CN103691360B - A kind of oligo surfactant prepared by tetramethylethylenediamine and preparation method thereof - Google Patents
A kind of oligo surfactant prepared by tetramethylethylenediamine and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of oligo surfactant prepared by tetramethylethylenediamine and preparation method thereof.Containing the cationic oligo surfactant of phenyl with benzene or substituted benzene for core, molecular structure is star-like arrangement mode, and general formula is: (m-n)
3ph.The present invention also provides this to contain the preparation method of the cationic oligo surfactant of phenyl, and it is with 4-methyl-diaminopropane or tetramethylethylenediamine, and brominated alkanes and 2,4,6-trisbromomethyl trimethylbenzene are that Material synthesis contains the cationic oligo surfactant of phenyl.The present invention utilizes with benzene or substituted benzene for core, and molecular structure, based on the oligo surfactant of star-like arrangement mode, has surface-active high, the feature that self assembly ability is strong, is the desirable template preparing ordered mesoporous material.
Description
Technical field
The present invention relates to a kind of oligo surfactant prepared by tetramethylethylenediamine and preparation method thereof, particularly a kind of utilize tetramethylethylenediamine to prepare containing the cationic oligo surfactant of phenyl and preparation method thereof, belong to chemical material technical field.
Background technology
In recent years the oligo surfactant occurred or poly surfactant (Oligomeric surfactants), by two or more amphiphilic composition, at the class novel surfactant that its base or close head Ji Chu are connected together by chemical bond-linking by spacer group and are formed.Compared with traditional surfactant, it is lower that it has critical micelle concentration, wetability is good, surface tension, Krafft point is lower, the surface-active that the special grade of accumulation shape is higher, therefore relatively low applied amount can obtain higher effect, so development oligo surfactant has great importance for the character and the self assembly ability of itself studying surfactant.From when come, oligo surfactant is worldwide all treated as a very promising exploration project, the hot issue that the surfactant that exploitation performance is more superior receives much concern especially.
Bunton in 1971 etc. take the lead in having synthesized the cationic oligo surfactant of gang.Menger has synthesized the two hydrocarbon chain surfactant of double ion head base that rigidity base connects in 1991, and called after Geminis.Rosen group adopts the name of " Gemini ", and system synthesis and the Gemini surface active that have studied oxygen ethene and oxypropylene flexible group and be connected, then people have just really systematically carried out the research work of this respect.Zana group is also connected clique with methylene, have studied a series of Quaternary ammonium gemini surfactants.
Chinese patent literature CN102614805A(application number 201210042527.1) disclose a kind of Quaternary Ammonium Gemini Surfactants.Primarily of fat tertiary amine and halogenated hydrocarbons, back flow reaction in organic solvent obtains described Quaternary Ammonium Gemini Surfactants at least 24 hours.
Chinese patent literature CN101279219A(application number 200810052006.8) disclose a kind of GEMINI quaternary ammonium salt cationic surfactant with bactericidal effect.Two halides and fatty amine are reacted by the preparation method of GEMINI quaternary cationics of the present invention in organic solvent, namely dibromo is used for thing and alkyl tertiary amine in ethanol (or acetone, ethyl acetate) solution, under room temperature or low-heat, condition of normal pressure, carry out the method for chemical reaction, synthesize a series of GEMINI quaternary ammonium salt cationic surfactant.
The appearance of novel surfactant oligo surfactant, has broken the structure that conventional surfactant list hydrophobic group single parent is water base, has made it have the performance more more excellent than conventional surfactant.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of oligo surfactant prepared by tetramethylethylenediamine and preparation method thereof is provided.
A kind of containing the cationic oligo surfactant of phenyl, structural formula is as follows:
Wherein: 6Br
-refer to hydrophilic cations with bromine counter ion.
The above-mentioned preparation method containing the cationic oligo surfactant of phenyl, step is as follows:
(1), after being mixed with the bromotetradecane being dissolved in organic solvent by the excessive tetramethylethylenediamine be dissolved in organic solvent, the monolateral quaterisation 40 ~ 60 hours of tetramethyl diamines under heated reflux condition, is carried out, purified, obtained intermediate product;
(2) intermediate product that step (1) is obtained is dissolved in organic solvent, then add and be dissolved in 2 of organic solvent, 4,6-trisbromomethyl trimethylbenzene, intermediate product and 2,4, the mol ratio of 6-trisbromomethyl trimethylbenzene is (3 ~ 4): 1, through heating reflux reaction 24 ~ 48 hours, purifying, obtained containing the cationic oligo surfactant of phenyl.
Preferred according to the present invention, the organic solvent in described step (1) is absolute ethyl alcohol.
Preferred according to the present invention, the tetramethylethylenediamine in described step (1) and the mixed concentration of organic solvent are 1.5 ~ 2.5mmol/ml.
Preferred according to the present invention, the brominated alkanes in described step (1) and the mixed concentration of organic solvent are 1 ~ 1.5mmol/ml; Preferred further, described brominated alkanes is bromotetradecane.
Preferred according to the present invention, the heating reflux temperature in described step (1) is 80 DEG C.
Preferred according to the present invention, the purification step in described step (1) is: remove organic solvents at 35 DEG C of rotary evaporation 30min, after then using n-hexane 2 ~ 4 times, obtains intermediate product through vacuum drying.
Preferred according to the present invention, the organic solvent in described step (2) is acetone.
Preferred according to the present invention, 2,4,6-trisbromomethyl trimethylbenzenes in described step (2) and the mixed concentration of organic solvent are 0.02 ~ 0.03mmol/ml.
Preferred according to the present invention, the heating reflux temperature in described step (2) is 56 DEG C.
Preferred according to the present invention, the purification step in described step (2) is: after filtration under diminished pressure, and filter residue is with after acetone washing 2 ~ 4 times, with absolute ethyl alcohol recrystallization, obtained containing the cationic oligo surfactant of phenyl.
The present invention has following advantage and effect:
1. the present invention utilizes with benzene or substituted benzene for core, and molecular structure, based on the oligo surfactant of star-like arrangement mode, has surface-active high, the feature that self assembly ability is strong, is the desirable template preparing ordered mesoporous material.
2. the present invention utilizes simple quaterisation to obtain oligomeric cationic surface active agent, and reaction condition is gentle, and output is high.
Accompanying drawing explanation
Fig. 1 be test example 2 record with containing phenyl cationic oligo surfactant synthesis Porous materials little angle XRD scheme;
Wherein: Grey curves is the mol ratio of surfactant and tetraethyl orthosilicate is 0.03:1;
Black curve is the mol ratio of surfactant and tetraethyl orthosilicate is 0.04:1;
Fig. 2 is the 1H nuclear magnetic spectrogram containing the cationic oligo surfactant of phenyl that embodiment 1 obtains.
Detailed description of the invention
Below in conjunction with embodiment, further detailed description is done to technical scheme of the present invention, but institute of the present invention protection domain is not limited thereto.
Embodiment 1
Containing the preparation method of the cationic oligo surfactant of phenyl, step is as follows:
(1) in there-necked flask, by 23.24g(200mmol) tetramethylethylenediamine be dissolved in 120ml solvent, under 80 DEG C of conditions, backflow 10min after, by 27.73g(100mmol) bromotetradecane is dissolved in 80ml absolute ethyl alcohol, slowly drip in above-mentioned there-necked flask, under 80 DEG C of conditions, back flow reaction 48h, then rotary evaporation is except desolventizing, with n-hexane to residue cyclic washing 3 times, vacuum drying, obtains orange wax-like products; Product is by the monolateral quaternised tetramethylethylenediamine of bromotetradecane, quality 24.2g, productive rate 61.6%.
(2) the orange wax-like products 23.61g(60mmol that step (1) is obtained is taken), join in the there-necked flask filling 100ml acetone, be heated to 56 DEG C dissolve and reflux half an hour, by 6.14g(15.38mmol) 2,4,6-trisbromomethyl trimethylbenzene is dissolved in acetone, and is added drop-wise in there-necked flask, can see after half an hour that white precipitate is separated out, mixture is back flow reaction 48h at 56 DEG C; Obtain white solid through filtration under diminished pressure, white solid acetone washs 3 times, with absolute ethyl alcohol recrystallization, obtains containing the cationic oligo surfactant of phenyl.
Through nuclear magnetic resonance
1h composes detection, and data are as follows: 5.03 (d, 6H, ArCH
2), 4.49 (t, 6H, NCH
2), 4.19 (t, 6H, CH
2n), 3.44-3.10 (m, 36H, NCH
3), 2.75 (d, 9H, ArCH
3), 2.81-0.84 (C
14).As shown in Figure 2.General formula is (14-2)
3ph; Product quality 20.16g, productive rate 83.0%.
Embodiment 2
Containing the preparation method of the cationic oligo surfactant of phenyl, step is as follows:
(1) in there-necked flask, by 17.43g(150mmol) tetramethylethylenediamine be dissolved in 100ml solvent, under 80 DEG C of conditions, backflow 10min after, by 27.73g(100mmol) bromotetradecane is dissolved in 80ml absolute ethyl alcohol, slowly drip in above-mentioned there-necked flask, under 80 DEG C of conditions, back flow reaction 48h, then rotary evaporation is except desolventizing, with n-hexane to residue cyclic washing 3 times, vacuum drying, obtains orange wax-like products; Product is by the monolateral quaternised tetramethylethylenediamine of bromotetradecane, quality 22.6g, productive rate 57.5%.
(2) the orange wax-like products 9.04g(23mmol that step (1) is obtained is taken), join in the there-necked flask filling 100ml acetone, be heated to 56 DEG C dissolve and reflux half an hour, by 2.91g(7.3mmol) 2,4,6-trisbromomethyl trimethylbenzene is dissolved in acetone, and is added drop-wise in there-necked flask, can see after half an hour that white precipitate is separated out, mixture is back flow reaction 48h at 56 DEG C; Obtain white solid through filtration under diminished pressure, white solid acetone washs 3 times, with absolute ethyl alcohol recrystallization, obtains containing the cationic oligo surfactant 7.67g of phenyl, productive rate 66.6%.
Embodiment 3
Containing the preparation method of the cationic oligo surfactant of phenyl, step is as follows:
(1) in there-necked flask, by 13.95g(120mmol) tetramethylethylenediamine be dissolved in 100ml solvent, under 80 DEG C of conditions, backflow 10min after, by 27.73g(100mmol) bromotetradecane is dissolved in 80ml absolute ethyl alcohol, slowly drip in above-mentioned there-necked flask, under 80 DEG C of conditions, back flow reaction 48h, then rotary evaporation is except desolventizing, with n-hexane to residue cyclic washing 3 times, vacuum drying, obtains orange wax-like products; Product is by the monolateral quaternised tetramethylethylenediamine of bromotetradecane, quality 22.31g, productive rate 56.7%.
(2) the orange wax-like products 15.35g(39mmol that step (1) is obtained is taken), join in the there-necked flask filling 100ml acetone, be heated to 56 DEG C dissolve and reflux half an hour, by 3.99g(10mmol) 2,4,6-trisbromomethyl trimethylbenzene is dissolved in acetone, and is added drop-wise in there-necked flask, can see after half an hour that white precipitate is separated out, mixture is back flow reaction 48h at 56 DEG C; Obtain white solid through filtration under diminished pressure, white solid acetone washs 3 times, with absolute ethyl alcohol recrystallization, obtains containing the cationic oligo surfactant 12.57g of phenyl, productive rate 79.6%.
Test example 1
What embodiment 1 obtained contains the solubility experiment of the cationic oligo surfactant of phenyl in water:
Under the condition of at room temperature (25 DEG C), every hundred ml waters dissolve (14-2) that be no more than 0.01g
3ph.
Test example 2
What obtain with embodiment 1 contains the cationic oligo surfactant of phenyl for template, synthesizing SiO 2 mesoporous materials, and step is as follows:
Get 0.4g(or 0.3g) be dissolved in the mixed solvent of 54ml water and 4ml n-butanol containing the cationic oligo surfactant of phenyl, until completely dissolved, add 2.5ml concentrated ammonia liquor, pH is regulated to be 10, under the condition stirred, add 1.254g tetraethyl orthosilicate, after stirring 20min, mixed solvent is transferred to thermostat, at 50 DEG C, is hydrolyzed 5h, then move in 80 DEG C of baking ovens, ageing 3 days.Then by gained white precipitate filtering and washing, dry.In Muffle furnace, 5h is calcined at 550 DEG C after drying, removing is containing the cationic oligo surfactant of phenyl, the ordered structure of resulting materials is tested by small angle X-ray diffraction, result shows just can obtain ordered structure when template and silicon source ratio reach 0.03:1, when ratio reaches 0.04:1, ordered structure is better, as shown in Figure 1.
Claims (9)
1., containing a preparation method for the cationic oligo surfactant of phenyl, it is characterized in that, step is as follows:
(1), after being mixed with the brominated alkanes being dissolved in organic solvent by the excessive tetramethylethylenediamine be dissolved in organic solvent, the monolateral quaterisation 40 ~ 60 hours of tetramethyl diamines under heated reflux condition, is carried out, purified, obtained intermediate product;
(2) intermediate product that step (1) is obtained is dissolved in organic solvent, then add and be dissolved in 2 of organic solvent, 4,6-trisbromomethyl trimethylbenzene, intermediate product and 2,4, the mol ratio of 6-trisbromomethyl trimethylbenzene is 3:1, through back flow reaction 24 ~ 48 hours, purified, obtained containing the cationic oligo surfactant of phenyl;
Obtained is as follows containing phenyl cationic oligo surfactant structural formula:
Wherein: 6Br
-refer to hydrophilic cations with bromine counter ion.
2. preparation method as claimed in claim 1, it is characterized in that, the organic solvent in described step (1) is absolute ethyl alcohol.
3.
preparation method as claimed in claim 1, is characterized in that, the tetramethylethylenediamine in described step (1) and the mixed concentration of organic solvent are 1.5 ~ 2.5mmol/ml; Brominated alkanes and the mixed concentration of organic solvent are 1 ~ 1.5 mmol/ml; Described brominated alkanes is bromotetradecane.
4.
preparation method as claimed in claim 1, is characterized in that, the heating reflux temperature in described step (1) is 80 DEG C.
5.
preparation method as claimed in claim 1, is characterized in that, the purification step in described step (1) is: rotary evaporation removing organic solvent, after then using n-hexane 2 ~ 4 times, obtains intermediate product through vacuum drying.
6.
preparation method as claimed in claim 1, is characterized in that, the organic solvent in described step (2) is acetone.
7.
preparation method as claimed in claim 1, is characterized in that, 2,4,6-trisbromomethyl trimethylbenzenes in described step (2) and the mixed concentration of organic solvent are 0.02 ~ 0.03mmol/ml.
8.
preparation method as claimed in claim 1, is characterized in that, the heating reflux temperature in described step (2) is 56 DEG C.
9.
preparation method as claimed in claim 1, is characterized in that, the purification step in described step (2) is: after filtration under diminished pressure, and filter residue is with after acetone washing 2 ~ 4 times, with absolute ethyl alcohol recrystallization, obtained containing the cationic oligo surfactant of phenyl.
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