CN102941035A - Gemini surface active agent using pyrrole ring as hydrophilic head group and preparation method of Gemini surface active agent using pyrrole ring as hydrophilic head group - Google Patents
Gemini surface active agent using pyrrole ring as hydrophilic head group and preparation method of Gemini surface active agent using pyrrole ring as hydrophilic head group Download PDFInfo
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Abstract
The invention discloses a cation Gemini surface active agent using a pyrrole ring as a hydrophilic head group, and relates to a preparation method of the surface active agent. The preparation method comprises the specific steps of generating N-alkyl pyrrolidine by pyrrolidine and long-chain alkyl under the actions of N2 (nitrogen) protection and catalyst function, and carrying out reaction of the obtained N-alkyl pyrrolidine and dibromo-paraffin so as to obtain the cation Gemini surface active agent using the pyrrole ring as the hydrophilic head group. The Gemini surface active agent has good surface activity and viscoelasticity, the Gemini surface active agent can be singly used or compounded with other surface active agents due to the good property, and further the Gemini surface active agent is widely applied to the industrial practices, such as daily-use chemical industry, sterilizers, pesticide agents, petroleum production, and thick oil viscosity reduction.
Description
Technical field
The present invention relates to a kind ofly take the Cationic Gemini Surfactant of pyrrole ring as hydrophilic head base, also relate to the preparation method of this Gemini surfactant, belong to the surfactant preparing technical field.
Background technology
Surfactant refers to have fixedly hydrophilic and oleophilic group, forms at the surface energy of solution to align, and the large class material that surface tension is significantly descended.According to the textural classification method of traditional surfactant, surfactant can be divided into ionic and nonionic, wherein ionic comprise again cationic, anionic and amphoteric ion type.The Gemini surfactant is because their architectural characteristic, so that they are compared with traditional list surfactant very many advantages are arranged, such as lower critical micelle concentration (cmc), lower surface tension and Krafft point, higher surface-active, more abundant aggregate structure and the better characteristics such as synergy.
Some cheap Gemini surfactants are developed so that the Gemini surfactant seems more economical using, and they on using, also have advantages of very many, such as outstanding emulsification, dispersion, infiltration and foaming capacity etc.The superpower solubilising power that they show, better sterilization sustained release performance and good biocompatibility are so that they are able at daily use chemicals, medicine, food, material, and the industry such as tertiary oil recovery is widely used.
In recent years, various surfactants with heterocycle head base have been subject to people's extensive concern, as: the surfactant of pyridine head base, imidazoles head base, pyrrolidones head base, pyrrole ring head base etc. heterocycle head base.Yet the surfactant with advantageous property still has to be developed, and the preparation process of Gemini surfactant is complicated, and the reaction condition in the preparation process of current Gemini surfactant is wayward, is not suitable for large-scale production and application.That has reported at present has take the Gemini surfactant (C of pyrrole ring as hydrophilic head base
n-s-
nPB), s=4 wherein, n=10 ~ 16, Journal of Colloid and InterfaceScience 370 (2012) 111 – 116, but its surface-active is still waiting to improve.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provide a kind of surface property good take the Gemini surfactant of pyrrole ring as hydrophilic head base.
It is a kind of above-mentioned take the preparation method of pyrrole ring as the Gemini surfactant of hydrophilic head base that the object of the invention is also to provide.
Technical scheme of the present invention is: a kind of take the Gemini surfactant (C of pyrrole ring as hydrophilic head base
n-s-
nPB), concrete general formula is as follows:
In the formula: n=8 ~ 18; S=3,6 ~ 16.
As a kind of preferred, the s=3 in the general formula, 6,8,10,12,14,16.
A kind of above-mentioned take the preparation method of pyrrole ring as the Gemini surfactant of hydrophilic head base, may further comprise the steps:
1) synthetic N-alkyl pyrrolidine: under the condition of nitrogen protection, pyrrolidines is added in the polar solvent, then add inorganic base and brominated alkanes, pyrrolidines is 1:3 ~ 1:4 with the amount ratio of inorganic base, the molar ratio of pyrrolidines and brominated alkanes is 1:2.2 ~ 1:4, in 40 ~ 80 ℃ of reactions 6 ~ 24 hours, separating-purifying obtained the N-alkyl pyrrolidine;
2) synthetic take the Gemini surfactant of pyrrole ring as hydrophilic head base: that the N-alkyl pyrrolidine that obtains in the step 1) and the two bromoalkanes mol ratio with 2.5:1 ~ 6:1 is joined in the polar solvent, reacted under 80 ~ 120 ℃ condition 12 ~ 72 hours, product obtains take the Cationic Gemini Surfactant of pyrrole ring as hydrophilic head base through recrystallization.
Wherein, the polar solvent in the step 1) is ethanol, methyl alcohol, acetonitrile, N, a kind of in N-METHYLFORMAMIDE or the methyl-sulfoxide; Step 2) polar solvent in is normal propyl alcohol, isopropyl alcohol, acetonitrile, N, a kind of in N-METHYLFORMAMIDE or the methyl-sulfoxide; The solvent of recrystallization usefulness is one or more in ethanol/acetone, ethanol/ethyl acetate, ethanol/ether, normal propyl alcohol/ethyl acetate, methanol/ethyl acetate, the methanol/ether.
Inorganic base is a kind of in sodium carbonate, sodium acid carbonate, potash or the NaOH.
Brominated alkanes is n-octane bromide, bromo n-decane, bromododecane, bromotetradecane, bromohexadecane or bromo-octadecane; Two bromoalkanes are 1,3-dibromopropane, 1,6-dibromo-hexane, 1,8-two bromooctanes, 1,10-dibromo-decane, 1,12-dibromo-dodecane, 1,14-, two bromo-tetradecanes or 1,16-dibromo hexadecane.
Of the present invention take the preparation method of pyrrole ring as the Gemini surfactant of hydrophilic head base, concrete synthesis step is as follows:
The present invention has following beneficial effect:
1. preparation technology of the present invention is simple, and the gentle and easy control of reaction condition has very strong industrial operability.
2. the present invention preparation is a kind of take the Gemini type surfactant of pyrrole ring as hydrophilic head base, have different hydrophobic tail chains, different connection base length, so the synthetic surfactant of the method has different character.
3. compare with traditional list surfactant, the present invention preparation take pyrrole ring as the critical micelle concentration (cmc) of the Gemini type surfactant of hydrophilic head base is lower than conventional surfactant, have higher surface property.
4. with the Gemini surfactant take pyrrole ring as hydrophilic head base of having reported (s=4 wherein, n=10 ~ 16) compare, under the identical condition of n, the present invention prepared take pyrrole ring as the critical micelle concentration (cmc) of the Gemini type surfactant of hydrophilic head base is lower, have higher surface property.
5. interfacial film has extraordinary viscoplasticity.
Description of drawings
Fig. 1 is the surfactant C that the present invention prepares
12-3-
12PB and the surface tension curve map of conventional surfactants dodecyl bromination ammonium (DTAB) under 25 ℃.
Fig. 2 is the surfactant C that the present invention prepares
12-s-
12PB (s=3,6,8,10,12,14,16) with reported take the comparison diagram of pyrrole ring as the critical micelle concentration of the Gemini surfactant (s=4, n=12, C12-4-12PB) of hydrophilic head base, abscissa s is surfactant C
12-s-
12The value of s among the PB.
Fig. 3 frequency and surface pressure are to the surfactant C of the present invention's preparation
18-3-
18The interfacial viscoelasticity of the interfacial film of PB.
The specific embodiment
By the following examples the present invention is done further introduction, but do not limit the present invention in any way.
Embodiment 1
Preparation (the C of the two pyrrole ring quaternary ammonium salts of two octyl group acrylic
8-3-
8PB)
14.2g (0.2 mole) pyrrolidines is joined in the 200ml methyl alcohol, add successively NaOH 24g (0.6 mole) and 84.5g (0.44 mole) bromooctane, keep 40 ℃ of reactions 6 hours; After reaction is finished, methyl alcohol and unreacted pyrrolidines are removed in decompression, the light yellow liquid body and function that obtains is equipped with the chromatographic column separation of the silica gel of 40 times of its weight, successively take benzinum, carrene, ethyl acetate/dichloromethane/ammoniacal liquor as eluant, eluent, collect eluent, concentrated, can get N-octyl group pyrrolidines, productive rate is 96%.Add 250ml isopropyl alcohol or acetonitrile and 1,3-dibromopropane 13.3g (0.0665 mole) in the N-octyl group pyrrolidines of above-mentioned gained, vigorous stirring was in 100 ℃ of reactions 12 hours; After reaction finished, isopropyl alcohol was removed in decompression, and the mixed solvent recrystallization of the pale yellow colored solid body and function ethanol/acetone that obtains gets final product the product vacuum drying of gained and to get the two pyrrole ring quaternary ammonium salts of two octyl group acrylic, is white solid, and productive rate is 87%.
Elementary analysis: C
27H
56N
2Br
2
High resolution mass spec: [M-Br]
+=487.4
1H-NMR(CDCl
3,δ/ppm?relative?to?TMS):0.88(t,6H),1.26(m,20H),1.79(m,4H),2.14-2.40（m,8H),2.68(m,2H),3.26-4.01(m,16H)
13C-NMR(CDCl
3,δ/ppm?relative?to?CDCl
3):14.26,20.15,22.44-22.90,23.94,26.68,29.55-29.84,32.12,57.42,61.21,63.30
Fusing point: 197.2 ~ 197.7 ℃.
Embodiment 2
Preparation (the C of the two pyrrole ring quaternary ammonium salts of two dodecyl acrylic
12-3-
12PB)
14.2g (0.2 mole) pyrrolidines is joined in the 200ml ethanol, add successively NaOH 32g (0.8 mole) and 124g (0.5 mole) bromododecane, keep 60 ℃ of reactions 10 hours; After reaction is finished, ethanol and unreacted pyrrolidines are removed in decompression, the light yellow liquid body and function that obtains is equipped with the chromatographic column separation of the silica gel of 40 times of its weight, successively take n-hexane, carrene, ethyl acetate/dichloromethane/ammoniacal liquor as eluant, eluent, collect eluent, concentrated, can get N-dodecyl pyrrolidines, productive rate is 98%.Add 250ml isopropyl alcohol and 1,3-dibromopropane 15.7g (0.0784 mole) in the N-dodecyl pyrrolidines of above-mentioned gained, vigorous stirring was in 80 ℃ of reactions 48 hours; After reaction finished, isopropyl alcohol was removed in decompression, and the mixed solvent recrystallization of the pale yellow colored solid body and function ethanol/ethyl acetate that obtains gets final product the product vacuum drying of gained and to get the two pyrrole ring quaternary ammonium salts of two dodecyl acrylic, is white solid, and productive rate is 91%.To C
12-3-
12PB and conventional surfactants dodecyl bromination ammonium (DTAB) carry out the surface property test.As shown in Figure 1, C
12-3-
12The critical micelle concentration of PB (cmc) is 10
-5~ 10
-3Between the mol/L, lower than conventional surfactant DTAB.C
12-3-
12PB with reported take Gemini surfactant (s=4, n=12, the C of pyrrole ring as hydrophilic head base
12-4-
12PB) critical micelle concentration more as shown in Figure 2.
Elementary analysis: C
35H
72N
2Br
2
High resolution mass spec: [M-Br]
+=599.3.
1H-NMR(CDCl
3,δ/ppm?relative?to?TMS):0.88(t,6H),1.26(m,36H),1.79(m,4H),2.14-2.40（m,8H),2.68(m,2H),3.26-4.01(m,16H).
13C-NMR(CDCl
3,δ/ppm?relative?to?CDCl
3):14.36,20.55,22.74-22.90,23.94,26.68,29.55-29.84,32.12,57.42,61.21,63.40.
Fusing point: 199.2 ~ 199.6 ℃.
Preparation (the C of the two pyrrole ring quaternary ammonium salts of two octadecyl acrylic
18-3-
18PB)
14.2g (0.2 mole) pyrrole ring is joined in the 200ml DMF, add successively sodium acid carbonate 50.4g (0.6 mole) and 353g (0.8 mole) bromo-octadecane, keep 80 ℃ of reactions 24 hours; After reaction is finished, N is removed in decompression, dinethylformamide and unreacted pyrrolidines, the light yellow liquid body and function that obtains is equipped with the chromatographic column separation of the silica gel of 40 times of its weight, successively take n-hexane, carrene, ethyl acetate/dichloromethane/ammoniacal liquor as eluant, eluent, collects eluent, concentrated, can get N-octadecyl pyrrolidines, productive rate is 95%.Add 250ml DMF and 1,3-dibromopropane 13.3g (0.0665 mole) in the N-octadecyl pyrrolidines of above-mentioned gained, vigorous stirring was in 120 ℃ of reactions 72 hours; After reaction finishes, N is removed in decompression, dinethylformamide, the solid of the claret that obtains, mixed solvent with ethanol/ethyl acetate and ethanol/ether is recrystallized successively, the product vacuum drying of gained is got final product to get the two pyrrole ring quaternary ammonium salts of two octadecyl acrylic, be white solid, productive rate is 85%.This surfactant (C
18-3-
18The interfacial viscoelasticity of interfacial film PB) can be found out C as shown in Figure 3
18-3-
18The lowest surface tension of PB is between 33 ~ 41mN/m, and this interfacial film has extraordinary viscoplasticity.
Elementary analysis: C
47H
96N
2Br
2
High resolution mass spec: [M-Br]
+=767.7
1H-NMR(CDCl
3,δ/ppm?relative?to?TMS):0.88(t,6H),1.26(m,60H),1.79(m,4H),2.13-2.38（m,8H),2.67(m,2H),3.26-4.01(m,16H).
13C-NMR(CDCl
3,δ/ppm?relative?to?CDCl
3):14.16,20.25,22.34-22.90,23.84,26.68,29.65-29.84,32.12,57.42,61.21,63.30
Fusing point: 202.1 ~ 202.5 ℃.
Embodiment 4
Preparation (the C of the two pyrrole ring quaternary ammonium salts of two decyl hexenyls
10-6-
10PB)
14.2g (0.2 mole) pyrrolidines is joined in the 200ml acetonitrile, add successively sodium carbonate 31.8g (0.3 mole) and 110g (0.5 mole) bromodecane, keep 80 ℃ of reactions 12 hours; After reaction is finished, acetonitrile and unreacted pyrrolidines are removed in decompression, the light yellow liquid body and function that obtains is equipped with the chromatographic column separation of the silica gel of 40 times of its weight, successively take ethyl acetate, carrene, ethyl acetate/dichloromethane/ammoniacal liquor as eluant, eluent, collect eluent, concentrated, can get N-decyl pyrrolidines, productive rate is 94%.Add 250ml normal propyl alcohol and 1,6-dibromo-hexane 14.5g (0.0665 mole) in the N-decyl pyrrolidines of above-mentioned gained, vigorous stirring was in 80 ℃ of reactions 48 hours; After reaction finishes, normal propyl alcohol is removed in decompression, the flaxen solid that obtains, mixed solvent with normal propyl alcohol/ethyl acetate, ethanol/ethyl acetate and ethanol/acetone is recrystallized successively, the product vacuum drying of gained is got final product to get the two pyrrole ring quaternary ammonium salts of two decyl hexenyls, be white solid, productive rate is 93%.
Elementary analysis: C
34H
70N
2Br
2
High resolution mass spec: [M-Br]
+=585.5
1H-NMR(CDCl
3,δ/ppm?relative?to?TMS):0.88(t,6H),1.26(m,32H),1.79(m,4H),2.07（m,8H),2.44(m,4H),3.26-4.01(m,16H).
13C-NMR(CDCl
3,δ/ppm?relative?to?CDCl
3):14.32,22.28,22.84,23.70,25.03,26.65,29.43-29.75,59.70,60.18,63.21
Fusing point: 198.3 ~ 198.6 ℃.
Embodiment 5
Preparation (the C of the two pyrrole ring quaternary ammonium salts of two dodecyl octenyl
12-8-
12PB)
14.2g (0.2 mole) pyrrolidines is joined in the 200ml acetonitrile, add successively NaOH 32g (0.8 mole) and 124g (0.5 mole) bromododecane, keep 60 ℃ of reactions 10 hours; After reaction is finished, acetonitrile and unreacted pyrrolidines are removed in decompression, the light yellow liquid body and function that obtains is equipped with the chromatographic column separation of the silica gel of 40 times of its weight, successively take n-hexane, carrene, ethyl acetate/dichloromethane/ammoniacal liquor as eluant, eluent, collect eluent, concentrated, can get N-dodecyl pyrrolidines, productive rate is 98%.Add 250ml DMF and 1,8-, two bromooctane 18g (0.0666 mole) in the N-dodecyl pyrrolidines of above-mentioned gained, vigorous stirring was in 110 ℃ of reactions 48 hours; After reaction finished, DMF was removed in decompression, the mixed solvent recrystallization of the pale yellow colored solid body and function ethanol/ethyl acetate that obtains, the product vacuum drying of gained is got final product to get the two pyrrole ring quaternary ammonium salts of two dodecyl octenyl, be white solid, productive rate is 90%.
Elementary analysis: C
40H
82N
2Br
2
High resolution mass spec: [M-Br]
+=669.5.
1H-NMR(CDCl
3,δ/ppm?relative?to?TMS):0.88(t,6H),1.26(m,44H),1.79(m,4H),2.14-2.40（m,12H),3.26-4.01(m,16H).
13C-NMR(CDCl
3,δ/ppm?relative?to?CDCl
3):14.32,22.25,22.84,23.72,25.89,26.36,28.12,29.48-29.75,59.75,60.31,63.18.
Fusing point: 199.8-200.4 ° C.
Embodiment 6
Preparation (the C of the two pyrrole ring quaternary ammonium salts of double hexadecyl decene base
16-10-
16PB)
14.2g (0.2 mole) pyrrolidines is joined in the 200ml acetonitrile, add successively 24g NaOH (0.6 mole) and 110g (0.5 mole) bromohexadecane, keep 80 ℃ of reactions 18 hours; After reaction is finished, acetonitrile and unreacted pyrrolidines are removed in decompression, the light yellow liquid body and function that obtains is equipped with the chromatographic column separation of the silica gel of 40 times of its weight, successively take carrene, ethyl acetate/dichloromethane/ammoniacal liquor as eluant, eluent, collect eluent, concentrated, can get N-cetyl pyrrolidines, productive rate is 95%.Add 250ml methyl-sulfoxide and 1,10-dibromo-decane 9.5g (0.032 mole) in the N-cetyl pyrrolidines of above-mentioned gained, vigorous stirring was in 120 ℃ of reactions 48 hours; After reaction finishes, methyl-sulfoxide is removed in decompression, the flaxen solid that obtains, mixed solvent with methanol/ethyl acetate, ethanol/ethyl acetate and ethanol/acetone is recrystallized successively, the product vacuum drying of gained is got final product to get the two pyrrole ring quaternary ammonium salts of double hexadecyl decene base, be white solid, productive rate is 92%.
Elementary analysis: C
50H
102N
2Br
2
High resolution mass spec: [M-Br]
+=809.6
1H-NMR(CDCl
3,δ/ppm?relative?to?TMS):0.88(t,6H),1.26(m,64H),1.79(m,4H),2.20（m,8H),2.52(m,4H),3.36-3.93(m,16H)
13C-NMR(CDCl
3,δ/ppm?relative?to?CDCl
3):14.23,22.12,22.74,23.63,26.27,26.49,28.59,28.79,29.27-29.65,31.95,59.70,59.95,63.12
Fusing point: 203.4 ~ 203.8 ℃.
Embodiment 7
Preparation (the C of the two pyrrole ring quaternary ammonium salts of two dodecyl laurylene bases
12-12-
12PB)
14.2g (0.2 mole) pyrrolidines is joined in the 200ml acetonitrile, add successively NaOH 32g (0.8 mole) and 124g (0.5 mole) bromododecane, keep 60 ℃ of reactions 10 hours; After reaction is finished, acetonitrile and unreacted pyrrolidines are removed in decompression, the light yellow liquid body and function that obtains is equipped with the chromatographic column separation of the silica gel of 40 times of its weight, successively take n-hexane, carrene, ethyl acetate/dichloromethane/ammoniacal liquor as eluant, eluent, collect eluent, concentrated, can get N-dodecyl pyrrolidines, productive rate is 98%.Add 250ml methyl-sulfoxide and 1,12-dibromo-dodecane 22g (0.0676 mole) in the N-dodecyl pyrrolidines of above-mentioned gained, vigorous stirring was in 110 ℃ of reactions 48 hours; After reaction finished, methyl-sulfoxide was removed in decompression, and the mixed solvent recrystallization of the pale yellow colored solid body and function ethanol/ethyl acetate that obtains gets final product the product vacuum drying of gained and to get the two pyrrole ring quaternary ammonium salts of two dodecyl laurylene bases, is white solid, and productive rate is 89%.
Elementary analysis: C
44H
90N
2Br
2
High resolution mass spec: [M-Br]
+=725.6.
1H-NMR(CDCl
3,δ/ppm?relative?to?TMS):0.88(t,6H),1.26(m,52H),1.79(m,4H),2.14-2.40（m,12H),3.26-4.01(m,16H).
13C-NMR(CDCl
3,δ/ppm?relative?to?CDCl
3):14.32,22.15,22.84,23.77,26.45,29.08-29.75,32.04,59.70,59.96,63.20.
Fusing point: 200.5 ~ 201.1 ℃.
Embodiment 8
Preparation (the C of the two pyrrole ring quaternary ammonium salts of two myristyl tetradecene bases
14-14-
14PB)
14.2g (0.2 mole) pyrrolidines is joined in the 200ml methyl-sulfoxide, add successively potash 41.4g (0.3 mole) and 138g (0.5 mole) bromotetradecane, keep 80 ℃ of reactions 24 hours; After reaction is finished, methyl-sulfoxide and unreacted pyrrolidines are removed in decompression, the light yellow liquid body and function that obtains is equipped with the chromatographic column separation of the silica gel of 40 times of its weight, successively take ethyl acetate, ethyl acetate/dichloromethane/ammoniacal liquor as eluant, eluent, collect eluent, concentrated, can get N-myristyl pyrrolidines, productive rate is 96%.Add 250ml methyl-sulfoxide and 1,14-dibromo hexadecane 17.7g (0.05 mole) in the N-myristyl pyrrolidines of above-mentioned gained, vigorous stirring was in 110 ℃ of reactions 72 hours; After reaction finishes, methyl-sulfoxide is removed in decompression, the flaxen solid that obtains, mixed solvent with methanol/ether, ethanol/ethyl acetate and ethanol/acetone is recrystallized successively, the product vacuum drying of gained is got final product to get the two pyrrole ring quaternary ammonium salts of two myristyl tetradecene bases, be white solid, productive rate is 85%.
Elementary analysis: C
50H
102N
2Br
2
High resolution mass spec: [M-Br]
+=809.7
1H-NMR(CDCl
3,δ/ppm?relative?to?TMS):0.88(t,6H),1.26(m,64H),1.75(m,4H),2.10（m,8H),2.30(m,4H),3.39-3.94(m,16H)
13C-NMR(CDCl
3,δ/ppm?relative?to?CDCl
3):14.32,22.12,22.84,23.71,26.57,29.34-29.75,32.05,59.68,59.87,63.22
Fusing point: 202.0 ~ 202.4 ℃.
Embodiment 9
Preparation (the C of the two pyrrole ring quaternary ammonium salts of two myristyl hexadecylene bases
14-16-
14PB)
14.2g (0.2 mole) pyrrolidines is joined in the 200ml methyl-sulfoxide, add successively potash 41.4g (0.3 mole) and 138g (0.5 mole) bromotetradecane, keep 80 ℃ of reactions 24 hours; After reaction is finished, methyl-sulfoxide and unreacted pyrrolidines are removed in decompression, the light yellow liquid body and function that obtains is equipped with the chromatographic column separation of the silica gel of 40 times of its weight, successively take ethyl acetate, ethyl acetate/dichloromethane/ammoniacal liquor as eluant, eluent, collect eluent, concentrated, can get N-myristyl pyrrolidines, productive rate is 96%.Add 250ml isopropyl alcohol and 1,16-dibromo hexadecane 19.1g (0.05 mole) in the N-myristyl pyrrolidines of above-mentioned gained, vigorous stirring was in 100 ℃ of reactions 72 hours; After reaction finishes, isopropyl alcohol is removed in decompression, the flaxen solid that obtains, mixed solvent with methanol/ether, ethanol/ethyl acetate and ethanol/acetone is recrystallized successively, the product vacuum drying of gained is got final product to get the two pyrrole ring quaternary ammonium salts of two myristyl hexadecylene bases, be white solid, productive rate is 83%.
Elementary analysis: C
52H
106N
2Br
2
High resolution mass spec: [M-Br]
+=837.6
1H-NMR(CDCl
3,δ/ppm?relative?to?TMS):0.88(t,6H),1.26(m,68H),1.75(m,4H),2.10（m,8H),2.30(m,4H),3.39-3.94(m,16H)
13C-NMR(CDCl
3,δ/ppm?relative?to?CDCl
3):14.30,22.10,22.82,23.69,26.53,29.47-29.73,32.03
Fusing point: 202.7 ~ 203.2 ℃.
Claims (6)
1. one kind take the Gemini surfactant of pyrrole ring as hydrophilic head base, it is characterized in that, concrete general formula is as follows:
In the formula: n=8 ~ 18; S=3,6 ~ 16.
2. according to claim 1 a kind of take the Gemini surfactant of pyrrole ring as hydrophilic head base, it is characterized in that: the s=3 in the described general formula, 6,8,10,12,14,16.
3. one kind as claimed in claim 1ly is characterized in that take the preparation method of pyrrole ring as the Gemini surfactant of hydrophilic head base, may further comprise the steps:
1) synthetic N-alkyl pyrrolidine: under the condition of nitrogen protection, pyrrolidines is added in the polar solvent, then add inorganic base and brominated alkanes, pyrrolidines is 1:3 ~ 1:4 with the amount ratio of inorganic base, the molar ratio of pyrrolidines and brominated alkanes is 1:2.2 ~ 1:4, in 40 ~ 80 ℃ of reactions 6 ~ 24 hours, separating-purifying obtained the N-alkyl pyrrolidine;
2) synthetic take the Gemini surfactant of pyrrole ring as hydrophilic head base: that the N-alkyl pyrrolidine that obtains in the step 1) and the two bromoalkanes mol ratio with 2.5:1 ~ 6:1 is joined in the polar solvent, reacted under 80 ~ 120 ℃ condition 12 ~ 72 hours, product obtains take the Cationic Gemini Surfactant of pyrrole ring as hydrophilic head base through recrystallization.
4. according to claim 3 a kind of take the preparation method of pyrrole ring as the Gemini surfactant of hydrophilic head base, it is characterized in that: the polar solvent in the described step 1) is a kind of in ethanol, methyl alcohol, acetonitrile, DMF or the methyl-sulfoxide; Described step 2) polar solvent in is a kind of in normal propyl alcohol, isopropyl alcohol, acetonitrile, DMF or the methyl-sulfoxide; The solvent of described recrystallization usefulness is one or more in ethanol/acetone, ethanol/ethyl acetate, ethanol/ether, normal propyl alcohol/ethyl acetate, methanol/ethyl acetate, the methanol/ether.
5. according to claim 3 a kind of take the preparation method of pyrrole ring as the Gemini surfactant of hydrophilic head base, it is characterized in that: described inorganic base is a kind of in sodium carbonate, sodium acid carbonate, potash or the NaOH.
6. according to claim 3 a kind of take the preparation method of pyrrole ring as the Gemini surfactant of hydrophilic head base, it is characterized in that: described brominated alkanes is n-octane bromide, bromo n-decane, bromododecane, bromotetradecane, bromohexadecane or bromo-octadecane; Described two bromoalkanes are 1,3-dibromopropane, 1,6-dibromo-hexane, 1,8-two bromooctanes, 1,10-dibromo-decane, 1,12-dibromo-dodecane, 1,14-, two bromo-tetradecanes or 1,16-dibromo hexadecane.
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| CN110042235A (en) * | 2019-04-29 | 2019-07-23 | 山东大学 | A kind of extractant and extracting process of separation gold |
| CN111359530A (en) * | 2020-03-20 | 2020-07-03 | 陕西科技大学 | Preparation method of heterocyclic cationic gemini surfactant |
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| CN103341338A (en) * | 2013-07-22 | 2013-10-09 | 武汉大学 | PH sensitive-type single-chain surfactants as well as synthetic method thereof |
| JP2015168680A (en) * | 2014-03-11 | 2015-09-28 | 東ソー株式会社 | Gemini type surfactant |
| CN108854841A (en) * | 2018-06-25 | 2018-11-23 | 长治学院 | A kind of pyrrolidines chirality Gemini surface active and preparation method thereof of the linker containing ester group |
| CN110042235A (en) * | 2019-04-29 | 2019-07-23 | 山东大学 | A kind of extractant and extracting process of separation gold |
| CN110042235B (en) * | 2019-04-29 | 2020-10-02 | 山东大学 | Extracting agent and extracting method for separating gold |
| CN111359530A (en) * | 2020-03-20 | 2020-07-03 | 陕西科技大学 | Preparation method of heterocyclic cationic gemini surfactant |
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