CN116478704A - Chlorine-free organic counter ion quaternary ammonium salt gemini surfactant and preparation method and application thereof - Google Patents
Chlorine-free organic counter ion quaternary ammonium salt gemini surfactant and preparation method and application thereof Download PDFInfo
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- -1 ion quaternary ammonium salt Chemical class 0.000 title claims abstract description 86
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000004659 sterilization and disinfection Methods 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 abstract description 9
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000009931 harmful effect Effects 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000005956 quaternization reaction Methods 0.000 abstract description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 239000003595 mist Substances 0.000 description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 13
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 description 6
- NVKSMKFBUGBIGE-UHFFFAOYSA-N 2-(tetradecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCOCC1CO1 NVKSMKFBUGBIGE-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229940098779 methanesulfonic acid Drugs 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
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- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- 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
- C09K23/38—Alcohols, e.g. oxidation products of paraffins
-
- 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
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
- C09K23/46—Ethers of aminoalcohols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of surfactants, and discloses a chlorine-free organic counter ion quaternary ammonium salt gemini surfactant, and a preparation method and application thereof. The chlorine-free organic counter ion quaternary ammonium salt gemini surfactant is prepared by mixing the organic counter ion quaternary ammonium salt gemini surfactant with the surfactant in the formula C 1 ～C 18 The alkyl glycidyl ether is added with quantitative alkyl diamine compound which is acidified by organic acid for quaternization reaction. The chlorine-free organic counter ion quaternary ammonium salt gemini surfactant contains two organic counter ions and two hydroxyl groups, and is synthesizedThe method has the advantages of simple process flow and mild conditions, does not generate toxic and harmful byproducts, and can avoid the corrosion hazard of halogen ions to equipment and environmental pollution in the preparation process.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to a chlorine-free organic counter ion quaternary ammonium salt gemini surfactant, and a preparation method and application thereof.
Background
Gemini surfactants can be seen as being formed by the attachment of two single chain surfactants via a spacer group. Compared with the common single-chain surfactant, the gemini surfactant has two tail chains, has a stronger hydrophobic effect, and the spacer group connected with the hydrophilic head group can effectively reduce electrostatic repulsive force, so that the gemini surfactant has the advantages of lower Krafft point, CMC, higher interfacial adsorption trend, easier formation of aggregates, special rheological property and the like. Gemini surfactants can be classified as cationic, anionic, nonionic, and zwitterionic depending on the charge of their head groups. Among them, quaternary ammonium salt type gemini surfactants have been studied most extensively, and are mainly nitrogen-containing organic amine derivatives. The quaternary ammonium salt gemini surfactant is widely applied to the fields of disinfection, oil exploitation, printing and dyeing auxiliary agents and the like.
The traditional quaternary ammonium salt gemini surfactant is generally synthesized by tertiary amine and toxic and corrosive quaternizing agent haloalkane through quaternization reaction, and has a certain environmental pollution problem. And the counter ion type of the common quaternary ammonium salt gemini surfactant is mainly halogen counter ion (Cl) - 、Br - And I - Etc.), the development of quaternary ammonium salt gemini surfactants is limited. To meet different demands, researchers have synthesized quaternary ammonium salt gemini surfactants with different functionalities by designing different structures, but these researches have often focused on improvements to hydrophobic hydrocarbon groups or hydrophilic head groups, which are limited in variety and difficult to meet the market demands.
The counter ion is used as an important component of the quaternary ammonium salt gemini surfactant, and influences the interfacial adsorption, micelle aggregation behavior and application performance of the surfactant. The organic counter ion is used for replacing the traditional halogen counter ion to prepare the novel quaternary ammonium salt type gemini surfactant, so that the property of a product can be improved, the corrosion to equipment can be reduced, and the variety of the quaternary ammonium salt type gemini surfactant is enriched. In addition, the introduction of organic counter ions is expected to further improve the potential of the quaternary ammonium salt type gemini surfactant in the aspects of sterilization, disinfection, metal corrosion inhibition and other application performances.
Therefore, a new quaternary ammonium salt gemini surfactant containing organic counter ions is needed to be designed in the field, so that the novel structure can be ensured, the types of the quaternary ammonium salt gemini surfactant are enriched, the simple synthesis method of the surfactant can be ensured, the process condition is mild, equipment is not corroded in the synthesis process, toxic and harmful byproducts are not generated, and the requirements of economy and environmental protection and the requirements of green chemistry are met.
Disclosure of Invention
The invention aims to provide a chlorine-free organic counter ion quaternary ammonium salt gemini surfactant, and a preparation method and application thereof, so as to solve the problems of corrosion hazard and environmental pollution of halogen ions to equipment in the preparation process of the traditional halogen-containing counter ion quaternary ammonium salt cationic gemini surfactant.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a chlorine-free organic counter ion quaternary ammonium salt gemini surfactant, which has the structural formula:
wherein R is C 1 ～C 18 Alkyl of (a); n is any integer from 2 to 10; x is a monobasic organic acid radical.
The invention also provides a preparation method of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant, which comprises the following steps:
(1) Mixing an alkyl diamine compound, an organic acid and a solvent, and reacting to obtain a protonated intermediate compound;
(2) And mixing the protonated intermediate compound, the alkyl glycidyl ether and the solvent, and reacting to obtain the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant.
Preferably, the structural formula of the alkyl diamine compound is:wherein n is any integer from 2 to 10; the organic acid is a monobasic organic acid; the structural formula of the alkyl glycidyl ether is as follows: />Wherein R is C 1 ～C 18 Alkyl of (a); the solvents in the step (1) and the step (2) are independently C 1 ～C 4 Lower alcohols of (3).
Preferably, the molar ratio of the alkyl diamine compound to the organic acid is 1:2 to 2.2; the molar ratio of the alkyl diamine compound to the alkyl glycidyl ether is 1:2 to 2.4.
Preferably, the total mass of the solvent in the step (1) and the step (2) is 30 to 50% of the total mass of the solvent, the organic acid and the alkyl glycidyl ether.
Preferably, the mass ratio of the solvent in the step (1) to the solvent in the step (2) is 1 to 2:1 to 4.
Preferably, in the step (1), the specific steps of mixing are: the organic acid and the solvent are mixed and then added dropwise to the alkyl diamine compound.
Preferably, in the step (1), the reaction time is 0.5 to 2 hours.
Preferably, in the step (2), the reaction temperature is 80 to 120 ℃ and the reaction time is 4 to 12 hours.
The invention also provides application of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant in disinfection, petroleum exploitation and printing and dyeing.
Compared with the prior art, the invention has the following beneficial effects:
1. the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant provided by the invention contains two organic counter ions and two hydroxyl groups, is an organic compound with stable structure, has a novel molecular structure, and can enrich the diversity of the quaternary ammonium salt type cationic gemini surfactant;
2. the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant disclosed by the invention has the advantages of simple preparation process, easiness in obtaining reaction raw materials, mild reaction conditions, environment friendliness in the whole reaction process, no use of corrosive halogenated alkyl reagent which is easy to cause environmental pollution, avoidance of corrosion of halogen elements to equipment and effective reduction of toxicity and irritation of products.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic spectrum of the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant obtained in examples 1 and 2, wherein b is 9 corresponding to the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant obtained in example 1, and b is 11 corresponding to the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant obtained in example 2;
FIG. 2 is a nuclear magnetic spectrum of the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant of examples 3 and 4, wherein b is 9 for the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant of example 3 and b is 11 for the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant of example 4;
FIG. 3 is a nuclear magnetic resonance spectrum of the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant obtained in examples 5 and 6, wherein b is 9 corresponding to the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant obtained in example 5, and b is 11 corresponding to the chlorine-free organic counter ion quaternary ammonium salt type gemini surfactant obtained in example 6.
Detailed Description
The invention provides a chlorine-free organic counter ion quaternary ammonium salt gemini surfactant, which has the structural formula:
wherein R is preferably C 1 ～C 18 More preferably C 2 ～C 16 Alkyl of (a); n is preferably an integer of 2 to 10, and more preferably an integer of 3 to 8; x is preferably a monobasic organic acid radical, more preferably formate, methanesulfonate or benzenesulfonate.
The invention also provides a preparation method of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant, which comprises the following steps:
(1) Mixing an alkyl diamine compound, an organic acid and a solvent, and reacting to obtain a protonated intermediate compound;
(2) And mixing the protonated intermediate compound, the alkyl glycidyl ether and the solvent, and reacting to obtain the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant.
In the present invention, the structural formula of the alkyl diamine compound is preferably:wherein n is preferably an integer of 2 to 10, more preferably an integer of 3 to 8; the organic acid is preferably a monobasic organic acid, further preferably formic acid, acetic acid, propionic acid, butyric acid, lactic acid, methanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid; the structural formula of the alkyl glycidyl ether is preferably: />Wherein R is preferably C 1 ～C 18 More preferably C 2 ～C 16 Alkyl of (a); the solvents in the step (1) and the step (2) are independent and are preferably C 1 ～C 4 Lower alcohols of (C) are further preferred 2 ～C 3 Lower alcohols of (3).
In the present invention, the molar ratio of the alkyl diamine compound and the organic acid is preferably 1:2 to 2.2, more preferably 1:2.1 to 2.2; the molar ratio of the alkyl diamine compound to the alkyl glycidyl ether is preferably 1:2 to 2.4, more preferably 1:2.2 to 2.3.
The total mass of the solvent in the step (1) and the step (2) in the present invention is preferably 30 to 50% by mass, more preferably 40 to 50% by mass, of the total mass of the solvent, the organic acid and the alkyl glycidyl ether.
The mass ratio of the solvent in the step (1) to the solvent in the step (2) is preferably 1-2: 1 to 4, more preferably 1.2 to 1.8:2 to 3.
In the step (1) of the invention, the specific steps of mixing are as follows: mixing an organic acid and a solvent, and then dropwise adding the mixture into an alkyl diamine compound; the dropping speed is preferably 3 to 5 s/drop, more preferably 4 s/drop.
In the step (1) of the present invention, the reaction time is preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours.
In step (1) according to the invention, the reaction is ended at a time which is based on the free amine content of the reaction vessel of < 2%.
In the step (2) of the present invention, the specific steps of mixing the protonated intermediate compound, the alkyl glycidyl ether and the solvent are as follows: after the acid mist in the reaction vessel to be charged with the protonated intermediate compound has disappeared, the alkyl glycidyl ether and the solvent are added.
In the step (2) of the present invention, the reaction temperature is preferably 80 to 120 ℃, and more preferably 90 to 110 ℃; the reaction time is preferably 4 to 12 hours, more preferably 6 to 10 hours.
In the step (2) of the present invention, the reaction is carried out under stirring, and the stirring speed is preferably 800 to 1000r/min, more preferably 900 to 950r/min.
In the step (2), after the reaction is finished, the obtained product is subjected to reduced pressure distillation, recrystallization and drying in sequence to obtain the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant;
the purpose of the reduced pressure distillation is to remove the solvent from the resulting product;
the reagent used for recrystallization is ethyl acetate or methanol;
the drying temperature is preferably 60 to 80 ℃, and more preferably 70 to 75 ℃; the drying time is preferably 0.5 to 1 hour, more preferably 40 to 50 minutes.
The invention also provides application of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant in disinfection, petroleum exploitation and printing and dyeing.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant comprises the following steps:
s1, 8.6g (0.05 mol) of N, N, N ', N' -1, 6-tetramethylhexamethylenediamine (N is 6) is taken in a four-neck flask, an N-propanol solution of formic acid (5.44 g of N-propanol, 4.60g of formic acid and 0.1 mol) is added dropwise at a rate of 3S/drop while stirring, the rotating speed is 800r/min, heat is released and acid mist is generated during the dropwise adding process, the free amine content is 0.2% measured after 0.5h of reaction, and the reaction is ended.
S2, acid generated by the reaction in S1After the mist disappeared, dodecyl glycidyl ether (R is C) 12 ) (n-propanol (10.89 g, dodecyl glycidyl ether (24.9 g,0.1 mol)) at 90 ℃ C. With stirring at 800r/min for 6h to give a yellow clear and transparent product; the solvent of the product is removed by reduced pressure distillation, the product is recrystallized by ethyl acetate and dried for 40min at 80 ℃ to obtain the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant with the yield of 92.1 percent.
Example 2
The preparation method of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant comprises the following steps:
s1, 5.68g (0.033 mol) of N, N, N ', N' -1, 6-tetramethylhexamethylenediamine (N is 6) is taken in a four-neck flask, an N-propanol solution of formic acid (8.99 g of N-propanol and 3.34g of formic acid and 0.0726 mol) is added dropwise at a speed of 3S/drop while stirring, the rotating speed is 950r/min, heat is released and acid mist is generated in the dropping process, the free amine content is 0.2% as measured in 0.5h of reaction, and the reaction is ended.
S2, adding tetradecyl glycidyl ether (R is C) after acid mist generated by the reaction in S1 disappears 14 ) (19.77 g of n-propanol and 19.72g of tetradecyl glycidyl ether, 0.0729 mol) at 90 ℃ for 10 hours under the condition of stirring speed of 800r/min to obtain a yellow, clear and transparent product; the solvent of the product is removed by reduced pressure distillation, the product is recrystallized by ethyl acetate and dried for 40min at 80 ℃ to obtain the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant, and the yield is 95.6%.
Example 3
The preparation method of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant comprises the following steps:
s1, 8.6g (0.05 mol) of N, N, N ', N' -1, 6-tetramethylhexamethylenediamine (N is 6) is taken in a four-neck flask, an N-propanol solution of methanesulfonic acid (12.07 g of N-propanol, 10.57g of methanesulfonic acid and 0.11 mol) is dropwise added at a rate of 3S/drop while stirring, the rotating speed is 800r/min, heat is released and acid mist is generated in the dropwise adding process, the free amine content is 0.3% when the free amine content is measured in 1h of reaction, and the reaction is ended.
S2, after the acid mist generated by the reaction in S1 disappears, adding dodecyl glycidyl ether (R is C) 12 ) N-propanol (25.19 g n-propanol, 29.09g dodecyl glycidyl ether, 0.12 mol) at 90℃for 6h with stirring at 800r/min to give a yellow, clear and transparent product; the solvent of the product is removed by reduced pressure distillation, ethanol is used for recrystallization, and the organic counter ion quaternary ammonium salt gemini surfactant without chlorine is obtained after drying for 40min at 80 ℃, and the yield is 90.7%.
Example 4
The preparation method of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant comprises the following steps:
s1, taking 6g (0.0344 mol) of N, N, N ', N' -1, 6-tetramethylhexamethylenediamine (N is 6) into a four-neck flask, dropwise adding an N-propanol solution of methanesulfonic acid (10 g of N-propanol, 6.81g of methanesulfonic acid and 0.0709 mol) at a rate of 3S/drop while stirring, keeping the rotating speed at 900r/min, releasing heat and generating acid mist during the dropwise adding process, and measuring the free amine content to be 0.3% after 1h of reaction, and ending the reaction.
S2, adding tetradecyl glycidyl ether (R is C) after acid mist generated by the reaction in S1 disappears 14 ) N-propanol (11.1 g of n-propanol, 18.84g of tetradecyl glycidyl ether, 0.0697 mol) at 90 ℃ for 10 hours under the condition of stirring speed of 800r/min to obtain yellow, clear and transparent product; the solvent of the product is removed by reduced pressure distillation, ethanol is used for recrystallization, and the organic counter ion quaternary ammonium salt gemini surfactant without chlorine is obtained after drying for 40min at 80 ℃, and the yield is 96.5%.
Example 5
The preparation method of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant comprises the following steps:
s1, 8.6g (0.05 mol) of N, N, N ', N' -1, 6-tetramethylhexamethylenediamine (N is 6) is taken in a four-neck flask, an N-propanol solution of benzenesulfonic acid (10.97 g of N-propanol, 17.08g of benzenesulfonic acid and 0.108 mol) is dropwise added at a rate of 3S/drop while stirring, the rotating speed is 1000r/min, heat is released and acid mist is generated during the dropwise addition, the free amine content is 0.4% measured after 1.5h of reaction, and the reaction is ended.
S2, after the acid mist generated by the reaction in S1 disappears, adding dodecyl glycidyl ether (R is C) 12 ) N-propanol (18.28 g n-propanol, 28.64g dodecyl glycidyl ether, 0.118 mol) at 90 ℃ for 6h under the condition of stirring speed of 800r/min to obtain yellow, clear and transparent product; the solvent of the product is removed by reduced pressure distillation, the product is recrystallized by ethyl acetate and dried for 40min at 80 ℃ to obtain the organic counter ion quaternary ammonium salt gemini surfactant without chlorine, and the yield is 93.5%.
Example 6
The preparation method of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant comprises the following steps:
s1, taking 4.47g (0.026 mol) of N, N, N ', N' -1, 6-tetramethylhexamethylenediamine (N is 6) into a four-neck flask, dropwise adding an N-propanol solution of benzenesulfonic acid (7.27 g of N-propanol, 9.05g of benzenesulfonic acid and 0.0572 mol) at a speed of 3S/drop while stirring, wherein the rotating speed is 900r/min, releasing heat and generating acid mist in the dropwise adding process, and reacting for 1.5h to obtain the free amine content of 0.4%, and ending the reaction.
S2, adding tetradecyl glycidyl ether (R is C) after acid mist generated by the reaction in S1 disappears 14 ) N-propanol (8.54 g of n-propanol, 12.1g of tetradecyl glycidyl ether, 0.0574 mol) at 90 ℃ for 10 hours under the condition of stirring speed of 800r/min to obtain yellow, clear and transparent product; the solvent of the product is removed by reduced pressure distillation, the product is recrystallized by ethyl acetate and dried for 40min at 80 ℃ to obtain the organic counter ion quaternary ammonium salt gemini surfactant without chlorine, and the yield is 97.4%.
As can be seen from FIGS. 1 to 3 and examples 1 to 6, the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant obtained by the invention has high yield (90.7 to 97.4%), simple preparation process, easy acquisition of required raw materials, no halogen, no corrosion of halogen ions to equipment and no environmental pollution, and meets the requirements of economy and environmental protection and green chemistry.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The chlorine-free organic counter ion quaternary ammonium salt gemini surfactant is characterized by having the structural formula:
wherein R is C 1 ～C 18 Alkyl of (a); n is any integer from 2 to 10; x is a monobasic organic acid radical.
2. The method for preparing the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant according to claim 1, which is characterized by comprising the following steps:
(1) Mixing an alkyl diamine compound, an organic acid and a solvent, and reacting to obtain a protonated intermediate compound;
(2) And mixing the protonated intermediate compound, the alkyl glycidyl ether and the solvent, and reacting to obtain the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant.
3. The method for preparing chlorine-free organic counter ion quaternary ammonium salt gemini surfactant according to claim 2, wherein the alkyl diamine compound has a structural formula:wherein n is any integer from 2 to 10; the organic acid is a monobasic organic acid; the structural formula of the alkyl glycidyl ether is as follows: />Wherein R is C 1 ～C 18 Alkyl of (a); the solvents in the step (1) and the step (2) are independently C 1 ～C 4 Lower alcohols of (3).
4. The method for preparing chlorine-free organic counter ion quaternary ammonium salt gemini surfactant according to claim 3, wherein the molar ratio of the alkyl diamine compound to the organic acid is 1:2 to 2.2; the molar ratio of the alkyl diamine compound to the alkyl glycidyl ether is 1:2 to 2.4.
5. The method for preparing chlorine-free organic counter ion quaternary ammonium salt gemini surfactant according to any one of claims 2 to 4, wherein the total mass of the solvent in step (1) and step (2) is 30 to 50% of the total mass of the solvent, the organic acid and the alkyl glycidyl ether.
6. The method for preparing chlorine-free organic counter ion quaternary ammonium salt gemini surfactant according to claim 5, wherein the mass ratio of the solvent in the step (1) to the solvent in the step (2) is 1-2: 1 to 4.
7. The method for preparing chlorine-free organic counter ion quaternary ammonium salt gemini surfactant according to claim 6, wherein in the step (1), the specific steps of mixing are as follows: the organic acid and the solvent are mixed and then added dropwise to the alkyl diamine compound.
8. The method for preparing chlorine-free organic counter ion quaternary ammonium salt gemini surfactant according to claim 7, wherein in the step (1), the reaction time is 0.5-2 h.
9. The method for preparing chlorine-free organic counter ion quaternary ammonium salt gemini surfactant according to claim 6, 7 or 8, wherein in the step (2), the reaction temperature is 80-120 ℃ and the reaction time is 4-12 h.
10. Use of the chlorine-free organic counter ion quaternary ammonium salt gemini surfactant according to claim 1 for disinfection, oil exploitation and printing.
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