A compound having surfactant function, a surfactant and a preparation method thereof

Abstract

The present invention relates to the field of surfactant technology, disclosing a compound with surfactant functionality, a surfactant, and a method for preparing the same. The compound has the structure represented by Formula (A). The surfactant provided by the present invention exhibits strong salt tolerance and excellent solubilization. Furthermore, the preparation method provided by the present invention utilizes amino-functionalized cyclodextrin as a raw material, producing the product through a two-step reaction, offering the advantages of simplicity and high efficiency. #imgabs0#

Description

Technical Field

[0001] The present invention relates to the technical field of surfactants, and in particular to a compound with surfactant function, a surfactant and a preparation method thereof. Background Art

[0002] Currently, anionic surfactants are the most commonly used oil-displacing agents in oilfield chemistry. However, as my country's crude oil production enters the middle and late stages, improving heavy oil recovery has become crucial for ensuring national energy security. Heavy oil, rich in polycyclic aromatic hydrocarbons, has strong adhesion to rock surfaces, preventing the effective removal of oil films from formations, a technological bottleneck in deep-drain heavy oil development. Therefore, there is an urgent need to develop synergistic anionic surfactants that interact more effectively with polycyclic aromatic hydrocarbons.

[0003] Host-guest interactions are an effective means of strengthening molecular interactions within polycyclic aromatic hydrocarbons. Because host molecules typically possess a spatial cavity structure, they interact strongly with polycyclic aromatic hydrocarbons, effectively encapsulating the hydrocarbons within the cavity to form a stable complex. Cyclodextrin is one of the most commonly used, low-cost, bio-based functional host molecules. Incorporating the cyclodextrin structure into the molecular structure of a surfactant could integrate the host-guest interaction into the surfactant, potentially significantly enhancing the interaction between the surfactant and polycyclic aromatic hydrocarbons and improving both oil washing and displacement efficiency.

[0004] At present, there are document and patent report to prepare cationic quaternary ammonium salt type surfactant based on cyclodextrin skeleton.For example, CN109836512A discloses a novel cationic gemini type surfactant with host-guest effect prepared based on cyclodextrin, which has good viscoelasticity and excellent temperature resistance and is a promising clean fracturing fluid.But, as oil-displacing agent and soil eluting agent, the adsorption of cationic quaternary ammonium salt type surfactant in oil reservoir stratum and soil surface is more serious, and its application effect is limited, and application cost is too high.

[0005] Therefore, there is an urgent need to develop a new host-guest synergistic anionic surfactant with cyclodextrin as raw material and simple and efficient preparation method to improve the application effect of surfactants. Summary of the Invention

[0006] The purpose of the present invention is to solve the problems of poor solubilization effect of surfactants and complicated preparation methods in the prior art.

[0007] In order to achieve the above object, the first aspect of the present invention provides a compound having a surfactant function, which has a structure shown in formula (A):

[0008]

[0009] Wherein, in formula (A),

[0010] M is selected from Li + 、Na + , K + NH4 + Any of the following;

[0011] R is selected from -OH, a group represented by formula (I); R1 is selected from -OH, -OSO3M, a group represented by formula (I); and only one of R and R1 is a group represented by formula (I);

[0012] In formula (I),

[0013] s is any integer selected from 0-20;

[0014] Each R2 is independently selected from H, C 1-100 Alkyl, C 2-100 Alkenyl, C 2-100 Alkynyl, C containing at least one oxygen atom 2-100 Alkyl;

[0015] R3 is selected from C 2-20 The alkylene group contains at least one C substituted by a heteroatom selected from O, N, S 2-50 Alkylene, C 3-20 Cycloalkylene, C 6-20 Arylene, C 5-20 Heteroarylene, C 3-20 Heterocyclylene, -(C 1-20 alkylene)-Y-(C 1-20 alkylene)-; Y is selected from C 3-20 Cycloalkylene, C 6-20 Arylene, C 5-20 Heteroarylene, C 3-20 Heterocyclylene;

[0016] m and n are each independently selected from any integer from 0 to 12, and the sum of m and n is any integer from 5 to 11; and when m is 0, R1 is -OSO3M.

[0017] A second aspect of the present invention provides a method for preparing a surfactant, wherein the surfactant is selected from at least one compound having a structure represented by formula (A); the method comprises:

[0018] (1) in the presence of solvent I, the amino-functionalized cyclodextrin represented by formula (B) is first contacted with the 1,2-epoxyalkane represented by formula (C) to obtain intermediate I;

[0019] (2) in the presence of solvent II, the intermediate I and the sulfonating agent are contacted for a second time to obtain intermediate II;

[0020] (3) adjusting the pH value of the intermediate II to 7-10 using an alkaline substance containing element M;

[0021]

[0022] Wherein, in formula (B), one of R4 and R5 is -OH, and the other is s and R3 are defined the same as in the first aspect;

[0023] In formula (A), formula (B), formula (C) and the basic substance, the definitions of m, n, R1, R2, and M are the same as those in the first aspect.

[0024] The third aspect of the present invention provides a surfactant prepared by the method described in the second aspect.

[0025] The present invention uses amino-functionalized cyclodextrin as a raw material to prepare a surfactant, which can be obtained through a two-step reaction. This method has the advantages of being simple and efficient. The obtained surfactant also has the advantages of strong salt resistance, good solubilization effect, easy biodegradation, and no secondary pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The intermediate 3-N-α-CD-2C prepared in Example 1 of the present invention 12 H 25 Mass spectrometry spectrum.

[0027] Figure 2 It is the mass spectrum of the surfactant prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0028] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0029] The following terms are explained for the present invention:

[0030] In this article, the wavy lines in the groups Indicates the bonding position.

[0031] “C 1-100 "alkyl" means an alkyl group having a total carbon atom count of 1 to 100, including C1-100 Straight chain alkyl, C 1-100 The branched chain alkyl group may be, for example, a straight chain alkyl group or a branched chain alkyl group having a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100. For example, the group may be methyl, ethyl, isopropyl, n-pentyl, n-hexyl, n-dodecyl, n-heptadecyl, n-tetracosyl, n-hexacosyl, or the like. 5-50 Alkyl", "C 5-25 The "alkyl group" has a similar explanation, except that the number of carbon atoms is different.

[0032] “C 2-100 The term "alkenyl" refers to a hydrocarbon group formed by removing one or more hydrogen atoms from an olefin molecule, and the total number of carbon atoms in the alkenyl group is 2-100. The double bond in the group can be at any position, for example, etc. Regarding “C 5-50 Alkenyl", "C 5-25 The "alkenyl" has a similar explanation, except that the number of carbon atoms is different.

[0033] “C 2-100 "Alkynyl" means a monovalent hydrocarbon group formed by removing one or more hydrogen atoms from an alkyne molecule, and the total number of carbon atoms in the alkynyl group is 2-100. The carbon-carbon triple bond (C≡C) in the group can be at any position, for example, etc. Regarding “C 5-50 Alkynyl", "C 5-25 The "alkynyl" has a similar explanation, except that the number of carbon atoms is different.

[0034] "C containing at least one oxygen atom 2-100 "Alkyl" means a branched or linear alkyl group with a total carbon atom count of 2 to 100, wherein the carbon atoms in the group may be interrupted by at least one oxygen atom, for example, CH3OCH2OCH2-, CH3OCH2-, CH3OCH2OCH2OCH2CH2-, etc. 5-50 Alkyl groups", "C containing at least one oxygen atom 5-25 The "alkyl group" has a similar explanation, except that the number of carbon atoms is different.

[0035] When the substituent is a non-terminal substituent or a related group removes a H atom, it is a subunit of the corresponding group, usually a divalent group. For example, an alkyl group removes a H atom to become an alkylene group, a cycloalkyl group corresponds to a cycloalkylene group, an aryl group corresponds to an arylene group, a heterocyclyl group corresponds to a heterocyclylene group, and a heteroaryl group corresponds to a heteroarylene group.

[0036] “C 2-20 "Alkylene" means a straight or branched divalent alkyl group having a total of 2 to 20 carbon atoms, for example, an alkylene group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. For example, the group can be methylene, ethylene, propylene, butylene, etc. Regarding “C 2-15 The "alkylene" has a similar explanation, except that the number of carbon atoms is different.

[0037] "Contains at least one heteroatom substituted C selected from O, N, S 2-50 "Alkylene" means that the carbon atoms in a branched or straight chain alkylene with a total carbon atom count of 2 to 50 may be interrupted by at least one heteroatom selected from O, N, and S, for example, Etc. For "containing at least one heteroatom substituted C selected from O, N, S 10-45 The "alkylene" has a similar explanation, except that the number of carbon atoms is different.

[0038] “C 3-20 "Cycloalkylene" means a divalent group of a cycloalkyl group having a total number of carbon atoms of 3 to 20, for example, a monocycloalkylene group having a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. For example, the group can be etc. Regarding “C 3-15 Cycloalkylene"C 3-10 The "cycloalkylene" has a similar interpretation, except that the number of carbon atoms is different.

[0039] “C 6-20 "Arylene" means a divalent group of an aromatic group having a total carbon atom count of 6 to 20, and the aromatic group may be a monocyclic or fused aromatic group. For example, etc. Regarding “C 6-15 Arylene", "C 6-10 The "arylene group" has a similar explanation, except that the number of carbon atoms is different.

[0040] “C 5-20 "Heteroarylene" means a divalent group of a heteroaromatic group having a total of 5 to 20 carbon atoms, and the ring atoms in the heteroaromatic ring contain one or more heteroatoms, and the heteroatoms are selected from at least one of O, N, and S. For example, it can be etc. “C 5-15 Heteroarylene", "C 5-10The "heteroarylene" has a similar explanation, except that the number of carbon atoms is different.

[0041] “C 3-20 The heterocyclic group "heterocyclic group" means a divalent group of a cycloalkyl group having a total of 3 to 20 carbon atoms, and one or more carbon atoms forming the ring are substituted by heteroatoms such as O, N, and S atoms. For example, etc. Regarding “C 3-15 Heterocyclylene", "C 3-10 The "heterocyclylene" has a similar explanation, except that the number of carbon atoms is different.

[0042] “-(C 1-20 alkylene)-Y-(C 1-20 "alkylene)-" means that any two H in the Y group are replaced by C 1-20 The alkylene group is substituted, and the Y group is selected from C 3-10 Cycloalkylene, C 6-10 Arylene, C 5-10 Heteroarylene, C 3-10 For example, it can be any one of the heterocyclic groups of wait.

[0043] As mentioned above, the first aspect of the present invention provides a compound having surfactant function, which has a structure shown in formula (A):

[0044]

[0045] Wherein, in formula (A),

[0046] M is selected from Li + 、Na + , K + NH4 + Any of the following;

[0047] R is selected from -OH, a group represented by formula (I); R1 is selected from -OH, -OSO3M, a group represented by formula (I); and only one of R and R1 is a group represented by formula (I);

[0048] In formula (I),

[0049] s is any integer selected from 0-20;

[0050] Each R2 is independently selected from H, C 1-100 Alkyl, C 2-100 Alkenyl, C 2-100 Alkynyl, C containing at least one oxygen atom 2-100 Alkyl;

[0051] R3 is selected from C 2-20 The alkylene group contains at least one C substituted by a heteroatom selected from O, N, S 2-50 Alkylene, C 3-20 Cycloalkylene, C 6-20 Arylene, C 5-20 Heteroarylene, C 3-20 Heterocyclylene, -(C 1-20 alkylene)-Y-(C 1-20 alkylene)-; Y is selected from C 3-20 Cycloalkylene, C 6-20 Arylene, C 5-20 Heteroarylene, C 3-20 Heterocyclylene;

[0052] m and n are each independently selected from any integer from 0 to 12, and the sum of m and n is any integer from 5 to 11; and when m is 0, R1 is -OSO3M.

[0053] Preferably, in formula (I), s is selected from any integer from 0 to 10. More preferably, s is selected from any integer from 0 to 5.

[0054] Preferably, in formula (I), each R2 is independently selected from H, C 5-50 Alkyl, C 5-50 Alkenyl, C 5-50 Alkynyl, C containing at least one oxygen atom 5-50 More preferably, each R2 is independently selected from H, C 5-25 Alkyl, C 5-25 Alkenyl, C 5-25 Alkynyl, C containing at least one oxygen atom 5-25 of alkyl.

[0055] Preferably, each R2 is independently selected from Any one of the following, a is selected from any integer from 1 to 17, b is selected from any integer from 1 to 17, and d is selected from any integer from 1 to 30.

[0056] Preferably, R3 is selected from C 2-15 The alkylene group contains at least one C substituted by a heteroatom selected from O, N, S 10-45 Alkylene, C 3-15 Cycloalkylene, C 6-15 Arylene, C 5-15 Heteroarylene, C 3-15 Heterocyclylene, -(C 1-5 alkylene)-Y-(C 1-5 alkylene)-; Y is selected from C3-10 Cycloalkylene, C 6-10 Arylene, C 5-10 Heteroarylene, C 3-10 of a heterocyclylene group.

[0057] More preferably, R3 is selected from C 2-15 Alkylene, cyclohexylene, phenylene, k is selected from any integer of 1-20.

[0058] Preferably, m and n are each independently selected from any integer from 0 to 7, and the sum of m and n is any integer from 5 to 7; and when m is 0, R1 is -OSO3M.

[0059] In order to make the compound with surfactant function provided by the present invention have a better solubilization effect, the present invention provides several preferred specific embodiments hereinafter to illustrate the preferred conditions of the compound represented by formula (A) of the present invention.

[0060] Preferred embodiment 1:

[0061] In formula (A),

[0062] M is selected from Li + 、Na + , K + NH4 + Any of the following;

[0063] R is selected from -OH, a group represented by formula (I);

[0064] R1 is selected from -OH, -OSO3M, and a group represented by formula (I), and only one of R and R1 is a group represented by formula (I);

[0065] In formula (I),

[0066] s is any integer selected from 0-10;

[0067] Each R2 is independently selected from H, C 5-50 Alkyl, C 5-50 Alkenyl, C 5-50 Alkynyl, C containing at least one oxygen atom 5-50 Alkyl;

[0068] R3 is selected from C 2-15 The alkylene group contains at least one C substituted by a heteroatom selected from O, N, S 10-45 Alkylene, C 3-15 Cycloalkylene, C 6-15 Arylene, C 5-15Heteroarylene, C 3-15 Heterocyclylene, -(C 1-10 alkylene)-Y-(C 1-10 alkylene)-; Y is selected from C 3-15 Cycloalkylene, C 6-15 Arylene, C 5-15 Heteroarylene, C 3-15 Heterocyclylene;

[0069] m and n are each independently selected from any integer from 0 to 7, and the sum of m and n is any integer from 5 to 7; and when m is 0, R1 is -OSO3M.

[0070] Preferred embodiment 2:

[0071] In formula (A),

[0072] M is selected from Li + 、Na + , K + NH4 + Any of the following;

[0073] R is selected from -OH, a group represented by formula (I);

[0074] R1 is selected from -OH, -OSO3M, and a group represented by formula (I), and only one of R and R1 is a group represented by formula (I);

[0075] In formula (I),

[0076] s is any integer selected from 0-5;

[0077] Each R2 is independently selected from H, C 5-25 Alkyl, C 5-25 Alkenyl, C 5-25 Alkynyl, C containing at least one oxygen atom 5-25 Alkyl;

[0078] R3 is selected from C 2-15 The alkylene group contains at least one C substituted by a heteroatom selected from O, N, S 10-45 Alkylene, C 3-15 Cycloalkylene, C 6-15 Arylene, C 5-15 Heteroarylene, C 3-15 Heterocyclylene, -(C 1-5 alkylene)-Y-(C 1-5 alkylene)-; Y is selected from C 3-10 Cycloalkylene, C 6-10 Arylene, C 5-10 Heteroarylene, C 3-10Heterocyclylene;

[0079] m and n are each independently selected from any integer from 0 to 7, and the sum of m and n is any integer from 5 to 7; and when m is 0, R1 is -OSO3M.

[0080] Preferred embodiment 3:

[0081] In formula (I),

[0082] R3 is selected from C 2-15 Alkylene, cyclohexylene, phenylene, k is selected from any integer of 1-20.

[0083] As mentioned above, the second aspect of the present invention provides a method for preparing a surfactant, wherein the surfactant is selected from at least one compound having a structure represented by formula (A); the method comprises:

[0084] (1) in the presence of solvent I, the amino-functionalized cyclodextrin represented by formula (B) is first contacted with the 1,2-epoxyalkane represented by formula (C) to obtain intermediate I;

[0085] (2) in the presence of solvent II, the intermediate I and the sulfonating agent are contacted for a second time to obtain intermediate II;

[0086] (3) adjusting the pH value of the intermediate II to 7-10 using an alkaline substance containing element M;

[0087]

[0088] Wherein, in formula (B), one of R4 and R5 is -OH, and the other is s and R3 are defined the same as in the first aspect;

[0089] In formula (A), formula (B), formula (C) and the alkaline substance, the definitions of m, n, R1, R2, and M are the same as those in the first aspect. They are not described in detail here and should not be construed as limiting the present invention by those skilled in the art.

[0090] Preferably, in step (1), the amino-functionalized cyclodextrin is selected from the group consisting of amino-α-cyclodextrin, amino-β-cyclodextrin, and amino-γ-cyclodextrin.

[0091] It should be noted that, in the amino-functionalized cyclodextrin, the position of the amino-functionalized cyclodextrin can be at the 3-hydroxyl position or the 6-hydroxyl position of the cyclodextrin.

[0092] More preferably, the formula (B) is a structure represented by formula (II) or formula (III):

[0093]

[0094] Preferably, in step (1), the 1,2-epoxyalkane is selected from One of them.

[0095] The aforementioned preparation method of the present invention may also involve various post-processing operations known in the art, such as rotary evaporation, extraction, washing, filtration, recrystallization, column chromatography, etc. The present invention has no particular limitation thereto, and those skilled in the art should not understand this as a limitation of the present invention.

[0096] Illustratively, after the first contact reaction, the solvent in the reaction system is removed by rotary evaporation, and then purified by recrystallization or column separation to obtain the intermediate I. The mixed solvent used for the recrystallization is one of methanol-ethyl acetate, methanol-acetone, ethanol-ethyl acetate, and ethanol-acetone; the eluent used for the column separation method is dichloromethane and ethanol in a volume ratio of 5-20:1.

[0097] For example, the pH value of the intermediate II is adjusted to 7-10, and then filtered to remove insoluble matter, and then the solvent in the system is removed by rotary evaporation to obtain a surfactant.

[0098] The amino-functionalized cyclodextrin and the 1,2-epoxyalkane in the preparation method of the present invention can be prepared by methods known in the art or purchased.

[0099] Preferably, the molar ratio of the 1,2-epoxyalkylene to the amino-functionalized cyclodextrin calculated based on NH bonds is (0.2-10):1.

[0100] More preferably, the molar ratio of the 1,2-alkylene oxide to the amino-functionalized cyclodextrin calculated based on NH bonds is (1-5):1.

[0101] Preferably, the volume of the solvent I is 10-30 mL relative to 1 mmol of amino-functionalized cyclodextrin.

[0102] Preferably, in step (1), the solvent I is selected from at least one of methanol, ethanol, isopropanol, n-butanol, water, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and ethylene glycol.

[0103] Preferably, in step (1), the conditions for the first contact at least meet the following requirements: temperature of 30-100° C. and time of 1-7 days.

[0104] More preferably, in step (1), the conditions for the first contact at least meet the following requirements: temperature of 60-90° C.; time of 2-5 days.

[0105] Preferably, in step (2), the solvent II is selected from at least one of N,N-dimethylformamide, pyridine, N,N-dimethylacetamide, dioxane, tetrahydrofuran, dichloromethane, chloroform, and dimethyl sulfoxide.

[0106] Preferably, the mass ratio of the intermediate I to the solvent II is 1:8-12.

[0107] Preferably, in step (2), the molar ratio of the sulfonating agent to the intermediate I is 1:(0.1-20). Preferably, the amount used here is based on the intermediate main product directly obtained when the purity of the intermediate I is greater than 92%.

[0108] More preferably, the molar ratio of the sulfonating agent to the intermediate I is 1:(1-10).

[0109] Preferably, in step (2), the second contacting conditions at least meet the following conditions: temperature is -5°C to 80°C, and time is 0.5-48h.

[0110] Preferably, in step (2), the alkaline substance is at least one of a hydroxide containing element M and a hydroxide alcohol solution containing element M.

[0111] Preferably, the alkaline substance is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia water.

[0112] More preferably, the alkaline substance is selected from at least one of an aqueous sodium hydroxide solution, a methanolic sodium hydroxide solution, and an ethanolic sodium hydroxide solution.

[0113] Preferably, the sulfonating agent is selected from at least one of a complex of sulfur trioxide and an organic compound, chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, and aminosulfonic acid; and the organic compound is selected from at least one of an amine compound, an amide compound, and an ether compound.

[0114] More preferably, the complex of sulfur trioxide and an organic compound is at least one selected from a sulfur trioxide pyridine complex, a sulfur trioxide dimethylformamide complex, and a sulfur trioxide dioxane complex.

[0115] As mentioned above, the third aspect of the present invention provides a surfactant prepared by the method described in the second aspect.

[0116] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0117] (1) The preparation method of the surfactant provided by the present invention is simple and efficient.

[0118] (2) The surfactant provided by the present invention has a critical aggregation concentration as low as 0.015 mM, which is two orders of magnitude lower than that of traditional single-chain anionic surfactants. Furthermore, the solubilization ability of the surfactant is increased by more than 12 times compared to single-chain surfactants.

[0119] (3) The surfactant provided by the present invention is easily biodegradable and does not cause secondary pollution, and is an environmentally friendly surfactant.

[0120] (4) The surfactant provided by the present invention has strong salt resistance and a Krafft point below 0 degrees, and is a new surfactant with very high practical application value.

[0121] The technical solutions of the present invention are described in detail below using specific examples. Unless otherwise specified, all raw materials used were commercially available and of analytical grade. The experimental methods and detection methods involved in the following examples, unless otherwise specified, are conventional experimental methods and detection methods already available in the prior art. The water used in the following examples was all deionized water, and room temperature refers to a temperature of 25±5°C.

[0122] The main raw materials used in the examples are shown in Table 1:

[0123] Table 1

[0124]

[0125] Example 1

[0126] Preparation of surfactant T1 based on amino-α-cyclodextrin:

[0127] Intermediate 3-N-α-CD-2C 12 H 25 The structure is shown in formula (Y1), and the compound with the structure shown in formula (A1) is the main product of surfactant T1.

[0128]

[0129]

[0130] In formula (Y1) and (A1), -CH 12 H 25 represents n-dodecyl.

[0131] Weigh 0.972 g of 3A-amino-3A-deoxy-(2AS,3AS)-α-cyclodextrin hydrate and 0.85 g of 1,2-epoxytetradecane into a reaction flask, then add 20 mL of anhydrous ethanol and stir evenly. Stir the reaction at 75°C for 3 days, stop the reaction, and remove the solvent by rotary evaporation. The residue is recrystallized from ethanol / acetone to obtain the intermediate 3-N-α-CD-2C 12 H 25 The intermediate was characterized by MALDI-TOF-MS. Figure 1 As shown in the product spectrum, the peak at 1396.76721 is the highest, which is the intermediate 3-N-α-CD-2C 12 H 25 The molecular ion peak of 12 H 25 .

[0132] Weigh 1g of intermediate 3-N-α-CD-2C 12 H 25 1.2 g of sulfur trioxide-pyridine complex was placed in a single-necked flask, followed by 10 g of pyridine. The mixture was stirred in a sealed container at room temperature for 24 hours. A 1 mol / L methanolic NaOH solution was then added dropwise to adjust the pH of the system to 8. The insoluble matter was then removed by filtration, and the organic solvent in the resulting filtrate was evaporated to dryness. Surfactant T1 was obtained with a yield of 95%.

[0133] Surfactant T1 was characterized by MALDI-TOF-MS, as Figure 2 As shown, the peak at 357.5000 in the product spectrum corresponds to the main product, [(M-5Na) 5- ] / 5 peak, with a peak value of 343.5304 being the highest, which also corresponds to the main product of sulfonation, namely [(M-5Na-4H2O) 5- ] / 5 peak. This proves that surfactant T1 was successfully prepared. In this product, the six primary hydroxyl groups on the cyclodextrin backbone were sulfonated to generate sulfate anions, and the main product was the compound formed by the sulfonation of the five primary hydroxyl groups.

[0134] Example 2

[0135] Preparation of surfactant T2 based on amino-β-cyclodextrin:

[0136] Intermediate 6-N-β-CD-2C 12 H 25 The structure is shown in formula (Y2), and the compound with the structure shown in formula (A2) is the main product of surfactant T2.

[0137]

[0138] In formula (Y2) and (A2), -CH 12 H 25 represents n-dodecyl.

[0139] Weigh 1.134 g of mono-(6-amino-6-deoxy)-β-cyclodextrin and 0.85 g of 1,2-epoxytetradecane into a reaction flask, then add 20 mL of anhydrous ethanol and stir evenly. Stir the reaction at 75°C for 3 days, then stop the reaction and remove the solvent by rotary evaporation. The residue is recrystallized from an ethanol / acetone mixed solvent to obtain the intermediate 6-N-β-CD-2C 12 H 25 The yield was 97%. 12 H 25 Characterized by MALDI-TOF-MS, MALDI-TOF-MS characterization result: 1558.580.

[0140] Weigh 1g of intermediate 6-N-β-CD-2C 12 H 25 , 0.2 g of chlorosulfonic acid was added to a single-necked flask, and 10 g of N,N-dimethylformamide was added. The mixture was stirred in a sealed container at room temperature for 24 hours, and then a 1 mol / L NaOH ethanol solution was added dropwise to adjust the pH of the system to 8. The insoluble matter was then removed by filtration, and the organic solvent in the resulting filtrate was dried to obtain surfactant T2 with a yield of 94%. Surfactant T2 was characterized by MALDI-TOF-MS. The MALDI-TOF-MS characterization results were: 856.8 [(M-2Na) 2- ] / 2.

[0141] Example 3

[0142] Preparation of surfactant T3 based on amino-β-cyclodextrin:

[0143] Intermediate 3-N-β-CD-2C 12 H 25 The structure is shown in formula (Y3), and the compound with the structure shown in formula (A3) is the main product of surfactant T3.

[0144]

[0145] In formula (Y2) and (A2), -CH 12 H 25 represents n-dodecyl.

[0146] Weigh 1.134 g of 3A-amino-3A-deoxy-(2AS,3AS)-β-cyclodextrin hydrate and 0.85 g of 1,2-epoxytetradecane into a reaction flask, then add 20 mL of anhydrous ethanol and stir evenly. Stir the reaction at 75°C for 3 days, then stop the reaction and remove the solvent by rotary evaporation. The residue is recrystallized from an ethanol / acetone mixed solvent to obtain the intermediate 3-N-β-CD-2C 12 H 25 The yield was 98%. 12 H 25 Characterized by MALDI-TOF-MS, MALDI-TOF-MS characterization results: 1558.8942 ((M+H + ).

[0147] Weigh 1g of intermediate 3-N-β-CD-2C 12 H 25 , 0.5 g of aminosulfonic acid was added to a single-necked flask, and 10 g of N,N-dimethylformamide was added. The mixture was stirred in a sealed container at room temperature for 12 hours, and then a 1 mol / L aqueous NaOH solution was added to adjust the pH of the system to 8. The insoluble matter was then removed by filtration, and the organic solvent in the resulting filtrate was dried to obtain surfactant T3 with a yield of 92%. Surfactant T3 was characterized by MALDI-TOF-MS. The MALDI-TOF-MS characterization results were: 598.8 ([(M-3Na) 3- ] / 3).

[0148] Test Example 1: Surface activity test

[0149] The surface tension of the three surfactants at different concentrations was measured using a K100 surface tension meter from KRUSS, Germany, using the hanging plate method. The test temperature was 25°C.

[0150] As surfactant concentration increases, surface tension decreases until it remains essentially constant above a certain critical concentration. This critical concentration is defined as the critical aggregation concentration (CAC), and the value at which the surface tension remains constant is defined as the surface tension γCAC of the surfactant. For comparison, the CAC and γCAC of the commonly used industrial anionic surfactant SDS were evaluated under the same conditions. The test results are shown in Table 2.

[0151] Table 2: Surface tension of different surfactants

[0152] surfactants <![CDATA[γ CAC / (mN / m)]]> CAC / mM Surfactant T1 35.01 0.015 Surfactant T2 37.28 0.052 Surfactant T3 36.80 0.045 SDS 38.33 7.7

[0153] Test Example 2: Solubilization ability test

[0154] Solubilization ability determination: Naphthalene was used as a simulated molecule of polycyclic aromatic hydrocarbons to evaluate the solubilization ability of surfactants. 50 mg of naphthalene was added to 10 mL of a 3000 mg / L surfactant aqueous solution and stirred at 500 rpm for 24 hours. Undissolved naphthalene was removed by centrifugation. In order to further remove a small amount of naphthalene solid residue, the upper aqueous solution after centrifugation was filtered with a membrane with a pore size of 0.45 μm. The amount of naphthalene dissolved in the solution was calculated using the Lambert-Beer law based on the peak value at 276 nm of the ultraviolet spectrum. The calculation formula is:

[0155] C=A / Kb,

[0156] Wherein, C is the molar concentration of naphthalene in the solution after passing through the membrane;

[0157] A is the UV absorption peak of the solution at 276 nm after passing through the membrane;

[0158] K is the molar absorption coefficient of naphthalene, and its value is 4920M -1 cm -1 ;

[0159] b is the thickness of the absorption layer, which is 2 cm.

[0160] The evaluation results of the solubilization ability of several surfactants are shown in Table 3:

[0161] Table 3: Solubilization of naphthalene by different surfactants (unit: degrees)

[0162] surfactants Solubilizing naphthalene concentration / mM Surfactant T1 1.21 Surfactant T2 0.98 Surfactant T3 1.05 SDS 0.08

[0163] Test Example 3: Salt resistance test

[0164] Salt tolerance and Krafft point determination: Prepare 10 mL of a 3000 mg / L surfactant aqueous solution and gradually lower the temperature from room temperature to 0°C to observe whether precipitation occurs. Simultaneously, add 1 g of sodium chloride to 9 mL of the 3000 mg / L surfactant aqueous solution at room temperature and observe whether precipitation occurs. The results are shown in Table 4.

[0165] Table 4: Solubility of surfactants at different temperatures and salt concentrations

[0166] surfactants Room temperature 0℃ Add sodium chloride Surfactant T1 Dissolve Dissolve Dissolve Surfactant T2 Dissolve Dissolve Dissolve Surfactant T3 Dissolve Dissolve Dissolve SDS Dissolve Insoluble Insoluble

[0167] The results of Examples 1-3 show that, through the preparation method provided by the present invention, using amino-functionalized cyclodextrin as a raw material, a surfactant can be efficiently prepared through a two-step reaction, and the reaction yield can reach more than 90%.

[0168] The results of Test Example 1 show that the CAC of the surfactant produced by the present invention is two orders of magnitude lower than that of traditional industrial anionic surfactants, and its aggregation ability is significantly improved. The results of Test Example 2 show that due to the presence of the cyclodextrin main cavity structure, the surfactant provided by the present invention has a solubilization ability for condensed aromatic hydrocarbons that is more than 12 times higher than that of industrial single-chain anionic surfactants.

[0169] The results of Test Example 3 demonstrate that the three surfactants provided by the present invention all have Krafft points below 0°C and can tolerate salt concentrations up to 10%. Furthermore, the Krafft points and salt tolerance of these surfactants are significantly superior to those of traditional single-chain anionic surfactants. Furthermore, the cyclodextrin polysaccharide structure makes the provided surfactants readily biodegradable, thus offering broad potential for application.

[0170] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A compound having surfactant function, characterized in that The compound has the structure shown in formula (A): Formula (A), Formula (I), Wherein, in formula (A), M is selected from Li + 、Na + , K + NH4 + Any of the following; R is selected from -OH, a group represented by formula (I); R1 is selected from -OH, -OSO3M, a group represented by formula (I); and only one of R and R1 is a group represented by formula (I); In formula (I), s is any integer selected from 0-20; Each R2 is independently selected from C 5-100 Alkyl, C 5-100 Alkenyl, C 5-100 Alkynyl; R3 is selected from C 2-20 The alkylene group contains at least one C substituted by a heteroatom selected from O, N, S 2-50 Alkylene, C 3-20 Cycloalkylene, C 6-20 Arylene, C 5-20 Heteroarylene, C 3-20 Heterocyclylene, -(C 1-20 alkylene)-Y-(C 1-20 alkylene)-; Y is selected from C 3-20 Cycloalkylene, C 6-20 Arylene, C 5-20 Heteroarylene, C 3-20 Heterocyclylene; m and n are each independently selected from any integer from 0 to 12, and the sum of m and n is any integer from 5 to 11; and when m is 0, R1 is -OSO3M.

2. The compound according to claim 1, wherein In formula (A), M is selected from Li + 、Na + , K + NH4 + Any of the following; R is selected from -OH, a group represented by formula (I); R1 is selected from -OH, -OSO3M, and a group represented by formula (I), and only one of R and R1 is a group represented by formula (I); In formula (I), s is any integer selected from 0-10; Each R2 is independently selected from C 5-50 Alkyl, C 5-50 Alkenyl, C 5-50 Alkynyl; R3 is selected from C 2-15 The alkylene group contains at least one C substituted by a heteroatom selected from O, N, S 10-45 Alkylene, C 3-15 Cycloalkylene, C 6-15 Arylene, C 5-15 Heteroarylene, C 3-15 Heterocyclylene, -(C 1-10 alkylene)-Y-(C 1-10 alkylene)-; Y is selected from C 3-15 Cycloalkylene, C 6-15 Arylene, C 5-15 Heteroarylene, C 3-15 Heterocyclylene; m and n are each independently selected from any integer from 0 to 7, and the sum of m and n is any integer from 5 to 7; and when m is 0, R1 is -OSO3M.

3. The compound according to claim 1 or 2, wherein In formula (A), M is selected from Li + 、Na + , K + NH4 + Any of the following; R is selected from -OH, a group represented by formula (I); R1 is selected from -OH, -OSO3M, and a group represented by formula (I), and only one of R and R1 is a group represented by formula (I); In formula (I), s is any integer selected from 0-5; Each R2 is independently selected from C 5-25 Alkyl, C 5-25 Alkenyl, C 5-25 Alkynyl; R3 is selected from C 2-15 The alkylene group contains at least one C substituted by a heteroatom selected from O, N, S 10-45 Alkylene, C 3-15 Cycloalkylene, C 6-15 Arylene, C 5-15 Heteroarylene, C 3-15 Heterocyclylene, -(C 1-5 alkylene)-Y-(C 1-5 alkylene)-; Y is selected from C 3-10 Cycloalkylene, C 6-10 Arylene, C 5-10 Heteroarylene, C 3-10 Heterocyclylene; m and n are each independently selected from any integer from 0 to 7, and the sum of m and n is any integer from 5 to 7; and when m is 0, R1 is -OSO3M.

4. The compound according to claim 1 or 2, wherein R3 is selected from C 2-15 Alkylene, cyclohexylene, phenylene, 、 、 、 、 、 、 、 , k is selected from any integer between 1 and 20.

5. A method for preparing a surfactant, characterized in that: The surfactant is selected from at least one compound having a structure represented by formula (A); the method comprises: (1) In the presence of solvent I, the amino-functionalized cyclodextrin represented by formula (B) is first contacted with the 1,2-epoxyalkane represented by formula (C) to obtain intermediate I; (2) in the presence of solvent II, the intermediate I is contacted with a sulfonating agent for a second time to obtain intermediate II; (3) adjusting the pH value of the intermediate II to 7-10 using an alkaline substance containing element M; Formula (A), Formula (B), Formula (C), Wherein, in formula (B), one of R4 and R5 is -OH, and the other is ; s, R3 are defined as defined in any one of claims 1-3; In formula (A), formula (B), formula (C) and the basic substance, m, n, R1, R2, and M are defined as in any one of claims 1 to 3.

6. The method according to claim 5, wherein: In step (1), the molar ratio of the 1,2-epoxyalkylene to the amino-functionalized cyclodextrin calculated based on NH bonds is (0.2-10):

1.

7. The method according to claim 6, wherein: The molar ratio of the 1,2-epoxyalkylene to the amino-functionalized cyclodextrin calculated based on NH bonds is (1-5):

1.

8. The method according to claim 5, wherein In step (1), the conditions for the first contact at least meet the following requirements: temperature of 30-100° C. and time of 1-7 days.

9. The method according to claim 8, wherein The conditions for the first contact at least meet the following requirements: temperature of 60-90° C.; time of 2-5 days.

10. The method according to any one of claims 5 to 9, wherein: In step (2), the molar ratio of the sulfonating agent to the intermediate I is 1:(0.1-20).

11. The method according to claim 10, wherein: The molar ratio of the sulfonating agent to the intermediate I is 1:(1-10).

12. The method according to any one of claims 5 to 9, wherein: In step (2), the second contacting conditions at least meet the following requirements: temperature is -5°C to 80°C, and time is 0.5-48h.

13. The method according to any one of claims 5 to 9, wherein: In step (2), the alkaline substance is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonia water.

14. The method according to claim 13, wherein The sulfonating agent is selected from at least one of a complex of sulfur trioxide and an organic compound, chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, and aminosulfonic acid; and the organic compound is selected from at least one of an amine compound, an amide compound, and an ether compound.

15. A surfactant prepared by the method according to any one of claims 5 to 14.

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