CN103611471A - Carboxylate surfactant containing aryl groups and preparation method thereof - Google Patents
Carboxylate surfactant containing aryl groups and preparation method thereof Download PDFInfo
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- CN103611471A CN103611471A CN201310664201.7A CN201310664201A CN103611471A CN 103611471 A CN103611471 A CN 103611471A CN 201310664201 A CN201310664201 A CN 201310664201A CN 103611471 A CN103611471 A CN 103611471A
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Abstract
The invention relates to a carboxylate surfactant containing aryl groups and a preparation method thereof. The surfactant has the molecular structure as shown in the specification, and in the molecular structure R is equal to C8H17, C10H21, C12H25Or and C14H29Ar=any aryl groups that contain no more than 3 aryl groups, wherein R is any one of straight chain alkyls C8H17, C10H21, C12H25 or C14H29; and Ar represents the aryl groups with the number of aryls in the molecule not greater than 3. The preparation method of the surfactant mainly comprises the following three steps: synthesis of 2-bromoacid ester; synthesis of 2-aryloxy alkyl ester; and saponification. The surfactant containing the aryl groups can be used as a fluorescent probe with surface activity to probe the microstructure of a mesoscopic aggregate, can be further used in a surfactant complex system, and has important applications in the fields of detergents, drug releasers, skincare articles and the like.
Description
Technical field
The present invention relates to a class and contain carboxylate surface active agent of aromatic group and preparation method thereof.This surfactant has good water-soluble, can be used for, in surfactant compound system and fluorescence analysis method, belonging to surfactant scientific domain.
Background technology
Surfactant molecule has amphiphilic structure, can form multiple gathering pattern in the aqueous solution.The performance that Jie sees aggregation has often determined surfactant system macroscopic property, thereby has a wide range of applications in a plurality of fields.And the form of surfactant Jie sight aggregation and character and molecular structure are closely related.The research of Surfactant structure-performance is the focus of surfactant scientific research always.The change of any structural element, all likely affects the self-organizing performance of surfactant, and then has influence on form and the character of aggregation.
What surfactant formed that the process of aggregation relies on is intermolecular interaction force, and modal is electrostatic interaction between a base or the hydrophobic interaction between dipole effect and hydrophobic chain.In fact, intermolecular interaction also comprises π-π effect between hydrogen bond, aromatic ring etc.If autotelic introducing can produce the functional group of above-mentioned effect in the molecular structure of surfactant, just likely rely on the interaction between different kinds of molecules, construct the surfactant aggregates with novel structure.The present invention proposes a class containing structure of the surfactant of aromatic group and preparation method thereof, be convenient for people to research containing the self-organizing behavior of aromatic group surfactant and the relation between molecular structure, be also conducive to deepen the understanding of people to interaction of molecules rule.
Summary of the invention
The present invention relates to a class and contain carboxylate surface active agent of aromatic group and preparation method thereof.With aliphatic acid, phenol etc., as main initiation material, a synthetic class is containing the carboxylate surface active agent of aromatic group.
Containing the carboxylate surface active agent of aromatic group, structural formula is as follows:
R=C
8H
17，C
10H
21，C
12H
25Or?C
14H
29
Ar=any?aryl?groups?that?contain?no?more?than3aryl?groups
A kind of method containing aromatic group carboxylate surface active agent described in preparation, with aliphatic acid, react and obtain acyl chlorides with thionyl chloride or oxalyl chloride, the acyl chlorides obtaining reacts with bromine and obtains 2-bromacyl chloride again, in 2-bromacyl chloride, drip methyl alcohol and obtain 2-bromo acid esters, 2-bromo acid esters reacts with phenol and obtains 2-aryloxy alkyl ester, and 2-aryloxy alkyl ester obtains the carboxylate surface active agent containing aromatic group through saponification.Concrete reaction equation is as follows:
The synthetic route that contains the carboxylate surface active agent of aromatic group:
In the reaction of synthetic 2-bromo acid esters, to react and obtain acyl chlorides with thionyl chloride or oxalyl chloride with aliphatic acid, acyl chlorides reacts with simple substance bromine and obtains 2-bromacyl chloride again, in 2-bromacyl chloride, drip methyl alcohol or ethanol and obtain 2-bromo acid esters, wherein the mol ratio of aliphatic acid and chloride reagent is 1:1～5, the mol ratio of aliphatic acid and bromine is 1:1～10, and the mol ratio of aliphatic acid and alcohol is 1:1～20.The crude product obtaining is through decompression distillation, and collecting boiling point is the cut of 195 ℃ (5mmHg), obtains water white liquid.
In the reaction of synthetic 2-aryloxy alkyl ester, the mol ratio of 2-bromo acid esters and phenol is 1:1～10, and reaction condition is at 90 ℃, to react 8～20 hours, and solvent for use is DMF, and crude product ester is through silica gel column chromatogram separating purification.
In the reaction of the synthetic carboxylate surface active agent containing aromatic group, the mol ratio of 2-aryloxy alkyl ester and NaOH is 1:1～5, reaction condition is at 80 ℃, to react 8～20 hours, and solvent for use is the mixed solvent that mix with arbitrary proportion any solvents such as absolute methanol, absolute ethyl alcohol or isopropyl alcohol or they.
The present invention obtains following effect:
1. the present invention, mainly through the synthetic carboxylate surface active agent containing aromatic group of three-step reaction, has explored concrete reaction condition and has obtained good productive rate.
2. the carboxylate surface active agent containing aromatic group synthesizing, its critical micelle concentration cmc can reach 3.24 * 10
-3mol/L
-1, shown stronger ability of aggregation.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic resonance of embodiment target product
1hNMR spectrogram, solvent for use is CD
3oD.
Fig. 2 is the surface tension curve of embodiment target product, in the alkali lye of pH12, records.
The specific embodiment
The present embodiment is for illustrating the protection domain of unrestricted this patent.
Containing synthesizing of aromatic group surfactant 2-phenoxy group sodium laurate, its synthetic route is as follows:
(1) preparation of 2-bromolauric acid methyl esters
In three-necked bottle, add laurate (130.2g, 0.65mol), load onto reflux condensing tube, device for absorbing tail gas and constant pressure funnel.First slowly will bathe temperature rise to 50 ℃, solid is melted, then slowly drip thionyl chloride (105.2g, 0.81mol).After reaction finishes, add 0.5g iodine as catalyst, temperature is risen to 90 ℃, slowly drip the bromine (121.1g, 0.758mol) being dried through the concentrated sulfuric acid, about 5h drips off, and continues reaction 3h after dripping.Temperature is down to 55 ℃, stirs the lower 100ml of dropping absolute methanol, and 4h again refluxes after adding.Reaction is cooled to room temperature, with saturated sodium sulfite solution, washes away bromine residual in crude product, standing, minute water-yielding stratum, organic layer washes with water, and with anhydrous magnesium sulfate drying, collecting boiling point is the cut of 195 ℃ (5mmHg), obtains water white liquid, productive rate 78.3%.
The preparation of (, 2) 2-phenoxy group methyl dodecanoate
In eggplant-shape bottle, add K
2cO
3(30g, 0.217mol) and appropriate DMF, N
2protection, starts magnetic stirring apparatus, stirs after 0.5h, adds phenol (10.2g, 0.108mol), is warming up to 60 ℃, then adds 2-bromolauric acid methyl esters (20.0g, 0.068mol), is warming up to 80 ℃ and continues reaction 6h after 1h.Question response liquid is down to after room temperature, under agitation to reactant liquor, adds suitable quantity of water, with appropriate petroleum ether extraction three times, merge organic layer, after organic layer washes three times with water, rotary evaporation goes out whole benzinums and part water, and the thick product obtaining obtains sterling with silica gel column chromatography separation, productive rate 75.1%.
(3) 2-phenoxy group sodium laurate is synthetic
In eggplant-shape bottle, add 2-phenoxy group methyl dodecanoate (14.3g, 0.047mol), NaOH (2.06g, 0.051mol) and appropriate absolute ethyl alcohol, 70 ℃ of magnetic agitation backflow 12h, question response liquid is cooled to room temperature, revolve and steam except desolventizing, solids washed with acetone 4～6 times, vacuum drying, obtain 2-phenoxy group sodium laurate, productive rate 92.5%.
The capillary mensuration of 2-phenoxy group sodium laurate
2-phenoxy group sodium laurate is dissolved in the alkali lye of pH12, prepares the surfactant solution of serial variable concentrations, then at 25 ℃, measure the equilibrium surface tension of this surfactant.
Claims (8)
1. a class is containing the carboxylate surface active agent of aromatic group, and its molecular structure is as follows:
R=C
8H
17，C
10H
21，C
12H
25Or?C
14H
29
Ar=any?aryl?groups?that?contain?no?more?than3aryl?groups
Wherein R is straight chained alkyl C
8h
17, C
10h
21, C
12h
25or C
14h
29in any one; Ar represents that molecule includes aromatic ring number and is no more than 3 aromatic group.
2. a class, containing the carboxylate surface active agent of aromatic group, is characterized in that, this surfactant has water-soluble and lower Krafft point preferably.
3. a class, containing the carboxylate surface active agent of aromatic group, is characterized in that, the ability of aggregation of this surfactant is stronger, and its critical micelle concentration is lower than 5mmolL
-1.
4. a class is prepared the carboxylate surface active agent containing aromatic group claimed in claim 1, and preparation process mainly comprises the synthetic of 2-bromo acid esters, synthetic and saponification three steps of 2-aryloxy alkyl ester.Its synthetic route is as follows:
5. the preparation process containing aromatic group surfactant according to claim 4, is characterized in that, wherein R is straight chained alkyl C
8h
17, C
10h
21, C
12h
25or C
14h
29in any one; Ar represents that molecule includes aromatic ring number and is no more than 3 aromatic group; R1 is methyl or ethyl.
6. the preparation process containing aromatic group surfactant according to claim 4, is characterized in that, in the process of synthetic 2-aryloxy alkyl ester, solvent for use is DMF, and reaction temperature is 60 ℃-100 ℃.
7. the preparation process containing aromatic group surfactant according to claim 4, is characterized in that, the purification process of 2-aryloxy alkyl ester is that silica gel column chromatography is separated.
8. the preparation process containing aromatic group surfactant according to claim 4, it is characterized in that, in the saponification process of 2-aryloxy alkyl ester, solvent for use is the mixed solvent that mix with arbitrary proportion any solvents such as absolute methanol, absolute ethyl alcohol or isopropyl alcohol or they.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179111A (en) * | 2016-07-16 | 2016-12-07 | 江南大学 | A kind of viscoelastic solution formed by carboxylate anion's surfactant and two polyquaternary ammonium salt |
| CN106512848A (en) * | 2016-09-30 | 2017-03-22 | 武汉工程大学 | Cyclic quaternary ammonium salt gemini surfactant and preparation method thereof |
| CN107088386A (en) * | 2017-06-14 | 2017-08-25 | 江南大学 | A kind of Long carbon chain carboxylate surface active agent of high-dissolvability and its viscoelastic solution of formation |
| CN110585991A (en) * | 2019-09-23 | 2019-12-20 | 江南大学 | Two-phase transition emulsion with stable carboxylate surfactant and nanoparticles |
| CN111054263A (en) * | 2019-12-23 | 2020-04-24 | 万华化学集团股份有限公司 | Fluorescent surfactant and preparation method thereof |
| CN111635390A (en) * | 2020-06-30 | 2020-09-08 | 江南大学 | Low-foam alpha-tocopherol surfactant and preparation method thereof |
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| US4867972A (en) * | 1985-05-06 | 1989-09-19 | Rhone-Poulenc Specialites Chimiques | Novel surface-active compositions containing polydicarboxylic acid polymer and surfactant |
| CN1730144A (en) * | 2004-08-04 | 2006-02-08 | 大庆高新区鑫诺精细化工有限公司 | Carboxylate surface active agent, its formula system and its application in tertiary oil extraction |
| CN101723822A (en) * | 2008-10-29 | 2010-06-09 | 天津工业大学 | Polymerizable negative ion surfactant and preparing method thereof |
-
2013
- 2013-12-06 CN CN201310664201.7A patent/CN103611471B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4867972A (en) * | 1985-05-06 | 1989-09-19 | Rhone-Poulenc Specialites Chimiques | Novel surface-active compositions containing polydicarboxylic acid polymer and surfactant |
| CN1730144A (en) * | 2004-08-04 | 2006-02-08 | 大庆高新区鑫诺精细化工有限公司 | Carboxylate surface active agent, its formula system and its application in tertiary oil extraction |
| CN101723822A (en) * | 2008-10-29 | 2010-06-09 | 天津工业大学 | Polymerizable negative ion surfactant and preparing method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179111A (en) * | 2016-07-16 | 2016-12-07 | 江南大学 | A kind of viscoelastic solution formed by carboxylate anion's surfactant and two polyquaternary ammonium salt |
| CN106512848A (en) * | 2016-09-30 | 2017-03-22 | 武汉工程大学 | Cyclic quaternary ammonium salt gemini surfactant and preparation method thereof |
| CN106512848B (en) * | 2016-09-30 | 2018-07-17 | 武汉工程大学 | A kind of cyclic quaternary ammonium salts Gemini surface active agent and preparation method thereof |
| CN107088386A (en) * | 2017-06-14 | 2017-08-25 | 江南大学 | A kind of Long carbon chain carboxylate surface active agent of high-dissolvability and its viscoelastic solution of formation |
| CN107088386B (en) * | 2017-06-14 | 2019-06-07 | 江南大学 | A kind of Long carbon chain carboxylate surface active agent of high-dissolvability and its viscoelastic solution of formation |
| CN110585991A (en) * | 2019-09-23 | 2019-12-20 | 江南大学 | Two-phase transition emulsion with stable carboxylate surfactant and nanoparticles |
| CN110585991B (en) * | 2019-09-23 | 2020-10-09 | 江南大学 | Two-phase transition emulsion with stable carboxylate surfactant and nanoparticles |
| CN111054263A (en) * | 2019-12-23 | 2020-04-24 | 万华化学集团股份有限公司 | Fluorescent surfactant and preparation method thereof |
| CN111635390A (en) * | 2020-06-30 | 2020-09-08 | 江南大学 | Low-foam alpha-tocopherol surfactant and preparation method thereof |
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Effective date of registration: 20181017 Address after: 050000 288 Pearl River Road, hi tech Industrial Development Zone, Shijiazhuang, Hebei Patentee after: HANLIN BIOTECHNOLOGY Co.,Ltd. Address before: 214122 College of chemistry and materials engineering, Jiangnan University 1800, Lihu Avenue, Wuxi, Jiangsu Patentee before: Jiangnan University |
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Address after: No. 369 Lijiang Road, High tech Industrial Development Zone, Shijiazhuang City, Hebei Province, 050000 Patentee after: HANLIN BIOTECHNOLOGY Co.,Ltd. Address before: 050000 288 Pearl River Road, hi tech Industrial Development Zone, Shijiazhuang, Hebei Patentee before: HANLIN BIOTECHNOLOGY Co.,Ltd. |
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