CN106823985A - A kind of biomass-based surfactant of nonionic and preparation method thereof - Google Patents
A kind of biomass-based surfactant of nonionic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses biomass-based surfactant of a kind of nonionic and preparation method thereof.The structural formula of the biomass-based surfactant of the nonionic is as shown in the formula III of formula I shown in compound.In the formula III of formula I, R1、R2、R3、R4It is independently selected from the branched-chain or straight-chain alkyl that H, carbon number are 1~22, but R1、R2It is asynchronously H, R3、R4It is asynchronously H.Also can as shown in formula VII compound, in formula VII, R1、R2It is independently selected from the branched-chain or straight-chain alkyl that H, carbon number are 1~22, but R1、R2It is asynchronously H.Can also as shown in the formula Ⅺ of formula Ⅸ compound.In the formula Ⅺ of formula Ⅸ, R1、R2、R3、R4With the formula III of formula I., with cheap, environment-friendly biomass as raw material, by the use of the polar group of carbohydrate as head base, synthesis is simple, meets the developing direction of environmental protection for the biomass-based surfactant of nonionic of the present invention；Good with dissolubility, the ability for reducing surface tension is strong, and emulsifiability is good, and consumption is few, the features such as biological degradability is good.
Description
Technical field
The present invention relates to biomass-based surfactant of a kind of nonionic and preparation method thereof.
Background technology
Surfactant is the amphiphile, amphiphilic molecule containing hydrophilic radical and hydrophobic grouping simultaneously in a class formation, due to that can show
Writing reduces liquid-vapor interface and liquid-liquid interface tension force, the effect such as wetting, emulsification, solubilising is played, so as in fields such as chemical industry, food
There is utilization extensively.The total output of current global various surfactants is 17,800,000 tons, average growth rate per annum about 6%.However, big
The preparing raw material of the surfactant of amount all derives from chemical process product.Meanwhile, such surfactant is difficult to degrade, to environment
Pollution be also the problem that should not be underestimated.Therefore, the surfactant of development environment friendly and superior performance is Green Chemistry
Developing direction.
The content of the invention
It is an object of the invention to provide biomass-based surfactant of a kind of nonionic and preparation method thereof, using biology
Polar head-group in matter in carbohydrate, introduces hydrophobic grouping and is translated into surfactant this functionalization by designing
Product, for surfactant field provides new approach and thinking.
Compound shown in I-formula of formula III that the present invention is provided,
In I-formula of formula III, R1、R2、R3、R4Be independently selected from H, carbon number for 1~22 (preferably 6~16, more preferably
8~branched-chain or straight-chain alkyl 12), but R1、R2It is asynchronously H, R3、R4It is asynchronously H.
Compound shown in the formula I concretely-A of following formula I or compound shown in I-B：
The preparation method of compound, comprises the following steps shown in I-formula of formula III that the present invention is provided：
(1) sorbierite (D-glucitol) obtains compound shown in formula IV, shown in formula V through the selective halogenation of halide reagent
Compound or compound shown in formula VI；
In IV-formula of formula VI, X is halogen (such as Cl, Br or I, preferably Br)；
(2) compound shown in formula IV, compound shown in formula V, compound shown in formula VI take with alkylamine through nucleophilic respectively
In generation, obtain compound shown in formula I, compound shown in formula II, compound shown in formula III；
In I-formula of formula III, R1、R2、R3、R4The branched-chain or straight-chain alkyl that H, carbon number are 1~22 is independently selected from,
But R1、R2It is asynchronously H, R3、R4It is asynchronously H.
Above-mentioned preparation method, in step (1), the ratio between the sorbierite and amount of material of the halide reagent can be 1：
(1~6), preferably 1：2.2.
The halide reagent can be chloroacetic chloride, acetyl bromide, thionyl chloride, phosphonium bromide, phosphorus pentachloride, phosphorus triiodide, hydrogen chlorine
One kind in the organic halogens such as acid, hydrobromic acid and hydroiodic acid.
The temperature of the selective halogenation can be 15~35 DEG C, and preferably 20 DEG C, 18 DEG C, the time can be 2~24 hours, preferably
14 hours.
The selective halogenation is carried out in organic solvent I, and the organic solvent I can be Isosorbide-5-Nitrae-dioxane, N, N- bis-
Any one in NMF, chloroform and dichloromethane etc..
The sorbierite can be 1g with the mass volume ratio of the organic solvent I：(3~20) mL, preferably 1g：(5~
10) mL, more preferably 1g：5mL、1g：8mL.
Above-mentioned preparation method, in step (2), compound shown in formula IV, compound shown in formula V or chemical combination shown in formula VI
The ratio between thing and amount of material of the alkylamine can be 1：(1~6), preferably 1：(1~3), more preferably 1：2.5.
R in alkylamine compound according to I-formula of formula III1、R2、R3、R4Group is selected accordingly.
The temperature of the nucleophilic displacement of fluorine can be 30~50 DEG C, and preferably 40 DEG C, the time can be 5~24 hours, and preferably 8~12 is small
When, more preferably 12 hours.
The nucleophilic displacement of fluorine is carried out in organic solvent II, and the organic solvent II can be methyl alcohol, ethanol, acetone, dichloro
Any one in methane and chloroform.
The mass body of compound shown in formula IV, compound shown in formula V or compound shown in formula VI and the organic solvent II
Product ratio can be 1g：(0.5~20) mL, preferably 1g：(3~10) mL, more preferably 1g：4mL.
Compound shown in the formula VII that the present invention is provided,
In formula VII, R1、R2It is independently selected from the branch that H, carbon number are 1~22 (preferably 6~16, more preferably 8~12)
Chain or straight chained alkyl, but R1、R2It is asynchronously H.
The concretely compound shown in the-A of following formula VII of compound shown in formula VII：
The preparation method of compound, comprises the following steps shown in the formula VII that the present invention is provided：
(1) 1,5- dehydration-D-glucitol obtain compound shown in formula VIII through the selective halogenation of halide reagent；
In formula VIII, X is halogen (such as Cl, Br or I, preferably Br)；
(2) compound shown in formula VIII obtains compound shown in formula VII with alkylamine through nucleophilic displacement of fluorine；
In formula VII, R1、R2It is independently selected from the branched-chain or straight-chain alkyl that H, carbon number are 1~22, but R1、R2No
It is simultaneously H.
Above-mentioned preparation method, in step (1), 1, the 5- dehydration-D-glucitols and the material of the halide reagent
The ratio between amount can be 1：(1~6), preferably 1：1.1.
The halide reagent can be chloroacetic chloride, acetyl bromide, thionyl chloride, phosphonium bromide, phosphorus pentachloride, phosphorus triiodide, hydrogen chlorine
One kind in the organic halogens such as acid, hydrobromic acid and hydroiodic acid.
The temperature of the selective halogenation can be 15~35 DEG C, and preferably 20 DEG C, 18 DEG C, the time can be 2~24 hours, preferably
14 hours.
The selective halogenation is carried out in organic solvent I, and the organic solvent I can be Isosorbide-5-Nitrae-dioxane, N, N- bis-
Any one in NMF, chloroform and dichloromethane etc..
1,5- dehydration-the D-glucitols can be 1g with the mass volume ratio of the organic solvent I：(3~20) mL, preferably
It is 1g：(5~10) mL, more preferably 1g：5mL、1g：8mL.
Above-mentioned preparation method, in step (2), the ratio between compound shown in formula VIII and amount of material of the alkylamine can be
1：(1~6), preferably 1：(1~3), more preferably 1：2.5.
R in alkylamine compound according to formula VII1、R2Group is selected accordingly.
The temperature of the nucleophilic displacement of fluorine can be 30~50 DEG C, and preferably 40 DEG C, the time can be 5~24 hours, and preferably 8~12 is small
When, more preferably 12 hours.
The nucleophilic displacement of fluorine is carried out in organic solvent II, and the organic solvent II can be methyl alcohol, ethanol, acetone, dichloro
Any one in methane and chloroform.
Compound shown in formula VIII can be 1g with the mass volume ratio of the organic solvent II：(0.5~20) mL, preferably
1g：(3~10) mL, more preferably 1g：4mL.
Compound shown in Ⅸ-formula of formula Ⅺ that the present invention is provided,
In Ⅸ-formula of formula Ⅺ, R1、R2、R3、R4Be independently selected from H, carbon number for 1~22 (preferably 6~16, it is more excellent
Select 8~branched-chain or straight-chain alkyl 12), but R1、R2It is asynchronously H, R3、R4It is asynchronously H.
Compound shown in formula Ⅸ concretely compound shown in the-A of following formula Ⅸ or compound shown in the-B of formula Ⅸ：
Invention further provides the preparation method of compound shown in the Ⅸ-formula of formula Ⅺ described in any of the above-described, including
Following steps：
(1) isobide is through halide reagent selective halogenation, obtain compound shown in formula Ⅹ II, compound shown in Ⅹ III or
Compound shown in Ⅹ IV；
In Ⅹ II-Ⅹ IV, X is halogen (such as Cl, Br or I, preferably Br)；
(2) compound shown in formula Ⅹ II, compound shown in Ⅹ III, compound shown in Ⅹ IV take with alkylamine through nucleophilic respectively
In generation, obtain compound shown in formula Ⅸ, compound shown in formula Ⅹ, compound shown in formula Ⅺ；
In Ⅸ-formula of formula Ⅺ, R1、R2、R3、R4It is independently selected from side chain or straight chain alkane that H, carbon number are 1~22
Base, but R1、R2It is asynchronously H, R3、R4It is asynchronously H.
Above-mentioned preparation method, in step (1), the ratio between the isobide and amount of material of the halide reagent can be
1：(1~6), preferably 1：2.2.
The halide reagent can be chloroacetic chloride, acetyl bromide, thionyl chloride, phosphonium bromide, phosphorus pentachloride, phosphorus triiodide, hydrogen chlorine
One kind in the organic halogens such as acid, hydrobromic acid and hydroiodic acid.
The temperature of the selective halogenation can be 15~35 DEG C, and preferably 20 DEG C, 18 DEG C, the time can be 2~24 hours, preferably
14 hours.
The selective halogenation is carried out in organic solvent I, and the organic solvent I can be Isosorbide-5-Nitrae-dioxane, N, N- bis-
Any one in NMF, chloroform and dichloromethane etc..
The isobide can be 1g with the mass volume ratio of the organic solvent：(3~20) mL, preferably 1g：(5~
10) mL, more preferably 1g：5mL、1g：8mL.
Above-mentioned preparation method, in step (2), compound shown in formula Ⅹ II, compound shown in Ⅹ III or Ⅹ IV shownization
The ratio between compound and amount of material of the alkylamine can be 1：(1~6), preferably 1：(1~3), more preferably 1：2.5.
R in alkylamine compound according to Ⅸ-formula of formula Ⅺ1、R2、R3、R4Group is selected accordingly.
The temperature of the nucleophilic displacement of fluorine can be 30~50 DEG C, and preferably 40 DEG C, the time can be 5~24 hours, and preferably 8~12 is small
When, more preferably 12 hours.
The nucleophilic displacement of fluorine is carried out in organic solvent II, and the organic solvent II can be methyl alcohol, ethanol, acetone, dichloro
Any one in methane and chloroform.
The quality of compound shown in formula Ⅹ II, compound shown in compound or Ⅹ IV shown in Ⅹ III and the organic solvent II
Volume ratio can be 1g：(0.5~20) mL, preferably 1g：(3~10) mL, more preferably 1g：4mL.
Present invention also offers compound shown in the formula I described in any of the above-described, compound shown in formula II, shownization of formula III
Compound, compound shown in formula VII, compound shown in formula Ⅸ, compound shown in Formula Ⅺ shown in formula Ⅹ as or prepare table
Application in the activating agent of face.
The present invention has the advantages that：
The biomass-based surfactant of nonionic of the present invention is sharp with cheap, environment-friendly biomass as raw material
With the polar group of carbohydrate as head base, building-up process is simple, meets the developing direction of environmental protection.Nonionic life of the present invention
Material based surfactants have dissolubility good, and the ability for reducing surface tension is strong, and emulsifiability is good, and consumption is few, biodegradable
The features such as property is good, can make emulsifying agent, tackifier, solubilizer, wetting agent, detergent etc. and be applied to chemical industry, food, oil exploitation
Deng field.Additionally, the alkyl-substituted molecular structures of N- cause that the surfactant has Modulatory character in structure, and it can
There is response to environmental factors such as pH, the application of the biomass-based surfactant of the nonionic has been widened.
Brief description of the drawings
Fig. 1 be compound shown in formula I, compound shown in formula VII, the synthetic route of compound shown in formula Ⅸ, wherein
Figure 1A is the synthetic route of compound shown in formula I, and Figure 1B is compound shown in formula VII, and Fig. 1 C are the synthesis of compound shown in formula Ⅸ
Route.
Fig. 2 is the surface tension curve of the biomass-based surfactant of nonionic, wherein, BS-1 is prepared for embodiment 1
The surfactant for obtaining, BS-2 is the surfactant that embodiment 2 is prepared, and BS-3 is the table that embodiment 3 is prepared
Face activating agent.
The emulsion photo that Fig. 3 is formed by the biomass-based surfactant of nonionic, wherein being followed successively by BS- from left to right
1- methylene chloride/waters -4:1, BS-2- methylene chloride/water -6:1, BS-3- methylene chloride/water -5:1, BS-1- normal heptane/water -5:
1, BS-2- normal heptane/water -10:1；Wherein, the consumption of the biomass-based surfactant of the nonionic is followed successively by：BS-1,
200ppm；BS-2,300ppm；BS-3,150ppm.
The microphotograph of the emulsion that Fig. 4 is formed by the biomass-based surfactant of nonionic, wherein Fig. 4 A are BS-
1- methylene chloride/waters -4:The microphotograph of 1 emulsion, Fig. 4 a are the corresponding fluorescent microscopy images of 4A；4B is BS-1- positive heptan
Alkane/water -5:The microphotograph of 1 emulsion, Fig. 4 b are the corresponding fluorescent microscopy images of 4B.Wherein, it is used in fluorescence microscope
Dyestuff is tonyred.
Fig. 5 is the surface tension curve of the biomass-based surfactant of nonionic, wherein, BS-5 is prepared for embodiment 5
The surfactant for obtaining.
Fig. 6 is the solubilizing effect of the biomass-based surfactant of nonionic, wherein, BS-5 is prepared for embodiment 5
Surfactant.
Specific embodiment
Experimental technique used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc. in following embodiments, unless otherwise specified, commercially obtain.
Embodiment 1, the biomass-based surfactant B S-1 of synthesis nonionic
Synthesize the biomass-based surfactant of nonionic according to route shown in Fig. 1 (A), comprise the following steps that：
(1) 10.1g D-glucitols are added in reaction vessel, 80mL Isosorbide-5-Nitraes-dioxane is added, is placed in ice bath and is stirred
Mix, 10.1mL acetyl bromides are added dropwise.Regulation reaction temperature stirs 14h to 18 DEG C.Vacuum distillation removes solvent, dichloromethane extraction
Obtain bromo sorbierite shown in the-A of formula IV, yellow liquid, yield 85%.Structure verification data are as follows：1H-NMR(400MHz,
D2O):δ=3.27 (dd, 1H), 3.33 (dd, 1H), 5.30 (m, 1H), 5.41 (dd, 1H), 5.08 (m, 1H), 3.37 (dd,
1H),3.51(dd,1H)；MALDI-TOF-MS(M+H)+:Calcd.for C6H12Br2O4:307.Found:308. empirical tests, knot
Structure is correct.
(2) by bromo sorbierite shown in the-A of 6.2g formulas IV, 5.68g n-octyl amines, 20mL absolute methanols add reaction vessel, rise
Be concentrated under reduced pressure for reaction solution after terminating by temperature to 40 DEG C of stirring 12h, reaction, and-the A of white solid formula I is recrystallized to give with acetone/diethyl ether
Shown compound, yield 73%.Structure verification data are following (BS-1)：1H-NMR(400MHz,D2O):δ=0.76-0.78 (t, J
=6.0Hz, 6H ,-CH3), 1.19-1.21 (m, 24H), 1.23-1.29 (m, J=12.0,6.0Hz, 4H), 1.54-1.59 (m,
4H), 2.88-2.91 (m, J=6.0Hz, 4H)；MALDI-TOF-MS(M+Na)+:Calcd.for C22H48N2O4:
404.3.Found:427；Empirical tests, structure is correct.
Embodiment 2, the biomass-based surfactant B S-2 of synthesis nonionic
Synthesize the biomass-based surfactant of nonionic according to route shown in Fig. 1 (A), comprise the following steps that：
(1) 10.1g D-glucitols are added in reaction vessel, 80mL Isosorbide-5-Nitraes-dioxane is added, is placed in ice bath and is stirred
Mix, 10.1mL acetyl bromides are added dropwise.Regulation reaction temperature stirs 14h to 18 DEG C.Vacuum distillation removes solvent, dichloromethane extraction
Obtain bromo sorbierite shown in the-A of formula IV, yellow liquid, yield 85%.1H-NMR(400MHz,D2O):δ=3.27 (dd, 1H),
3.33(dd,1H),5.30(m,1H),5.41(dd,1H),5.08(m,1H),3.37(dd,1H),3.51(dd,1H)；MALDI-
TOF-MS(M+H)+:Calcd.for C6H12Br2O4:307.Found:308. empirical tests, structure is correct.
(2) by bromo sorbierite shown in the-A of 6.2g formulas IV, 8.15g n-dodecylamines, 25mL absolute methanols add reaction vessel,
40 DEG C of stirring 12h are warming up to, be concentrated under reduced pressure for reaction solution after terminating by reaction, and white solid formula is recrystallized to give with acetone/diethyl ether
Compound shown in I-B, yield 67%.Structure verification data are following (BS-2):1H-NMR(400MHz,D2O):δ=0.77-0.79
(t, J=6.0Hz, 6H), 1.20-1.22 (m, 44H), 1.23-1.30 (m, 4H), 1.54-1.59 (m, J=12.0,6.0Hz,
4H), 2.89-2.91 (m, J=12.0,6.0Hz, 4H)；MALDI-TOF-MS(M+H)+:Calcd.for C30H64N2O4:
516.4.Found:517.6；Empirical tests, structure is correct.
Embodiment 3, the biomass-based surfactant B S-3 of synthesis nonionic
Synthesize the biomass-based surfactant of nonionic according to route shown in Fig. 1 (C), comprise the following steps that：
(1) 10.1g isobides are added in reaction vessel, 80mL Isosorbide-5-Nitraes-dioxane is added, is placed in ice bath and is stirred
Mix, 10.1mL acetyl bromides are added dropwise.Regulation reaction temperature stirs 14h to 18 DEG C.Vacuum distillation removes solvent, dichloromethane extraction
Obtain bromo sorbierite anhydro derivatives shown in Ⅹ II-A, light yellow liquid, yield 90%.Structure verification data are as follows：1H-
NMR(400MHz,D2O):δ=3.82 (dd, 1H), 3.88 (dd, 1H), 5.42 (m, 1H), 5.36 (dd, 1H), 5.12 (m, 1H),
3.94(dd,1H),3.86(dd,1H)；MALDI-TOF-MS:Calcd.for C6H12Br2O2:271.Found:294(M+Na)；
Empirical tests, structure is correct.
(2) by bromo sorbierite anhydro derivatives, 12.0g n-dodecylamines, 25mL absolute methanols shown in the-A of 8.0g formulas Ⅹ II
Reaction vessel is added, 40 DEG C of stirring 12h are warming up to, be concentrated under reduced pressure for reaction solution after terminating, recrystallized with acetone/ethanol by reaction
To compound, yield 78% shown in the-A of white solid formula Ⅸ.Structure verification data are following (BS-3)：1H-NMR(400MHz,D2O):
δ=0.78-0.82 (t, J=6.0Hz, 6H), 1.21-1.24 (m, 44H), 1.26-1.31 (m, 4H), 1.53-1.59 (m, J=
12.0,6.0Hz, 4H), 2.92-2.96 (m, J=12.0,6.0Hz, 4H)；MALDI-TOF-MS:Calcd.for C30H60N2O2:
480.Found:503(M+Na)；Empirical tests, structure is correct.
Embodiment 4, the biomass-based surfactant B S-4 of synthesis nonionic
Synthesize the biomass-based surfactant of nonionic according to route shown in Fig. 1 (C), comprise the following steps that：
(1) with embodiment 3.
(2) by bromo isobide shown in the-A of 8.0g formulas Ⅹ II, 15.6g hexadecylamines, 30mL absolute methanols add reaction
Container, is warming up to 40 DEG C of stirring 12h, and be concentrated under reduced pressure for reaction solution after terminating by reaction, and it is solid to be recrystallized to give white with acetone/ethanol
Compound shown in the-B of body formula Ⅸ, yield 86%.Structure verification data are following (BS-4)：1H-NMR(400MHz,D2O):δ=0.79-
0.82 (t, J=6.0Hz, 6H), 1.22-1.26 (m, 48H), 1.25-1.31 (m, 4H), 1.53-1.59 (m, J=12.0,
6.0Hz, 4H), 2.92-2.96 (m, J=12.0,6.0Hz, 4H)；MALDI-TOF-MS:Calcd.for C38H76N2O2:
592.Found:615(M+Na).Empirical tests, structure is correct.
Embodiment 5, the biomass-based surfactant B S-5 of synthesis nonionic
Synthesize the biomass-based surfactant of nonionic according to route shown in Fig. 1 (B), comprise the following steps that：
(1) 10.1g 1 is added in reaction vessel, 5- dehydrations-D-glucitol add 50mL Isosorbide-5-Nitraes-dioxane, are placed in
Stirred in ice bath, 4.8mL acetyl bromides are added dropwise.Regulation reaction temperature stirs 12h to 18 DEG C.Vacuum distillation removes solvent, obtains
Bromo 1 shown in VIII-A, 5- dehydrations-D-glucitol, colourless liquid, yield 87%.Structure verification data are as follows：1H-NMR
(400MHz,D2O):δ=3.58 (dd, 1H), 3.63 (dd, 1H), 5.21 (dd, 1H), 5.13 (dd, 1H), 3.91 (dd, 1H),
4.02(dd,1H)；δ=3.95 (m, 1H), δ=3.98 (m, 1H)；MALDI-TOF-MS:Calcd.for C6H11BrO4:
225.Found:226(M+H)；Empirical tests, structure is correct.
(2) by bromo 1 shown in the-A of 4.0g formulas VIII, 5- dehydrations-D-glucitol, 6.25g n-Decylamines, 25mL absolute methanols are added
Reaction vessel, is warming up to 40 DEG C of stirring 12h, and be concentrated under reduced pressure for reaction solution after terminating, recrystallized with acetone/absolute ether by reaction
To compound shown in white solid formula VII, yield 72%.Structure verification data are following (BS-5)：1H-NMR(400MHz,D2O):δ
=0.77-0.79 (t, J=6.0Hz, 6H), 1.20-1.22 (m, 32H), 1.24-1.30 (m, J=12.0,6.0Hz, 4H),
1.56-1.60 (m, 4H), 2.89-2.92 (m, J=6.0Hz, 4H), 4.01 (dd, 1H)；δ=3.92 (m, 1H), δ=3.94 (m,
1H)；MALDI-TOF-MS(M+H)+:Calcd.for C16H33NO4:303.Found:304；Empirical tests, structure is correct.
The evaluation of the surface-active and emulsifiability of the biomass-based surfactant of embodiment 6, nonionic
First, surface tension
Instrument：Dataphysics DCAT-21 surface tension measuring instruments (German Dataphysics companies)；BX-101 types
Super constant temperature trough Control release temperature is (25 ± 0.1) DEG C.
Measuring method：A series of biomass-based surfactant of nonionic of concentration is determined with Wilhelmy-plate methods
Equilibrium surface tension at 25 DEG C.Since low concentration, determine surface tension value and change with time, take value during equalization point
It is then the equilibrium surface tension under the concentration.
Curve is made to concentration by surface tension, γ-logC curves are obtained, point of inflexion on a curve is the nonionic biomass
The critical micelle concentration (CMC) of based surfactants.
Experimental result is as shown in Figure 2.Figure it is seen that the biomass-based surfactant of nonionic of the present invention has
Relatively low surface tension (10-5~10-6mol/L)。
2nd, emulsifiability
Assay method：Under the conditions of 25 DEG C, weigh the biomass-based surfactant of 5mg nonionics and be placed in container, plus
Enter 15mL normal heptanes, 3mL deionized waters, both hands are fluctuated 5 times simultaneously, and emulsion is formed, stand the property of observation emulsion.
Experimental result is as shown in Figure 3 and Figure 4, it can be seen that nonionic biological surface activating agent emulsifiability of the present invention
It is good.By the interfacial film arranged on interface so as to form varying strength such that it is able to stable emulsion.
Embodiment 7, solubilization
Solubilising experiment is mainly by determining solubilising to the polarization index I of pyrene in surfactant solution1/I3Value is before CMC
Change afterwards, so as to obtain surface active agent solubilization effect.The foundation of the method is：Hydrophobic fluorescence probe pyrene solubilising is arrived and is situated between
The fluorescent characteristic corresponding with medium character can be shown in matter.Pyrene is solubilized in surfactant solution, due to aggregation
The microenvironment of body is sensitive, and different Fluorescence behaviours are then shown before micellization and after micellization.I1And I3It is pyrene fluorescence emission
First (373nm) and the 3rd (384nm) electronic vibration peak in spectrum.Fluorescence intensity is surveyed using Hitachi F-4500 luminoscopes
It is fixed.The excitation wavelength of pyrene is 335nm, and the sweep limits of emission spectrum is 350-500nm.Exciting light and transmitting optical slits are respectively provided with
It is 2.5nm, sweep speed selection 240nm/min.With first peak (at 373nm) in the fluorescence emission spectrum of pyrene and the 3rd
Intensity ratio (the I at peak (at 384nm)1/I3) evaluate micropolar inside aggregation, wherein with I1/I3Surfactant concentration
Make curve, be the CMC of surfactant at point of inflexion on a curve.
Specific experiment method：It is 1 × 10 by 4 μ l concentration-3Ethanol is treated in the ethanol solution injection sample bottle of M fluorescence probe pyrenes
Volatilize, add the sample solution of 4ml various concentrations, determined after stirring 24h.Experimental temperature is controlled in (25.0 ± 0.1) DEG C.
Experimental result as it can be seen in figures 5 and 6, it can be seen that nonionic biological surface activating agent of the present invention not only have compared with
Low surface tension, and have stronger solubilization to strong hydrophobic molecule pyrene.
Claims (10)
1. compound shown in I-formula of formula III,
In I-formula of formula III, R1、R2、R3、R4It is independently selected from the branched-chain or straight-chain alkyl that H, carbon number are 1~22, but R1、
R2It is asynchronously H, R3、R4It is asynchronously H.
2. the preparation method of compound shown in I-formula of claim 1 Chinese style III, comprises the following steps：
(1) sorbierite obtains compound shown in formula IV, compound shown in formula V or the institute of formula VI through the selective halogenation of halide reagent
Show compound；
In IV-formula of formula VI, X is halogen；
(2) compound shown in formula IV, compound shown in formula V, compound shown in formula VI are obtained respectively with alkylamine through nucleophilic displacement of fluorine
To compound shown in formula I, compound shown in formula II, compound shown in formula III；
In I-formula of formula III, R1、R2、R3、R4It is independently selected from the branched-chain or straight-chain alkyl that H, carbon number are 1~22, but R1、
R2It is asynchronously H, R3、R4It is asynchronously H.
3. preparation method according to claim 2, it is characterised in that：In step (1), the sorbierite is tried with the halogenation
The ratio between amount of material of agent is 1：(1~6)；
The halide reagent is chloroacetic chloride, acetyl bromide, thionyl chloride, phosphonium bromide, phosphorus pentachloride, phosphorus triiodide, hydrochloric acid, hydrogen bromine
One kind in acid and hydroiodic acid；
The temperature of the selective halogenation is 15~35 DEG C, and the time is 2~24 hours；
The selective halogenation is carried out in organic solvent I, and the organic solvent I is Isosorbide-5-Nitrae-dioxane, N, N- dimethyl methyls
Any one in acid amides, chloroform and dichloromethane；
The sorbierite is 1g with the mass volume ratio of the organic solvent I：(3~20) mL；
In step (2), the material of compound shown in formula IV, compound shown in formula V or compound shown in formula VI and the alkylamine
The ratio between amount be 1：(1~6)；
It is 5~24 hours 30~50 DEG C of times that the temperature of the nucleophilic displacement of fluorine is；
The nucleophilic displacement of fluorine is carried out in organic solvent II, the organic solvent II be methyl alcohol, ethanol, acetone, dichloromethane and
Any one in chloroform；
The mass volume ratio of compound shown in formula IV, compound shown in formula V or compound shown in formula VI and the organic solvent II
It is 1g：(0.5~20) mL.
4. compound shown in formula VII,
In formula VII, R1、R2It is independently selected from the branched-chain or straight-chain alkyl that H, carbon number are 1~22, but R1、R2It is asynchronously
H。
5. the preparation method of compound shown in formula VII, comprises the following steps：
(1) 1,5- dehydration-D-glucitol obtain compound shown in formula VIII through the selective halogenation of halide reagent；
In formula VIII, X is halogen；
(2) compound shown in formula VIII obtains compound shown in formula VIII with alkylamine through nucleophilic displacement of fluorine；
In formula VII, R1、R2It is independently selected from the branched-chain or straight-chain alkyl that H, carbon number are 1~22, but R1、R2It is asynchronously
H。
6. preparation method according to claim 5, it is characterised in that：In step (1), 1, the 5- dehydrations-D-glucitol
It is 1 with the ratio between the amount of material of the halide reagent：(1~6)；
The halide reagent is chloroacetic chloride, acetyl bromide, thionyl chloride, phosphonium bromide, phosphorus pentachloride, phosphorus triiodide, hydrochloric acid, hydrogen bromine
One kind in acid and hydroiodic acid；
The temperature of the selective halogenation is 15~35 DEG C, and the time is 2~24 hours；
The selective halogenation is carried out in organic solvent I, and the organic solvent I is Isosorbide-5-Nitrae-dioxane, N, N- dimethyl methyls
Any one in acid amides, chloroform and dichloromethane etc.；
1,5- dehydration-the D-glucitols are 1g with the mass volume ratio of the organic solvent I：(3~20) mL；
In step (2), the ratio between compound shown in formula VIII and amount of material of the alkylamine are 1：(1~6)；
The temperature of the nucleophilic displacement of fluorine is 30~50 DEG C, and the time is 5~24 hours；
The nucleophilic displacement of fluorine is carried out in organic solvent II, the organic solvent II be methyl alcohol, ethanol, acetone, dichloromethane and
Any one in chloroform；
Compound shown in formula VIII is 1g with the mass volume ratio of the organic solvent II：(0.5~20) mL.
7. compound shown in Ⅸ-formula of formula Ⅺ,
In Ⅸ-formula of formula Ⅺ, R1、R2、R3、R4The branched-chain or straight-chain alkyl that H, carbon number are 1~22 is independently selected from, but
R1、R2It is asynchronously H, R3、R4It is asynchronously H.
8. the preparation method of compound shown in the Ⅸ-formula of formula Ⅺ described in claim 7, comprises the following steps：
(1) isobide obtains compound shown in formula Ⅹ II, compound or Ⅹ IV shown in Ⅹ III through halide reagent selective halogenation
Shown compound；
In Ⅹ II-Ⅹ IV, X is halogen；
(2) compound shown in formula Ⅹ II, compound shown in compound or Ⅹ IV shown in Ⅹ III be respectively with alkylamine through nucleophilic displacement of fluorine,
Obtain compound shown in formula Ⅸ, compound shown in formula Ⅹ, compound shown in formula Ⅺ；
In Ⅸ-formula of formula Ⅺ, R1、R2、R3、R4The branched-chain or straight-chain alkyl that H, carbon number are 1~22 is independently selected from, but
R1、R2It is asynchronously H, R3、R4It is asynchronously H.
9. preparation method according to claim 8, it is characterised in that：In step (1), the isobide and the halogenation
The ratio between amount of material of reagent is 1：(1~6)；
The halide reagent is chloroacetic chloride, acetyl bromide, thionyl chloride, phosphonium bromide, phosphorus pentachloride, phosphorus triiodide, hydrochloric acid, hydrogen bromine
One kind in acid and hydroiodic acid；
The temperature of the selective halogenation is 15~35 DEG C, and the time is 2~24 hours；
The selective halogenation is carried out in organic solvent I, and the organic solvent I is Isosorbide-5-Nitrae-dioxane, N, N- dimethyl methyls
Any one in acid amides, chloroform and dichloromethane etc.；
The isobide is 1g with the mass volume ratio of the organic solvent I：(3~20) mL；
In step (2), the thing of compound shown in formula Ⅹ II, compound shown in compound or Ⅹ IV shown in Ⅹ III and the alkylamine
The ratio between amount of matter is 1：(1~6)；
The temperature of the nucleophilic displacement of fluorine is 30~50 DEG C, and the time is 5~24 hours；
The nucleophilic displacement of fluorine is carried out in organic solvent II, the organic solvent II be methyl alcohol, ethanol, acetone, dichloromethane and
Any one in chloroform.
The quality volume of compound shown in formula Ⅹ II, compound shown in compound or Ⅹ IV shown in Ⅹ III and the organic solvent II
Than being 1g：(0.5~20) mL.
10. compound, right shown in the formula VII shown in the I-formula of formula III described in claim 1 described in compound, claim 4 will
Ask compound shown in the Ⅸ-formula of formula Ⅺ described in 7 as or application in preparing surfactant.
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| CN109369630A (en) * | 2018-10-18 | 2019-02-22 | 中国科学院化学研究所 | Replace glucose acids surfactant and its preparation and application |
| CN112999971A (en) * | 2019-12-18 | 2021-06-22 | 中国科学院大连化学物理研究所 | Preparation method of surfactant and surfactant prepared by preparation method |
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| CN1127158A (en) * | 1994-08-19 | 1996-07-24 | 罗纳-布朗克公司 | Anionic surfactants having multiple hydrophobic and hydrophilic groups |
| US20080269190A1 (en) * | 2007-04-24 | 2008-10-30 | Theravance, Inc. | Quaternary ammonium compounds useful as muscarinic receptor antagonists |
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| CN1127158A (en) * | 1994-08-19 | 1996-07-24 | 罗纳-布朗克公司 | Anionic surfactants having multiple hydrophobic and hydrophilic groups |
| US20080269190A1 (en) * | 2007-04-24 | 2008-10-30 | Theravance, Inc. | Quaternary ammonium compounds useful as muscarinic receptor antagonists |
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| CN109369630A (en) * | 2018-10-18 | 2019-02-22 | 中国科学院化学研究所 | Replace glucose acids surfactant and its preparation and application |
| CN112999971A (en) * | 2019-12-18 | 2021-06-22 | 中国科学院大连化学物理研究所 | Preparation method of surfactant and surfactant prepared by preparation method |
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