CN103406062B - Gemini amine salt type fluorated surfactant and preparation method thereof - Google Patents
Gemini amine salt type fluorated surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Gemini amine salt type fluorated surfactant and a preparation method thereof. The Gemini amine salt type fluorated surfactant is represented by formula I; in the formula I, R is a group represented by CmH2m+1, wherein m is an integer in a range of 0 to 3, and n is an integer in a range of 2 to 8. The preparation method for the surfactant comprises the following steps: (1) reacting 3-perfluorohexyl-1,2-epoxypropane with diamine represented by formula II so as to obtain a compound represented by formula III, wherein n is the integer in a range of 2 to 8, R is the group represented by CmH2m+1, and m is the integer in a range of 0 to 3; and (2) introducing HCl gas into an alcoholic solution of the compound represented by the formula III and carrying out a salt forming reaction so as to obtain the Gemini amine salt type fluorated surfactant represented by the formula I. The Gemini amine salt type fluorated surfactant provided by the invention has excellent surface properties and good foaming performance. According to the invention, raw materials used in the preparation method are cheap and easily available, the preparation method is simple, reaction conditions are easy to control, and the product--the surfactant is easy to purify.
Description
Technical field
The present invention relates to a kind of Gemini amine salt type fluorine surfactant and preparation method thereof.
Background technology
Conventional surfactants only includes a hydrophilic group and a lipophilic group, is strand single head base.And Gemini type surfactant is formed by connecting by chemical bond at ion head Ji Chu by two strand single head base conventional surfactants, the existence hydrophobic binding power strengthened between hydrocarbon chain of chemical bond has prevented the head base separating force in the orderly accumulation process of surfactant simultaneously, therefore has higher surface-active.Special molecular structure makes it have the advantage of many uniquenesses, as being easily adsorbed in solution-air surface, has lower surface tension, reduces the tendency of the capillary tendency of the aqueous solution much larger than aggregation formation micelle; The low 2-3 of a ratio of the CMC conventional surfactants order of magnitude; There is very low Krafft point; Especially composite energy produce larger cooperative effect with non-ionic surface active agent with conventional surfactants; Excellent wetting agent and blowing agent is can be used as in a lot of occasion.
Summary of the invention
The object of this invention is to provide a kind of Gemini amine salt type fluorine surfactant and preparation method thereof, amine salt type fluorine surfactant provided by the invention has excellent surface property and good frothing capacity.
The type of Gemini amine salt shown in formula I provided by the present invention fluorine surfactant,
In formula I, R is C
mh
2m+1shown group, wherein m is the integer between 0 ~ 3, and n is the integer between 2 ~ 8.
In above-mentioned Gemini amine salt type fluorine surfactant, m is preferably 0, n and is preferably 6.
The preparation method of the type of Gemini amine salt shown in formula I provided by the invention fluorine surfactant, comprises the steps:
(1) diamines shown in 3-perfluoro hexyl-1,2-expoxy propane and formula II carries out being obtained by reacting compound shown in formula III;
Wherein, n is the integer between 2 ~ 8; R is C
mh
2m+1shown group, m is the integer between 0 ~ 3;
(2) in the alcoholic solution of compound shown in formula III, pass into HCl gas, obtain the amine salt of Gemini shown in formula I type fluorine surfactant through salt-forming reaction.
In above-mentioned preparation method, n is preferably 6, m and is preferably 0.
In above-mentioned preparation method, in step (1), shown in 3-perfluoro hexyl-1,2-expoxy propane and formula II, the mol ratio of diamines can be 2:1 ~ 1.5.
In above-mentioned preparation method, in step (1), the temperature of described reaction can be 10 ~ 80 DEG C, and the time can be 3 ~ 12h, specifically can be 3h or 12h, after reaction terminates, and available THF recrystallization.
In above-mentioned preparation method, in step (1), the temperature of described reaction specifically can be 35 ~ 80 DEG C, specifically can be 35 DEG C or 80 DEG C.
In above-mentioned preparation method, in step (2), the temperature of described salt-forming reaction can be 20 ~ 90 DEG C, and the time can be 5 ~ 10h, after reaction terminates, and available THF recrystallization.
In above-mentioned preparation method, in step (2), the temperature of described salt-forming reaction can be preferably 60 ~ 80 DEG C, specifically can be 70 DEG C, and the time can be preferably 6 ~ 8h, specifically can be 6h.
In above-mentioned preparation method, in step (2), described alcoholic solution specifically can be methyl alcohol or ethanol, can be preferably ethanol.
Gemini amine salt type fluorine surfactant provided by the invention has excellent surface property and good frothing capacity.The preparation method of Gemini amine salt type fluorine surfactant provided by the invention, its raw materials used cheap and easy to get, preparation method is simple, reaction condition is easy to control, product is easy to purify.
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The synthesis of embodiment 1, N, N '-two (3-perfluoro hexyl-2-hydroxypropyl) hexamethylene diamine (formula III-1)
In the 500ml there-necked flask that mechanical agitator, thermometer and reflux condensing tube are housed, add hexamethylene diamine 11.6g(0.1mol) and 3-perfluoro hexyl-1,2-expoxy propane 75.2g(0.2mol), at 80 DEG C, (solvent is V in stirring reaction 3h, TLC tracking reaction
ethyl acetate: V
methyl alcohol=2:1), reaction terminates to obtain yellow, viscous mixture, and product 200ml THF is recrystallized, and obtains white solid product 43.2g.
The synthesis of embodiment 2, N, N '-two (3-perfluoro hexyl-2-hydroxypropyl) hexamethylene diamine (formula III-1)
In the 500ml four-hole bottle that mechanical agitator, thermometer, reflux condensing tube, constant pressure funnel are housed, add hexamethylene diamine 11.6g(0.1mol), solvent made by absolute ethyl alcohol, 3-perfluoro hexyl-1 is dripped with constant pressure funnel, 2-expoxy propane 75.2g(0.2mol), after dripping at 35 DEG C stirring reaction 12h, TLC follow the tracks of reaction (solvent is V
ethyl acetate: V
methyl alcohol=2:1), obtain solidliquid mixture after reaction terminates, remove ethanol, product with methylalcohol and Diethyl ether recrystallization, obtain white solid product 72.5g.
The synthesis of embodiment 3, N, N '-two (3-perfluoro hexyl-2-hydroxypropyl) hexamethylene-diamine hydrochloride (formula I-1)
In the 500ml four-hole bottle that mechanical agitator, reflux condensing tube and thermometer are housed, add the 58.0g(0.067mol of compound shown in formula III-1) and 250ml ethanol, throughput HCl(g in this ethanolic solution), stirring reaction 6h at 70 DEG C, obtain solidliquid mixture, remove ethanol, solid THF is recrystallized, final white solid product 58.2g.
The characterization data of formula I-1 is as follows:
1H NMR(400MHz,CD
3OD,δ/ppm):δ=1.484(m,4H,N-CH
2-CH
2-(CH
2)
2-CH
2-CH
2-N),δ=1.775(m,4H,N-CH
2-CH
2-(CH
2)
2-CH
2-CH
2-N),δ=2.466(m,4H,2CH
2-C
6F
13),δ=3.04-3.32(m,8H,4CH
2-N),δ=4.409(m,2H,CH-O).
19f NMR (300MHz, CDCl
3, δ/ppm): δ=-82.418 (m, 6F, CF
3), δ=-113.834 (m, 4F, CF
2α), δ=-122.760 (m, 4F, CF
2β), δ=-123.858 (m, 4F, CF
2γ), δ=-124.582 (m, 4F, CF
2δ), δ=-127.307 (m, 4F, CF
2ω). structure is correct.
The synthesis of embodiment 4, N, N '-two (3-perfluoro hexyl-2-hydroxypropyl) hexamethylene-diamine hydrochloride (formula I-1)
In the 500ml four-hole bottle that mechanical agitator, reflux condensing tube and thermometer are housed, add the 58.0g(0.067mol of compound shown in formula III-1) and 350.0ml methyl alcohol, throughput HCl(g in this methanol solution), stirring reaction 6h at 60-65 DEG C, obtain solidliquid mixture, methanol removal, solid THF is recrystallized, final white solid product 49.6g.
The synthesis of embodiment 5, N, N '-two (3-perfluoro hexyl-2-hydroxypropyl) hexamethylene-diamine hydrochloride (formula I-1)
In the 500ml four-hole bottle that mechanical agitator, reflux condensing tube and thermometer are housed, add the 58.0g(0.067mol of compound shown in formula III-1) and 250.0ml ethanol, throughput HCl(g in this ethanolic solution), back flow reaction 6h at 75-78 DEG C, obtain solidliquid mixture, remove ethanol, solid THF is recrystallized, final white solid product 56.5g.
Embodiment 6, prepare the pure water solution of the amine salt of Gemini shown in formula I-1 type fluorine surfactant with high purity water (ρ=18.23M Ω .cm), after equilibrate at room temperature 48h, utilize surface tension instrument (K12, Kruss Co., Germany) adopt suspension ring method to measure the surface tension of the variable concentrations aqueous solution at 25 DEG C.
Record the critical micelle concentration CMC(mol/L of amine salt type fluorine surfactant prepared by the present invention) and critical micelle concentration under surface tension γ
cmc(mN/m) be respectively 0.1009mmol/L and 27.03mN/m, can learn, the Gemini amine salt type fluorine surfactant synthesized by the present invention has lower surface tension, reduces the tendency of the capillary tendency of the aqueous solution much larger than aggregation formation micelle; Low 2 ~ 3 orders of magnitude of ratio of the CMC conventional surfactants.
Claims (6)
1. the amine salt of Gemini shown in formula I type fluorine surfactant,
In formula I, R is C
mh
2m+1shown group, wherein m is the integer between 0 ~ 3, and n is the integer between 2 ~ 8.
2. fluorine surfactant according to claim 1, is characterized in that: m is 0, n is 6.
3. the preparation method of the amine salt of Gemini shown in formula I type fluorine surfactant, comprises the steps:
(1) diamines shown in 3-perfluoro hexyl-1,2-expoxy propane and formula II carries out being obtained by reacting compound shown in formula III;
Wherein, n is the integer between 2 ~ 8; R is C
mh
2m+1shown group, m is the integer between 0 ~ 3;
(2) in the alcoholic solution of compound shown in formula III, pass into HCl gas, obtain the amine salt of Gemini shown in formula I type fluorine surfactant through salt-forming reaction;
In step (1), the temperature of described reaction is 10 ~ 80 DEG C, and the time is 3 ~ 12h;
In step (1), the mol ratio of diamines shown in 3-perfluoro hexyl-1,2-expoxy propane and formula II is 2:1 ~ 1.5;
In step (2), the temperature of described salt-forming reaction is 20 ~ 90 DEG C, and the time is 5 ~ 10h.
4. preparation method according to claim 3, is characterized in that: in step (1), and the temperature of described reaction is 35 ~ 80 DEG C.
5. preparation method according to claim 3, is characterized in that: in step (2), and the temperature of described salt-forming reaction is 60 ~ 80 DEG C, and the time is 6 ~ 8h.
6. the preparation method according to claim 3 or 5, is characterized in that: in step (2), and described alcoholic solution is methanol solution or ethanolic solution.
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Citations (4)
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|---|---|---|---|---|
| JP4170209B2 (en) * | 2003-12-16 | 2008-10-22 | 花王株式会社 | Quaternary ammonium salt composition and process for producing the same |
| CN102794133A (en) * | 2012-05-08 | 2012-11-28 | 内蒙古大学 | Cationic surfactant and preparation method thereof |
| CN102814144A (en) * | 2012-09-03 | 2012-12-12 | 山东大学 | Environment-friendly positive ion fluorinated surfactant based on short perfluorocarbon chain and preparation method thereof |
| CN103111229A (en) * | 2013-03-08 | 2013-05-22 | 山东大学 | Gemini type fluorocarbon surfactant containing sulfonic group and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4170209B2 (en) * | 2003-12-16 | 2008-10-22 | 花王株式会社 | Quaternary ammonium salt composition and process for producing the same |
| CN102794133A (en) * | 2012-05-08 | 2012-11-28 | 内蒙古大学 | Cationic surfactant and preparation method thereof |
| CN102814144A (en) * | 2012-09-03 | 2012-12-12 | 山东大学 | Environment-friendly positive ion fluorinated surfactant based on short perfluorocarbon chain and preparation method thereof |
| CN103111229A (en) * | 2013-03-08 | 2013-05-22 | 山东大学 | Gemini type fluorocarbon surfactant containing sulfonic group and preparation method thereof |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC research institute limited liability company Patentee after: China Offshore Oil Group Co., Ltd. Co-patentee after: Shandong University Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC Research Institute Patentee before: China National Offshore Oil Corporation Co-patentee before: Shandong University |
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