CN115894309A - Tertiary amine quaternary ammonium salt sulfonic acid surfactant, and preparation method and application thereof - Google Patents
Tertiary amine quaternary ammonium salt sulfonic acid surfactant, and preparation method and application thereof Download PDFInfo
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- CN115894309A CN115894309A CN202111165392.3A CN202111165392A CN115894309A CN 115894309 A CN115894309 A CN 115894309A CN 202111165392 A CN202111165392 A CN 202111165392A CN 115894309 A CN115894309 A CN 115894309A
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 77
- 150000003512 tertiary amines Chemical class 0.000 title claims abstract description 50
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 49
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000005187 foaming Methods 0.000 claims abstract description 17
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 6
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 3
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 62
- 238000000746 purification Methods 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000001953 recrystallisation Methods 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 3
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 54
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 41
- 125000000542 sulfonic acid group Chemical group 0.000 description 39
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- 239000000047 product Substances 0.000 description 26
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- 239000000543 intermediate Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 10
- 230000001804 emulsifying effect Effects 0.000 description 10
- 238000004949 mass spectrometry Methods 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000003534 oscillatory effect Effects 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012521 purified sample Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005273 aeration Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- -1 alkyl glycol Chemical compound 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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Images
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a tertiary amine quaternary ammonium salt sulfonic acid surfactant and a preparation method thereof, wherein the molecular structure general formula of the tertiary amine quaternary ammonium salt sulfonic acid surfactant is as follows:
wherein n is an even number not less than 12, preferably, n =12,14,16,18; c n H 2n+1 Is a straight chain or branched chain structure; r is selected from methyl, ethyl or hydroxyethyl. The tertiary amine quaternary ammonium salt sulfonic acid surfactant is prepared from the following raw materials in molar ratio: fatty amine, alcohol solvent, 1, 3-propane sultone and low-carbon tertiary amineThe mol ratio of the hydrochloric acid to the epoxy chloropropane is 1: (31.00-51.00): (1.00-1.15): (1.00-1.15): (1.00-1.15): (1.00-1.15), and the surfactant can be used as a low-foaming surfactant or an emulsifier.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a tertiary amine quaternary ammonium salt sulfonic acid surfactant, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In industrial production and application processes, the surfactant often generates a large amount of foam due to stirring, aeration, air blowing and the like, brings a lot of influence on field production and operation, and also influences the quality of products, so that the foam generation must be effectively inhibited in the production process, and therefore, the low-foam or non-foam surfactant is needed. Low foaming surfactants are surfactants that exhibit low foaming properties in spray cleaning or in other use situations and processes. The low foam properties are set primarily to meet production and environmental requirements.
In the prior art, a preparation method of polyalkyl polyol polyoxyethylene ether (Chinese patent CN 109293909A) comprises the following steps: adding alkyl glycol and ethylene glycol diglyceride into a reaction bottle, raising the temperature of the reaction bottle to a first set temperature, and uniformly stirring; adding a catalyst, and standing for a first set time; after the temperature is increased to a second set temperature, standing for a second set time; after the temperature is raised to a third set temperature, standing for a third set time to obtain polyalkyl polyol; adding polyalkyl polyol into an autoclave, and adding potassium hydride and dimethylethylamine; heating to a fourth set temperature, adding an alkoxylation reagent, and continuously reacting for a fourth set time; cooling and depressurizing to obtain the oxyalkylation reagent and the catalyst, thus obtaining the polyalkyl polyol polyoxyethylene ether. In addition, another research discloses a sulfonate surfactant for water-based paint and a preparation method thereof (CN 106590124A), acetylene and small molecular alcohol are adopted to react to generate vinyl ether, the vinyl ether is grafted to an aromatic ring, and long-chain alkane is used for replacing alkoxy, so that the sulfonate surfactant with changeable long-chain alkyl is obtained.
The inventor notices that the research of the low-foaming surfactant is mainly embodied in the aspects of formula and compounding, and the low-foaming surfactant with single component is rare; also note that the sulfonate surfactant products are also of a lesser variety and expensive; the prior surfactant product also has the defects of low foaming performance, poor emulsifying performance and surface performance and complex preparation process and technology.
Disclosure of Invention
In order to solve the problems of less types of low-foaming surfactants and poor low-foaming performance in the prior art, the invention aims to provide the tertiary amine quaternary ammonium salt sulfonic acid surfactant and the preparation method and the application thereof; the preparation process of the tertiary amine quaternary ammonium salt sulfonic acid surfactant is simple, the tertiary amine quaternary ammonium salt sulfonic acid surfactant is prepared at a lower reaction temperature, high-temperature reaction is not needed, and the energy consumption is reduced; the raw materials are cheap, the sources are sufficient, and the production cost is low.
In order to achieve the above object, the technical solution of the present invention is as follows:
in a first aspect of the present invention, there is provided a tertiary amine quaternary ammonium sulfonate surfactant having a general molecular structural formula:
formula X, wherein n is an even number not less than 12, preferably, n =12,14,16,18; c n H 2n+1 Is a straight chain or branched chain structure; r is selected from methyl (-CH) 3 ) Ethyl (-CH) 2 CH 3 ) Or hydroxyethyl (-CH) 2 CH 2 OH)。
As an example, the present invention provides a series of compounds having the structure of formula X selected from:
X1：
X2：
X3：
X4：
X5：
X6：
X7：
X8：
X9：
X10：
X11：
X12：
the tertiary amine quaternary ammonium salt sulfonic acid surfactant disclosed by the invention combines sulfonic acid groups, quaternary ammonium salts, hydroxyl groups, amino hydrophilic groups and lipophilic groups with certain carbon chain length to form the tertiary amine quaternary ammonium salt sulfonic acid surfactant with the structure shown in the formula X, and the surfactant with the structure has low foaming performance and good surface performance and emulsifying performance.
In a second aspect of the present invention, there is provided a method for preparing the tertiary amine quaternary ammonium salt sulfonic acid type surfactant according to the first aspect, comprising the steps of:
mixing fatty amine, an alcohol solvent and 1, 3-propane sultone for reaction to obtain a reaction intermediate E; mixing and reacting low-carbon tertiary amine, hydrochloric acid and epichlorohydrin to obtain a reaction intermediate G, adding the reaction intermediate G into the reaction intermediate E, and mixing and reacting to obtain a tertiary amine quaternary ammonium salt sulfonic acid surfactant;
the structural general formula of the reaction intermediate E is as follows: c n H 2n+1 NHCH 2 CH 2 CH 2 SO 3 H，
Wherein n is an even number not less than 12, preferably, n =12,14,16,18; c n H 2n+1 Is a straight chain or branched chain structure;
the structural general formula of the reaction intermediate G is as follows:
wherein R is methyl (-CH) 3 ) Ethyl (-CH) 2 CH 3 ) Hydroxyethyl (-CH) 2 CH 2 OH)；
The reaction route is as follows:
in one or more embodiments, the molar ratio of the fatty amine to the alcohol solvent to the 1, 3-propane sultone to the low-carbon tertiary amine to the hydrochloric acid to the epichlorohydrin is 1: 31.00 to 51.00: 1.00 to 1.15.
In one or more embodiments, the fatty amine is selected from dodecylamine, tetradecylamine, hexadecylamine, or octadecylamine.
In one or more embodiments, C in the fatty amine n H 2n+1 Is a linear or branched structure, preferably a linear structure.
In one or more embodiments, the low-carbon number tertiary amine is selected from trimethylamine, triethylamine, and triethanolamine, preferably, the trimethylamine is an aqueous trimethylamine solution and the triethanolamine is an aqueous triethanolamine solution.
In one or more embodiments, the alcoholic solvent is a lower carbon number alcohol, preferably ethanol or isopropanol.
In one or more embodiments, in the process of synthesizing the reaction intermediate E, the reaction temperature is 60-85 ℃, and the reaction time is 3-5 h;
or in the process of synthesizing the reaction intermediate G, the reaction temperature is 40-55 ℃, and the reaction time is 2-3 h.
Or the temperature of the mixed reaction of the reaction intermediate G and the reaction intermediate E is 60-85 ℃, and the reaction time is 2-3 h.
Experiments show that the reaction temperature of the synthetic intermediate E is different from that of the synthetic intermediate G, which is related to the difference of the molecular structures of the raw materials and the products of the two. If the reaction temperature for synthesizing the intermediate G is too high, the epoxy bond in the intermediate G molecule is opened; if the reaction temperature for synthesizing the intermediate G is too low, no reaction is carried out between the raw materials, and the solution is layered. The reaction of intermediate E with intermediate G to form the final product is carried out at a temperature close to the synthesis temperature of intermediate E, which helps to allow the epoxy bond in intermediate G to be opened and react with intermediate E to give the product.
In a preferred embodiment, the preparation method of the tertiary amine quaternary ammonium salt sulfonic acid type surfactant specifically comprises the following steps:
(1) Adding fatty amine into a reaction container, adding an alcohol solvent, heating, stirring and dissolving, then adding 1, 3-propane sultone in batches, and after the addition is finished, stirring and reacting for 3-5 hours at the temperature of 60-85 ℃ to obtain a reaction intermediate E;
(2) Adding low-carbon tertiary amine into another reaction container, adding hydrochloric acid in batches, adding epoxy chloropropane in batches after the hydrochloric acid is added, and stirring and reacting at 40-55 ℃ for 2-3 h after the epoxy chloropropane is added to obtain a reaction intermediate G, wherein the low-carbon tertiary amine is a trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution;
(3) Adding the reaction intermediate G into the reaction intermediate E in batches, stirring and reacting for 2-3 h at the temperature of 60-85 ℃, and obtaining the tertiary amine quaternary ammonium salt sulfonic acid surfactant.
The preparation order of steps (1) and (2) can be interchanged.
In one or more embodiments of the present invention, in the operation of adding 1, 3-propane sultone in portions, 1, 3-propane sultone is divided into 5 portions on average, and added in 5 portions;
in the operation of adding the hydrochloric acid in batches, the hydrochloric acid is averagely divided into 5 parts and added in 5 times;
in the operation of adding epichlorohydrin in batches, the epichlorohydrin is averagely divided into 5 parts and added in 5 times;
in the operation of adding the reaction intermediate G in portions, the reaction intermediate G was equally divided into 5 portions and added in 5 portions.
In one or more embodiments of the present invention, the method further comprises: separation and purification;
preferably, the solvent of the synthetic product in the step (1) or the step (3) is distilled off, and then recrystallization separation and purification are carried out by adopting an organic solvent;
more preferably, the organic solvent is ethyl acetate or methanol.
In a third aspect of the present invention, there is provided a tertiary amine quaternary ammonium sulfonate surfactant prepared by the preparation method of the second aspect.
In a fourth aspect of the present invention there is provided the use of a tertiary amine quaternary ammonium sulphonate surfactant of the first aspect as a low foaming surfactant or emulsifier. For example, in industrial cleaning agents, foam generation is not conducive to the control of the production process, and material spillage and environmental pollution are caused. As another example, in the case of emulsified asphalt, foam generation would be detrimental to the transportation of the emulsified asphalt.
In the invention, fatty amine is used as a main reaction raw material of the tertiary amine quaternary ammonium salt sulfonic acid surfactant, and a sulfonic acid group, a quaternary ammonium salt, a hydroxyl group and an amino group are introduced into a molecular structure by adding raw materials such as 1, 3-propane sultone, low-carbon tertiary amine, hydrochloric acid, epoxy chloropropane and the like in the step of synthesizing the tertiary amine quaternary ammonium salt sulfonic acid surfactant, so that the low foaming property, the surface property and the emulsifying property are improved.
The specific embodiment of the invention has the following beneficial effects:
(a) The invention provides a tertiary amine quaternary ammonium salt sulfonic acid type low-foaming surfactant, which combines sulfonic acid group, quaternary ammonium salt, hydroxyl group, amino hydrophilic group and oleophylic group with a certain carbon chain length to form the tertiary amine quaternary ammonium salt sulfonic acid type surfactant with a novel structure. Experiments show that the low-foaming performance of the tertiary amine quaternary ammonium salt sulfonic acid surfactant is superior to that of sodium dodecyl benzene sulfonate.
(b) The main synthetic raw material is fatty amine, and compared with the raw materials used by the prior commonly used sulfonate surfactant, the synthetic method has the advantages of low price, sufficient sources and lower production cost.
(c) In the prior art, the sulfonate surfactant prepared by sulfonation reaction has high reaction temperature, complex preparation technology and process, and high danger and corrosivity. The tertiary amine quaternary ammonium salt sulfonic acid surfactant is simple in preparation process, is carried out at a lower reaction temperature, does not need high-temperature reaction, and reduces energy consumption.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows the FTIR spectrum of the reaction intermediate E1 of example 1 after recrystallization and purification.
FIG. 2 shows the NMR chart of example 1 reaction intermediate E1 after purification by recrystallization.
FIG. 3 shows the MS diagram of the reaction intermediate E1 of example 1 after recrystallization purification.
FIG. 4 shows the FTIR spectrum of the product of example 1 after recrystallization and purification.
FIG. 5 shows the FTIR spectrum of the reaction intermediate E2 of example 2 after recrystallization purification.
FIG. 6 shows the NMR chart of example 2 reaction intermediate E2 after purification by recrystallization.
FIG. 7 shows the MS pattern of the reaction intermediate E2 of example 2 after recrystallization purification.
FIG. 8 shows the FTIR spectrum of the product of example 2 after recrystallization purification.
FIG. 9 shows FTIR spectra of the reaction intermediate E3 of example 3 after recrystallization and purification.
FIG. 10 shows the NMR chart of example 3 reaction intermediate E3 after purification by recrystallization.
FIG. 11 shows the MS pattern of the reaction intermediate E3 of example 3 after recrystallization purification.
FIG. 12 shows the FTIR spectrum of the product of example 3 after recrystallization and purification.
FIG. 13 shows the FTIR spectrum of the reaction intermediate E4 of example 4 after recrystallization purification.
FIG. 14 shows an NMR chart of reaction intermediate E4 of example 4 after purification by recrystallization.
FIG. 15 shows the MS pattern of the reaction intermediate E4 of example 4 after recrystallization purification.
FIG. 16 shows the FTIR spectrum of the product of example 4 after recrystallization and purification.
FIG. 17 shows the FTIR spectrum of the product of example 5 after recrystallization and purification.
FIG. 18 shows the MS diagram of the product of example 5 after recrystallization purification.
FIG. 19 shows the surface tension of the product of example 1 after recrystallization and purification as a function of the logarithm of the concentration.
FIG. 20 is a graph showing the surface tension of the product of example 2 after recrystallization and purification in logarithmic concentration.
FIG. 21 shows the surface tension of the product of example 3 after recrystallization and purification as a function of the logarithm of the concentration.
FIG. 22 shows the surface tension of the product of example 4 after recrystallization and purification as a function of the logarithm of the concentration.
FIG. 23 shows the surface tension of the product of example 5 after recrystallization and purification as a function of the logarithm of the concentration.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
(1) Preparation of tertiary amine quaternary ammonium salt sulfonic acid surfactant:
1) 185.35g of dodecylamine and 2200g of isopropyl alcohol were charged into a three-necked flask, and dissolved by heating with stirring. Then 124.6g of 1, 3-propane sultone is added in 5 portions, and the mixture is stirred and reacted for 4 hours at 70 ℃ to obtain a reaction intermediate E1.
The solvent of the synthetic intermediate E1 is evaporated, and then the infrared, nuclear magnetic and mass spectrometry analysis is carried out after the recrystallization separation and purification are carried out for 3 times by adopting ethyl acetate as the solvent.
Infrared analysis (fig. 1): 3440cm -1 (Peak 1) is the stretching vibration peak of O-H in the sulfonic acid group, 3109cm -1 (Peak 2) is a secondary amine N-H stretching vibration peak, 2918cm -1 (Peak 3) is the asymmetric stretching vibration absorption peak of methylene, 2854cm -1 (Peak 4) is the symmetric stretching vibration peak of methylene, 1576cm -1 (Peak 5) is the deformation vibration absorption peak of N-H, 1472cm -1 (Peak 6) asymmetric bending vibration of methylene group, 1219cm -1 (Peak 7) C-N stretching vibration, 1165cm -1 (Peak 8) is a symmetric stretching vibration absorption peak of sulfonic acid group S = O, 1041cm -1 (Peak 9) is an asymmetric stretching vibration absorption peak of sulfonic acid group S = O, 719cm -1 (Peak 10) is the methylene in-plane oscillatory vibration, 607cm -1 (Peak 11) is the absorption peak of S-O for stretching vibration, 521cm -1 (Peak 12) is a bending vibration absorption peak of O-H in the sulfonic acid group.
Nuclear magnetic analysis (fig. 2): 1 H NMR(400MHz,CD 3 OD),δ:0.904-0.938(3H,t,-CH 3 ),1.318-1.413(18H,s,CH 3 (CH 2 ) 9 CH 2 CH 2 -),1.649-1.686(2H,m,CH 3 (CH 2 ) 9 CH 2 CH 2 -),2.044-2.233(2H,m,-NHCH 2 CH 2 CH 2 SO 3 H),2.910-3.032(4H,m,-CH 2 NHCH 2 -),3.173-3.215(2H,t,-CH 2 SO 3 H)ppm.
mass spectrometry (fig. 3): HRMS (ESI) (positive) M/z: [ M + H ]] + Calcd for C 15 H 34 NO 3 S,308.2259；Found 308.2305。
2) 189.5g of 33 percent (mass fraction) trimethylamine aqueous solution is added into another three-neck flask, 108.3g of 36 percent (mass fraction) hydrochloric acid is added into the three-neck flask in 5 batches, 96.1G of epichlorohydrin is added into the three-neck flask in 5 batches, and the mixture is stirred and reacted for 3 hours at 42 ℃ to obtain a reaction intermediate G1.
3) The reaction intermediate G1 is added into the reaction intermediate E1 in 5 batches and reacted for 2h at 75 ℃. Thus obtaining the tertiary amine quaternary ammonium salt sulfonic acid type surfactant.
The solvent of the synthesized product is evaporated, and then the synthesized product is subjected to recrystallization, separation and purification for 3 times by using methanol as the solvent and then subjected to infrared analysis.
FTIR analysis (see fig. 4): 3479cm -1 (peak 1) is stretching vibration peak of O-H in hydroxyl and sulfonic acid group in molecule, 2916cm -1 (peak 2) is the asymmetric stretching vibration absorption peak of methylene, 2853cm -1 (peak 3) is the symmetric stretching vibration peak of methylene, 1472cm -1 (peak 4) asymmetric flexural vibration of methylene, 1244cm -1 (peak 5) symmetric stretching vibration absorption peak of sulfonic acid group S = O, 1047cm -1 (peak 6) asymmetric stretching vibration absorption peak of sulfonic acid group S = O, 904cm -1 (peak 7) is the absorption peak of out-of-plane bending vibration of methylene at 719cm -1 (peak 8) is the methylene in-plane rocking vibration, 604cm -1 (peak 9) is the absorption peak of S-O for stretching vibration, 523cm -1 (peak 10) shows the bending vibration absorption peak of O-H in the hydroxyl group and the sulfonic acid group.
The reaction equation is as follows:
example 2
(1) Preparation of tertiary amine quaternary ammonium salt sulfonic acid surfactant:
1) 213.4g of tetradecylamine and 2200g of isopropanol were charged in a three-necked flask, and dissolved by heating with stirring. Then 124.6g of 1, 3-propane sultone was added in 5 portions, and the reaction was carried out for 4 hours with stirring at 70 ℃ to obtain a reaction intermediate E2.
The solvent of the synthetic intermediate E2 is evaporated, and then the infrared, nuclear magnetic and mass spectrometry analysis is carried out after the recrystallization separation and purification are carried out for 3 times by adopting ethyl acetate as the solvent.
Infrared analysis (fig. 5): 3441cm -1 (Peak 1) is the stretching vibration peak of O-H in the sulfonic acid group, 3117cm -1 (Peak 2) is the secondary amine N-H stretching vibration peak, 2924cm -1 (Peak 3) is the asymmetric stretching vibration absorption peak of methylene, 2852cm -1 (Peak 4) is the symmetric stretching vibration peak of methylene, 1575cm -1 (Peak 5) is the deformation vibration absorption peak of N-H, 1470cm -1 (Peak 6) asymmetric bending vibration of methylene group, 1213cm -1 (Peak 7) C-N stretching vibration, 1167cm -1 (Peak 8) is a symmetric stretching vibration absorption peak of sulfonic acid group S = O, 1041cm -1 (Peak 9) is an asymmetric stretching vibration absorption peak of sulfonic acid group S = O, 721cm -1 (Peak 10) is methylene in-plane oscillatory vibration, 601cm -1 (Peak 11) is the absorption peak of S-O for stretching vibration, 525cm -1 (Peak 12) is a bending vibration absorption peak of O-H in the sulfonic acid group.
Nuclear magnetic analysis (fig. 6): 1 H NMR(400MHz,CD 3 OD),δ:0.904-0.939(3H,t,-CH 3 ),1.312-1.413(22H,s,CH 3 (CH 2 ) 11 CH 2 CH 2 -),1.653-1.692(2H,m,CH 3 (CH 2 ) 11 CH 2 CH 2 -),2.125-2.233(2H,m,-NHCH 2 CH 2 CH 2 SO 3 H),2.909-3.031(4H,m,-CH 2 NHCH 2 -),3.180-3.216(2H,t,-CH 2 SO 3 H)ppm.
mass spectrometry (fig. 7): HRMS (ESI) (positive) M/z: [ M + H ]] + Calcd for C 17 H 38 NO 3 S,336.2572；Found 336.2568.
2) 189.5g of 33 percent (mass fraction) trimethylamine aqueous solution is added into another three-neck flask, 108.3g of 36 percent (mass fraction) hydrochloric acid is added into the three-neck flask in 5 batches, 96.1G of epichlorohydrin is added into the three-neck flask in 5 batches, and the mixture is stirred and reacted for 3 hours at 42 ℃ to obtain a reaction intermediate G1.
3) The reaction intermediate G1 was added to the reaction intermediate E2 in 5 portions and reacted at 75 ℃ for 2 hours. Thus obtaining the tertiary amine quaternary ammonium salt sulfonic acid type surfactant.
The solvent of the synthesized product is evaporated, and FTIR analysis is carried out after recrystallization, separation and purification are carried out for 3 times by adopting methanol as the solvent.
FTIR analysis (see fig. 8): 3439cm -1 (peak 1) is stretching vibration peak of O-H in hydroxyl and sulfonic acid group in molecule, 2916cm -1 (peak 2) is the asymmetric stretching vibration absorption peak of methylene, 2849cm -1 (peak 3) is the peak of methylene symmetrical stretching vibration, 1468cm -1 (peak 4) asymmetric bending vibration of methylene, 1215cm -1 (peak 5) symmetric stretching vibration absorption peak of sulfonic acid group S = O, 1043cm -1 (peak 6) asymmetric stretching vibration absorption peak of sulfonic acid group S = O, 928cm -1 (peak 7) methylene out-of-plane bending vibration absorption Peak, 721cm -1 (peak 8) is the methylene in-plane rocking vibration, 602cm -1 (peak 9) is the absorption peak of stretching vibration of S-O, 521cm -1 (peak 10) is a bending vibration absorption peak of O-H in the hydroxyl group and the sulfonic acid group.
The reaction equation is as follows:
example 3
(1) Preparation of tertiary amine quaternary ammonium salt sulfonic acid surfactant:
1) 241.46g of hexadecylamine and 2200g of isopropyl alcohol were charged in a three-necked flask, and dissolved by heating with stirring. Then 124.6g of 1, 3-propane sultone is added in 5 portions, and the mixture is stirred and reacted for 4 hours at 70 ℃ to obtain a reaction intermediate E3.
The solvent of the synthetic intermediate E3 is evaporated, and then the infrared, nuclear magnetic and mass spectrometry analysis is carried out after the recrystallization separation and purification are carried out for 3 times by adopting ethyl acetate as the solvent.
Infrared analysis (fig. 9): 3442cm -1 (Peak 1) is an O-H stretching vibration peak in a sulfonic acid group, 3113cm -1 (Peak 2) is the secondary amine N-H stretching vibration peak, 2916cm -1 (Peak 3) is an asymmetric stretching vibration absorption peak of methylene, 2852cm -1 (Peak 4) is the symmetric stretching vibration peak of methylene, 1575cm -1 (Peak 5) is the deformation vibration absorption peak of N-H, 1471cm -1 (Peak 6) asymmetric bending vibration of methylene, 1215cm -1 (Peak 7) C-N stretching vibration, 1166cm -1 (Peak 8) is a symmetric stretching vibration absorption peak of sulfonic acid group S = O, 1041cm -1 (Peak 9) is an asymmetric stretching vibration absorption peak of sulfonic acid group S = O, 717cm -1 (Peak 10) is the methylene in-plane oscillatory vibration, 607cm -1 (Peak 11) is an S-O stretching vibration absorption peak, 518cm -1 (Peak 12) is a bending vibration absorption peak of O-H in a sulfonic acid group.
Nuclear magnetic analysis (fig. 10): 1 H NMR(400MHz,CD 3 OD),δ:0.904-0.938(3H,t,-CH 3 ),1.310-1.410(26H,s,CH 3 (CH 2 ) 13 CH 2 CH 2 -),1.665(2H,m,CH 3 (CH 2 ) 13 CH 2 CH 2 -),2.123-2.227(2H,m,-NHCH 2 CH 2 CH 2 SO 3 H),2.906-3.028(4H,m,-CH 2 NHCH 2 -),3.189-3.212(2H,t,-CH 2 SO 3 H)ppm.
mass spectrometry (fig. 11): HRMS (ESI) (positive) M/z: [ M + H ]] + Calcd for C 19 H 42 NO 3 S,364.2885；Found 364.2881.
2) 189.5g of 33 percent (mass fraction) trimethylamine aqueous solution is added into another three-neck flask, 108.3g of 36 percent (mass fraction) hydrochloric acid is added into the three-neck flask in 5 batches, 96.1G of epichlorohydrin is added into the three-neck flask in 5 batches, and the mixture is stirred and reacted for 3 hours at 42 ℃ to obtain a reaction intermediate G1.
3) The reaction intermediate G1 was added to the reaction intermediate E3 in 5 portions and reacted at 75 ℃ for 2 hours. Thus obtaining the tertiary amine quaternary ammonium salt sulfonic acid type surfactant.
The solvent of the synthesized product is evaporated, and FTIR analysis is carried out after recrystallization, separation and purification are carried out for 3 times by adopting methanol as the solvent.
FTIR analysis (see fig. 12): 3437cm -1 (peak 1) is the stretching vibration peak of O-H in hydroxyl and sulfonic acid groups in the molecule, 2916cm -1 (peak 2) is the asymmetric stretching vibration absorption peak of methylene, 2847cm -1 (peak 3) symmetric stretching vibration peak of methylene, 1470cm -1 (peak 4) asymmetric flexural vibration of methylene, 1219cm -1 (peak 5) symmetric stretching vibration absorption peak of sulfonic acid group S = O, 1043cm -1 (peak 6) is an asymmetric stretching vibration absorption peak of sulfonic acid group S = O, 916cm -1 (peak 7) is the absorption peak of out-of-plane bending vibration of methylene, 721cm -1 (peak 8) is the methylene in-plane rocking vibration at 602cm -1 (peak 9) is the absorption peak of S-O stretching vibration, 519cm -1 (peak 10) is a bending vibration absorption peak of O-H in the hydroxyl group and the sulfonic acid group.
The reaction equation is as follows:
example 4
(1) Preparation of tertiary amine quaternary ammonium salt sulfonic acid surfactant:
1) 269.51g of octadecylamine and 2200g of isopropanol were charged in a three-necked flask, and dissolved by heating with stirring. Then 124.6g of 1, 3-propane sultone is added in 5 portions, and the mixture is stirred and reacted for 4 hours at 70 ℃ to obtain a reaction intermediate E4.
The solvent of the synthetic intermediate E4 is evaporated, and then the infrared, nuclear magnetic and mass spectrometry analysis is carried out after the recrystallization separation and purification are carried out for 3 times by adopting ethyl acetate as the solvent.
Infrared analysis (fig. 13): 3448cm -1 (Peak 1) is the stretching vibration peak of O-H in the sulfonic acid group, 3109cm -1 (Peak 2) is the secondary amine N-H stretching vibration peak, 2922cm -1 (Peak 3) is an asymmetric stretching vibration absorption peak of methylene, 2852cm -1 (Peak 4) is the symmetric stretching vibration peak of methylene, 1560cm -1 (Peak 5) is the deformation vibration absorption peak of N-H, 1473cm -1 (Peak 6) asymmetric bending vibration of methylene group, 1215cm -1 (Peak 7) C-N stretching vibration, 1165cm -1 (Peak 8) is a symmetric stretching vibration absorption peak of sulfonic acid group S = O, 1041cm -1 (Peak 9) is an asymmetric stretching vibration absorption peak of sulfonic acid group S = O, 721cm -1 (Peak 10) methylene in-plane rocking vibration of 603cm -1 (Peak 11) is an S-O stretching vibration absorption peak of 518cm -1 (Peak 12) is a bending vibration absorption peak of O-H in the sulfonic acid group.
Nuclear magnetic analysis (fig. 14): 1 H NMR(400MHz,CD 3 OD),δ:0.904-0.939(3H,t,-CH 3 ),1.309-1.408(30H,s,CH 3 (CH 2 ) 15 CH 2 CH 2 -),1.643-1.681(2H,m,CH 3 (CH 2 ) 15 CH 2 CH 2 -),2.123-2.223(2H,m,-NHCH 2 CH 2 CH 2 SO 3 H),2.903-3.026(4H,m,-CH 2 NHCH 2 -),3.144-3.210(2H,t,-CH 2 SO 3 H)ppm.
mass spectrometry (fig. 15): HRMS (ESI) (positive) M/z: [ M + H ]] + Calcd for C 21 H 46 NO 3 S,392.3198；Found 392.3258.
2) 189.5g of 33 percent (mass fraction) trimethylamine aqueous solution is added into another three-neck flask, 108.3g of 36 percent (mass fraction) hydrochloric acid is added into the three-neck flask in 5 batches, 96.1G of epichlorohydrin is added into the three-neck flask in 5 batches, and the mixture is stirred and reacted for 3 hours at 42 ℃ to obtain a reaction intermediate G1.
3) The reaction intermediate G1 is added into the reaction intermediate E4 in 5 portions and reacted for 2h at 75 ℃. Thus obtaining the tertiary amine quaternary ammonium salt sulfonic acid type surfactant.
The solvent of the synthesized product is evaporated, and the FTIR analysis is carried out after recrystallization separation and purification are carried out for 3 times by adopting methanol as the solvent.
FTIR analysis (see fig. 16): 3470cm -1 (peak 1) is the stretching vibration peak of O-H in hydroxyl and sulfonic acid groups in the molecule, 2920cm -1 (peak 2) is the asymmetric stretching vibration absorption peak of methylene, 2855cm -1 (peak 3) is the symmetric stretching vibration peak of methylene, 1474cm -1 (peak 4) asymmetric bending vibration of methylene, 1215cm -1 (peak 5) symmetric stretching vibration absorption peak of sulfonic acid group S = O, 1047cm -1 (peak 6) asymmetric stretching vibration absorption peak of sulfonic acid group S = O, 899cm -1 (peak 7) methylene out-of-plane bending vibration absorption peak at 719cm -1 (peak 8) is the methylene in-plane rocking vibration, 602cm -1 (peak 9) is the absorption peak of S-O for stretching vibration, 520cm -1 (peak 10) is a bending vibration absorption peak of O-H in the hydroxyl group and the sulfonic acid group.
The reaction equation is as follows:
example 5
(1) Preparation of tertiary amine quaternary ammonium salt sulfonic acid surfactant:
1) 269.51g of octadecylamine and 2200g of isopropanol were charged in a three-necked flask, and dissolved by heating with stirring. Then 124.6g of 1, 3-propane sultone was added in 5 portions, and the reaction was carried out for 4 hours with stirring at 70 ℃ to obtain a reaction intermediate E4.
2) 107.1G of triethylamine was added to another three-necked flask, 108.3G of 36 mass% hydrochloric acid was added in 5 portions, 96.1G of epichlorohydrin was added in 5 portions, and the mixture was stirred at 42 ℃ for reaction for 3 hours to obtain a reaction intermediate G2.
3) The reaction intermediate G2 is added into the reaction intermediate E4 in 5 batches and reacted for 2h at 75 ℃. Thus obtaining the tertiary amine quaternary ammonium salt sulfonic acid type surfactant.
The solvent of the synthesized product is evaporated, and the synthesized product is recrystallized, separated and purified for 3 times by adopting ethyl acetate as the solvent and then subjected to FTIR and mass spectrum analysis.
FTIR analysis (see fig. 17): 3442cm -1 (peak 1) is the stretching vibration peak of O-H in sulfonic acid group, 2922cm -1 (peak 2) is the asymmetric stretching vibration absorption peak of methylene, 2850cm -1 (peak 3) is the symmetric stretching vibration peak of methylene, 1470cm -1 (peak 4) asymmetric flexural vibration of methylene, 1190cm -1 (peak 5) symmetric stretching vibration absorption peak of sulfonic acid group S = O, 1045cm -1 (peak 6) asymmetric stretching vibration absorption peak of sulfonic acid group S = O, 899cm -1 (peak 7) is the absorption peak of out-of-plane bending vibration of methylene at 719cm -1 (peak 8) is the methylene in-plane oscillatory vibration at 603cm -1 (peak 9) is the absorption peak of the stretching vibration of S-O, 524cm -1 (peak 10) shows the bending vibration absorption peak of O-H in the hydroxyl group and the sulfonic acid group.
Mass spectrometry (fig. 18): HRMS (ESI) (positive) M/z [ M-Cl ] - ] + Calcd for C 30 H 65 N 2 O 4 S,549.4665；Found 549.4630.
The reaction equation is as follows:
experimental example 1
In this experimental example, the tertiary amine quaternary ammonium salt sulfonic acid type surfactants prepared in examples 1 to 5 were subjected to a foam suppressing performance test, and the foam suppressing performance before and after purification thereof was measured, respectively.
The method comprises the following steps: pouring 10mL of sodium dodecyl benzene sulfonate (LBS) aqueous solution with the mass fraction of 0.5% and a certain amount of sample into a 100mL measuring cylinder with a plug at room temperature, plugging the measuring cylinder with the plug, and recording the total volume V of the foam immediately after 20 times of violent oscillation 1 . The foam inhibition value P is obtained according to the following formula, and the size of the foam inhibition value P reflects the foam inhibition capability of the sample.
P＝(V 0 -V 1 )/V 0
Wherein, V 0 Represents the foam volume immediately after shaking in the blank, mL; v 1 Represents the foam volume immediately after shaking upon addition of the sample, mL.
The experimental results are as follows: the tertiary amine quaternary ammonium sulfonic acid type surfactant prepared in examples 1 to 5 and OP-10 (commercially available product) were compared, and foam suppressing properties before, after and at OP-10 of each sample are shown in tables 1 and 2.
TABLE 1 foam inhibition Performance of each sample and OP-10 before purification
TABLE 2 foam suppressing Properties of each purified sample and OP-10
Shows that: the tertiary amine quaternary ammonium salt sulfonic acid type surfactants prepared in examples 4 and 5 have certain foam inhibition capability before and after purification; the tertiary amine quaternary ammonium salt sulfonic acid type surfactant prepared in examples 2 to 3 had a certain foam suppressing ability after purification.
Experimental example 2
In this experimental example, the tertiary amine quaternary ammonium salt sulfonic acid type surfactants prepared in examples 1 to 5 were subjected to an emulsifying ability test, and the emulsifying ability before and after purification thereof was measured.
The method comprises the following steps: at room temperature, 20mL of sample aqueous solution with the mass fraction of 0.1 percent, OP-10 aqueous solution and 20mL of liquid paraffin are poured into a 100mL stoppered measuring cylinder, a stoppered measuring cylinder is plugged, the measuring cylinder is stood for 1min after 5 times of violent oscillation, and the time for separating 10mL of water is recorded after 5 times of repetition.
As a result: the tertiary amine quaternary ammonium salt sulfonic acid type surfactant prepared in examples 1 to 5 was compared with OP-10 (commercially available product), and the emulsifying ability before, after purification and of OP-10 of each sample are shown in Table 3.
TABLE 3 emulsifying Capacity of the surfactants
The results show that: the tertiary amine quaternary ammonium salt sulfonic acid surfactant prepared in the embodiment 2 has good emulsifying capacity before and after purification; the tertiary amine quaternary ammonium salt sulfonic acid type surfactants prepared in the embodiments 3 to 4 have better emulsifying capacity before purification; the tertiary amine quaternary ammonium salt sulfonic acid type surfactant prepared in example 5 has better emulsifying capacity after purification.
Experimental example 3
In this experimental example, the tertiary amine quaternary ammonium salt sulfonic acid type surfactants prepared in examples 1 to 5 were subjected to foaming property and foam stability tests, and the foaming property and foam stability of the purified products were measured.
The method comprises the following steps: 80mL of aqueous solution of the purified product with the concentration of 0.001mol/L is prepared for standby. 20mL of the aqueous solution prepared above was placed in a 100mL measuring cylinder with a stopper, and the temperature was maintained in a water bath at 25 ℃ for 10min. The thermostated solution was shaken vigorously up and down 20 times and left in a water bath, and the initial volume of foam (H) was recorded immediately 0 ) (ii) a After 5min the volume of foam (H) was recorded 5 ) (ii) a Time (t) for the foam volume to decay to half of the initial volume 1/2 I.e., half-life). The experimental procedure was repeated 3 times and the average was taken.
The experimental results are as follows: the tertiary amine quaternary ammonium salt sulfonic acid type surfactant prepared in examples 1 to 5 was compared with sodium dodecylbenzenesulfonate, and the purified samples and the foamability and foam stability of the sodium dodecylbenzenesulfonate are shown in table 4.
TABLE 4 foamability and foam stability of the respective surfactants
The results show that: compared with sodium dodecyl benzene sulfonate, the tertiary amine quaternary ammonium salt sulfonic acid surfactants prepared in the embodiments 2 to 5 have poor foamability and good foam stability after purification. The surfactants prepared in examples 2 to 5 are low foaming surfactants. The tertiary amine quaternary ammonium salt sulfonic acid surfactant prepared in example 1 had better foamability after purification.
Experimental example 4
In this experimental example, the surface tension of the surfactant prepared in examples 1 to 5 was measured, and the surface tension and Critical Micelle Concentration (CMC) of the purified sample were measured.
The method comprises the following steps: adopting a K100 type full-automatic surface-interface tensiometer (Germany) to measure, preparing a series of surfactant aqueous solutions with different concentrations, adopting a hanging piece method to measure the surface tension, drawing a surface tension-log c curve, and obtaining the CMC and the surface tension (gamma) under the CMC CMC )。
The experimental results are as follows: the surface tension versus log concentration for the surfactants prepared in examples 1-5 are shown in FIGS. 19-23. It can be seen that the CMC of example 1 was 5.69X 10 -5 mol/L, gamma at CMC CMC Was 45.80mN/m. The CMC of example 2 was 1.05X 10 -5 mol/L in CMGamma under C CMC It was 56.80mN/m. The CMC of example 3 was 4.68X 10 -5 mol/L, gamma at CMC CMC Was 53.10mN/m. The CMC of example 4 was 4.12X 10 -5 mol/L, gamma at CMC CMC Was 51.20mN/m. The CMC of example 5 was 2.30X 10 -5 mol/L, gamma at CMC CMC The concentration was 48.70mN/m.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The tertiary amine quaternary ammonium salt sulfonic acid surfactant is characterized in that the molecular structural general formula is as follows:
wherein n is an even number not less than 12, preferably, n =12,14,16,18; c n H 2n+1 Is a straight chain or branched chain structure; r is selected from methyl, ethyl or hydroxyethyl.
2. The method for producing a tertiary amine quaternary ammonium sulfonate surfactant according to claim 1, comprising the steps of: mixing fatty amine, an alcohol solvent and 1, 3-propane sultone for reaction to obtain a reaction intermediate E; mixing and reacting low-carbon tertiary amine, hydrochloric acid and epichlorohydrin to obtain a reaction intermediate G, adding the reaction intermediate G into the reaction intermediate E, and mixing and reacting to obtain a tertiary amine quaternary ammonium salt sulfonic acid surfactant;
the structural general formula of the reaction intermediate E is as follows: c n H 2n+1 NHCH 2 CH 2 CH 2 SO 3 H，
Wherein n is an even number not less than 12, preferably, n =12,14,16,18; c n H 2n+1 Is straight chain orA branched structure;
the structural general formula of the reaction intermediate G is as follows:
wherein R is selected from methyl, ethyl or hydroxyethyl.
3. The method according to claim 2, wherein the low-carbon tertiary amine is selected from trimethylamine, triethylamine and triethanolamine.
4. The method of claim 2, wherein the aliphatic amine is selected from the group consisting of dodecylamine, tetradecylamine, hexadecylamine, and octadecylamine; c in the fatty amine n H 2n+1 Is a linear or branched structure, preferably a linear structure.
5. The method according to claim 2, wherein the alcohol solvent is a lower alcohol, preferably ethanol or isopropanol.
6. The preparation method according to claim 2, wherein in the process of synthesizing the reaction intermediate E, the reaction temperature is 60-85 ℃, and the reaction time is 3-5 h;
or, in the process of synthesizing the reaction intermediate G, the reaction temperature is 40-55 ℃, and the reaction time is 2-3 h;
or the temperature of the mixed reaction of the reaction intermediate G and the reaction intermediate E is 60-85 ℃, and the reaction time is 2-3 h.
7. The method according to claim 2, wherein the aliphatic amine, the alcohol solvent, the 1, 3-propane sultone, the low-carbon tertiary amine, the hydrochloric acid and the epichlorohydrin are used in a molar ratio of 1: (31.00-51.00): (1.00-1.15): (1.00-1.15): (1.00-1.15): (1.00-1.15).
8. The preparation method according to claim 2, comprising the following steps:
(1) Adding fatty amine into a reaction container, adding an alcohol solvent, heating, stirring and dissolving, then adding 1, 3-propane sultone in batches, and after the addition is finished, stirring and reacting for 3-5 hours at the temperature of 60-85 ℃ to obtain a reaction intermediate E;
(2) Adding low-carbon tertiary amine into another reaction container, adding hydrochloric acid in batches, adding epoxy chloropropane in batches after the hydrochloric acid is added, and stirring and reacting at 40-55 ℃ for 2-3 h to obtain a reaction intermediate G after the epoxy chloropropane is added;
(3) Adding the reaction intermediate G into the reaction intermediate E in batches, stirring and reacting for 2-3 h at the temperature of 60-85 ℃ to obtain the tertiary amine quaternary ammonium salt sulfonic acid surfactant;
the preparation order of steps (1) and (2) can be interchanged.
9. The method of claim 8, further comprising: separation and purification; evaporating the solvent of the synthetic product in the step (1) or the step (3), and then carrying out recrystallization separation and purification by adopting an organic solvent; preferably, the organic solvent is ethyl acetate or methanol.
10. Use of the tertiary amine quaternary ammonium sulfonic acid type surfactant according to claim 1 as a low foaming surfactant or emulsifier.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04351698A (en) * | 1991-05-30 | 1992-12-07 | Kao Corp | Detergent composition |
| JPH0551352A (en) * | 1991-08-22 | 1993-03-02 | Kao Corp | Novel cationic compound and surfactant containing the same |
| JPH0551351A (en) * | 1991-08-22 | 1993-03-02 | Kao Corp | Production of betaine compound |
| CN103228665A (en) * | 2010-11-24 | 2013-07-31 | 塞克姆公司 | Method for buffering chemical or biological composition |
| CN110950782A (en) * | 2019-12-16 | 2020-04-03 | 西南石油大学 | Temperature-resistant and salt-resistant gemini amphoteric surfactant and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04351698A (en) * | 1991-05-30 | 1992-12-07 | Kao Corp | Detergent composition |
| JPH0551352A (en) * | 1991-08-22 | 1993-03-02 | Kao Corp | Novel cationic compound and surfactant containing the same |
| JPH0551351A (en) * | 1991-08-22 | 1993-03-02 | Kao Corp | Production of betaine compound |
| CN103228665A (en) * | 2010-11-24 | 2013-07-31 | 塞克姆公司 | Method for buffering chemical or biological composition |
| CN110950782A (en) * | 2019-12-16 | 2020-04-03 | 西南石油大学 | Temperature-resistant and salt-resistant gemini amphoteric surfactant and preparation method and application thereof |
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