CN105664784B - fluorine-containing surfactant and preparation method thereof - Google Patents
fluorine-containing surfactant and preparation method thereof Download PDFInfo
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- CN105664784B CN105664784B CN201511031114.3A CN201511031114A CN105664784B CN 105664784 B CN105664784 B CN 105664784B CN 201511031114 A CN201511031114 A CN 201511031114A CN 105664784 B CN105664784 B CN 105664784B
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Abstract
The present invention relates to a kind of fluorine-containing surfactant and preparation method thereof, a kind of fluorine-containing surfactant of the present invention, the structural formula of compound is：Surface property of the present invention is excellent, the discharge without waste water and exhaust gas in preparation process, and the foam solution after compounding can be used as fire foam.It does not pollute the environment in use, it is environmentally friendly, it is widely used, can be used in the fields such as oil, chemical industry and fire-fighting foams.
Description
Technical field
The present invention relates to a kind of surfactants, and in particular to a kind of fluorine-containing surfactant and preparation method thereof.
Background of invention
Fluorine-containing surfactant have high surface, high thermal stability, high chemical stability and not only hydrophobic but also hate oil
Property has the Some features that other surfactants do not possess.Using PFOA and PFOS and its derivative as the one of representative
Class surfactant is used by relevant industries with its excellent performance, receives pro-gaze.But due to PFOA and PFOS and its
The refractory organics of derivative and enrichment in vivo, cause environment seriously to pollute, the mankind are caused directly and
The life threat connect, and the cycle is permanent.2004, though have《Convention of Stockholm on persistence organic pollutant》
It comes into force in the world, but since the temporary irreplaceability of its performance, PFOA and PFOS and its derivative still exist in some fields
It uses.Therefore, exploitation has excellent performance, is multi-functional, safety and environmental protection substitute becomes the task of top priority.
Bola types surfactant causes scientific research people as a kind of surfactant that is new, having property
The extensive concern of member.
The content of the invention
The object of the present invention is to provide a kind of fluorine-containing surfactant and preparation method thereof, the compound surface performance is excellent
Different, the discharge without waste water and exhaust gas in preparation process, the foam solution after compounding can be used as fire foam.In use
It does not pollute the environment, it is environmentally friendly, it can be applied in fields such as oil, chemical industry and fire-fighting foams.
A kind of fluorine-containing surfactant of the present invention, the structural formula of compound are：
Wherein,
R1、R2、R3、R4Structure is CH3Or straight chain C H3(CH2)p, p is the integer of 1-4；
R5、R6Structure is H or CH3；
M, the integer that it is 1-6 that n, which is,；
RfIt is fluorine-containing linking group, structure isWherein q is the integer of 1-6；
X, the chemical constitution of Y is (CH2)sCOO-、O-、CH3(CH2)t、(CH2)gSO3 -In one kind, wherein s be 1-7 it is whole
Number, t are the integer of 0-7, and g is the integer of 1-4.
When X, Y are (CH2)sCOO-、CH3(CH2)tIt is linear chain structure or branched structure, in same chemistry knot during structure
In structure formula, the chemical constitution of X and Y are identical or different.
At 20 DEG C, have in the aqueous solution of the compound concentration 1wt% no more than 21mN/m surface tension；At 20 DEG C,
Have in the aqueous solution of the compound concentration 0.1wt% no more than 22mN/m surface tension.
The order of magnitude of aqueous solution CMC is 10-5-10-4g/g。
The preparation method of the fluorine-containing surfactant, including two-step reaction, the first step is amidation process, second step
It is quaterisation.
Acid binding agent in amidation process is ammonium carbonate, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, calcium carbonate,
One or more in magnesium carbonate, ammonium hydrogen carbonate or triethylamine.It is preferred that sodium carbonate.
Involved in amidation process to diamine structures general formula be
It is preferred that N, N- dimethyl -1,3- propane diamine.
In amidation process, reaction temperature is 0-100 DEG C, reaction time 1-36h；In quaterisation, reaction temperature
For 50-260 DEG C, reaction time 4-120h.
The molar ratio of each substance is n in amidation processReactive fluorochemical object:nDiamines:nAcid binding agent=1:2.0-5.5:2.0-10；It is quaternized
Reactant ratio, the molar ratio of each substance is nIntermediate:nQuaternized raw material=1:2.0-5.5.
The structural formula of reactive fluorochemical object is FSO2-Rf-COF；
The structural formula of intermediate is
Quaternized raw material includes Cl (CH2)hCOONa、Br(CH2)hCOONa、Cl(CH2)iSO3Na、Br(CH2)iSO3Na、
H2O2, 1,3- propane sultones, any one in 1,4- butane sultones；Wherein h is 1~7 integer, and i is 1-4's
Integer.Quaterisation object ratio, when quaternized raw material is hydrogen peroxide, nHydrogen peroxide:nManganese dioxide=1:0.0001-1.
The compound of the present invention is a kind of single-stranded Bola types fluorine-containing surfactant.
The Bola type surfactants of the present invention are to be respectively provided with the complete of sulfuryl fluoride and carbonyl fluoride functional group with molecule both ends
Fluorine ether polymer is starting material, and a series of fluorine-containing amphoteric surfaces obtained successively by amidation process and quaterisation live
Property agent, structure and performance can be good at serving as substitute in some fields using PFOA and PFOS and its derivative.
The compound of the present invention performance is stablized, the discharge without waste water and exhaust gas in preparation process, the foam liquid energy after compounding
It is enough to make fire foam.In use, the dosage very little of actual fluorine-containing surfactant, thus during use not
It pollutes the environment, it is environmentally friendly.Due to the special construction of Bola type molecules, therefore the monomolecular film table formed in air liquid interface
Reveal some unique performances, therefore, as the foam stabiliser and extinguishing chemical in efficient foam extinguishing chemical, as nytron
The wetting agent of object solid or liquid surface, dispersant, the decontaminating cleaning agents as metal surface, tool in terms of the synthesis of nano material
Have broad application prospects.
Compound of the present invention is suitable as foam fire-fighting agent addition agent, metal conditioner, emulsifier.
Compared with prior art, the invention has the advantages that：
Fluorine-containing surfactant of the present invention and preparation method thereof, surface property is excellent, in preparation process without waste water and
The discharge of exhaust gas, the foam solution after compounding can be used as fire foam.It does not pollute the environment in use, to environment friend
It is good, it is widely used, can be used in the fields such as oil, chemical industry and fire-fighting foams.
Description of the drawings
The surface tension of aqueous solution of Fig. 1 embodiments 1 under various concentration；
The surface tension of aqueous solution of Fig. 2 embodiments 2 under various concentration.
Specific embodiment
With reference to embodiment, the present invention is described further, but the present invention is not limited thereto.
Embodiment 1
The preparation (amidation process) of intermediate -1：Sequentially add N in 500ml three neck round bottom, N- dimethyl -1,
3- propane diamine 30.8g (302mmol), dichloromethane 200ml, sodium carbonate 17.2g (182mmol), are placed in 30min in ice-water bath.
Stirring is started, 100g (147.4mmol) FO will be housed with liquid separation constant pressure funnel2S-CF2CF2OCF(CF3)CF2OCF(CF3)
CF2OCF(CF3) COF is slowly dropped in the three neck round bottom with temperature probe, controlling reaction temperature≤30 DEG C.It drips
Bi Hou, the 6h that controls at≤40 DEG C that the reaction was continued, the mixture after reaction is filtered.With white after 100ml ethyl alcohol dissolution filters
Color solid filters desalination again, and rotary evaporation removes the solvent in filtrate, and residue is dried in vacuo for 24 hours, obtains clear yellow viscous glue
Shape object 118g, yield 98%.The structural formula of intermediate is as follows：
Quaterisation：Gained -1 10g of intermediate (11.8mmol) is taken to be added in 100ml three neck round bottom, successively
Add in sodium chloroacetate 2.8g (24.3mmol), ethyl alcohol 30ml, triethylamine 0.06g, deionized water 0.15g, stirring, reflux at 80 DEG C
Reaction is for 24 hours.Filter while hot after completion of the reaction, decompression boils off solvent in filtrate, by clear yellow viscous jelly at 60 DEG C vacuum
Dry 36h, obtains product 10.2g, yield 85.7%.Product structure formula is as follows：
The surface tension of aqueous solution of Fig. 1 embodiments 1 under various concentration；
As shown in Figure 1, the CMC of aqueous solution is 4.9 × 10-5G/g, γCMCFor 21.5mN/m.
Embodiment 2
Quaterisation：Intermediate -1 10g, the ethyl alcohol 30ml of Example 1 are placed in the three neck round bottom of 100ml
In, 4.3g hydrogen peroxide (30%, wt) adds in three times, and 1.45g is added in per 8h.It is stirred at 50 DEG C, back flow reaction is for 24 hours.It adds in
Manganese dioxide 0.003g, the reaction was continued 3h.With starch potassium iodide paper verification hydrogen peroxide, the reaction was complete does not remain.It crosses while hot
Filter, boils off the solvent in filtrate, product 10g, yield is obtained after clear yellow viscous jelly is dried in vacuo 48h at 60 DEG C
93.5%.Product structure formula is as follows：
The surface tension of aqueous solution of Fig. 2 embodiments 2 under various concentration.
As shown in Figure 2, the CMC of aqueous solution is 2.0 × 10-4G/g, γCMCFor 21.6mN/m,.
Embodiment 3
Quaterisation：1 intermediate of Example -1 20g (23.7mmmol), isopropanol 80ml put into the three of 250ml
In neck round-bottom flask.80 DEG C are warming up to, 1,3- propane sultones 6.37g (52.2mmol), back flow reaction is slowly added dropwise in stirring
96h.It filters while hot after reaction, boils off the solvent in filtrate, clear yellow viscous jelly is dried in vacuo 48h, obtains product
22g, yield 85%.Product structure formula is as follows：
Embodiment 4
Quaterisation：- 1 15g (17.7mmol) of 1 intermediate of Example is added in 100ml three neck round bottom,
Sequentially add bromomethyl sodium sulfonate 8.37g (42.5mmol), isopropanol 50ml, triethylamine 0.09g, deionized water 0.22g, 80 DEG C
Lower stirring, condensing reflux reaction 36h.It filters while hot after completion of the reaction, boils off the solvent in filtrate, by clear yellow viscous jelly 60
DEG C vacuum drying 56h after obtain 17g, yield 92%.Product structure formula is as follows：
Embodiment 5
The preparation (amidation process) of intermediate -2：N, N- dimethyl -1,3- are sequentially added in 500ml three neck round bottom
Propane diamine 18.2g, dichloromethane 250ml, sodium carbonate 11.2g are placed in 30min in ice-water bath.Stirring is started, by 100gFO2S-
CF2(CF2OCF(CF3))6COF is slowly pumped into the three neck round bottom with temperature probe, controlling reaction temperature≤30 DEG C.
After being added dropwise, the 12h that controls at≤40 DEG C that the reaction was continued filters the mixture after reaction.With 150ml ethyl alcohol dissolution filters
White solid afterwards filters desalination again, and evaporation removes the solvent in filtrate, is dried in vacuo residue 65h, obtains buff and glue
Thick jelly 107g, yield 95%.The structural formula of intermediate -2 is as follows：
Wherein R "fFor CF2(CF2OCF
(CF3))6。
Quaterisation：- 2 15g of 5 gained intermediate of Example is added to the tri- neck round bottoms of 100ml with temperature probe
In flask, chloropropionic acid sodium 3.1g, ethyl alcohol 35ml, triethylamine 0.67g are sequentially added, deionized water 0.16g, stirring at 85 DEG C is returned
Stream reaction 45h.It filters while hot after completion of the reaction, decompression boils off the solvent in filtrate, by buff viscous gum at 65 DEG C
50h is dried in vacuo, obtains product 14.6g, yield 90.0%.Product structure formula is as follows：
Embodiment 6
The preparation (amidation process) of intermediate -3：Sequentially add N in 250ml three neck round bottom, N- dimethyl -1,
3- propane diamine 51.5g, chloroform 200ml, sodium carbonate 46g are placed in ice-water bath and keep 25min.Stirring is started, by 50gFO2S-
CF2CF2OCF(CF3) COF is slowly dropped in the three neck round bottom with temperature probe, controlling reaction temperature≤30 DEG C.Drop
After adding, the 9h that controls at≤40 DEG C that the reaction was continued filters the mixture after reaction.After 60ml propyl alcohol dissolution filters
White solid filters desalination again, and evaporation removes the solvent in filtrate, is dried in vacuo residue 75h, obtains faint yellow sticky glue
Shape object 72.9g, yield 99%.The structural formula of intermediate -3 is as follows：
Wherein R " 'fFor CF2CF2OCF
(CF3)。
Intermediate -3 25g, propyl alcohol 45ml of Example 6 are in the three neck round bottom of 100ml, 25g hydrogen peroxide
(30%, wt) is added in three times, and 8.3g is added in per 6h.Stirring, back flow reaction 35h at 60 DEG C.Manganese dioxide 0.12g is added in, after
Continuous reaction 7h.With starch potassium iodide paper verification hydrogen peroxide, the reaction was complete without being filtered while hot after residual, boils off in filtrate
Faint yellow clear yellow viscous jelly is dried in vacuo at 60 DEG C after 52h and obtains product 24.7g by solvent, yield 93.0%.Product
Structural formula is as follows：
Test method
The surface tension of sample aqueous solution under various concentration is tested using DuNouy hanging rings method.
At 20 DEG C, respectively prepare 1%, 0.5%, 0.2%, 0.1%, 0.05%, 0.02%, 0.01%, 0.005%,
0.002%th, under a series of 0.001% concentration sample aqueous solution, test 10 surface tension under each concentration of each sample
Value, is finally averaged as last surface tension value.Accuracy is ± 0.2mN/m.Graphing method acquires critical surface tension
With critical micelle concentration (CMC).Referring to attached drawing 1 and attached drawing 2.
The surface tension test data of 1 embodiment 1-4 of table：(unit：MN/m, 20 DEG C, test equipment is KRUSS100 interfaces
Tensiometer).
The surface tension test data of 1 embodiment 1-6 of table
| Sequence number | 1% (wt) | 0.1% (wt) | 0.01% (wt) |
| Embodiment 1 | 21.3 | 21.4 | 22.2 |
| Embodiment 2 | 21.4 | 21.9 | 23.3 |
| Embodiment 3 | 21.3 | 21.6 | 23.7 |
| Embodiment 4 | 21.1 | 22.0 | 23.6 |
| Embodiment 5 | 20.5 | 21.1 | 21.9 |
| Embodiment 6 | 21.0 | 21.5 | 22.0 |
Claims (1)
1. a kind of preparation method of fluorine-containing surfactant, which is characterized in that preparation process is as follows：
The preparation of intermediate -1：N, N- dimethyl -1,3- propane diamine 30.8g are sequentially added in 500mL three neck round bottom
(302mmol), dichloromethane 200mL, sodium carbonate 17.2g (182mmol) are placed in 30min in ice-water bath；Start stirring, with point
Liquid constant-pressure funnel will be equipped with 100g FO2S-CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3) COF is slowly dropped to and carries
In the three neck round bottom of temperature probe, controlling reaction temperature≤30 DEG C；After being added dropwise, control at≤40 DEG C that the reaction was continued
6h filters the mixture after reaction, with the white solid after 100mL ethyl alcohol dissolution filters, filters desalination again, rotation is steamed
Hair removes the solvent in filtrate, and residue is dried in vacuo for 24 hours, obtains clear yellow viscous jelly 118g, yield 98%；Intermediate -1
Structural formula it is as follows：
Quaterisation：Gained -1 10g of intermediate (11.8mmol) is taken to be added in 100mL three neck round bottom, is added successively
Enter sodium chloroacetate 2.8g (24.3mmol), ethyl alcohol 30mL, triethylamine 0.06g, deionized water 0.15g, stirring, reflux at 80 DEG C
Reaction is for 24 hours；Filter while hot after completion of the reaction, decompression boils off solvent in filtrate, by clear yellow viscous jelly at 60 DEG C vacuum
Dry 36h, obtains product 10.2g, yield 85.7%；
Product structure formula is as follows：
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1431037A (en) * | 2003-01-24 | 2003-07-23 | 中国科学院上海有机化学研究所 | 3 oxide heteroperfluoro-nonyl fluorocarbon surfactant, its systhesizing method and usages |
| US6624328B1 (en) * | 2002-12-17 | 2003-09-23 | 3M Innovative Properties Company | Preparation of perfluorinated vinyl ethers having a sulfonyl fluoride end-group |
| CN101367938A (en) * | 2008-10-10 | 2009-02-18 | 张永明 | Novel fluorine-containing polyamide sulfonylamine polymer and preparation method thereof |
| CN102389745A (en) * | 2011-08-15 | 2012-03-28 | 华中师范大学 | Preparation method of fluorine-containing double-type cationic surfactant and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6624328B1 (en) * | 2002-12-17 | 2003-09-23 | 3M Innovative Properties Company | Preparation of perfluorinated vinyl ethers having a sulfonyl fluoride end-group |
| CN1431037A (en) * | 2003-01-24 | 2003-07-23 | 中国科学院上海有机化学研究所 | 3 oxide heteroperfluoro-nonyl fluorocarbon surfactant, its systhesizing method and usages |
| CN101367938A (en) * | 2008-10-10 | 2009-02-18 | 张永明 | Novel fluorine-containing polyamide sulfonylamine polymer and preparation method thereof |
| CN102389745A (en) * | 2011-08-15 | 2012-03-28 | 华中师范大学 | Preparation method of fluorine-containing double-type cationic surfactant and use thereof |
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Effective date of registration: 20201202 Address after: 255401 Dongyue fluorosilicone Material Industrial Park, Huantai County, Zibo City, Shandong Province Patentee after: Shandong Dongyue future hydrogen energy materials Co., Ltd Address before: 256401 Tangshan Town, Huantai County, Zibo, Shandong Patentee before: SHANDONG HUAXIA SHENZHOU NEW MATERIAL Co.,Ltd. |
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