CN117534602A - Nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, and preparation method and application thereof - Google Patents
Nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, and preparation method and application thereof Download PDFInfo
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 54
- 239000011734 sodium Substances 0.000 title claims abstract description 48
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 48
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 43
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 42
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 14
- 229940035437 1,3-propanediol Drugs 0.000 claims description 14
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- ONGGURNBDHMMTE-UHFFFAOYSA-N ClCC(C[Na])O Chemical compound ClCC(C[Na])O ONGGURNBDHMMTE-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000543 intermediate Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 32
- 239000006260 foam Substances 0.000 description 30
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- -1 diamine compound Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical class O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/273—2-Pyrrolidones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
- C07D207/277—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/18—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/32—Heterocyclic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention belongs to the technical field of surfactants, and relates to a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, a preparation method and application thereof, wherein the molecular structural general formula of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant is as follows:the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant is prepared from the following raw materials in molar ratio: the molar ratio of the N-alkyl-1, 3-propylene diamine to the alcohol solvent to the itaconic acid to the acrylamide to the 3-chlorine-2-hydroxypropyl sodium sulfonate is 1: (11.5-25.0): (1.00-1.05): (1.00-1.07): (1.00-1.07). The alcohol solvent is one or two of ethanol and isopropanol. The invention relates to a nitrogenous five-membered heterocycleSodium sulfonate surfactants may be used as suds suppressors, low sudsing surfactants, mid sudsing surfactants and/or emulsifiers.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the 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 already known to those of ordinary skill in the art.
At present, research on low-foam or medium-foam surfactants focuses on the formulation composition of the surfactants, few substances with single chemical compositions are reported, and the disadvantage of complex synthesis methods exists.
Disclosure of Invention
Aiming at the problems of low-foam or medium-foam surfactant quantity, poor performance and complicated synthesis method existing in the prior art, the invention aims to provide the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant which has the advantages of foam inhibition, low-foam or medium-foam and good surface activity.
The invention aims at providing a preparation method of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, which is simple in preparation method, easy in raw material acquisition and low in preparation cost.
The invention aims at providing an application of the nitrogenous five-membered heterocyclic sodium sulfonate surfactant as a foam inhibitor, a low-foam or medium-foam surfactant and an emulsifier.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a nitrogen-containing penta-heterocyclic sodium sulfonate surfactant having a molecular structural formula (G) represented by:
wherein n=12, 14, 16 or 18; c (C) n H 2n+1 Is a straight chain alkyl group.
In the design route of the invention, if the structures of the sodium sulfonate group, the quaternary ammonium salt, the amide group, the carboxyl group and the nitrogen-containing five-membered heterocyclic ring are designed and introduced into the molecules of the surfactant, the nitrogen-containing five-membered heterocyclic ring sodium sulfonate surfactant with a novel structure is formed by matching with a long carbon chain lipophilic group with a certain length. The surfactant has foam inhibition, low foam or medium foam and surface activity.
In a second aspect of the present invention, there is provided a method for preparing the nitrogen-containing pentaheterocycle sodium sulfonate surfactant of the first aspect, comprising the steps of:
1) Mixing N-alkyl-1, 3-propylene diamine, an alcohol solvent and itaconic acid for reaction to obtain a reaction intermediate M-1, wherein the structural general formula of the reaction intermediate M-1 is as follows:
wherein n=12, 14, 16 or 18; c (C) n H 2n+1 Is a linear alkyl group;
2) Adding acrylamide into the reaction intermediate M-1, and mixing and reacting to obtain a reaction intermediate M-2, wherein the structural general formula of the reaction intermediate M-2 is as follows:
wherein n=12, 14, 16 or 18; c (C) n H 2n+1 Is a linear alkyl group;
3) And adding 3-chloro-2-hydroxypropyl sodium sulfonate aqueous solution into the reaction intermediate M-2, and mixing for reaction to obtain a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant product G.
The reaction is as follows:
in one or more embodiments, the molar ratio of the N-alkyl-1, 3-propanediol diamine, the alcoholic solvent, itaconic acid, acrylamide, sodium 3-chloro-2-hydroxypropyl sulfonate is 1: (11.5-25.0): (1.00-1.05): (1.00-1.07): (1.00-1.07).
Experiments prove that the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant prepared from the raw materials in the molar ratio has good performance, and the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant cannot be prepared from the unsuitable molar ratio.
In one or more embodiments, in step 1), the N-alkyl-1, 3-propanediol is N-octadecyl-1, 3-propanediol, N-hexadecyl-1, 3-propanediol, N-tetradecyl-1, 3-propanediol, N-dodecyl-1, 3-propanediol, or N-hydrogenated tallow-1, 3-propanediol.
In one or more embodiments, in step 1), the alcoholic solvent is any one or two of ethanol and isopropanol.
In one or more embodiments, in step 1), during the synthesis of intermediate M-1, the reaction temperature is 65-81℃and the reaction time is 3-5h.
In one or more embodiments, in step 2), during the synthesis of intermediate M-2, the reaction temperature is 65-81℃and the reaction time is 3-5h.
In one or more embodiments, during the synthesis of product G in step 3), the reaction temperature is 65-81 ℃ and the reaction time is 4-6h.
In one or more embodiments, in step 3), the mass fraction of the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate is 40-60%.
In one or more embodiments, the purification process for product G is: and (3) evaporating the solvent from the product G under normal pressure, and recrystallizing, separating and purifying by using an organic solvent to obtain the product G. More specifically, the organic solvent for recrystallization, separation and purification is methanol, petroleum ether or ethyl acetate.
In a preferred embodiment, the preparation method of the nitrogen-containing penta-heterocyclic sodium sulfonate surfactant G specifically includes the following steps:
(1) Adding N-alkyl-1, 3-propylene diamine into a reaction vessel, adding an alcohol solvent, heating, stirring and dissolving, adding itaconic acid in batches, and stirring and reacting at 65-81 ℃ for 3-5h after the addition is completed to obtain a reaction intermediate M-1;
(2) Adding acrylamide into the reaction intermediate M-1 in batches, and stirring at 65-81 ℃ for reaction for 3-5h to obtain a reaction intermediate M-2;
(3) Adding 40-60% 3-chloro-2-hydroxypropyl sodium sulfonate aqueous solution into the reaction intermediate M-2 in batches, stirring and reacting for 4-6 hours at 65-81 ℃ to obtain a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant product G, evaporating the solvent from the product G under normal pressure, and carrying out recrystallization, separation and purification on the product G by an organic solvent for 3-5 times to obtain a pure product G.
In a third aspect of the present invention there is provided the use of the nitrogen-containing penta-heterocyclic sodium sulfonate surfactant of the first aspect as a suds suppressor, low sudsing surfactant, medium sudsing surfactant and/or emulsifier. For example, in industrial cleaning applications, the generation of large amounts of foam can lead to difficult production control and cause spillage of materials and environmental pollution.
According to the invention, N-alkyl-1, 3-propylene diamine is used as a main raw material for preparing the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, itaconic acid, acrylamide and 3-chloro-2-hydroxypropyl sodium sulfonate are added in the preparation process of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, and sodium sulfonate, carboxylic acid, quaternary ammonium salt base and amide hydrophilic groups are introduced into the molecular structure of the emulsifier, so that the foam inhibition performance, low foam or middle foam performance and surface activity are improved.
The specific embodiment of the invention has the following beneficial effects:
(a) According to the invention, sodium sulfonate, carboxylic acid, quaternary ammonium salt group and amide hydrophilic group are effectively combined in a certain form and combined with a lipophilic group with a carbon chain structure with a certain length, so that the novel structure of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant G is formed, and the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant G has more hydrophilic groups and has better surface performance.
(b) The main raw material of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant is diamine compound, and the raw material is easy to obtain and the cost is low.
(c) The preparation method has the advantages of simple preparation process, no need of high-temperature reaction and low energy consumption.
(d) The invention has the advantages of uncomplicated production operation, strong practicability and remarkable benefit.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an infrared spectrum of the pure product G of example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of the pure product G of example 1 of the present invention.
FIG. 3 is a mass spectrum of the pure product G of example 1 of the present invention.
FIG. 4 is a graph showing the relationship between the surface tension and the logarithmic concentration of the pure product G of example 1 of the present invention.
Detailed Description
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and experimental examples.
Example 1
(1) Preparation of nitrogen-containing penta-heterocyclic sodium sulfonate surfactant product G (n=18):
1) 326g N-hydrogenated tallow-1, 3-propylene diamine and 900g of isopropanol are added into a reaction vessel, heated and stirred at 75 ℃ for dissolution, then 134.0g of itaconic acid is added into the reaction vessel in 6 batches, and the reaction is carried out at 75 ℃ for 4 hours under stirring, thus obtaining a reaction intermediate M-1.
2) To reaction intermediate M-1, 74.6g of acrylamide was added in 6 portions, and the mixture was heated and stirred at 75℃for 4 hours to give reaction intermediate M-2.
3) 411.2G of 50% aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate (purity: 98.5%) was added to the reaction intermediate M-2 in 6 portions, and the mixture was heated and stirred at 75℃for reaction for 5 hours to obtain a nitrogen-containing penta-heterocyclic sodium sulfonate surfactant product G. And (3) evaporating the solvent from the product G at normal pressure, and recrystallizing, separating and purifying for 3 times by adopting methanol to obtain a pure product G.
Pure product G was subjected to FTIR, NMR, MS structural characterization.
FTIR analysis (fig. 1): 3357cm -1 (peak 1) is an O-H stretching vibration absorption peak, 3202cm -1 (peak 2) N-H stretching vibration peak, 2920cm -1 (peak 3) asymmetric stretching vibration absorption peak of methylene, 2852cm -1 (peak 4) is a symmetrical telescopic vibration absorption peak of methylene, 1681cm -1 (peak 5) C=O stretching vibration peak of amide, 1575cm -1 (peak 6) asymmetric stretching vibration absorption peak of C-O, 1465cm -1 (peak 7) asymmetric flexural vibration of methylene group, 1396cm -1 (peak 8) symmetrical flexural vibration of methylene group, 1197cm -1 (peak 9) symmetrical telescopic vibration absorption peak of sulfonic acid group S=O, 1050cm -1 (peak 10) is an asymmetric stretching vibration absorption peak of sulfonic acid group S=O, 721cm -1 (peak 11) is the vibration absorption peak of the vibration in the methylene basal plane, 619cm -1 (peak 12) is the telescopic vibration absorption peak of S-O.
1 H-NMR analysis (FIG. 2): 1 H NMR(400MHz,CD 3 OD),δ:0.8841-0.9184(3H,t,J＝6.86Hz,-CH 3 ),1.2893(30H,s,CH 3 (CH 2 ) 15 CH 2 CH 2 -),1.3758(2H,s,CH 3 (CH 2 ) 15 CH 2 CH 2 -),1.6508-1.7339(2H,m,-NCH 2 CH 2 CH 2 N-),2.3871-2.4128(2H,t,J＝5.14Hz,-CH 3 (CH 2 ) 15 CH 2 CH 2 -),2.6426-2.6745(2H,t,J＝6.38Hz,-CH 2 CH 2 NCH 2 CH 2 CH 2 N-),2.9694-3.0042(2H,t,J＝6.96Hz,-CH 2 CH 2 CONH 2 ),3.0589-3.0783(2H,t,J＝3.88Hz,-NCH 2 CH 2 CONH 2 ),3.0964-3.1110(4H,d,J＝2.92Hz,-NCH 2 CH(OH)CH 2 SO 3 Na and-COCH 2 CHCOOH),3.4743-3.4907(1H,m,-CHCOOH),3.6601-3.7025(2H,t,J＝8.48Hz,-NCH 2 CH 2 CH 2 NCO-),3.7766-3.7866(2H,d,J＝2Hz,-CH 2 SO 3 Na),3.8048-3.8149(2H,d,J＝2.02Hz,-NCH 2 CHCOOH),4.2593-4.2937(1H,m,-CH 2 CH(OH)CH 2 SO 3 Na),5.5310(1H,s,-CH 2 CH(OH)CH 2 SO 3 Na),6.0453(2H,s,-CH 2 CH 2 CONH 2 ) ppm.3.3103ppm as deuterated methanol solvent peak; 4.8566ppm is the deuterated methanol water peak.
Mass spectrometry (fig. 3): HRMS (ESI) (negative) M/z: [ M-Na ] + ] - Calcd for C 32 H 61 O 8 N 3 SCl,682.3868；Found 682.4372.
The reaction involved:
experimental example 1
The foam inhibition performance of the pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant synthesized in example 1 is measured: 10mL of 0.5% by mass sodium dodecyl benzene sulfonate (LBS) aqueous solution and a certain amount of sample were taken in a 100mL stoppered cylinder, the stopper was stoppered, and then vigorously shaken 20 times, and the volume of foam generated (mL) was recorded instantaneously. The bubble suppression value (Q) was calculated and represents the bubble suppression capacity of the sample.
Q＝(V 0 -V 1 )/V 0
Wherein V is 0 Foam volume in blank test, mL; v (V) 1 Foam volume, mL, at the time of sample addition.
The foam inhibition properties are shown in Table 1, as compared with the pure product G and OP-10 (commercial product) of the nitrogen-containing penta-heterocyclic sodium sulfonate surfactant. Therefore, the pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant prepared in the example 1 has good foam inhibition capability.
TABLE 1 foam inhibition Properties
Experimental example 2
The emulsification performance of pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant synthesized in example 1 is measured: taking 20mL of pure product G aqueous solution of nitrogen-containing penta heterocycle sodium sulfonate surfactant with mass fraction of 0.1% or aqueous solution of OP-10 (commercial product) and 20mL of liquid paraffin, transferring into a 100mL cylinder with a stopper, plugging the stopper, then vigorously shaking for 5 times, standing for 1 minute, repeating for 5 times, and immediately recording the time required for separating 10mL of water.
The measurement data are shown in Table 2. It can be seen that the pure product G of the nitrogen-containing penta-heterocyclic sodium sulfonate surfactant prepared in example 1 has good emulsifying capacity.
TABLE 2 emulsifying capacity
Experimental example 3
Foaming property and foam stability of the pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant synthesized in example 1 are measured: 80mL of an aqueous solution of the sample having a concentration of 0.001mol/L was prepared. 20mL of the solution is taken out and placed in a 100mL measuring cylinder with a plug, and the solution is placed in a constant temperature water bath kettle at 25 ℃ for 10 minutes. Shaking the constant temperature solution for 20 times, standing on a water bath, and immediately recording the initial volume (H 0 ) Thereafter, the volume of foam at 5 minutes (H 5 ) The time (t) required for the foam volume to decay to 1/2 of the original initial volume 1/2 Half-life).
The foamability and foam stability test data are shown in Table 3. It can be seen that the foamability of the pure product G prepared in example 1 is centered and the foam stability is better compared with sodium dodecylbenzenesulfonate, indicating that the pure product G prepared in example 1 is a medium foaming surfactant.
TABLE 3 foamability and foam stability
Experimental example 4
Surface tension and Critical Micelle Concentration (CMC) measurements were performed on pure product G of the nitrogen-containing penta-heterocyclic sodium sulfonate surfactant synthesized in example 1: measuring with JHZL full-automatic surface tension meter (manufactured by Jun electric Co., yangzhou) to obtain gamma-log variation curve (see figure 4), and calculating CMC and surface tension (gamma) under CMC CMC )、C 20 、pC 20 And CMC/C 20 (see Table 4). It can be seen that the surface properties of the pure product G of example 1 are better.
TABLE 4 surface Property parameters of product G
| Product(s) | CMC(mol·L -1 ) | γ CMC (mN·m -1 ) | C 20 (mol·L -1 ) | pC 20 | CMC/C 20 |
| Pure product G | 1.92×10 -4 | 39.4 | 5.77×10 -6 | 5.24 | 33.28 |
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. 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 nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant is characterized in that the molecular structural general formula (G) is as follows:
wherein n=12, 14, 16 or 18; c (C) n H 2n+1 Is a straight chain alkyl group.
2. The method for preparing the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant as described in claim 1, which is characterized by comprising the following steps:
1) Mixing N-alkyl-1, 3-propylene diamine, an alcohol solvent and itaconic acid for reaction to obtain a reaction intermediate M-1, wherein the structural general formula of the reaction intermediate M-1 is as follows:
wherein n=12, 14, 16 or 18; c (C) n H 2n+1 Is straight chain alkaneA base;
2) Adding acrylamide into the reaction intermediate M-1, and mixing and reacting to obtain a reaction intermediate M-2, wherein the structural general formula of the reaction intermediate M-2 is as follows:
wherein n=12, 14, 16 or 18; c (C) n H 2n+1 Is a linear alkyl group;
3) And adding 3-chloro-2-hydroxypropyl sodium sulfonate aqueous solution into the reaction intermediate M-2, and mixing for reaction to obtain a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant product G.
3. The method according to claim 2, wherein the molar ratio of the N-alkyl-1, 3-propanediol diamine, the alcoholic solvent, itaconic acid, acrylamide, and sodium 3-chloro-2-hydroxypropyl sulfonate is 1:11.5 to 25.0:1.00 to 1.05:1.00 to 1.07:1.00 to 1.07.
4. The method of claim 2, wherein in step 1), the N-alkyl-1, 3-propanediol is N-octadecyl-1, 3-propanediol, N-hexadecyl-1, 3-propanediol, N-tetradecyl-1, 3-propanediol, N-dodecyl-1, 3-propanediol, or N-hydrogenated tallow-1, 3-propanediol;
or in the step 1), the alcohol solvent is any one or two of ethanol and isopropanol.
5. The process according to claim 2, wherein in step 1), the reaction temperature is 65 to 81℃and the reaction time is 3 to 5 hours during the synthesis of intermediate M-1.
6. The process according to claim 2, wherein in step 2), the reaction temperature is 65 to 81℃and the reaction time is 3 to 5 hours during the synthesis of intermediate M-2.
7. The process according to claim 2, wherein in step 3), the reaction temperature is 65 to 81℃and the reaction time is 4 to 6 hours during the synthesis of the product G;
or the mass fraction of the 3-chlorine-2-hydroxypropyl sodium sulfonate aqueous solution is 40-60%.
8. The process of claim 2, wherein the purification of product G is: evaporating the solvent from the product G under normal pressure, and recrystallizing, separating and purifying by using an organic solvent to obtain the product G; preferably, the organic solvent for recrystallization, separation and purification is methanol, petroleum ether or ethyl acetate.
9. The preparation method as claimed in claim 2, comprising the following steps:
(1) Adding N-alkyl-1, 3-propylene diamine into a reaction vessel, adding an alcohol solvent, heating, stirring and dissolving, adding itaconic acid in batches, and stirring and reacting at 65-81 ℃ for 3-5h after the addition is completed to obtain a reaction intermediate M-1;
(2) Adding acrylamide into the reaction intermediate M-1 in batches, and stirring at 65-81 ℃ for reaction for 3-5h to obtain a reaction intermediate M-2;
(3) Adding 40-60% 3-chloro-2-hydroxypropyl sodium sulfonate aqueous solution into the reaction intermediate M-2 in batches, stirring and reacting for 4-6 hours at 65-81 ℃ to obtain a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant product G, evaporating the solvent from the product G under normal pressure, and carrying out recrystallization, separation and purification on the product G by an organic solvent for 3-5 times to obtain a pure product G.
10. Use of a nitrogen-containing penta-heterocyclic sodium sulfonate surfactant according to claim 1 as suds suppressor, low sudsing surfactant, mid sudsing surfactant and/or emulsifier.
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