CN103877909A - Anionic fluorocarbon surfactant and preparation method thereof - Google Patents
Anionic fluorocarbon surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an anionic fluorocarbon surfactant and a preparation method thereof. The structural formula of the anionic fluorocarbon surfactant is as follows: CF3CF2CF2C(CF3)2CH2C6H4PO(OM)2, wherein M is equal to Li, Na, K or NH4. The preparation method comprises the following steps: (1) reacting hexafluoropropylene dimer and p-Bromobenzyl bromide to generate a fluorine-containing intermediate compound 1; (2) coupling the fluorine-containing intermediate compound 1 with dimethyl phosphite to obtain a fluorine-containing intermediate compound 2; (3) hydrolyzing the fluorine-containing intermediate compound 2 to generate a fluorine-containing organic acid 3; and (4) neutralizing the fluorine-containing organic acid 3 with alkali to obtain a product. The method has the advantages of being, simple, low in cost and good in repeatability, and raw materials can be easily obtained. The surface tension performance of the product is good.
Description
Technical field
The invention belongs to fluorocarbon surfactant technology of preparing, particularly a kind of containing branch fluorocarbon chain environment-friendly type high surface tension activity anion fluorocarbon surfactant and technology of preparing thereof.
Background technology
Fluorocarbon surfactant is most important kind in special surfactant, requires in special field many, has the irreplaceable important use of a lot of hc-surfactants.
The special performance of fluorocarbon surfactant is often summarized as " three height ", " two hate ", i.e. high surface, high heat-resistant stability and high chemical stability; Not only hydrophobic but also hate oil of its fluorine-containing alkyl.
Fluorocarbon surfactant has very high heat resistance and very high chemical stability, the effect that it can resist strong oxidizer, strong acid and highly basic, and in this solution, still can keep good surface-active.If be made into oil soluble surfactant and also can reduce the surface tension of organic solvent.It is hc-surfactant 0.1～0.01 that fluorine surfactant reaches with the same surface tension desired concn of hc-surfactant.
In early days, fluorocarbon surfactant was once used as the emulsifying agent of tetrafluoroethene emulsion polymerisation, later progressively as wetting agent, spreading agent, foaming agent, antitackiness agent and anti-fouling agent etc., be widely used in each neighborhoods such as fire-fighting, weaving, leather, papermaking, ore dressing, electronics, agricultural chemicals and chemical industry, kind is more, and purposes is extremely wide.
Fluorocarbon surfactant is normally made up of perfluor chain and hydrophilic chain, modal fluorocarbon surfactant mainly comprises: the perfluoro octane sulfonate (PFOS of different hydrophobic chain lengths, Perfluorooctanesulfonate), the perfluoro caprylic acid (PFOA, Perfluorooctanoicacid) of different hydrophobic chain lengths etc.As mentioned above, this class fluorocarbon surfactant has very high chemical stability, and they even can resist the effect of strong oxidizer, strong acid and highly basic.Current research shows, intermolecular Van der Waals force is little causes due to it for the high surface of fluorocarbon surfactant, it is little that surfactant molecule moves to the required tension force of solution surface from the aqueous solution, cause active agent molecule in a large amount of gathering of solution surface, form strong adsorption, and this class fluorocarbon surfactant is not only little to the affinity of water, and also less to the affinity of hydrocarbon, therefore forms not only hydrophobic but also hated oily characteristic.In view of above-mentioned distinctive very good physicochemical properties, fluorocarbon surfactant, the especially fundamental research of PFOS/PFOA class fluorocarbon surfactant attract widespread attention always.
At present, PFOS/PFOA class fluorocarbon surfactant has been widely used in the fields such as extinguishing chemical, photosensitive material surface conditioning agent, textile finish, semi-conductor industry clean and surface treatment liquid, aerospace industry inert fluid, electrodeposited chromium mist suppressing agent, industry and daily cleaning agent aid, coating and additive paint, insecticides adjuvant, cosmetic additive, oil exploitation auxiliary agent, the efficient emulsifying agent of fluorine chemical.
But research shows: PFOS/PFOA class fluorocarbon surfactant is one of material of the difficult degradation found at present, and they not only have persistence, bioaccumulation, even also have the possibility of long distance environment migration.Once organism is taken in PFOS/PFOA class fluorocarbon surfactant, it can be distributed in blood of human body and liver, due to its intrinsic stability, therefore be difficult to decompose by the metabolism of human body, for example " half efflux time " of perfluoro octyl sulfonic acid in human body reaches 8.7 years, be that PFOS/PFOA fluorocarbon surfactant has very high bioconcentration and multiple toxicity in human body, not only can cause the injury to human respiratory, even can cause ewborn infant death.Accordingly, Environmental Protection Agency (EPA) has been issued 2010～2015 years perfluoro caprylic acids of voluntary and its esters environmental planning, i.e. 2010/15PFOA Stewardship Program; This plan regulation PFOS/PFOA class fluorocarbon surfactant can progressively be forbidden producing and selling and use.Therefore, develop brand-new degradable fluorocarbon surfactant to replace existing PFOS/PFOA class fluorocarbon surfactant comprehensively, and evaluate its biological degradability and the impact on environment simultaneously, become one of urgent theoretical research problem, and caused various countries researchers' great attention.
The preparation of fluorocarbon chain is the basic step of preparing in fluorocarbon surfactant method, then on the fluorocarbon chain making, introduces and connects base, and then introduce hydrophilic group.The method of preparing at present fluorocarbon chain monomer industrial be employed mainly contain three kinds: electrofluorination method, fluoroolefins telomerization method and fluoroolefins oligomerisation method.
Fluoroolefins oligomerisation method is to utilize fluoroolefins to obtain highly branched low polymerization degree (C4-C6) perfluoroolefine oligomer with fluorine anion catalysis generation oligomerisation reaction in aprotic polar solvent.It is developed at first by people such as the J.Hutchinson of ICI company of Britain, and the most frequently used is oligomerization of hexafluoropropylene method etc.
nCF
2=CF
2→(CF
2CF
2)
n (n=4-5)
nCF
3CF=CF
2+F
-→(CF
3CFCF
2)n (n=2-3)
Utilize the activity of the fluorine on the carbon atom being connected with two keys on these condensates to be easy to and the nucleopilic reagent generation necleophilic reaction of nitrogenous, oxygen and sulphur, thereby generate the fluorocarbon surfactant of branched chain type.The fluorocarbon surfactant production technology of this class branched chain type is simple, and cost compare is cheap, but because the surface-active of branched product is not high, therefore its application is subject to larger restriction.
From structure, fluorine surfactant is similar to conventional surfactants, is all made up of afterbody R hydrophilic group and hydrophobic group
fbe a not only hydrophobic but also hate oily fluorocarbon chain (can be straight or branched), general optimum carbon fluorine chain length is 6～10.The fluorocarbon surfactant of straight chain shows minimum surface tension under relatively high working concentration, and side chain fluorocarbon surfactant uses under relatively low concentration, reduces surface tension but more effective.
To sum up, we select take the hexafluoropropylene dimmer that obtains by oligomerisation method as initial feed, synthesize a series of branch type anionic fluorosurfactants, overcome the shortcomings such as electrofluorination method, telomerization method energy consumption are large, expensive, have raw material be easy to get, synthetic simple, cost is low, cost performance high.
Summary of the invention
The object of the present invention is to provide a kind of containing CF
3cF
2cF
2c (CF
3)
2group anionic fluorocarbon surfactant and preparation method thereof, method of the present invention comprises: (1) hexafluoropropylene dimmer and bromine cylite reaction is generated to fluoro-containing intermediate compound 1; (2) fluoro-containing intermediate compound 1 generates fluoro-containing intermediate compound 2 with dimethylphosphite coupling; (3) fluoro-containing intermediate compound 2 generates fluorine-containing organic acid 3 after hydrolysis; (4) fluorine-containing organic acid 3 neutralizes to obtain product with alkali.The method has following advantage: raw material is easy to get, technique is simple, cheap, reproducible and product surface tension force performance is good.
The present invention is as follows containing the structural formula of branch type fluorocarbon chain anionic fluorocarbon surfactant:
Wherein, M is Li, Na, K or NH
4.
Preparation method containing branch type fluorocarbon chain anionic fluorocarbon surfactant of the present invention, can represent by reaction equation:
Preparation method of the present invention comprise the steps: (1) to bromine cylite, perfluoro-2-methyl-2-amylene and fluoride by the mixed in molar ratio of 1:1～2:1～2, with polar solvent stirring reaction 10～48h or adopt thin-layer chromatography TLC to follow the tracks of to react, obtain fluoro-containing intermediate compound 1 at 40～100 ℃; Described alkali is inorganic base or organic base; Described organic polar solvent is glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, acetonitrile, dimethyl sulfoxide (DMSO) or dimethyl formamide; Described fluoride is monovalence metal fluoride, Methanaminium, N,N,N-trimethyl-, fluoride or their mixture; Described monovalence metal fluoride is NaF, KF, CsF or RbF.Described employing TLC follows the tracks of reaction, and solvent is PE and EA, volume ratio V
pE: V
eA=20～9:1～0.
(2) fluoro-containing intermediate 1, dimethylphosphite and four (triphenyl phosphorus) palladium are pressed the mixed in molar ratio of 1:1.1～2:0.01～0.1, react 2～24h or TLC tracking reaction with base catalyst and solvent at 60～120 ℃, obtain fluoro-containing intermediate compound 2;
Described inorganic base catalyst is one of following: natrium carbonicum calcinatum, Anhydrous potassium carbonate, natrium carbonicum calcinatum, NaOH, potassium hydroxide; Described organic base is triethylamine, diethylamine, pyridine, piperidines or N-methyl piperidine.
Described follows the tracks of and reacts with TLC, and solvent is PE and EA, volume ratio V
pE: V
eA=1:1～8.
(3) compound 2 back hydrolysis 1-2 days under excessive hydrochloric acid aqueous environment obtains fluorine-containing organic acid compound 3;
(4), in organic solvent, fluorine-containing organic acid, at room temperature with preparing corresponding salt after the metal hydroxides aqueous solution of lithium, sodium, potassium or ammonia neutralization, obtains described containing branch fluorocarbon chain anionic fluorocarbon surfactant; Described organic solvent is toluene, benzene, oxolane, acetonitrile, dimethyl sulfoxide (DMSO) DMSO, dimethyl formamide DMF, dioxane or cyclohexane.
The reaction suggestion of step (2) is carried out in inert gas, as nitrogen, argon gas etc.
The product of above-mentioned steps (1), (2), (3) or (4) is through solvent wash, dry, the removal solvent that filters, reduces pressure, post purification purifying.
Substantive distinguishing features of the present invention can be achieved from following examples of implementation, but the only conduct explanation of these examples of implementation, rather than limit the invention.
Accompanying drawing explanation
Fig. 1 is aqueous solution surface tension and the concentration curve of embodiment.
Wherein, surface tension presentation surface tension force, concentration represents concentration.
The specific embodiment
Below in conjunction with example, the present invention is described in further detail.
Embodiment 1: fluoro-containing intermediate compound 1 synthetic
In 50mL tube sealing, add successively 5g to bromine bromobenzyl, 12g perfluoro-2-methyl-2-amylene, 2.32g potassium fluoride and 30mLDMF, at 100 ℃, react 24 hours.System is down to room temperature, and mixed system is poured in ether, and organic phase washes twice through deionized water first, then with saturated common salt washing, finally adds anhydrous sodium sulfate drying, filters, and removes solvent.Mixture is crossed post through silicagel column and is purified, and eluant, eluent is benzinum, obtains 5.86g compound 1.
1H NMR(CDCl
3,300MHz):δ(ppm)3.50(s,CH
2,2H),7.12-7.22(d,J=8.4Hz,Ar-H,2H),7.40-7.50(d,J=8.4Hz,Ar-H,2H);
19F NMR(CDCl
3,282MHz,):δ(ppm)-62.63～-62.85(m,6F),-80.40～-80.60(t,3F),-106.20～-106.60(m,2F),-123.30～-123.60(m,2F).
Embodiment 2: fluoro-containing intermediate compound 2 synthetic
In 50mL tube sealing, add 0.046g tetra-(triphenyl phosphorus) palladium, substitute after gas three times, under argon shield, add 1.952g compound 1,0.54mL HPO (OMe)
2, 0.83mL Et
3n and 20mL toluene, add rear system sealing, reacts 12 hours at 100 ℃.System is down to room temperature, adds ether, filters, and filtrate decompression is removed solvent, and mixture is crossed post through silicagel column and purified, and eluant, eluent polarity rises to 1:4 by PE:EA=1:1, the final 1.55g colourless liquid 2 that obtains.
1H NMR(CDCl
3,300MHz):δ(ppm)3.54(s,CH
2,2H),3.73(d,J=11.1Hz,6H),7.38(dd,J=7.8,3.4Hz,Ar-H,2H),7.72(dd,J=13.1,8.2Hz,Ar-H,2H);
19F NMR(CDCl
3,282MHz,):δ(ppm)-62.70～-62.90(m,6F),-80.50～-80.70(t,3F),-106.30～-106.60(m,2F),-123.40～-123.60(m,2F);
31P NMR(CDCl
3,121MHz):δ(ppm)22.27(s);
13C NMR(100MHz,CDCl
3):δ(ppm)32.21,52.29,105～124,126.02,127.91,131.40,135.58;HRMS(EI):m/z calcd forC
6F
13CH
2C
6H
4PO(OCH
3)
2:518.0317,found518.0315.
Embodiment 3: fluoro-containing intermediate compound 3 synthetic
5g compound 2,30mL water and 20mL concentrated hydrochloric acid reflux two days.Product becomes blocks of solid, filters, and washing, then chloroform washing, decompression is lower to desolventizing, obtains 4.5g white solid 3.
1H NMR(DMSO-d
6,300MHz):δ(ppm)3.69(s,CH
2,2H),7.31～7.40(m,Ar-H,2H),7.58～7.70(m,Ar-H,2H);
19F NMR(DMSO-d
6,282MHz,):δ(ppm)-62.60～-62.83(m,6F),-80.95～-81.15(t,3F),-106.50～-106.90(m,2F),-123.50～-123.80(m,2F);
31P NMR(DMSO-d
6,121MHz):δ(ppm)13.70(s);
13C NMR(DMSO-d
6,100MHz):δ(ppm)31.56,110～130,130.41,131.46,132.86,133.76,134.67;IR(cm
-1):3400～3600,1455.2;LRMS(EI):490,171.;HRMS(EI):m/z calcd for C
6F
13CH
2C
6H
4PO(OH)
2:490.0005,found490.0003.
Embodiment 4: anionic fluorocarbon surfactant 4 synthetic
0.49g compound 3 is dissolved in 10mL oxolane, slowly drips the lithium hydroxide aqueous solution of 0.1mol/L to system PH=7.Under decompression, except desolventizing obtains white solid, after washing with acetone, obtain 0.37g white powder anionic fluorocarbon surfactant 4.
1H NMR(D
2O,300MHz):δ(ppm)3.55(s,C
6F
13CH
2C
6H
4,2H),7.15～7.55(m,Ar-H,4H);
19F NMR(D
2O,282MHz,):δ(ppm)-62.80～-63.20(m,6F),-80.60～-80.80(t,3F),-106.40～-106.80(m,2F),-123.30～-123.60(m,2F);
31P NMR(D
2O,121MHz):δ(ppm)12.45(s);IR(cm
-1):1610.1,1455.9,1411.4,1334.5;Anal.Calcd for C
13H
6F
13Li
2O
3P:Li,2.77.Found:Li,2.81.
Embodiment 5: the aqueous solution surface tension of compound 4
At 25 ℃, adopt the full-automatic surface tension instrument K100 plate of German Kruss method to measure respectively the surface tension of the aqueous solution of compound 4 under variable concentrations, obtain table 1 data.
The aqueous solution surface tension value of compound 4 under table 1. variable concentrations
Claims (7)
1. the anionic fluorocarbon surfactant as shown in structural formula I:
Wherein, M is Li, Na, K or NH
4.
2. according to claim 1 suc as formula the anionic fluorocarbon surfactant containing branch fluorocarbon chain shown in I, it is characterized in that described preparation method comprises the steps:
(1) bromine cylite, perfluoro-2-methyl-2-amylene and fluoride are pressed to the mixed in molar ratio of 1:1～2:1～2, stirring reaction 10～48h in organic polar solvent and at 40～100 ℃, obtains fluoro-containing intermediate compound 1; Described organic polar solvent is glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, acetonitrile, dimethyl sulfoxide (DMSO) or DMF; Described fluoride is monovalence metal fluoride, Methanaminium, N,N,N-trimethyl-, fluoride or their mixture;
(2) in organic solvent and at 60～120 ℃, fluoro-containing intermediate 1, dimethylphosphite and four (triphenyl phosphorus) palladium are pressed the mixed in molar ratio of 1:1.1～2:0.01～0.1, under nitrogen protection, inorganic base or organic alkali catalyst catalytic reaction 2～24h or TLC follow the tracks of and react to obtain fluoro-containing intermediate compound 2;
(3) compound 2 obtains fluorine-containing organic acid compound 3 under the aqueous environment of excessive hydrochloric acid;
(4) by described fluorine-containing organic acid 3 at room temperature with organic solvent in preparing corresponding salt after the metal hydroxides aqueous solution of lithium, sodium, potassium or ammonia neutralization, obtain the described anionic fluorocarbon surfactant containing branch fluorocarbon chain; Described organic solvent is toluene, benzene, oxolane, acetonitrile, dimethyl sulfoxide (DMSO), dimethyl formamide, dioxane or cyclohexane.
3. preparation method according to claim 2, is characterized in that the monovalence metal fluoride described in step (1) is NaF, KF, CsF or RbF.
4. preparation method according to claim 2, is characterized in that adopting TLC to follow the tracks of reaction in step (1), and solvent is PE and EA, volume ratio V
pE: V
eA=20～9:1～0.
5. preparation method according to claim 2, is characterized in that the inorganic base catalyst described in step (2) is one of following: natrium carbonicum calcinatum, Anhydrous potassium carbonate, natrium carbonicum calcinatum, NaOH, potassium hydroxide; Described organic base is triethylamine, diethylamine, pyridine, piperidines or N-methyl piperidine.
6. preparation method according to claim 2, is characterized in that adopting TLC to follow the tracks of reaction in step (2), and solvent is PE and EA, volume ratio V
pE: V
eA=1:1～8.
7. preparation method according to claim 2, is characterized in that the product of step (1), (2), (3) or (4) is through solvent wash, dry, the removal solvent that filters, reduces pressure, post purification purifying.
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| CN104941508B (en) * | 2015-03-24 | 2016-09-14 | 中国科学院上海有机化学研究所 | Fluorocarbon surfactant containing branch fluorocarbon chain and preparation method thereof |
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| CN104941508B (en) * | 2015-03-24 | 2016-09-14 | 中国科学院上海有机化学研究所 | Fluorocarbon surfactant containing branch fluorocarbon chain and preparation method thereof |
| CN104906996A (en) * | 2015-04-28 | 2015-09-16 | 三明市海斯福化工有限责任公司 | Sulfonate-type fluorine-containing surfactant and synthetic method and application thereof |
| CN108999022A (en) * | 2018-07-05 | 2018-12-14 | 常州思宇知识产权运营有限公司 | A kind of preparation method of high intensity greaseproof |
| CN112169242A (en) * | 2020-11-30 | 2021-01-05 | 河南理工大学 | Composite gas-liquid two-phase fire extinguishing agent for inhibiting flame enhancement at initial stage of water mist fire extinguishing |
| CN112169242B (en) * | 2020-11-30 | 2022-04-26 | 河南理工大学 | Composite gas-liquid two-phase fire extinguishing agent for inhibiting flame enhancement at initial stage of water mist fire extinguishing |
| CN116217447A (en) * | 2023-02-27 | 2023-06-06 | 南京理工大学 | Synthesis and compound mixture of sulfonate fluorocarbon surfactant |
| CN116217447B (en) * | 2023-02-27 | 2024-05-24 | 南京理工大学 | Synthesis and compound mixture of sulfonate fluorocarbon surfactant |
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