CN104525043B - A kind of quaternary terpolymer surfactant and preparation method thereof - Google Patents
A kind of quaternary terpolymer surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of quaternary terpolymer surfactant, its structural formula is:R1=CH3-, CH3CH2-, CH3CH2CH2-or CH3CH2CH2CH2-;R2=C8H17-, C10H21-, C12H25-, C14H29-or C16H33-, the preparation method of described quaternary terpolymer surfactant includes that phenol, formaldehyde and secondary amine are carried out Mannich condensation reaction and obtains 2,4,6-tri-((dialkyl amido) methyl) phenol and 2,4,6-tri-((dialkyl amido) methyl) phenol and brominated alkanes generation quaterisation obtain two steps of described quaternary terpolymer surfactant。The raw material sources that the present invention relates to are simple, cost is low, and preparation technology is simple, and products therefrom purity is higher, and has good 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 being 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 activity, less critical micelle concentration (CMC), less 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., washing, sterilization, emulsifying, dispersion, anticorrosion and cosmetics, printing and dyeing, tertiary oil recovery, gene therapy, ordered mesoporous material the field such as synthesis there is bigger application potential。
The one side that gets involved of spacer group enhances the hydrophobic interaction of hydrocarbon chain, the trend that hydrophobic group is escaped in aqueous solution is made to increase, on the other hand, because of the restriction by chemistry bond distance, the tendency being separated from each other due to electrical charge rejection effect between ion head base is weakened severely, what make that multiple surfactant monomer combines is more tight, and then greatly strengthen its surface activity。
Summary of the invention
It is an object of the invention 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 activity。
For achieving the above object, the technical solution used in the present invention is:
A kind of quaternary terpolymer surfactant, its structural formula is:
R1=CH3-、CH3CH2-、CH3CH2CH2-or CH3CH2CH2CH2-;R2=C8H17-、C10H21-、C12H25-、C14H29-or C16H33-。
The preparation method of above-mentioned a kind of quaternary terpolymer surfactant, carry out Mannich condensation reaction including phenol, formaldehyde and secondary amine 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 two steps of described quaternary terpolymer surfactant, 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, formaldehyde it is slowly added dropwise in 0.5~1h, the mixed liquor obtained is reacted 1~5h at 40~100 DEG C of temperature, then oil-water separation and decompression distillation are 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, the rotated evaporimeter of products therefrom removes solvent, and residue acetone/ethanol carries out 3 recrystallization, obtains described quaternary terpolymer surfactant through vacuum drying after。
According to such scheme, described solvent is methanol, dehydrated alcohol, isopropanol, normal propyl alcohol, ethyl acetate or butyl acetate。
Compared with prior art, beneficial effects of the present invention:
The present invention is with phenol, formaldehyde, secondary amine and brominated alkanes for raw material, a class quaternary terpolymer surfactant is prepared through Mannich condensation reaction and two steps of quaterisation, 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 activity。
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, NMR 1H-NMR spectrogram of the quaternary terpolymer surfactant that the embodiment of the present invention 1 prepares。
Fig. 2 is that the quaternary terpolymer surfactant for preparing of the embodiment of the present invention 1~4 electric conductivity value at 25 DEG C is with concentration curve。
Detailed description of the invention
For making the purpose 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 is only in order to explain the present invention, is not intended to limit the present invention。
In following example, agents useful for same is commercially available chemical reagent if no special instructions;
Described secondary amine is respectively selected from dimethylamine, diethylamine, di-n-propylamine and di-n-butylamine;
Described brominated alkanes is selected from bromododecane;
Described preparation method includes 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 two steps of quaternary terpolymer surfactant, the organic solvent that quaterisation adopts is dehydrated alcohol。
Embodiment 1
A kind of quaternary terpolymer surfactant, wherein R1=CH3-, R2=C12H25-, 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, it is slowly added dropwise formaldehyde, gained mixed liquor is reacted at 40 DEG C of temperature 5h, then oil-water separation and the water being distilled off in product that reduces pressure are carried out, obtain described 2,4,6-tri-((dimethylamino) methyl) phenol, for light yellow transparent liquid;
2) 2,4,6-tri-((dimethylamino) methyl) phenol and bromododecane are mixed for 1:3 in molar ratio, at 80 DEG C, react 2d with dehydrated alcohol for solvent。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 through vacuum drying, i.e. described quaternary terpolymer surfactant after。
The nuclear magnetic resonance, NMR 1H-NMR spectrogram of the terpolymer surfactant that the present embodiment prepares 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)。Chemical shift data analysis from nucleus magnetic hydrogen spectrum is it can be seen that end product is consistent with design object thing, and purity is higher。
The terpolymer surfactant that the present embodiment prepares, the electric conductivity value at 25 DEG C is shown in Fig. 2 with concentration curve。It is shown that the CMC of gained terpolymer surfactant (critical micelle concentration) is relatively low, CMC value is 4.51 × 10-5mol/L。
Embodiment 2
A kind of quaternary terpolymer surfactant, wherein R1=CH3CH2-, R2=C12H25-, 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, it is slowly added dropwise formalin, mixed liquor is reacted at 60 DEG C 4h, then oil-water separation and the water being distilled off in product that reduces pressure are carried out, obtain described 2,4,6-tri-((diethylamino) methyl) phenol, for faint yellow yellow transparent liquid。
2) 2,4,6-tri-((diethylamino) methyl) phenol and bromododecane are mixed for 1:3.5 in molar ratio, at 95 DEG C, react 2d with dehydrated alcohol for solvent。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 through vacuum drying after。
The terpolymer surfactant that the present embodiment prepares, the electric conductivity value at 25 DEG C is shown in Fig. 1 with concentration curve。It is shown that the CMC of gained terpolymer surfactant (critical micelle concentration) is relatively low, CMC value is 3.81 × 10-5mol/L。
Embodiment 3
A kind of quaternary terpolymer surfactant, wherein R1=CH3CH2CH2-, R2=C12H25-, preparation method comprises the following steps:
1) intermediate product 2,4, the synthesis step of 6-tri-((diη-propyl amino) methyl) phenol: by phenol, formaldehyde and di-n-propylamine are that 1:6:6 mixes according to mol ratio, first phenol and di-n-propylamine aqueous solution at room temperature Homogeneous phase mixing during reaction, then in 1h, it is slowly added dropwise formalin, mixed liquor is reacted at 80 DEG C 2h, then oil-water separation and the water being distilled off in product that reduces pressure are carried out, obtain described 2,4,6-tri-((diη-propyl amino) methyl) phenol, for faint yellow yellow transparent liquid。
2) 2,4,6-tri-((diη-propyl amino) methyl) phenol and bromododecane are mixed for 1:4 in molar ratio, at 95 DEG C, react 2d with dehydrated alcohol for solvent。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 through vacuum drying after。
The terpolymer surfactant that the present embodiment prepares, the electric conductivity value at 25 DEG C is shown in Fig. 1 with concentration curve。It is shown that the CMC of gained terpolymer surfactant (critical micelle concentration) is relatively low, CMC value is 3.56 × 10-5mol/L。
Embodiment 4
A kind of quaternary terpolymer surfactant, wherein R1=CH3CH2CH2CH2-, R2=C12H25-, preparation method comprises the following steps:
1) intermediate product 2,4, the synthesis step of 6-tri-((di-n-butyl amino) methyl) phenol: by phenol, formaldehyde and di-n-butylamine are that 1:10:10 mixes according to mol ratio, first phenol and di-n-butylamine aqueous solution at room temperature Homogeneous phase mixing during reaction, then in 1h, it is slowly added dropwise formalin, mixed liquor is reacted at 100 DEG C 1h, then carry out oil-water separation and the water being distilled off in product that reduces pressure, obtain described 2,4,6-tri-((di-n-butyl amino) methyl) phenol, for faint yellow yellow transparent liquid。
2) 2,4,6-tri-((di-n-butyl amino) methyl) phenol and bromododecane are mixed for 1:10 in molar ratio, at 95 DEG C, react 7d with dehydrated alcohol for solvent。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 through vacuum drying after。
The terpolymer surfactant that the present embodiment prepares, the electric conductivity value at 25 DEG C is shown in Fig. 1 with concentration curve。It is shown that the CMC of gained terpolymer surfactant (critical micelle concentration) is relatively low, CMC value is 3.13 × 10-5mol/L。
The bound value of each raw material, interval value that invention relates to can realize the present invention, and lower limit value and the interval value of the technological parameter (such as temperature, time etc.) related to can realize the present invention, embodiment numerous to list herein。
Claims (5)
1. the preparation method of quaternary terpolymer surfactant, described quaternary terpolymer surfactant structural formula is:
R1=CH3-、CH3CH2-、CH3CH2CH2-or CH3CH2CH2CH2-;R2=C8H17-、C10H21-、C12H25-、C14H29-or C16H33-, it is characterized in that, 2 are obtained including phenol, formaldehyde and secondary amine are carried out Mannich condensation reaction, 4,6-tri-((dialkyl amido) methyl) phenol and 2,4,6-tri-((dialkyl amido) methyl) phenol and brominated alkanes generation quaterisation obtain two steps of described quaternary terpolymer surfactant。
2. preparation method according to claim 1, 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)。
3. preparation method according to claim 1 and 2, it is characterized in that, the step of described Mannich condensation reaction is: by phenol and dimethylamine at room temperature Homogeneous phase mixing, formaldehyde it is slowly added dropwise in 0.5~1h, the mixed liquor obtained is reacted 1~5h at 40~100 DEG C of temperature, then carries out oil-water separation and decompression distillation, obtain described 2,4,6-tri-((dialkyl amido) methyl) phenol。
4. preparation method according to claim 1 and 2, 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, reacting 2~7d, products therefrom is through evaporative removal solvent, residue acetone/ethanol carries out recrystallization, obtains described quaternary terpolymer surfactant through vacuum drying after。
5. preparation method according to claim 4, it is characterised in that described solvent is methanol, dehydrated alcohol, isopropanol, normal propyl alcohol, ethyl acetate or butyl acetate。
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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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Publication number | Priority date | Publication date | Assignee | Title |
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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 |