CN100364650C - Cation fluoride Gemini surface activator - Google Patents

Cation fluoride Gemini surface activator Download PDF

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CN100364650C
CN100364650C CNB2005101123495A CN200510112349A CN100364650C CN 100364650 C CN100364650 C CN 100364650C CN B2005101123495 A CNB2005101123495 A CN B2005101123495A CN 200510112349 A CN200510112349 A CN 200510112349A CN 100364650 C CN100364650 C CN 100364650C
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formula
surfactant
gemini
present
compound
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CN1817431A (en
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王利民
刘博�
田禾
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Shanghai Institute of Organic Chemistry of CAS
East China University of Science and Technology
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Shanghai Institute of Organic Chemistry of CAS
East China University of Science and Technology
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Abstract

The present invention relates to a cation fluoride Gemini surface activator which is a compound of which structure is shown at a formula (1), wherein at the formula (1), R1 and R2 are respectively selected from one of alkyl group C1-C8; X is C1, Br or I; m equals 1 to 6; R3 is a radical satisfying a general formula CnF (2n+1) CO or CnF (2n+1) SO2, wherein n equals 3 to 8. Compared with a traditional Gemini surface activator without fluoride, the present invention has the advantages that the critical micelle concentration is low; few surface activators are required to achieve the same surface tension; the present invention has good dispersity, good foam stability, good penetrability and good wettability.

Description

Cation fluoride Gemini surface activator
Technical field
The present invention relates to a kind of cationic Gemini surfactants, particularly a kind of cation fluoride Gemini surface activator.
Background technology
Different with the molecular structure of traditional surfactant, contain two hydrophilic radicals and two hydrophobic groupings in the Gemini surfactant molecule at least, be tied by isolating group (Spacer) between hydrophilic group.Can know from the molecular structure of Gemini surfactant, this surfactant had both strengthened the hydrophobic effect of hydrocarbon chain, also adjust the distance of hydrophilic radical by Spacer, changed the geometry of unit molecule, make and the variation of micellar surface charge density, degree of hydration and micelle shape make it have certain characteristic.Compare with conventional surfactant, the Gemini surfactant has following characteristic:
(1) has quite low CMC value;
(2) the Gemini surfactant is easier is adsorbed on the two-phase interface, efficient more than conventional surfactant;
(3) lipophilic group of Gemini surfactant is being arranged compactlyer (particularly evident when the linking group between 2 hydrophilic radicals has only 4 carbon atoms (or still less)) on the interface, and this just makes it produce one deck from adhesive films on the interface.It means at the gas/liquid interface can effectively reduce surface tension, forms more stable foam; Mean at liquid/liquid interface and can form stable emulsion; Mean more stable solid dispersed in solid/liquid interfaces;
(4) more likely act synergistically between Gemini surfactant and other surfactant.For ionic Gemini surfactant, its ion head group has the electric charge of twice.Make solid granule stably to disperse and to be suspended in the water, and and other type list surface-active agent between may have stronger interaction (because a kind of surfactant and other surfactants synergism depend on the intensity of the hydrophilic radical interphase interaction of two kinds of surfactants to a great extent).Yet because the oil-soluble group of existing Gemini surfactant mostly is carbon-hydrogen group, its surface-active and other performance still have part not fully up to expectations.Therefore, the novel Gemini surfactant of research and development becomes the technical issues that need to address of the present invention.
Summary of the invention
The object of the invention is, a kind of cation fluoride Gemini surface activator is provided, and improves the some surface active property of existing Gemini surfactant with this.
Because fluorine (F) atom has very strong electronegativity, therefore the bond energy of the carbon-fluorine bond that forms is very high, and fluorine atom is also big than hydrogen atom to the shielding action of carbon carbon bond, thereby causes organofluorine compound to possess the not available property of traditional organic carbon hydrogen compound.The present invention utilizes some organofluorine compounds with property to come " modification " existing Gemini surfactant just, makes it have higher surface-active and other performance.
The compound of the said Gemini surfactant of the present invention for having structure shown in the formula (1):
Figure C20051011234900041
In the formula (1), R 1, R 2Be selected from C respectively 1～C 6Alkyl in a kind of; X is Cl, Br or I; M=1～6; R 3For satisfying general formula C nF 2n+1CO or C nF 2n+1SO 2Group, n=3～8 wherein.
A preferred version of the present invention is R 1, R 2Be selected from C respectively 1～C 3Alkyl in a kind of.
Another preferred version of the present invention is that X is Cl or Br.
The method for preparing the said Gemini surfactant of the present invention comprises the steps:
The preparation feedback equation is as follows:
Figure C20051011234900042
In the preparation feedback equation: R 1, R 2, R 3, the implication of X and m is described identical with preamble.
A. be 1 in molar ratio with perfluorocarboxylic acid or perfluorinated sulfonic acid [compound shown in the formula (2)] and organic amine [compound shown in the formula (3)]: (1.5～2) place reactor, in 110 ℃～120 ℃ back flow reaction 9～12 hours compound shown in the formula (4);
B. with compound shown in the formula (4) and Gemini quaternizing agent [compound shown in the formula (5), X is preferably chlorine] be 1 in molar ratio: (1.5～2) place reactor, with the ether is solvent, and back flow reaction got target compound [compound shown in the formula (1)] in 48 hours.Wherein, the preparation of compound shown in the formula (2) can be with reference to Japanese physical chemistry patent: 57, and 923-5 (1953) and United States Patent (USP) 3,475,333; The preparation of compound shown in the formula (3) can be with reference to McKay et al.; Can.J.Chem., 34,1956:1567～1569; The preparation of compound can be with reference to Subramaniam shown in the formula (5), G.; Gilpin, R.K.; Synthesis, 12,1992:1232～1234.
The not fluorine-containing Gemini surfactant of the cation fluoride Gemini surface activator of the present invention preparation and tradition is compared, has lower critical micelle concentration, the amount that reaches the surfactant that same surface tension needs still less and has better dispersiveness, foam stability, permeability and wetability.
The specific embodiment
The present invention is further illustrated below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention:
Embodiment 1
Synthesizing of surfactant (I):
Figure C20051011234900051
1, perfluor sulfonyl amine is synthetic:
In there-necked flask, add 100ml toluene and 0.01mol perfluorooctane sulfonate [compound, wherein R shown in the formula (2) 3=C nF 2n+1SO 2, n=8], slowly drip amine [compound shown in the formula (3), m=2 wherein, the R of 0.02mol then 1, R 2Be CH 3] 110 ℃～120 ℃ following back flow reaction 12 hours.After reaction finished, evaporate to dryness toluene obtained crude product, and the crude product recrystallization obtains perfluor sulfonyl amine.
2, the Gemini surfactant is synthetic:
In there-necked flask, add 0.01mol perfluor sulfonyl amine (making) and the 50ml ether for preparing previously, add 0.02mol 4 then by step 1,4 '-dichloromethyl biphenyl, back flow reaction 48 hours, the white solid that obtains is surfactant product. 1HNMR(DMSO-d 6)δ(ppm)：1.91(s，2H)，3.09(t，J＝7.2Hz，4H)，3.32(s，12H)，3.50(t，J＝5.7Hz，4H)，4.49(s，4H)，7.12(d，J＝8.5Hz，2H)，7.36(d，J＝6.4Hz，2H)。Because the cation part only occurs in the mass spectrum, cation part molecular weight is 1320, again owing to containing two positive charges, so molecular ion peak: M/Z=660 in mass spectrum, occurs.
Embodiment 2
Synthesizing of surfactant (II):
Figure C20051011234900061
1, perfluor sulfonyl amine is synthetic:
In there-necked flask, add 100ml toluene and 0.01mol perfluorooctane sulfonate [compound, wherein R shown in the formula (2) 3=C nF 2n+1SO 2, n=6], slowly drip amine [compound shown in the formula (3), m=4 wherein, the R of 0.02mol then 1, R 2Be-C 2H 5], 110 ℃～120 ℃ following back flow reaction 12 hours.After reaction finished, evaporate to dryness toluene obtained crude product, and the crude product recrystallization obtains perfluor sulfonyl amine.
2, the Gemini surfactant is synthetic:
In there-necked flask, add 0.01mol perfluor sulfonyl amine and the 50ml ether that makes by step 1, add 0.02mol 4 then, 4 '-dichloromethyl biphenyl, back flow reaction 48 hours, the white solid that obtains is surfactant product.
1HNMR(DMSO-d 6)δ(ppm)：0.89(t，J＝7.8Hz，12H)，1.41～1.47(m，4H)，1.77(m，4H)，1.81(s，2H)，2.65(t，4H)，3.22(t，J＝5.7Hz，4H)，3.28(m，4H)，4.53(s，4H)，7.12(d，J＝8.5Hz，2H)，7.36(d，J＝6.4Hz，2H)。
Because the cation part only occurs in the mass spectrum, cation part molecular weight is 1232, again owing to containing two positive charges, so molecular ion peak: M/Z=616 in mass spectrum, occurs.
Embodiment 3
Synthesizing of surfactant (III):
Figure C20051011234900062
1, the perfluor caprylamide is synthetic:
In there-necked flask, add 100ml toluene and 0.01mol perfluoro caprylic acid [compound, wherein R shown in the formula (2) 3=C nF 2n+1CO, n=7], slowly drip amine [compound shown in the formula (3), m=4 wherein, the R of 0.02mol then 1, R 2Be-CH 3], 110 ℃～120 ℃ following back flow reaction 12 hours.After reaction finished, evaporate to dryness toluene obtained crude product, and the crude product recrystallization obtains the perfluor caprylamide.
2, the Gemini surfactant is synthetic:
In there-necked flask, add 0.01mol perfluor caprylamide and the 50ml ether for preparing previously, add 0.02mol 4 then, 4 '-two bromomethylbiphenyls, back flow reaction 48 hours, the white solid that obtains is surfactant product.
1H NMR(DMSO-d 6)δ(ppm)：1.47～1.53(m，4H)，1.70～1.79(m，4H)，3.20(m，4H)，3.26(t，J＝5.7Hz，4H)，3.41(s，12H)，4.51(s，4H)，7.1 1(d，J＝8.5Hz，2H)，7.37(d，J＝6.4Hz，2H)，7.74(s，2H)。
Because the cation part only occurs in the mass spectrum, cation part molecular weight is 1204, again owing to containing two positive charges, so molecular ion peak: M/Z=602 in mass spectrum, occurs.
Embodiment 4
The fluorine-containing Gemini surfactant [is example with surfactant (I)] of the present invention's design and preparation and existing not fluorine-containing Gemini surfactant are [shown in the existing not fluorine-containing Gemini surfactant structure formula (6), ] some surface active property contrast, comparing result sees Table 1:
Figure C20051011234900071
25 ℃ of the surface-active data of each surfactant of table 1
Contrast 1 Contrast 2 Contrast 3 Surfactant (I)
Critical micelle concentration CCMC/mol ＊L -1 2.9854E-6 2.3931E-6 2.0893E-6 5.5378E-7
Surface tension γ CMC/dynes under the CMC ＊cm -1 45.0655 43.2700 37.2365 23.1540

Claims (4)

1. Gemini surfactant, its compound for having structure shown in the formula (1):
Figure C2005101123490002C1
In the formula (1), R 1, R 2Be selected from C respectively 1～C 6Alkyl in a kind of; X is Cl, Br or I; M=1～6; R 3For satisfying general formula C nF 2n+1CO or C nF 2n+1SO 2Group, n=3～8 wherein.
2. Gemini surfactant as claimed in claim 1 is characterized in that R 1, R 2Be selected from C respectively 1～C 3Alkyl in a kind of.
3. Gemini surfactant as claimed in claim 1 or 2 is characterized in that, wherein X is Cl or Br.
4. Gemini surfactant as claimed in claim 3 is characterized in that, described Gemini surfactant is a compound shown in formula (I), formula (II) or the formula (III):
Figure C2005101123490002C2
CNB2005101123495A 2005-12-29 2005-12-29 Cation fluoride Gemini surface activator Expired - Fee Related CN100364650C (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN102908937A (en) * 2012-09-12 2013-02-06 衢州学院 Cationic type gemini fluorinated surfactant based on perfluorinated nonene and perfluorinated hexene and preparation method of cationic type gemini fluorinated surfactant

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CN100446846C (en) * 2006-12-22 2008-12-31 江苏飞翔化工股份有限公司 Cationic Gemini surfactants
CN101440044B (en) * 2008-12-26 2012-07-18 华东理工大学 Fluoride-containing Gemini quaternary ammonium salt rare earth Lewis acid
CN102166494A (en) * 2011-02-25 2011-08-31 华东理工大学 Degradable cationic Gemini surface active agent
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
CN103446943B (en) * 2013-09-18 2014-10-22 华中师范大学 Gemini perfluoroalkylsulfonyloxybenzyl cationic surfactant as well as preparation and application thereof
CN107417635B (en) * 2016-12-21 2019-07-23 华东理工大学 Racemosus shape pyrrolotriazine derivatives and application thereof

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Cited By (2)

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CN102908937A (en) * 2012-09-12 2013-02-06 衢州学院 Cationic type gemini fluorinated surfactant based on perfluorinated nonene and perfluorinated hexene and preparation method of cationic type gemini fluorinated surfactant
CN102908937B (en) * 2012-09-12 2015-07-29 衢州学院 Based on the cationic Shuangzi fluorine surfactant and preparation method thereof of perfluorinated nonene and perfluor hexene

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Assignee: Shenzhen Tianding Fine Chemical Co., Ltd.

Assignor: East China University of Science and Technology|Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences

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