CN104525043A - Quaternary ammonium salt type trimeric surfactant and preparation method thereof - Google Patents
Quaternary ammonium salt type trimeric surfactant and preparation method thereof Download PDFInfo
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- CN104525043A CN104525043A CN201410796593.7A CN201410796593A CN104525043A CN 104525043 A CN104525043 A CN 104525043A CN 201410796593 A CN201410796593 A CN 201410796593A CN 104525043 A CN104525043 A CN 104525043A
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Abstract
The invention discloses a quaternary ammonium salt type trimeric surfactant with a structural formula shown in the specification, wherein R1=CH3-, CH3CH2-, CH3CH2CH2- or CH3CH2CH2CH2-; R2=C8H17-, C10H21-, C12H25-, C14H29- or C16H33-. The preparation method of the quaternary ammonium salt type trimeric surfactant comprises the following steps: performing Mannich condensation reaction of phenol, formaldehyde and secondary amine to obtain 2,4,6-tri((dialkylamino)methyl)phenol, and performing quaternization reaction of the 2,4,6-tri((dialkylamino)methyl)phenol and alkyl bromide to obtain the quaternary ammonium salt type trimeric surfactant. In the invention, the raw materials are easily available, and the cost is low; and moreover, the preparation process is simple, and the obtained product has relatively high purity and perfect surface activity.
Description
Technical field
The invention belongs to surfactant science and application, be specifically related to a kind of quaternary terpolymer surfactant and preparation method thereof.
Background technology
Terpolymer surfactant is the class novel surfactant be formed by connecting at its hydrophilic head base or close hydrophilic head Ji Chu by a connection base by three hydrophilic head bases and three hydrophobic tail bases, is a kind of oligo surfactant of new development on Gemini surface active agent basis.Compare with traditional surfactant, oligo surfactant has higher surface-active, lower critical micelle concentration (CMC), lower Krafft point, with other surfactant, there is better compound property, better cooperative effect can be produced, there is good calcium soap dispersive property, there is better wettability etc., in the field such as synthesis of washing, sterilization, emulsification, dispersion, anticorrosion and cosmetics, printing and dyeing, tertiary oil recovery, gene therapy, ordered mesoporous material, there is larger application potential.
The intervention of spacer group enhances the hydrophobic effect of hydrocarbon chain on the one hand, the trend that hydrophobic grouping is escaped in the aqueous solution increases, on the other hand, because of the restriction by chemical bond distance, the tendency be separated from each other due to electrical charge rejection effect between ion head base is weakened severely, what multiple surfactant monomer was combined is more tight, and then greatly strengthen its surface-active.
Summary of the invention
The object of the present invention is to provide a kind of quaternary terpolymer surfactant and preparation method thereof, the technique that the method relates to is simple, and cost of material is low, and products therefrom has higher purity, and has higher surface-active.
For achieving the above object, the technical solution used in the present invention is:
A kind of quaternary terpolymer surfactant, its structural formula is:
r
1=CH
3-, CH
3cH
2-, CH
3cH
2cH
2-or CH
3cH
2cH
2cH
2-; R
2=C
8h
17-, C
10h
21-, C
12h
25-, C
14h
29-or C
16h
33-.
The preparation method of above-mentioned a kind of quaternary terpolymer surfactant, comprise phenol, formaldehyde and secondary amine to carry out Mannich condensation reaction and obtain 2,4,6-tri-((dialkyl amido) methyl) phenol and 2,4,6-tri-((dialkyl amido) methyl) phenol and brominated alkanes generation quaterisation obtain described quaternary terpolymer surfactant two steps, and concrete reaction circuit is as follows:
According to such scheme, described phenol, formaldehyde, secondary amine and brominated alkanes are commercially available chemical reagent.
According to such scheme, the mol ratio of described phenol, formaldehyde and secondary amine is 1:(3 ~ 10): (3 ~ 10), the mol ratio of described 2,4,6-tri-((dialkyl amido) methyl) phenol and brominated alkanes is 1:(3 ~ 10).
According to such scheme, the step of described Mannich condensation reaction is: by phenol and dimethylamine at room temperature (0 ~ 40 DEG C) Homogeneous phase mixing, slowly formaldehyde is dripped in 0.5 ~ 1h, the mixed liquor obtained is reacted 1 ~ 5h at 40 ~ 100 DEG C of temperature, then water-oil separating and decompression distillation is carried out, obtain described 2,4,6-tri-((dialkyl amido) methyl) phenol.
According to such scheme, the step of described quaterisation is: by 2,4,6-tri-((dialkyl amido) methyl) phenol and brominated alkanes Homogeneous phase mixing, add in solvent, at 80 ~ 95 DEG C of temperature, reaction 2 ~ 7d, products therefrom is through Rotary Evaporators except desolventizing, and residue acetone/ethanol carries out 3 recrystallizations, obtains described quaternary terpolymer surfactant finally by vacuum drying.
According to such scheme, described solvent is methyl alcohol, absolute ethyl alcohol, isopropyl alcohol, normal propyl alcohol, ethyl acetate or butyl acetate.
Compared with prior art, beneficial effect of the present invention:
The present invention with phenol, formaldehyde, secondary amine and brominated alkanes for raw material, a class quaternary terpolymer surfactant is prepared through Mannich condensation reaction and quaterisation two steps, the cost of material that the method relates to is low, source is simple, and preparation technology is simple, products therefrom purity is higher, and has good surface-active.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described, in accompanying drawing:
Fig. 1 is the nuclear magnetic resonance 1H-NMR spectrogram of the quaternary terpolymer surfactant that the embodiment of the present invention 1 obtains.
Fig. 2 is that the electric conductivity value of the obtained quaternary terpolymer surfactant of the embodiment of the present invention 1 ~ 4 at 25 DEG C is with concentration curve.
Detailed description of the invention
For making object of the present invention, technical scheme and advantage clearly understand, below in conjunction with specific embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
In following examples, agents useful for same is commercially available chemical reagent if no special instructions;
Described secondary amine is selected from dimethylamine respectively, diethylamine, di-n-propylamine and di-n-butylamine;
Described brominated alkanes is selected from bromododecane;
Described preparation method comprises phenol, formaldehyde and secondary amine and carries out Mannich condensation reaction and prepare intermediate product 2,4,6-tri-((dimethylamino) methyl) phenol and gained intermediate product 2,4,6-tri-((dimethylamino) methyl) phenol again with brominated alkanes generation quaterisation, synthesis quaternary terpolymer surfactant two steps, the organic solvent that quaterisation adopts is absolute ethyl alcohol.
Embodiment 1
A kind of quaternary terpolymer surfactant, wherein R
1=CH
3-, R
2=C
12h
25-, preparation method comprises the following steps:
1) intermediate product 2,4, the synthesis step of 6-tri-((dimethylamino) methyl) phenol: be that 1:3:3 mixes according to mol ratio by phenol, formaldehyde and dimethylamine, first phenol and dimethylamine at room temperature Homogeneous phase mixing during reaction, then in 0.5h, slowly formaldehyde is dripped, gained mixed liquor is reacted 5h at 40 DEG C of temperature, then the water in water-oil separating and decompression distillation removing product is carried out, obtain described 2,4,6-tri-((dimethylamino) methyl) phenol is light yellow transparent liquid;
2) by 2,4,6-tri-((dimethylamino) methyl) phenol and bromododecane in molar ratio for 1:3 mixes, be that solvent reacts 2d at 80 DEG C with absolute ethyl alcohol.After completion of the reaction, etoh solvent is removed with Rotary Evaporators.Residue acetone/ethanol (volume ratio 20:1) carries out recrystallization 3 times, obtains white powder solid finally by vacuum drying, i.e. described quaternary terpolymer surfactant.
The nuclear magnetic resonance 1H-NMR spectrogram of the terpolymer surfactant that the present embodiment obtains is shown in Fig. 1.In Fig. 1, δ=3.39 place is the solvent peak of DMSO, and δ=2.5 place is the peak of residual water in DMSO, and δ is: 3.02 (t, 2H), 2.76 (S, 6H), 1.59 (S, 2H), 1.25 (m, 18H), 0.86 (t, 9H).From nucleus magnetic hydrogen spectrum, chemical shift data is analyzed known, and end product is consistent with design object thing, and purity is higher.
The terpolymer surfactant that the present embodiment is obtained, the electric conductivity value at 25 DEG C is shown in Fig. 2 with concentration curve.Result shows, the CMC (critical micelle concentration) of gained terpolymer surfactant is lower, and CMC value is 4.51 × 10
-5mol/L.
Embodiment 2
A kind of quaternary terpolymer surfactant, wherein R
1=CH
3cH
2-, R
2=C
12h
25-, preparation method comprises the following steps:
1) intermediate product 2,4, the synthesis step of 6-tri-((diethylamino) methyl) phenol: by phenol, formaldehyde and diethylamine are that 1:4:4 mixes according to mol ratio, first phenol and diethylamine aqueous solution at room temperature Homogeneous phase mixing during reaction, then in 1h, slowly formalin is dripped, mixed liquor is reacted 4h at 60 DEG C, then the water in water-oil separating and decompression distillation removing product is carried out, obtain described 2,4,6-tri-((diethylamino) methyl) phenol is faint yellow yellow transparent liquid.
2) by 2,4,6-tri-((diethylamino) methyl) phenol and bromododecane in molar ratio for 1:3.5 mixes, be that solvent reacts 2d at 95 DEG C with absolute ethyl alcohol.After completion of the reaction, etoh solvent is removed with Rotary Evaporators.Residue acetone/ethanol (volume ratio 20:1) carries out recrystallization 3 times, obtains described quaternary terpolymer surfactant white powder solid finally by vacuum drying.
The terpolymer surfactant that the present embodiment is obtained, the electric conductivity value at 25 DEG C is shown in Fig. 1 with concentration curve.Result shows, the CMC (critical micelle concentration) of gained terpolymer surfactant is lower, and CMC value is 3.81 × 10
-5mol/L.
Embodiment 3
A kind of quaternary terpolymer surfactant, wherein R
1=CH
3cH
2cH
2-, R
2=C
12h
25-, preparation method comprises the following steps:
1) intermediate product 2,4, the synthesis step of 6-tri-((diη-propyl is amino) methyl) phenol: by phenol, formaldehyde and di-n-propylamine are that 1:6:6 mixes according to mol ratio, first phenol and the di-n-propylamine aqueous solution at room temperature Homogeneous phase mixing during reaction, then in 1h, slowly formalin is dripped, mixed liquor is reacted 2h at 80 DEG C, then the water in water-oil separating and decompression distillation removing product is carried out, obtain described 2,4,6-tri-((diη-propyl is amino) methyl) phenol is faint yellow yellow transparent liquid.
2) by 2,4,6-tri-((diη-propyl is amino) methyl) phenol and bromododecane in molar ratio for 1:4 mixes, be that solvent reacts 2d at 95 DEG C with absolute ethyl alcohol.After completion of the reaction, etoh solvent is removed with Rotary Evaporators.Residue acetone/ethanol (volume ratio 20:1) carries out recrystallization 3 times, obtains described quaternary terpolymer surfactant white powder solid finally by vacuum drying.
The terpolymer surfactant that the present embodiment is obtained, the electric conductivity value at 25 DEG C is shown in Fig. 1 with concentration curve.Result shows, the CMC (critical micelle concentration) of gained terpolymer surfactant is lower, and CMC value is 3.56 × 10
-5mol/L.
Embodiment 4
A kind of quaternary terpolymer surfactant, wherein R
1=CH
3cH
2cH
2cH
2-, R
2=C
12h
25-, preparation method comprises the following steps:
1) intermediate product 2,4, the synthesis step of 6-tri-((di-n-butyl is amino) methyl) phenol: by phenol, formaldehyde and di-n-butylamine are that 1:10:10 mixes according to mol ratio, first phenol and the di-n-butylamine aqueous solution at room temperature Homogeneous phase mixing during reaction, then in 1h, slowly formalin is dripped, mixed liquor is reacted 1h at 100 DEG C, then carry out the water in water-oil separating and decompression distillation removing product, obtain described 2,4,6-tri-((di-n-butyl is amino) methyl) phenol is faint yellow yellow transparent liquid.
2) by 2,4,6-tri-((di-n-butyl is amino) methyl) phenol and bromododecane in molar ratio for 1:10 mixes, be that solvent reacts 7d at 95 DEG C with absolute ethyl alcohol.After completion of the reaction, etoh solvent is removed with Rotary Evaporators.Residue acetone/ethanol (volume ratio 20:1) carries out recrystallization 3 times, obtains described quaternary terpolymer surfactant white powder solid finally by vacuum drying.
The terpolymer surfactant that the present embodiment is obtained, the electric conductivity value at 25 DEG C is shown in Fig. 1 with concentration curve.Result shows, the CMC (critical micelle concentration) of gained terpolymer surfactant is lower, and CMC value is 3.13 × 10
-5mol/L.
Bound value, the interval value of inventing each raw material related to can realize the present invention, and lower limit value and the interval value of the technological parameter (as temperature, time etc.) related to can realize the present invention, do not enumerate embodiment at this.
Claims (6)
1. a quaternary terpolymer surfactant, its structural formula is:
r
1=CH
3-, CH
3cH
2-, CH
3cH
2cH
2-or CH
3cH
2cH
2cH
2-; R
2=C
8h
17-, C
10h
21-, C
12h
25-, C
14h
29-or C
16h
33-.
2. the preparation method of quaternary terpolymer surfactant according to claim 1, it is characterized in that, comprise and phenol, formaldehyde and secondary amine are carried out Mannich condensation reaction obtain 2,4,6-tri-((dialkyl amido) methyl) phenol and 2,4,6-tri-((dialkyl amido) methyl) phenol and brominated alkanes generation quaterisation obtain described quaternary terpolymer surfactant two steps.
3. preparation method according to claim 2, it is characterized in that, the mol ratio of described phenol, formaldehyde and secondary amine is 1:(3 ~ 10): (3 ~ 10), described 2, the mol ratio of 4,6-tri-((dialkyl amido) methyl) phenol and brominated alkanes is 1:(3 ~ 10).
4. the preparation method according to Claims 2 or 3, it is characterized in that, the step of described Mannich condensation reaction is: by phenol and dimethylamine at room temperature Homogeneous phase mixing, slowly formaldehyde is dripped in 0.5 ~ 1h, the mixed liquor obtained is reacted 1 ~ 5h at 40 ~ 100 DEG C of temperature, then carries out water-oil separating and decompression distillation, obtain described 2,4,6-tri-((dialkyl amido) methyl) phenol.
5. the preparation method according to Claims 2 or 3, it is characterized in that, the step of described quaterisation is: by 2,4,6-tri-((dialkyl amido) methyl) phenol and brominated alkanes Homogeneous phase mixing, add in solvent, at 80 ~ 95 DEG C of temperature, reaction 2 ~ 7d, products therefrom is through evaporative removal solvent, residue acetone/ethanol is recrystallized, and obtains described quaternary terpolymer surfactant finally by vacuum drying.
6. preparation method according to claim 5, is characterized in that, described solvent is methyl alcohol, absolute ethyl alcohol, isopropyl alcohol, normal propyl alcohol, ethyl acetate or butyl acetate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981420A (en) * | 1997-02-17 | 1999-11-09 | Daicel Chemical Industries, Ltd. | Oxidation catalytic system and oxidation process |
| CN101279219A (en) * | 2008-01-03 | 2008-10-08 | 天津师范大学 | Bis-quaternary ammonium salt cationic surfactant, preparation and use thereof |
| CN102513023A (en) * | 2011-10-31 | 2012-06-27 | 广东工业大学 | Trimeric surfactant and its synthetic method |
| CN103191671A (en) * | 2013-04-17 | 2013-07-10 | 重庆理工大学 | Trimeric quaternary ammonium salt type cationic surface active agent and preparation method thereof |
-
2014
- 2014-12-19 CN CN201410796593.7A patent/CN104525043B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981420A (en) * | 1997-02-17 | 1999-11-09 | Daicel Chemical Industries, Ltd. | Oxidation catalytic system and oxidation process |
| CN101279219A (en) * | 2008-01-03 | 2008-10-08 | 天津师范大学 | Bis-quaternary ammonium salt cationic surfactant, preparation and use thereof |
| CN102513023A (en) * | 2011-10-31 | 2012-06-27 | 广东工业大学 | Trimeric surfactant and its synthetic method |
| CN103191671A (en) * | 2013-04-17 | 2013-07-10 | 重庆理工大学 | Trimeric quaternary ammonium salt type cationic surface active agent and preparation method thereof |
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Effective date of registration: 20180503 Address after: 430023 130 chemical industry road, Wuhan chemical industry zone, Hubei Patentee after: Wuhan Jihe Chang new material Limited by Share Ltd Address before: 430074 No. 693, Xiong Chu street, Hongshan District, Wuhan, Hubei. Patentee before: Wuhan Institute of Technology |
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