromide is selected from 1, 4-di (bromomethyl) benzene;
the resulting product was labeled compound 30;
the compound 30 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results were as follows:
N,N'-(1,4-phenylenebis(methylene))bis(1,1,1,3,3,5,5,7,7,9,9-undecafluoro-N,N-dimethyl-10-oxo-2,4,6,8-tetraoxa-11-azatetradecan-14-aminium)bromide(30):
Figure BDA0002398706710000221
white solid, yield 92%.1H NMR(400MHz,CD3OD):7.77(s,4H),4.68(s,4H),3.49–3.39(m,8H),3.15(s,12H),2.25–2.15(m,4H).19F NMR(376MHz,CD3OD):-54.4–-54.5(m,4F),-56.2–-56.4(m,4F),-56.8–-56.9(m,4F),-58.6(t,J＝9Hz,6F),-81.3(t,J＝11Hz,4F).HRMS-ESI(m/z):calcd for C30H34Br2F22N4O10[M–H]－:1185.0218,found:1185.0222.IR(film)v/cm-1:3486,3069,2361,1702,1633,1566,1454,1231,1064,997,940,834,641,458.
Example 14
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
the compound C is selected from a compound 31, and the bromide is selected from 1, 4-dibromobutane;
the resulting product was labeled compound 32;
the compound 31 was subjected to a hydrogen nuclear magnetic resonance spectrum, a fluorine nuclear magnetic resonance spectrum, and an infrared absorption spectrum, and the obtained test results were as follows:
N-(3-(dimethylamino)propyl)-2,2,4,4,6,6,8,8,10,10,12,12,12-tridecafluoro-3,5,7,9,11-pentaoxadodecanamide(31):
Figure BDA0002398706710000231
light yellow liquid, yield 89%.1H NMR(400MHz,CD3OD):3.16(t,J＝7Hz,2H),2.23(t,J＝7Hz,2H),2.09(s,6H),1.64–1.53(m,2H).19F NMR(376MHz,CD3OD):-54.6–-54.7(m,2F),-56.4–-56.6(m,4F),-57.0–-57.2(m,2F),-58.9(t,J＝9Hz,3F),-81.6(t,J＝11Hz,2F).HRMS-ESI(m/z):calcd for C12H13F13N2O6[M+H]+:529.0639；found:529.0641.IR(film)v/cm-1:3317,2955,2870,2791,1717,1465,1054,1004,862,796,765,687.
N1,N1,N4,N4-tetramethyl-N1,N4-bis(1,1,1,3,3,5,5,7,7,9,9,11,11-tridecafluoro-12-oxo-2,4,6,8,10-pentaoxa-13-azahexadecan-16-yl)butane-1,4-diaminium bromide(32):
Figure BDA0002398706710000232
A pale yellow viscous liquid, 88% yield.1H NMR(400MHz,CD3OD):3.59–3.51(m,4H),3.46(m,8H),3.20(s,12H),2.93(s,2H),2.19–2.11(m,4H),2.03–1.87(m,4H).19F NMR(376MHz,CD3OD):-54.4–-54.6(m,4F),-56.2–-56.5(m,8F),-56.8–-57.0(m,4F),-58.7(t,J＝9Hz,6F),-81.3(t,J＝11Hz,4F).HRMS-ESI(m/z):calcd for C28H34Br2F26N4O12[M–Br]+:1191.0936；found:1191.0924.IR(film)v/cm-1:3418,3076,2958,1714,1633,1487,1227,1054,1003,958,683.
Example 15
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 14, except that:
compound C is selected from compound 31, bromide is selected from 1, 4-di (bromomethyl) benzene;
the resulting product was labeled compound 33;
the compound 33 was subjected to the nmr hydrogen spectrum, nmr fluorine spectrum and ir spectrum tests, and the test results were as follows:
N,N'-(1,4-phenylenebis(methylene))bis(1,1,1,3,3,5,5,7,7,9,9,11,11-tridecafluoro-N,N-dimethyl-12-oxo-2,4,6,8,10-pentaoxa-13-azahexadecan-16-aminium)bromide(33):
Figure BDA0002398706710000241
white solid, yield 93%.1H NMR(400MHz,CD3OD):7.78(s,4H),4.70(s,4H),3.50–3.42(m,8H),3.17(s,12H),2.28–2.18(m,4H).19F NMR(376MHz,CD3OD):-54.4–-54.6(m,4F),-56.2–-56.4(m,8F),-56.8–-57.0(m,4F),-58.7(t,J＝9Hz,6F),-81.3(t,J＝11Hz,4F).HRMS-ESI(m/z):calcd for C32H34Br2F26N4O12[M–H]－:1317.0052；found:1317.0056.IR(film)v/cm-1:3418,3073,1713,1636,1550,1484,1224,1053,687.
Example 16
This example is used to illustrate a gemini type perfluoro ether surfactant and a method for preparing the same disclosed in the present invention, and includes most of the operation steps of example 1, except that:
compound C is selected from compound 34, bromide is selected from 1, 4-dibromobutane;
the resulting product was labeled compound 35;
the compound 35 was subjected to the nuclear magnetic resonance hydrogen spectroscopy, nuclear magnetic resonance fluorine spectroscopy and infrared absorption spectroscopy, and the obtained test results were as follows:
N-(3-(dimethylamino)propyl)-2,3,3,3-tetrafluoro-2-(perfluoropropoxy)propanamide(34):
Figure BDA0002398706710000242
yellow liquid, yield 92%.1H NMR(400MHz,(CD3)2CO)9.48(s,1H),3.51–3.40(m,2H),2.41(t,J＝6Hz,2H),2.20(s,6H),1.74(m,2H).19F NMR(376MHz,(CD3)2CO)-81.6(ddq,J＝149,19,7Hz,1F),-82.2(t,J＝7Hz,3F),-83.4(d,J＝2Hz,3F),-85.6(dm,J＝149Hz,1F),-130.6(s,2F),-133.2(dd,J＝20,7Hz,1F).HRMS-ESI(m/z):calcd for C11H13F11N2O2[M–H]－:413.0729,found:413.0730.IR(film)v/cm-1:3341,2955,2831,1716,1533,1470,1343,1232,1163,991,809,720,629,535,456.
N1,N1,N4,N4-tetramethyl-N1,N4-bis(3-(2,3,3,3-tetrafluoro-2-(perfluoropropoxy)propanamido)propyl)butane-1,4-diaminium bromide(35)：
Figure BDA0002398706710000251
White solid, yield 88%.1H NMR(400MHz,CD3OD):3.57–3.41(m,12H),3.17(s,12H),2.18–2.08(m,4H),1.95-1.90(m,4H).19F NMR(376MHz,(CD3)2CO):-81.7(ddq,J＝149,19,7Hz,2F),,-82.9(t,J＝7Hz,6F),-83.9(s,6F),-86.1(dm,J＝150Hz,2F),-131.1(s,4F),-134.0(dd,J＝19,7Hz,2F).HRMS-ESI(m/z):calcd for C26H34Br2F22N4O4[M–H]－:1041.0523；found:1041.0509.IR(film)v/cm-1:3419,3049,1711,1541,1342,1396,1165,1072,990,906,809,748,629,540.
Example 17
This example is for explaining the gemini type perfluoro ether surfactant and the preparation method thereof disclosed in the present invention, including most of the operation steps of example 16, and the differences are as follows:
compound C is selected from compound 36, bromide is selected from 1, 4-dibromobutane;
the resulting product was labeled compound 37;
N-(3-(dimethylamino)propyl)-2,3,3,3-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy)propanamide(36):
Figure BDA0002398706710000261
light yellow liquid, yield 90%.1H NMR(400MHz,CD3OD):3.32–3.23(m,2H),2.32–2.23(m,2H),2.15(s,6H),1.70–1.61(m,2H).19F NMR(376MHz,CD3OD)-57.1(t,J＝9Hz,3F),-84.2(d,J＝2Hz,3F),-86.6(dd,J＝147,18Hz,1F),-90.3(dd,J＝147,8Hz,1F),-91.9–-92.1(m,4F),-134.1(dd,J＝18,8Hz,1F).HRMS-ESI(m/z):calcd for C11H13F11N2O3[M+H]+:431.0823,found:431.0825.IR(film)v/cm-1:3346,2654,1978.17,1711,1537,1469,1222,1075,1041,988,902,794,764,717,683,529.
N1,N1,N4,N4-tetramethyl-N1,N4-bis(3-(2,3,3,3-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy)propanamido)propyl)butane-1,4-diaminiumbromide(37)：
Figure BDA0002398706710000262
White solid, yield 91%.1H NMR(400MHz,CD3OD):3.55(m,4H),3.52–3.41(m,8H),3.20(s,12H),2.21–2.09(m,4H),2.02–1.90(m,4H).19F NMR(376MHz,(CD3)2CO):-56.9(t,J＝9Hz,6F),-83.8(s,6F),-86.2(dd,J＝147,18Hz,2F),-90.0(dd,J＝147,8Hz,2F),-91.6–-91.8(m,4F),-133.9(dd,J＝18,8Hz,2F).HRMS-ESI(m/z):calcd forC26H34Br2F22N4O6[M–Br]+:995.1305；found:995.1293.IR(film)v/cm-1:3418,3042,2963,2057,1713,1538,1485,1224,1068,985,903,795,720,616.
Performance testing
Compound 11, compound 12, compound 14, compound 15, compound 16, compound 17, compound 18, compound 20, compound 23, compound 26, compound 27, compound 29, compound 30, compound 32, compound 33, compound 35, compound 37 prepared in the above examples were selected for the following tests:
the surface tension was measured using a Dataphysics model DCAT 21 surface tension meter, a platinum plate method. The basic principle is as follows: when the test is carried out, the platinum plate is slightly immersed into the solution to be tested, the platinum plate is pulled downwards under the action of the surface tension of the liquid, and when the surface tension of the liquid and other related forces reach equilibrium with the reverse force tested by the instrument, the platinum plate stops immersing into the liquid, and the equilibrium sensor of the instrument measures the immersion depth and converts the immersion depth into the surface tension value of the liquid. The platinum plate method has the characteristics of simple equipment, convenient operation, intuition and reliability. Dissolving the gemini perfluoroether surfactant to be measured in pure water, ultrasonically promoting the dissolution, preparing aqueous solutions with different concentrations, measuring at 25 ℃, measuring the surface tension for 3 times, and taking an average value.
The test results obtained are filled in Table 1.
TABLE 1
Figure BDA0002398706710000271
The lowest surface tension of compound 14, compound 18, compound 27, compound 29, compound 30, compound 32, compound 33 was compared to the lowest surface tension of gemini surfactants known in the literature and the data is filled in table 2.
TABLE 2
Figure BDA0002398706710000281
Figure BDA0002398706710000291
As can be seen from the comparison of the test results in Table 1 and the data in Table 2, the gemini perfluoroether surfactant provided by the invention has better surface tension and can replace the existing various fluorocarbon surfactants.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (13)

1. A gemini perfluoroether surfactant is characterized by comprising the following structure:
Figure FDA0002398706700000011
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-、
Figure FDA0002398706700000012
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:
Figure FDA0002398706700000021
8. a gemini perfluoroether type surfactant according to claim 1, wherein said gemini perfluoroether type surfactant is selected from the following structures:
Figure FDA0002398706700000031
9. the method for preparing a Gemini perfluoroether surfactant according to any one of claims 1 to 8, comprising the following steps:
Figure FDA0002398706700000032
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;
Figure FDA0002398706700000033
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.
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