CN109261069A - A kind of quaternary fluorine silicon cationic surfactant and its synthetic method - Google Patents
A kind of quaternary fluorine silicon cationic surfactant and its synthetic method Download PDFInfo
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Abstract
A kind of quaternary fluorine silicon cationic surfactant and its synthetic method, the synthetic method is with degradable, less toxic fluorochemical C6F13SO2F is raw material, first with N- methyl allyl amine carry out bimolecular nucleophilic substitution (SN2) react preparation NSF6, then NSF6 successively with containing hydrogen silicone oil (PMHS) and N, N- dimethyl allylamine (DAEMA) progress silicon hydrogenation, finally again with CH3I carries out quaternization reaction and synthesizes fluorine silicon cationic surfactant PSF6DI.The present invention provides a kind of methods for preparing quaternary fluorine silicon cationic surfactant, the surfactant is compared with traditional fluorocarbon surfactant, while keeping higher surface-active, also there is preferable water-soluble and biological degradability, it is safe and environmentally friendly.
Description
Technical field
The present invention relates to a kind of quaternary fluorine silicon cationic surfactant and its synthetic methods.
Background technique
Fluorine silicon cationic surfactant is developed on the basis of fluorocarbon surfactant and organic silicon surfactant
A kind of novel surfactant come, the advantages of having organically combined fluorocarbon surfactant and organic silicon surfactant, because
And not only there is the lower surface energy and the excellent properties such as weather-proof, ageing-resistant, solvent resistant of fluorine material, but also have concurrently organic
The excellent properties such as heat resistance, the cold resistance of silicon materials；Simultaneously also with other types surfactant can not replace it is antistatic,
The special performances such as sterilization and softness, thus in fields such as space flight and aviation, automobile, electronics, liquid crystal, oil field, weaving, rubber and building materials
All it is with a wide range of applications.
Li Ting is with fluorine-containing hydrogen containing siloxane (FPHMS), epoxy terminated allyl polyethenoxy ether (APEE), triethanolamine
A kind of novel cation fluoride silicon surfactant is made through Si―H addition reaction, epoxy group ammonolysis ring-opening reaction Deng for raw material
(QAFS).The result shows that: the critical micelle concentration (cmc) of QAFS aqueous solution is 0.298g/L, surface tension (γ at cmccmc) be
27.74mN/m；The QAFS aqueous solution foaming power that mass fraction is 0.5% is that 1.93,5min foam stability is 0.821.
Currently, C8Class perfluor linear paraffin such as perfluorooctane sulfonate (PFOS) and perfluoro caprylic acid (PFOA) and its derivative,
It is widely used in fluorine-containing surfactant field because with good thermal stability and due to chemical stability.But it passes through
It crosses long-term the study found that the extremely difficult degradation in the environment of PFOS and PFOA and the two derivative, there is high biological cumulative bad, more
Kind of toxicity and can long distance environment migration the disadvantages of, in view of its lasting harm to environment, Convention of Stockholm is by it
It is classified as persistence organic pollutant (POPs), has begun to adopt various measures in the world and forbids or limit making for such product
With and find new substitute.
Pertinent literature report is it has been shown that can pass through " effective length " (usually C of shortening fluorocarbon chain4~C6) or in fluorine
It is inserted into the heteroatomic methods such as N, O in carbochain, makes fluorine-containing surfactant not only while keeping good surface-active, and
And also there is good degradability, so that it be made to substantially reduce the harm of environment.
Summary of the invention
Its of the invention purpose, which is that, provides a kind of quaternary fluorine silicon cationic surfactant and its synthetic method, solution
There is extremely difficult degradation in the environment in the existing surfactant of having determined, have high biological cumulative bad, a variety of toxicity and can long distance
The problem of from environmental transport and transfer.
It adopts the technical scheme that achieve the above object, a kind of quaternary fluorine silicon cationic surfactant, it should
The structural formula of compound are as follows:
Wherein RfAre as follows: C6F13SO2；Me is CH3；X and y is positive integer.
The lowest surface tension of the quaternary fluorine silicon cationic surfactant in aqueous solution be 19.8~
32.1mN/m, critical micelle concentration are 0.07~0.14g/L.
A kind of synthetic method of quaternary fluorine silicon cationic surfactant, the synthetic method include the following steps:
(1) 20mL acetic acid is added in the 50mL four-hole boiling flask equipped with blender, thermometer, dropping funel and reflux condensing tube
Ethyl ester and 1.78gN- methyl allyl amine are equipped with anhydrous CaCl on the reflux condensing tube2Drying tube, the 1.78g N- methyl
The concentration of allylamine is 0.025mol, and 4.02g perfluoro hexyl sulfuryl fluoride, the 4.02g perfluoro hexyl sulphur are gradually added dropwise at room temperature
The concentration of acyl fluorides is 0.01mol, and control 30min is added dropwise, continues to be stirred to react 2h at 40 DEG C；It, will be anti-after stopping reaction
It answers liquid to pour into 100mL water, is layered Hou Qu lower layer weak yellow liquid, successively use 50mL 5%HCl aqueous solution, 30m is saturated NaCO3
Aqueous solution and 2 × 30mL water washing, anhydrous sodium sulfate is dry, obtains light yellow transparent liquid, yellow transparent liquid NSF6；
(2) by high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol], NSF6 [1.80g, n (C=C)=4.09mmol]
It is added with toluene 20mL in the three neck round bottom flask of 100mL, the Karstedt catalyst that concentration is 16.123g/L is then added,
Condensing unit and thermometer, magnetic agitation are connected, oil bath heating is heated to 90 DEG C；When silicon hydrogenation conversion ratio reaches 10%,
It is added DAEMA [3.13g, n (C=C)=36.76mmol], the reaction was continued until silicon hydrogenation conversion ratio substantially constant；
(3) after reaction, by reaction mixture in 35 DEG C of rotary evaporation in vacuo to remove DAEMA, toluene and volatile components,
Then in a vacuum drying oven, 50 DEG C of vacuum drying 4h obtain n further to remove remaining toluene and volatile components
(PMHS): the silicon hydrogenated products PSF6D of n (NSF6): n (DAEMA)=10:1:9 is yellow viscous liquid；
(4) silicon hydrogenated products PSF6D 1.0g, toluene 10mL and ether 30mL is taken to be added in 100mL single necked round bottom flask, then
Iodomethane 1.0g is added, connects condensation reflux unit, magnetic agitation, oil bath heating is heated to 60 DEG C, and back flow reaction 12h has Huang
Color precipitating generates；Reactant is filtered, precipitating washs (3 × 20mL) with ether, and precipitating is then placed in surface plate and is put into vacuum
In drying box, dry 4h, obtains 1.22g yellow powder, and product is characterized with FT-IR under the conditions of 50 DEG C；
(5) it keeps the amount of high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol] constant, changes NSF6 and DAEMA bis-
The amount of person's substance, making n (PMHS): n (NSF6): n (DAEMA) ratio is respectively 10:0.3:9.7,10:0.5:9.5 and 10:
2:8, remaining operation is constant, then obtains the different quaternary fluorine silicon cationic surfactant PSF6DI of structure.
Beneficial effect
The present invention has the following advantages that compared with prior art.
1. the present invention enriches the type of fluorine silicon cationic surfactant, compared with traditional fluorocarbon surfactant,
Surface-active, good water solubility and biological degradability with higher；
2. with degradable fluorine-containing C6Class compound C6F13SO2F is starting point, passes through nucleophilic substitution, silicon hydrogenation and season
Ammoniumization reaction synthesis fluorine silicon cationic surfactant is the exploitation of China's quaternary fluorine silicon cationic surfactant and is answered
With offer one new research method and thinking.
Detailed description of the invention
Below in conjunction with attached drawing, the invention will be further described.
Fig. 1 is the infrared FT-IR spectrogram of Fourier of NSF6 in the present invention；
Fig. 2 is NSF6 in the present invention1HNMR figure；
Fig. 3 is the infrared FT-IR spectrogram of Fourier of PSF6DI in the present invention；
Fig. 4 is the γ-lgc curve of PSF6DI in the present invention.
Specific embodiment
A kind of quaternary fluorine silicon cationic surfactant, the structural formula of the compound are as follows:
Wherein RfAre as follows: C6F13SO2；Me is CH3；X and y is positive integer.
The lowest surface tension of the quaternary fluorine silicon cationic surfactant in aqueous solution be 19.8~
32.1mN/m, critical micelle concentration are 0.07~0.14g/L.
A kind of synthetic method of quaternary fluorine silicon cationic surfactant, as shown in Figs 1-4, which includes
Following steps:
(1) 20mL acetic acid is added in the 50mL four-hole boiling flask equipped with blender, thermometer, dropping funel and reflux condensing tube
Ethyl ester and 1.78gN- methyl allyl amine are equipped with anhydrous CaCl on the reflux condensing tube2Drying tube, the 1.78g N- methyl
The concentration of allylamine is 0.025mol, and 4.02g perfluoro hexyl sulfuryl fluoride, the 4.02g perfluoro hexyl sulphur are gradually added dropwise at room temperature
The concentration of acyl fluorides is 0.01mol, and control 30min is added dropwise, continues to be stirred to react 2h at 40 DEG C；It, will be anti-after stopping reaction
It answers liquid to pour into 100mL water, is layered Hou Qu lower layer weak yellow liquid, successively use 50mL 5%HCl aqueous solution, 30m is saturated NaCO3
Aqueous solution and 2 × 30mL water washing, anhydrous sodium sulfate is dry, obtains light yellow transparent liquid, yellow transparent liquid NSF6；
(2) by high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol], NSF6 [1.80g, n (C=C)=4.09mmol]
It is added with toluene 20mL in the three neck round bottom flask of 100mL, the Karstedt catalyst that concentration is 16.123g/L is then added,
Condensing unit and thermometer, magnetic agitation are connected, oil bath heating is heated to 90 DEG C；When silicon hydrogenation conversion ratio reaches 10%,
It is added DAEMA [3.13g, n (C=C)=36.76mmol], the reaction was continued until silicon hydrogenation conversion ratio substantially constant；
(3) after reaction, by reaction mixture in 35 DEG C of rotary evaporation in vacuo to remove DAEMA, toluene and volatile components,
Then in a vacuum drying oven, 50 DEG C of vacuum drying 4h obtain n further to remove remaining toluene and volatile components
(PMHS): the silicon hydrogenated products PSF6D of n (NSF6): n (DAEMA)=10:1:9 is yellow viscous liquid；
(4) silicon hydrogenated products PSF6D 1.0g, toluene 10mL and ether 30mL is taken to be added in 100mL single necked round bottom flask, then
Iodomethane 1.0g is added, connects condensation reflux unit, magnetic agitation, oil bath heating is heated to 60 DEG C, and back flow reaction 12h has Huang
Color precipitating generates；Reactant is filtered, precipitating washs (3 × 20mL) with ether, and precipitating is then placed in surface plate and is put into vacuum
In drying box, dry 4h, obtains 1.22g yellow powder, and product is characterized with FT-IR under the conditions of 50 DEG C；
(5) it keeps the amount of high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol] constant, changes NSF6 and DAEMA bis-
The amount of person's substance, making n (PMHS): n (NSF6): n (DAEMA) ratio is respectively 10:0.3:9.7,10:0.5:9.5 and 10:
2:8, remaining operation is constant, then obtains the different quaternary fluorine silicon cationic surfactant PSF6DI of structure.
Embodiment 1
One kind of the present embodiment is based on quaternary fluorine silicon cationic surfactant and preparation method thereof, includes the following steps:
(1) synthesis of NSF6
(an anhydrous CaCl is above being filled equipped with blender, thermometer, dropping funel and reflux condensing tube2Drying tube) 50mL tetra-
20mL ethyl acetate and 1.78g (0.025mol) N- methyl allyl amine is added in mouth flask, 4.02g is gradually added dropwise at room temperature
(0.01mol) perfluoro hexyl sulfuryl fluoride, control about 30min are added dropwise, continue to be stirred to react 2h at 40 DEG C；Stop reaction
Afterwards, reaction solution is poured into 100mL water, is layered Hou Qu lower layer weak yellow liquid, successively use 50mL5%HCl aqueous solution, 30mL is full
And NaCO3Aqueous solution and 2 × 30mL water washing, anhydrous sodium sulfate is dry, obtains light yellow transparent liquid, yield 91.8%(is with perfluor
Hexyl sulfuryl fluoride meter).
(2) synthesis of PSF6D
By high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol], NSF6 [1.80g, n (C=C)=4.09mmol] and first
Benzene 20mL is added in the three neck round bottom flask of 100mL, and the Karstedt catalyst that concentration is 16.123 g/L is then added, connects
Condensing unit and thermometer, magnetic agitation, oil bath heating are heated to 90 DEG C；When silicon hydride conversion rate reaches 10%, it is added
DAEMA [3.13g, n (C=C)=36.76mmol], the reaction was continued until silicon hydrogenation conversion ratio substantially constant.Reaction
After, by reaction mixture in 35 DEG C of rotary evaporation in vacuo to remove DAEMA, toluene and volatile components, then in vacuum
In drying box, 50 DEG C of vacuum drying 4h obtain n (PMHS): n (NSF6) to completely remove remaining toluene and volatile components:
N (DAEMA)=10:1:9 silicon hydrogenated products PSF6D is yellow viscous liquid.
(3) synthesis of PSF6DI
It takes silicon hydrogenated products PSF6D 1.0g, toluene 10mL and ether 30mL to be added in 100mL single necked round bottom flask, is then added
Iodomethane 1.0g connects condensation reflux unit, magnetic agitation, and oil bath heating is heated to 60 DEG C, back flow reaction 12h, has yellow heavy
It forms sediment and generates；Reactant is filtered, precipitating washs (3 × 20mL) with ether, and precipitating is then placed in surface plate and is put into vacuum drying
In case, dry 4h, obtains 1.22g yellow powder, and product is characterized with FT-IR under the conditions of 50 DEG C.
Three step process in the above method of this example, reaction principle are as follows:
(1) preparation of NSF6
(2) preparation of PSF6D
(3) preparation of PSF6DI
To above-mentioned prepared NSF6 carry out FT-IR and1HNMR characterization, data are as follows.
FTIR(cm-1): in 1351.0cm-1Place is sulfonamide nonsymmetrical vibration absorption peak；1140.6 cm-1Place is sulphur
Amide symmetric vibration absorption peak.
1HNMR(CDCl3, ppm): δ a=5.33 (dd, 1H), δ b=5.35 (dd, 1H), δ c=5.80 (m, 1H), δ d=
4.19 (s, 1H), δ e=3.81 (s, 1H), δ f=3.04 (s, 3H).
By the FT-IR of NSF6 and1The spectrogram of HNMR is it is found that synthesized product is consistent with target product structure.
FT-IR characterization is carried out to above-mentioned prepared PSF6DI, data are as follows.
FTIR(cm-1): 3449 cm-1It is caused by PSF6DI water suction deliquesces for-OH stretching vibration absworption peak；2960cm-1
For-CH2、-CH3Asymmetric stretching vibration absorption peak；1271cm-1For Si-CH3- CH3Symmetric deformation vibration shape vibration absorption peak；
1248cm-1And 1207cm-1For C-F stretching vibration suction；1029cm-1For Si-O-Si stretching vibration absworption peak；776cm-1For Si-C
Stretching vibration absworption peak.
By the spectrogram of the FT-IR of PSF6DI it is found that synthesized product is consistent with target product structure.
The present embodiment by the quaternary fluorine silicon cationic surfactant of preparation be configured to a series of various concentrations to
Sample solution, balances 48h at room temperature, hangs piece method using Wilhelmy using surface tension instrument (QBZY type) and surveys its dense critical glue
Surface tension (γ under beam concentration (cmc) and critical micelle concentration concentrationcmc).
The surface tension of quaternary fluorine silicon cationic surfactant is as shown in Figure 4 with concentration variation tendency；Its is dense to face
Boundary's micellar concentration (cmc) and the surface tension γ in critical micelle concentration concentrationcmcAs shown in table 1.As shown in Table 1, work as n
(PMHS): when n (NSF6): n (DAEMA)=10:1:9, the cmc and γ of PSF6DIcmcRespectively 0.09g/L and 19.8mN/m.
Embodiment 2
The present embodiment is same as Example 1, and difference is:
(2) synthesis of PSF6D
By high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol], NSF6 [0.54g, n (C=C)=1.23mmol] and first
Benzene 20mL is added in the three neck round bottom flask of 100mL, and the Karstedt catalyst that concentration is 16.123 g/L is then added, connects
Condensing unit and thermometer, magnetic agitation, oil bath heating are heated to 90 DEG C.When silicon hydride conversion rate reaches 3%, DAEMA is added
[3.37 g, n (C=C)=39.62 mmol], the reaction was continued until silicon hydrogenation conversion ratio substantially constant.As shown in Table 1,
As n (PMHS): n (NSF6): n (DAEMA)=10:0.3:9.7, the cmc and γ of PSF6DIcmcRespectively 0.14g/L and
32.1mN/m。
Embodiment 3
The present embodiment is same as Example 1, and difference is:
(2) synthesis of PSF6D
By high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol], NSF6 [0.54g, n (C=C)=2.04mmol] and first
Benzene 20mL is added in the three neck round bottom flask of 100mL, and the Karstedt catalyst that concentration is 16.123 g/L is then added, connects
Condensing unit and thermometer, magnetic agitation, oil bath heating are heated to 90 DEG C.When silicon hydrogenation conversion ratio reaches 5%, it is added
DAEMA [3.30g, n (C=C)=38.81 mmol], the reaction was continued until silicon hydrogenation conversion ratio substantially constant.By table 1
It is found that as n (PMHS): when n (NSF6): n (DAEMA)=10:0.5:9.5, the cmc and γ of PSF6DIcmcRespectively 0.11g/L
And 24.6mN/m.
Embodiment 4
The present embodiment is same as Example 1, and difference is:
(2) synthesis of PSF6D
By high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol], NSF6 [3.60g, n (C=C)=8.18mmol] and first
Benzene 20mL is added in the three neck round bottom flask of 100mL, and the Karstedt catalyst that concentration is 16.123 g/L is then added, connects
Condensing unit and thermometer, magnetic agitation, oil bath heating are heated to 90 DEG C.When silicon hydrogenation conversion ratio reaches 20%, it is added
DAEMA [2.78 g, n (C=C)=32.68 mmol], the reaction was continued until silicon hydrogenation conversion ratio substantially constant.By table
1 it is found that as n (PMHS): when n (NSF6): n (DAEMA)=10:2:8, the cmc and γ of PSF6DIcmcRespectively 0.07 g/L and
23.5mN/m。
The cmc and γ of 1 PSF6DI of tablecmc
| n(PMHS):n(NSF6): (DAEMA) | cmc / g/L | γcmc / mN/m |
| 10 : 0.3 : 9.7 | 0.14 | 32.1 |
| 10 : 0.5 : 9.5 | 0.11 | 24.6 |
| 10 : 1 : 9 | 0.09 | 19.8 |
| 10 : 2: 8 | 0.07 | 23.5 |
Claims (3)
1. a kind of quaternary fluorine silicon cationic surfactant, which is characterized in that the structural formula of the compound are as follows:
Wherein RfAre as follows: C6F13SO2；Me is CH3；X and y is positive integer.
2. a kind of quaternary fluorine silicon cationic surfactant according to claim 1, which is characterized in that the season
The lowest surface tension of ammonium salt type fluorine silicon cationic surfactant in aqueous solution is 19.8~32.1mN/m, and critical micell is dense
Degree is 0.07~0.14g/L.
3. a kind of synthetic method of quaternary fluorine silicon cationic surfactant according to claim 1, feature exist
In the synthetic method includes the following steps:
(1) 20mL acetic acid is added in the 50mL four-hole boiling flask equipped with blender, thermometer, dropping funel and reflux condensing tube
Ethyl ester and 1.78gN- methyl allyl amine are equipped with anhydrous CaCl on the reflux condensing tube2Drying tube, the 1.78g N- methyl
The concentration of allylamine is 0.025mol, and 4.02g perfluoro hexyl sulfuryl fluoride, the 4.02g perfluoro hexyl sulphur are gradually added dropwise at room temperature
The concentration of acyl fluorides is 0.01mol, and control 30min is added dropwise, continues to be stirred to react 2h at 40 DEG C；It, will be anti-after stopping reaction
It answers liquid to pour into 100mL water, is layered Hou Qu lower layer weak yellow liquid, successively use 50mL 5%HCl aqueous solution, 30m is saturated NaCO3
Aqueous solution and 2 × 30mL water washing, anhydrous sodium sulfate is dry, obtains light yellow transparent liquid, yellow transparent liquid NSF6；
(2) by high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol], NSF6 [1.80g, n (C=C)=4.09mmol]
It is added with toluene 20mL in the three neck round bottom flask of 100mL, the Karstedt catalyst that concentration is 16.123g/L is then added,
Condensing unit and thermometer, magnetic agitation are connected, oil bath heating is heated to 90 DEG C；When silicon hydrogenation conversion ratio reaches 10%,
It is added DAEMA [3.13g, n (C=C)=36.76mmol], the reaction was continued until silicon hydrogenation conversion ratio substantially constant；
(3) after reaction, by reaction mixture in 35 DEG C of rotary evaporation in vacuo to remove DAEMA, toluene and volatile components,
Then in a vacuum drying oven, 50 DEG C of vacuum drying 4h obtain n further to remove remaining toluene and volatile components
(PMHS): the silicon hydrogenated products PSF6D of n (NSF6): n (DAEMA)=10:1:9 is yellow viscous liquid；
(4) silicon hydrogenated products PSF6D 1.0g, toluene 10mL and ether 30mL is taken to be added in 100mL single necked round bottom flask, then
Iodomethane 1.0g is added, connects condensation reflux unit, magnetic agitation, oil bath heating is heated to 60 DEG C, and back flow reaction 12h has Huang
Color precipitating generates；Reactant is filtered, precipitating washs (3 × 20mL) with ether, and precipitating is then placed in surface plate and is put into vacuum
In drying box, dry 4h, obtains 1.22g yellow powder, and product is characterized with FT-IR under the conditions of 50 DEG C；
(5) it keeps the amount of high containing hydrogen silicone oil PMHS [2.5g, n (Si-H)=40.85mmol] constant, changes NSF6 and DAEMA bis-
The amount of person's substance, making n (PMHS): n (NSF6): n (DAEMA) ratio is respectively 10:0.3:9.7,10:0.5:9.5 and 10:
2:8, remaining operation is constant, then obtains the different quaternary fluorine silicon cationic surfactant PSF6DI of structure.
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| CN109970781A (en) * | 2019-05-09 | 2019-07-05 | 九江学院 | A kind of synthetic method of fluorine silicon zwitterionic surfactant |
| CN111925527A (en) * | 2020-08-21 | 2020-11-13 | 滨州医学院 | Long-chain alkyl grafted quaternized silicone and preparation method and application thereof |
| CN112552212A (en) * | 2020-10-26 | 2021-03-26 | 蒲城驭腾新材料科技有限公司 | Preparation method of cationic fluorocarbon surfactant |
| CN114571138A (en) * | 2020-12-01 | 2022-06-03 | 联泓(江苏)新材料研究院有限公司 | Environment-friendly soldering flux and preparation method and application thereof |
| CN114571138B (en) * | 2020-12-01 | 2024-05-17 | 联泓(江苏)新材料研究院有限公司 | Environment-friendly soldering flux and preparation method and application thereof |
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Application publication date: 20190125 |