CN107501134B - Asymmetric benzenesulfonic acid sodium salt Gemini surfactant and preparation method thereof - Google Patents
Asymmetric benzenesulfonic acid sodium salt Gemini surfactant and preparation method thereof Download PDFInfo
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 59
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims abstract description 49
- DHPWGEOXBYBHOY-YPKPFQOOSA-N (z)-2-dodecylbut-2-enedioic acid Chemical compound CCCCCCCCCCCC\C(C(O)=O)=C\C(O)=O DHPWGEOXBYBHOY-YPKPFQOOSA-N 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 6
- 239000011976 maleic acid Substances 0.000 claims abstract description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 6
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 40
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000005639 Lauric acid Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 150000005690 diesters Chemical class 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 10
- 239000012264 purified product Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000693 micelle Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 230000001804 emulsifying effect Effects 0.000 abstract description 6
- 238000005886 esterification reaction Methods 0.000 abstract description 6
- 238000006277 sulfonation reaction Methods 0.000 abstract description 4
- 238000007112 amidation reaction Methods 0.000 abstract description 3
- 239000004519 grease Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 2
- 229930195729 fatty acid Natural products 0.000 abstract description 2
- 239000000194 fatty acid Substances 0.000 abstract description 2
- 150000004665 fatty acids Chemical class 0.000 abstract description 2
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 3
- 229940077388 benzenesulfonate Drugs 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 alkylbenzene sulfonate Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/24—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/25—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/51—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/60—Maleic acid esters; Fumaric acid esters
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Abstract
The invention relates to an asymmetric benzenesulfonic acid sodium salt Gemini surfactant and a preparation method thereof.A 4- (dodecylamide) phenol is synthesized by carrying out amidation reaction on aminophenol and dodecanol, and a dodecanol maleic acid monoester is synthesized by carrying out esterification reaction on maleic anhydride and dodecanol; then 4- (dodecylamide) phenol and lauryl maleic acid monoester are subjected to esterification reaction to synthesize a Gemini surfactant intermediate; finally reacting with NaHSO3And carrying out sulfonation reaction to obtain the asymmetric benzene sulfonic acid sodium salt Gemini surfactant. The prepared surfactant has the excellent performances of low critical micelle concentration, high surface activity, good emulsifying capacity on grease and the like based on cheap and easily-obtained natural fatty acid as a raw material, and is an environment-friendly material with excellent performance due to the fact that molecules contain two molecular sulfonic acid groups and the hydrophilicity is good.
Description
Technical Field
The invention relates to a surfactant, in particular to an asymmetric benzene sulfonic acid sodium salt Gemini surfactant and a preparation method thereof.
Background
With the development of leather-making industry and the continuous emergence of new technology, new process and new material, the application range of the surfactant is gradually widened. The Gemini surfactant is formed by connecting 2 single-chain single-head-group traditional surfactant molecules together at an ion head group through a chemical bond, so that strong interaction is achieved among hydrophobic hydrocarbon chains, the head group separating force of the surfactant in the ordered aggregation process is inhibited, the combination among the hydrophobic hydrocarbon chains is enhanced, the surfactant is easier to aggregate into micelles, and the Gemini surfactant is a novel surfactant. Compared with the traditional surfactant, the surfactant has stronger hydrophobic tendency, is easier to adsorb on an interface, and is easier to aggregate to form micelles. Therefore, the micelle has lower critical micelle concentration, is more favorable for emulsification, dispersion and solubilization, and is an excellent wetting agent and penetrant. The alkylbenzene sulfonate Gemini surfactant is an important anionic Gemini surfactant, has high surface activity, good water solubility, good wettability, good dispersibility and good acid and alkali resistance, and is applied to a plurality of fields.
The asymmetric Gemini surfactant contains more abundant polar groups, hydrophobic chain segments and various connecting groups, so that the Gemini surfactant has more excellent properties and higher controllability on a molecular structure, can obtain Gemini surfactants with different aggregate forms by regulating and controlling the structure, further has better surface activity, better water solubility, lower Krafft point and higher hydrophilic capacity, has the characteristics of low critical micelle concentration, more aggregation numbers of micelles and micelles, good viscoelasticity, good foamability and the like, has better synergistic effect when being compounded with other surfactants, and has good application value in many fields. However, due to the difference between the hydrophilic group and the lipophilic group of the asymmetric Gemini surfactant, the synthesis and purification separation process is complicated, the synthetic route is complicated, and the large-scale production is difficult to realize. Therefore, the research on the asymmetric Gemini surfactant which has relatively mature synthesis process, simple purification and separation process, environmental protection and excellent performance has become one of the primary tasks of researchers.
Disclosure of Invention
The invention aims to provide an asymmetric benzenesulfonic acid sodium salt Gemini surfactant and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the asymmetric benzenesulfonic acid sodium salt Gemini surfactant is characterized by comprising the following steps:
the method is realized by the following steps:
the method comprises the following steps: taking 20.1 parts by mass of lauric acid and 11.5 parts by mass of p-aminophenol, adding ethyl acetate accounting for 0.5% of the total mass of the lauric acid and the p-aminophenol as a catalyst, and taking a mixture of sodium bisulfite accounting for 0.4% of the total mass of the lauric acid and the p-aminophenol and sodium borohydride as an antioxidant, wherein the mixing ratio is m (sodium bisulfite): m (sodium borohydride) ═ 3: 2, dissolving p-aminophenol by using dimethyl sulfoxide as a solvent, adding the p-aminophenol into a 250mL hydrothermal kettle, putting the hydrothermal kettle into an oven for reaction, heating to 160 ℃, reacting for 5 hours, and separating and purifying to obtain a product 4- (dodecylamide) phenol;
step two: adding 18.6 parts by mass of dodecanol and 9.8 parts by mass of maleic anhydride into a 250mL four-neck flask, adding anhydrous sodium acetate accounting for 0.1% of the total mass of the dodecanol and the maleic anhydride as a catalyst, heating to 85 ℃, reacting for 4 hours, separating and purifying to obtain dodecanol maleic acid monoester;
step three: taking 2.9 parts by mass of purified 4- (dodecylamide) phenol and 2.8 parts by mass of purified lauryl maleic acid monoester, adding zinc oxide accounting for 0.2% of the total mass of the 4- (dodecylamide) phenol and the lauryl maleic acid monoester as a catalyst into a 250mL hydrothermal kettle, putting the hydrothermal kettle into an oven for reaction, heating to 140 ℃, and reacting for 5 hours to obtain a product, namely 4- (dodecylamide) phenyl maleic acid diester;
step four: transferring 4- (dodecylamide) phenyl maleic diester into a three-neck flask, adjusting the pH value to 7 by using a NaOH solution with the mass fraction of 30%, adding dodecanol maleic monoester salt with the mass fraction of 0.6% of the 4- (dodecylamide) phenyl maleic diester as a phase transfer catalyst, uniformly stirring, and slowly dropwise adding 30% of NaHSO3Solution, NaHSO3By mass of (d) n (diester): n (NaHSO)3) 1: 2.2 weighing, heating to 150 ℃, reacting for 5h, separating and purifying to obtain the asymmetric sodium benzenesulfonate Gemini surfaceAn active agent.
In the first step, the separation and purification method comprises the following steps: extracting the crude product by mixing ethyl acetate and distilled water; and further carrying out rotary evaporation, drying and recrystallization to obtain a purified product.
In the second step, the separation and purification method comprises the following steps: and (5) recrystallizing.
In the fourth step, the separation and purification method comprises the following steps: extracting the crude product with distilled water, filtering, collecting filtrate, and evaporating to crystallize to obtain crystal; and then washing with absolute ethyl alcohol, and carrying out suction filtration to obtain the purified product, namely the asymmetric sodium benzenesulfonate Gemini surfactant.
The asymmetric benzene sulfonic acid sodium salt Gemini surfactant prepared by the method.
The invention has the following advantages:
in the present invention, the-COOH of dodecanoic acid and the-NH of p-aminophenol2Performing amide reaction to form polar group amide group, esterifying lauryl alcohol maleic acid monoester and 4- (dodecylamide) phenol to form two hydrophobic chain segments, and reacting with NaHSO3And carrying out sulfonation reaction to introduce two molecules of hydrophilic groups, namely sulfonic groups. The invention is based on cheap and easily available natural fatty acid, and has the advantages of wide source and low price. The surfactant prepared by the method has low critical micelle concentration (0.80 multiplied by 10)- 4mol/L) and high surface activity (gamma)cmc25.1mN/m), good emulsifying capacity (the emulsifying time is 283s) to grease, and the like, and because the molecules contain two molecular sulfonic acid groups, the material has good hydrophilicity, is environment-friendly and has excellent performance.
Drawings
FIG. 1 is a FT-IR spectrum of a benzenesulfonate Gemini surfactant.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The invention relates to a preparation method of an asymmetric benzenesulfonic acid sodium salt Gemini surfactant, which comprises the steps of carrying out amidation reaction on p-aminophenol and dodecanoic acid to synthesize 4- (dodecylamide) phenol, and carrying out esterification reaction on maleic anhydride and dodecanol to synthesize dodecanol maleic acidA monoester; then 4- (dodecylamide) phenol and lauryl maleic acid monoester are subjected to esterification reaction to synthesize a Gemini surfactant intermediate; finally reacting with NaHSO3And carrying out sulfonation reaction to obtain the asymmetric benzene sulfonic acid sodium salt Gemini surfactant.
First of all-COOH of dodecanoic acid and-NH of p-aminophenol2Amidation reaction to prepare 4- (dodecyl amide) phenol, esterification reaction of-OH of dodecanol and maleic anhydride to prepare dodecanol maleic monoester; then carrying out esterification reaction on the lauryl maleic acid monoester and 4- (dodecylamide) phenol to form two hydrophobic chain segments; finally reacting with NaHSO3The sulfonation reaction is carried out to introduce hydrophilic group sulfonic group, and the reaction equation is as follows:
note: r1Is an alkyl long chain of dodecanoic acid, R2-CH2Is an alkyl long chain of dodecanol.
The method is realized by the following steps:
the method comprises the following steps: taking 20.1 parts by mass of lauric acid and 11.5 parts by mass of p-aminophenol, adding ethyl acetate accounting for 0.5% of the total mass of the lauric acid and the p-aminophenol as a catalyst, taking a mixture of sodium bisulfite accounting for 0.4% of the total mass of the lauric acid and the p-aminophenol and sodium borohydride (the mixing ratio is m (sodium bisulfite): m (sodium borohydride): 3: 2) as an antioxidant, dissolving the p-aminophenol by taking dimethyl sulfoxide as a solvent, adding the mixture into a 250mL hydrothermal kettle, putting the hydrothermal kettle into an oven for reaction, heating to 160 ℃, reacting for 5 hours, separating and purifying to obtain a product, namely 4- (dodecylamide) phenol;
step two: adding 18.6 parts by mass of dodecanol and 9.8 parts by mass of maleic anhydride into a 250mL four-neck flask, adding anhydrous sodium acetate which is 0.1% of the total mass of the dodecanol and the maleic anhydride as a catalyst, heating to 85 ℃, reacting for 4 hours, separating and purifying to obtain dodecanol maleic acid monoester;
step three: taking 2.9 parts by mass of purified 4- (dodecylamide) phenol and 2.8 parts by mass of purified lauryl maleic acid monoester, adding zinc oxide which is 0.2% of the total mass of the 4- (dodecylamide) phenol and the lauryl maleic acid monoester as a catalyst into a 250mL hydrothermal kettle, putting the hydrothermal kettle into an oven for reaction, heating to 140 ℃, and reacting for 5 hours to obtain a product, namely 4- (dodecylamide) phenyl maleic acid diester;
step four: transferring the 4- (dodecylamide) phenyl maleic diester into a three-neck flask, adjusting the pH value to 7 by using a NaOH solution with the mass fraction of 30%, adding 10% of dodecanol maleic monoester salt with the mass fraction of the 4- (dodecylamide) phenyl maleic diester as a phase transfer catalyst, uniformly stirring, and slowly dropwise adding 30% of NaHSO3Solution, NaHSO3By mass of (d) n (diester): n (NaHSO)3) 1: 2.2, heating to 150 ℃, reacting for 5h, separating and purifying to obtain the asymmetric benzene sulfonic acid sodium salt Gemini surfactant.
In the first step, the separation and purification method comprises the following steps: extracting the crude product by mixing ethyl acetate and distilled water; and further carrying out rotary evaporation, drying and recrystallization to obtain a purified product.
In the second step, the separation and purification method comprises the following steps: and (5) recrystallizing.
In the fourth step, the separation and purification method comprises the following steps: extracting the crude product with distilled water, filtering, collecting filtrate, and evaporating to crystallize to obtain crystal; and then washing with absolute ethyl alcohol, and carrying out suction filtration to obtain the purified product, namely the asymmetric sodium benzenesulfonate Gemini surfactant.
Example 1:
the method comprises the following steps: taking 20.1 parts by weight of lauric acid and 11.5 parts by weight of p-aminophenol, adding ethyl acetate accounting for 0.5% of the total mass of the lauric acid and the p-aminophenol as a catalyst, taking a mixture of sodium bisulfite accounting for 0.4% of the total mass of the lauric acid and the p-aminophenol and sodium borohydride (the mixing ratio is m (sodium bisulfite): m (sodium borohydride): 3: 2) as an antioxidant, dissolving the p-aminophenol by taking dimethyl sulfoxide as a solvent, adding the mixture into a 250mL hydrothermal kettle, putting the hydrothermal kettle into an oven for reaction, heating to 160 ℃, and reacting for 5 hours to obtain a crude product, namely 4- (dodecylamide) phenol. Extracting the crude product by mixing ethyl acetate and distilled water; and further carrying out rotary evaporation, drying and recrystallization to obtain a purified product.
Step two: adding 18.6 parts by weight of dodecanol and 9.8 parts by weight of maleic anhydride into a 250mL four-neck flask, adding anhydrous sodium acetate which is 0.1 percent of the total mass of the dodecanol and the maleic anhydride as a catalyst, heating to 85 ℃, and reacting for 4 hours to obtain a crude product, namely dodecanol maleic acid monoester. Recrystallizing the crude product to obtain a purified product.
Step three: taking 2.9 parts by weight of purified 4- (dodecylamide) phenol and 2.8 parts by weight of purified lauryl maleic acid monoester, adding zinc oxide which is 0.2 percent of the total mass of the 4- (dodecylamide) phenol and the lauryl maleic acid monoester as a catalyst into a 250mL hydrothermal kettle, putting the hydrothermal kettle into a drying oven for reaction, heating to 140 ℃, and reacting for 5 hours to obtain a product, namely 4- (dodecylamide) phenyl maleic acid diester;
step four: transferring 4- (dodecylamide) phenyl maleic diester into a three-neck flask, adjusting the pH value to 7 by using a 30% NaOH solution, adding 10% of lauryl maleic monoester salt in the mass of the 4- (dodecylamide) phenyl maleic diester as a phase transfer catalyst, uniformly stirring, and slowly dropwise adding 30% of NaHSO3Solution (wherein NaHSO)3As n (diester): n (NaHSO)3) 1: 2.2), heating to 150 ℃, and reacting for 5h to obtain a crude product, namely the asymmetric benzenesulfonic acid sodium salt Gemini surfactant. Extracting the crude product with distilled water, filtering, collecting filtrate, and evaporating to crystallize to obtain crystal; then washing with absolute ethyl alcohol, and carrying out suction filtration to obtain a purified product.
Example 2: surface property determination of asymmetric benzenesulfonic acid sodium salt Gemini surfactant
Surfactants reduce the surface tension of water and are important parameters for evaluating the surface activity. In the research, the surface tension of a series of surfactant solutions with different concentrations is measured by a ring liquid-lifting membrane method, a curve of the surface tension changing along with the concentration is drawn, data are read from the inflection point of the curve, the concentration at the moment is the critical micelle concentration, and the corresponding surface tension is the surface tension (gamma) corresponding to the critical micelle concentrationcmc)。
With the increase of the concentration of the surfactant, the surface tension of the sodium benzenesulfonate Gemini surfactant is gradually reduced, and the critical micelle concentration is 0.80 multiplied by 10 respectively-4mol/L，γcmcThe concentration was 25.1 mN/m. Compared with the traditional surfactant, the surface activity of the surfactant is greatly improved.
Example 3: determination of emulsifying property of asymmetric benzenesulfonic acid sodium salt Gemini surfactant
The research adopts a water diversion time method to detect the emulsifying capacity of the modified rapeseed oil. As can be seen from Table 1, the emulsification time of the sodium benzenesulfonate Gemini surfactant to the modified rapeseed oil is 283s, and compared with the traditional sodium dodecylbenzenesulfonate, the sodium benzenesulfonate Gemini surfactant has better emulsibility and has good emulsification effect on grease.
TABLE 1 results of measuring emulsifying power of benzenesulfonate Gemini surfactant
| Surfactant type | Emulsifiability (time to divide water s) |
| Benzene sulfonate Gemini surfactant | 283 |
| SDBS | 176 |
Example 4: structural representation of asymmetric benzenesulfonic acid sodium salt Gemini surfactant
In the research, various functional groups in sodium benzenesulfonate Gemini surfactant molecules are preliminarily analyzed by an infrared spectroscopy method, and a final product is sampled by a KBr tabletting method and subjected to infrared analysis by a VECTOR-22 Fourier transform infrared spectrometer of Nicole corporation in America.
3472cm in FIG. 1-1The absorption peak of amide hydrogen is 2924cm-1、2852cm-1Is a stretching vibration absorption peak of methyl and methylene, 1720cm-1Characteristic absorption peak of ester carbonyl group, 1603cm-1Absorption peak of amide at 1409cm-1、1133cm-1Is an asymmetric stretching vibration absorption peak of-C-O-C-in ester, 1047cm-1And 624cm-1Is SO3A stretching vibration absorption peak.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (5)
1. The preparation method of the asymmetric benzenesulfonic acid sodium salt Gemini surfactant is characterized by comprising the following steps:
the method is realized by the following steps:
the method comprises the following steps: taking 20.1 parts by mass of lauric acid and 11.5 parts by mass of p-aminophenol, adding ethyl acetate accounting for 0.5% of the total mass of the lauric acid and the p-aminophenol as a catalyst, and taking a mixture of sodium bisulfite accounting for 0.4% of the total mass of the lauric acid and the p-aminophenol and sodium borohydride as an antioxidant, wherein the mixing ratio is m (sodium bisulfite): m (sodium borohydride) = 3: 2, dissolving p-aminophenol by using dimethyl sulfoxide as a solvent, adding the p-aminophenol into a 250mL hydrothermal kettle, putting the hydrothermal kettle into an oven for reaction, heating to 160 ℃, reacting for 5 hours, and separating and purifying to obtain a product 4- (dodecylamide) phenol;
step two: adding 18.6 parts by mass of dodecanol and 9.8 parts by mass of maleic anhydride into a 250mL four-neck flask, adding anhydrous sodium acetate accounting for 0.1% of the total mass of the dodecanol and the maleic anhydride as a catalyst, heating to 85 ℃, reacting for 4 hours, separating and purifying to obtain dodecanol maleic acid monoester;
step three: taking 2.9 parts by mass of purified 4- (dodecylamide) phenol and 2.8 parts by mass of purified lauryl maleic acid monoester, adding zinc oxide accounting for 0.2% of the total mass of the 4- (dodecylamide) phenol and the lauryl maleic acid monoester as a catalyst into a 250mL hydrothermal kettle, putting the hydrothermal kettle into an oven for reaction, heating to 140 ℃, and reacting for 5 hours to obtain a product, namely 4- (dodecylamide) phenyl maleic acid diester;
step four: transferring 4- (dodecylamide) phenyl maleic diester into a three-neck flask, adjusting the pH value to 7 by using a NaOH solution with the mass fraction of 30%, adding dodecanol maleic monoester salt with the mass fraction of 0.6% of the 4- (dodecylamide) phenyl maleic diester as a phase transfer catalyst, uniformly stirring, and slowly dropwise adding 30% of NaHSO3Solution, NaHSO3By mass of (d) n (diester): n (NaHSO)3) = 1: 2.2 weighing, heating to 150 ℃, reacting for 5h, separating and purifying to obtain the asymmetric sodium benzenesulfonate Gemini surfactant, wherein the structural formula is as follows:
in the formula, R1Is an alkyl long chain of dodecanoic acid, R2-CH2Is an alkyl long chain of dodecanol.
2. The method for preparing the asymmetric benzene sulfonic acid sodium salt Gemini surfactant as claimed in claim 1, characterized in that:
in the first step, the separation and purification method comprises the following steps: extracting the crude product by mixing ethyl acetate and distilled water; and further carrying out rotary evaporation, drying and recrystallization to obtain a purified product.
3. The method for preparing the asymmetric benzene sulfonic acid sodium salt Gemini surfactant as claimed in claim 1, characterized in that:
in the second step, the separation and purification method comprises the following steps: and (5) recrystallizing.
4. The method for preparing the asymmetric benzene sulfonic acid sodium salt Gemini surfactant as claimed in claim 1, characterized in that:
in the fourth step, the separation and purification method comprises the following steps: extracting the crude product with distilled water, filtering, collecting filtrate, and evaporating to crystallize to obtain crystal; and then washing with absolute ethyl alcohol, and carrying out suction filtration to obtain the purified product, namely the asymmetric sodium benzenesulfonate Gemini surfactant.
5. The Gemini surfactant of asymmetric sodium benzenesulfonate prepared according to the process of claim 1.
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