CN103406064B - Gemini quaternary fluorine surfactant and preparation method thereof - Google Patents
Gemini quaternary fluorine surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Gemini quaternary fluorine surfactant and preparation method thereof.Described Gemini quaternary fluorine surfactant is such as formula shown in I.In formula I, R is C
mh
2m+1shown group, wherein m is the integer between 1 ~ 3, and n is the integer between 2 ~ 8.The preparation method of the fluorine surfactant of Gemini quaternary shown in formula I provided by the present invention, comprises the steps: that shown in (1) 3-perfluoro hexyl-1,2-expoxy propane and formula II, diamines carries out being obtained by reacting compound shown in formula III; Wherein, n is the integer between 2 ~ 8; R ' is C
ph
2p+1shown group, p is the integer between 0 ~ 3; (2) under an inert atmosphere, compound shown in formula III and iodomethane obtain the quaternary of Gemini shown in formula I fluorine surfactant through quaterisation.Gemini quaternary fluorine surfactant provided by the invention has excellent surface property and good frothing capacity.Raw materials used cheap and easy to get, the preparation method of preparation method provided by the invention is simple, reaction condition is easy to control, product is easy to purify.
Description
Technical field
The present invention relates to a kind of Gemini quaternary 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; 4) 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 quaternary fluorine surfactant and preparation method thereof, quaternary fluorine surfactant provided by the invention has excellent surface property and good frothing capacity.
The fluorine surfactant of Gemini quaternary shown in formula I provided by the present invention,
In formula I, R is C
mh
2m+1shown group, wherein m is the integer between 1 ~ 3, and n is the integer between 2 ~ 8.
In above-mentioned Gemini quaternary fluorine surfactant, m is preferably 1, n and is preferably 6.
The preparation method of the fluorine surfactant of Gemini quaternary shown in formula I provided by the invention, 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
ph
2p+1shown group, p is the integer between 0 ~ 3;
(2) under nitrogen protection and acid binding agent existent condition, namely compound shown in formula III and iodomethane reaction obtain the quaternary amine of Gemini shown in formula I salt form fluorine surfactant.
In above-mentioned preparation method, n is preferably 6, m and is preferably 1, p 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 describedization reaction can be 0 ~ 70 DEG C, and the time can be 8 ~ 30h, after reaction terminates, and available methyl alcohol and re-crystallizing in ethyl acetate.
In above-mentioned preparation method, in step (2), the temperature of described reaction can be preferably 10 ~ 40 DEG C, specifically can be 20 DEG C, and the time can be preferably 12 ~ 24h, specifically can be 24h.
In above-mentioned preparation method, in step (2), the mol ratio of compound shown in formula III and iodomethane can be 1:3 ~ 6, specifically can be 1:4.
In above-mentioned preparation method, in step (2), described acid binding agent can be Anhydrous potassium carbonate, potassium hydroxide, pyridine or triethylamine, preferred Anhydrous potassium carbonate.
Gemini quaternary fluorine surfactant provided by the invention has excellent surface property and good frothing capacity.The preparation method of Gemini quaternary 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 200mlTHF 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, thermometer and constant pressure funnel are housed; the 22.0g(0.025mol of compound shown in formula III-1 is added) under nitrogen protection; 150ml acetone as solvent; 6.0g potash does acid binding agent; iodomethane 14.2g(0.1mol is dripped) with constant pressure funnel; in stirred at ambient temperature reaction 24h after dripping; a large amount of solid is had to separate out after reaction terminates; acetone and excessive iodomethane are steamed except reclaiming; obtain yellow solid product; by methyl alcohol and re-crystallizing in ethyl acetate, obtain white solid product 16.4g.
The structural characterization data of formula I-1 prepared by the present embodiment are as follows:
1HNMR(300MHz,CD
3OD,δ/ppm):δ=1.529(m,4H,N-CH
2-CH
2-(CH
2)
2-CH
2-CH
2-N),δ=1.909(m,4H,N-CH
2-CH
2-(CH
2)
2-CH
2-CH
2-N),δ=2.494(m,4H,2CH
2-C
6F
13),δ=3.26-3.63(m,20H,4CH2-N,4CH
3-N),δ=4.749(m,2H,CH-O)；
19fNMR (300MHz, CDCl3, δ/ppm): δ=-82.414 (m, 6F, CF3), δ=-113.955 (m, 4F, CF2 α), δ=-122.727 (m, 4F, CF2 β), δ=-123.850 (m, 4F, CF2 γ), δ=-124.560 (m, 4F, CF2 δ), δ=-127.247 (m, 4F, CF2 ω), structure is correct.
The synthesis of embodiment 4, N, N '-two (3-perfluoro hexyl-2-hydroxypropyl) hexamethylene-diamine hydrochloride (formula I-1)
Mechanical agitator is being housed, reflux condensing tube, in the 500ml four-hole bottle of thermometer and constant pressure funnel, the 22.0g(0.025mol of compound shown in formula III-1 is added) under nitrogen protection, 150ml acetone as solvent, 6.0g potash does acid binding agent, at 10 DEG C, iodomethane 14.2g(0.1mol is dripped) with constant pressure funnel, drip and slowly rise to room temperature afterwards, stirring reaction 24h, a large amount of solid is had to separate out after reaction terminates, acetone and excessive iodomethane are steamed except reclaiming, obtain yellow solid product, by methyl alcohol and re-crystallizing in ethyl acetate, obtain white solid product 16.8g.
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, thermometer and constant pressure funnel are housed; the 22.0g(0.025mol of compound shown in formula III-1 is added) under nitrogen protection; 150ml acetone as solvent; 4.5g triethylamine does acid binding agent; iodomethane 14.2g(0.1mol is dripped with constant pressure funnel) under room temperature; in stirred at ambient temperature reaction 24h after dripping; a large amount of solid is had to separate out after reaction terminates; acetone and excessive iodomethane are steamed except reclaiming; obtain yellow solid product; by methyl alcohol and re-crystallizing in ethyl acetate, obtain white solid product 15.6g.
Embodiment 6, prepare the pure water solution of the cation fluorine surfactant of Gemini type shown in formula I-1 with high purity water (ρ=18.23M Ω .cm), after equilibrate at room temperature 48h, utilize surface tension instrument (K12, KrussCo., 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 cation fluorine surfactant prepared by the present invention) and critical micelle concentration under surface tension γ
cmc(mN/m) be respectively 0.5085mmol/L and 23.14mN/m, can learn, the Gemini quaternary 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 (5)
1. the preparation method of the quaternary of Gemini shown in formula I fluorine surfactant, comprises the steps:
In formula I, R is C
mh
2m+1shown group, wherein m is the integer between 1 ~ 3, and n is the integer between 2 ~ 8;
(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
ph
2p+1shown group, p is the integer between 0 ~ 3;
(2) under nitrogen protection and acid binding agent existent condition, compound shown in formula III and iodomethane obtain the quaternary of Gemini shown in formula I fluorine surfactant through quaterisation;
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 (1), the temperature of described reaction is 10 ~ 80 DEG C, and the time is 3 ~ 12h;
In step (2), the mol ratio of compound shown in formula III and iodomethane is 1:3 ~ 6;
In step (2), the temperature of described quaterisation is 0 ~ 70 DEG C, and the time is 8 ~ 30h.
2. preparation method according to claim 1, is characterized in that: m is 1, n is 6.
3. preparation method according to claim 1, is characterized in that: described acid binding agent is Anhydrous potassium carbonate, potassium hydroxide, pyridine or triethylamine.
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 4, is characterized in that: in step (2), and the temperature of described quaterisation is 10 ~ 40 DEG C, and the time is 12 ~ 24h.
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| CN102688722A (en) * | 2012-06-07 | 2012-09-26 | 广西大学 | Hydrogenated rosin-based quaternary ammonium salt gemini 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102688722A (en) * | 2012-06-07 | 2012-09-26 | 广西大学 | Hydrogenated rosin-based quaternary ammonium salt gemini 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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| Title |
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| 磺酸盐型Gemini表面活性剂合成研究进展;周明等;《应用化学》;20110831;第28卷(第8期);第855-863页 * |
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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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Effective date of registration: 20191211 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. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC research institute limited liability company Patentee before: China Offshore Oil Group Co., Ltd. Co-patentee before: Shandong University |
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