CN106823985B - Non-ionic biomass-based surfactant of one kind and preparation method thereof - Google Patents
Non-ionic biomass-based surfactant of one kind and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of non-ionic biomass-based surfactants and preparation method thereof.Shown in structural formula compound as shown in I-formula of formula III of the non-ionic biomass-based surfactant.In I-formula of formula III, R1、R2、R3、R4It is independently selected from H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22, but R1、R2It is not simultaneously H, R3、R4It is not simultaneously H.Can also the compound as shown in formula VII, in formula VII, R1、R2It is independently selected from H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22, but R1、R2It is not simultaneously H.It can also the compound as shown in Ⅸ-formula of formula Ⅺ.In Ⅸ-formula of formula Ⅺ, R1、R2、R3、R4With I-formula of formula III.The non-ionic biomass-based surfactant of the present invention is using cheap, environmental-friendly biomass as raw material, and using the polar group of carbohydrate as head base, synthesis is simple, meets environmentally protective developing direction；It is good with dissolubility, the features such as ability for reducing surface tension is strong, and emulsifiability is good, and dosage is few, and biological degradability is good.
Description
Technical field
The present invention relates to a kind of non-ionic biomass-based surfactants and preparation method thereof.
Background technique
Surfactant is the amphiphile, amphiphilic molecule containing hydrophilic radical and hydrophobic grouping simultaneously in a class formation, due to that can show
The effects of writing reduces liquid-vapor interface and liquid-liquid interface tension, plays wetting, emulsification, solubilising, thus in fields such as chemical industry, food
There is extensive utilization.The total output of the various surfactants in the whole world is 17,800,000 tons at present, average growth rate per annum about 6%.However, big
The raw material for preparing 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 of should not be underestimated.Therefore, the surfactant of development environment friendly and superior performance is Green Chemistry
Developing direction.
Summary of the invention
The object of the present invention is to provide a kind of non-ionic biomass-based surfactants and preparation method thereof, utilize biology
Polar head-group in matter in carbohydrate introduces hydrophobic grouping by design and is translated into this functionalization of surfactant
Product provide new approach and thinking for surfactant field.
Compound shown in I-formula of formula III provided by the invention,
In I-formula of formula III, R1、R2、R3、R4Be independently selected from H, carbon atom number be 1~22 (preferably 6~16, more preferably
8~12) branched-chain or straight-chain alkyl, but R1、R2It is not simultaneously H, R3、R4It is not simultaneously H.
The concretely compound shown in I-A of following formula or I-B of compound shown in formula I:
The preparation method of compound shown in I-formula of formula III provided by the invention, includes the following steps:
(1) selective halogenation of sorbierite (D-glucitol) through halide reagent obtains shown in compound shown in formula IV, formula V
Compound shown in compound or 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 compound, formula VI shown in formula V take with alkylamine through nucleophilic respectively
In generation, obtains compound shown in compound shown in formula I, formula II, compound shown in formula III；
In I-formula of formula III, R1、R2、R3、R4It is independently selected from H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22,
But R1、R2It is not simultaneously H, R3、R4It is not simultaneously H.
Above-mentioned preparation method, in step (1), the ratio between amount of substance of the sorbierite and 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 of organic halogens such as acid, hydrobromic acid and hydroiodic acid.
The temperature of the selective halogenation can be 15~35 DEG C, preferably 20 DEG C, 18 DEG C, and the time can be 2~24 hours, preferably
14 hours.
The selective halogenation carries out in organic solvent I, and the organic solvent I can be Isosorbide-5-Nitrae-dioxane, N, N- bis-
Any one of methylformamide, chloroform and methylene chloride etc..
The mass volume ratio of the sorbierite and the organic solvent I can be 1g:(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, chemical combination shown in compound or formula VI shown in formula V
The ratio between the amount of substance of object and the alkylamine can be 1:(1~6), preferably 1:(1~3), more preferably 1:2.5.
R of the alkylamine in the 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 preferable 12 hours.
The nucleophilic displacement of fluorine carries out in organic solvent II, and the organic solvent II can be methanol, ethyl alcohol, acetone, dichloro
Any one of methane and chloroform.
The mass body of compound shown in formula IV, compound and the organic solvent II shown in compound or formula VI shown in formula V
Product ratio can be 1g:(0.5~20) mL, preferably 1g:(3~10) mL, more preferably 1g:4mL.
Compound shown in formula VII provided by the invention,
In formula VII, R1、R2It is independently selected from H, carbon atom number is 1~22 (preferably 6~16, the branch of more preferable 8~12)
Chain or straight chained alkyl, but R1、R2It is not simultaneously H.
The concretely compound shown in VII-A of following formula of compound shown in formula VII:
The preparation method of compound shown in formula VII provided by the invention, includes the following steps:
Selective halogenation of (1) 1, the 5- dehydration-D-glucitol through halide reagent, obtains compound shown in formula VIII；
In formula VIII, X is halogen (such as Cl, Br or I, preferably Br)；
(2) compound shown in formula VIII and alkylamine obtain compound shown in formula VII through nucleophilic displacement of fluorine；
In formula VII, R1、R2It is independently selected from H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22, but R1、R2No
It is simultaneously H.
Above-mentioned preparation method, in step (1), the substance of 1, the 5- dehydration-D-glucitol and 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 of organic halogens such as acid, hydrobromic acid and hydroiodic acid.
The temperature of the selective halogenation can be 15~35 DEG C, preferably 20 DEG C, 18 DEG C, and the time can be 2~24 hours, preferably
14 hours.
The selective halogenation carries out in organic solvent I, and the organic solvent I can be Isosorbide-5-Nitrae-dioxane, N, N- bis-
Any one of methylformamide, chloroform and methylene chloride etc..
The mass volume ratio of 1, the 5- dehydration-D-glucitol and the organic solvent I can be 1g:(3~20) mL, preferably
For 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 the amount of substance of the alkylamine can be
1:(1~6), preferably 1:(1~3), more preferably 1:2.5.
R of the alkylamine in the 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 preferable 12 hours.
The nucleophilic displacement of fluorine carries out in organic solvent II, and the organic solvent II can be methanol, ethyl alcohol, acetone, dichloro
Any one of methane and chloroform.
The mass volume ratio of compound shown in formula VIII and the organic solvent II can be 1g:(0.5~20) mL, preferably
1g:(3~10) mL, more preferably 1g:4mL.
Compound shown in Ⅸ-formula of formula Ⅺ provided by the invention,
In Ⅸ-formula of formula Ⅺ, R1、R2、R3、R4Be independently selected from H, carbon atom number be 1~22 (preferably 6~16, it is more excellent
Select 8~12) branched-chain or straight-chain alkyl, but R1、R2It is not simultaneously H, R3、R4It is not simultaneously H.
The concretely compound shown in Ⅸ-B of compound shown in Ⅸ-A of following formula or formula of compound shown in formula Ⅸ:
Invention further provides the preparation methods of compound shown in Ⅸ-formula of formula Ⅺ described in any of the above embodiments, 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, obtains compound shown in compound shown in formula Ⅸ, formula Ⅹ, compound shown in formula Ⅺ；
In Ⅸ-formula of formula Ⅺ, R1、R2、R3、R4It is independently selected from H, the branch or straight chain alkane that carbon atom number is 1~22
Base, but R1、R2It is not simultaneously H, R3、R4It is not simultaneously H.
Above-mentioned preparation method, in step (1), the ratio between the isobide and the amount of substance 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 of organic halogens such as acid, hydrobromic acid and hydroiodic acid.
The temperature of the selective halogenation can be 15~35 DEG C, preferably 20 DEG C, 18 DEG C, and the time can be 2~24 hours, preferably
14 hours.
The selective halogenation carries out in organic solvent I, and the organic solvent I can be Isosorbide-5-Nitrae-dioxane, N, N- bis-
Any one of methylformamide, chloroform and methylene chloride etc..
The mass volume ratio of the isobide and the organic solvent can be 1g:(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 the amount of substance for closing object and the alkylamine can be 1:(1~6), preferably 1:(1~3), more preferably 1:2.5.
R of the alkylamine in the 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 preferable 12 hours.
The nucleophilic displacement of fluorine carries out in organic solvent II, and the organic solvent II can be methanol, ethyl alcohol, acetone, dichloro
Any one of methane and chloroform.
The quality of compound shown in formula Ⅹ II, compound shown in compound shown in Ⅹ III or Ⅹ IV and the organic solvent II
Volume ratio can be 1g:(0.5~20) mL, preferably 1g:(3~10) mL, more preferably 1g:4mL.
The present invention also provides change shown in compound shown in compound shown in formula I described in any of the above embodiments, formula II, formula III
Close compound shown in compound shown in object, compound, formula Ⅸ shown in formula VII, Formula Ⅺ shown in formula Ⅹ as or prepare table
Application in the activating agent of face.
The invention has the following beneficial effects:
The non-ionic biomass-based surfactant of the present invention is using cheap, environmental-friendly biomass as raw material, benefit
Use the polar group of carbohydrate as head base, synthesis process is simple, meets environmentally protective developing direction.The non-ionic life of the present invention
Substance based surfactants have dissolubility good, and the ability for reducing surface tension is strong, and emulsifiability is good, and dosage is few, biodegrade
Property it is good the features such as, emulsifier, tackifier, solubilizer, wetting agent, detergent etc. can be made into applied to chemical industry, food, oil exploitation
Equal fields.In addition, the alkyl-substituted molecular structure of N- makes the surfactant have Modulatory character in structure, and it can
There is responsiveness to environmental factors such as pH, widened the application of the non-ionic biomass-based surfactant.
Detailed description of the invention
Fig. 1 is the synthetic route of compound shown in formula I, compound shown in compound, formula Ⅸ shown in formula VII, 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 is the synthesis of compound shown in formula Ⅸ
Route.
Fig. 2 is the surface tension curve of non-ionic biomass-based surfactant, wherein BS-1 is the preparation of embodiment 1
Obtained surfactant, BS-2 are the surfactant that embodiment 2 is prepared, and BS-3 is the table that embodiment 3 is prepared
Face activating agent.
Fig. 3 is that non-ionic biomass-based surfactant is formed by lotion photo, wherein being followed successively by BS- from left to right
1- methylene chloride/water -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 dosage of the non-ionic biomass-based surfactant is successively are as follows: BS-1,
200ppm；BS-2,300ppm；BS-3,150ppm.
Fig. 4 is the microscope photo that non-ionic biomass-based surfactant is formed by lotion, and wherein Fig. 4 A is BS-
The microscope photo of 1- methylene chloride/water -4:1 lotion, Fig. 4 a are the corresponding fluorescent microscopy images of 4A；4B is BS-1- positive heptan
Alkane/water -5:1 lotion microscope photo, Fig. 4 b are the corresponding fluorescent microscopy images of 4B.Wherein, used in fluorescence microscope
Dyestuff is tonyred.
Fig. 5 is the surface tension curve of non-ionic biomass-based surfactant, wherein BS-5 is the preparation of embodiment 5
Obtained surfactant.
Fig. 6 is the solubilizing effect of non-ionic biomass-based surfactant, wherein BS-5 is that embodiment 5 is prepared
Surfactant.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1, the non-ionic biomass-based surfactant B S-1 of synthesis
Non-ionic biomass-based surfactant is synthesized according to route shown in Fig. 1 (A), the specific steps are as follows:
(1) 10.1g D-glucitol is added in the reaction vessel, 80mL Isosorbide-5-Nitrae-dioxane is added, is placed in ice bath and stirs
It mixes, 10.1mL acetyl bromide is added dropwise.Reaction temperature is adjusted to 18 DEG C, stirs 14h.Vacuum distillation removes solvent, methylene chloride extraction
Obtain bromo sorbierite shown in IV-A of formula, 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. is verified, knot
Structure is correct.
(2) by bromo sorbierite shown in IV-A of 6.2g formula, 5.68g n-octyl amine, 20mL anhydrous methanol addition reaction vessel, liter
Reaction solution is concentrated under reduced pressure after reaction to 40 DEG C of stirring 12h, is recrystallized to give I-A of white solid formula with acetone/diethyl ether by temperature
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；Verified, structure is correct.
Embodiment 2, the non-ionic biomass-based surfactant B S-2 of synthesis
Non-ionic biomass-based surfactant is synthesized according to route shown in Fig. 1 (A), the specific steps are as follows:
(1) 10.1g D-glucitol is added in the reaction vessel, 80mL Isosorbide-5-Nitrae-dioxane is added, is placed in ice bath and stirs
It mixes, 10.1mL acetyl bromide is added dropwise.Reaction temperature is adjusted to 18 DEG C, stirs 14h.Vacuum distillation removes solvent, methylene chloride extraction
Obtain bromo sorbierite shown in IV-A of formula, 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. is verified, and structure is correct.
(2) by bromo sorbierite shown in IV-A of 6.2g formula, reaction vessel is added in 8.15g n-dodecylamine, 25mL anhydrous methanol,
40 DEG C of stirring 12h are warming up to, reaction solution is concentrated under reduced pressure after reaction, is recrystallized to give white solid formula 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；Verified, structure is correct.
Embodiment 3, the non-ionic biomass-based surfactant B S-3 of synthesis
Non-ionic biomass-based surfactant is synthesized according to route shown in Fig. 1 (C), the specific steps are as follows:
(1) 10.1g isobide is added in the reaction vessel, 80mL Isosorbide-5-Nitrae-dioxane is added, is placed in ice bath and stirs
It mixes, 10.1mL acetyl bromide is added dropwise.Reaction temperature is adjusted to 18 DEG C, stirs 14h.Vacuum distillation removes solvent, methylene chloride 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)；
Verified, structure is correct.
(2) by bromo sorbierite anhydro derivatives, 12.0g n-dodecylamine, 25mL anhydrous methanol shown in Ⅹ II-A of 8.0g formula
Reaction vessel is added, is warming up to 40 DEG C of stirring 12h, reaction solution is concentrated under reduced pressure after reaction, is recrystallized with acetone/ethanol
To compound shown in Ⅸ-A of white solid formula, yield 78%.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)；Verified, structure is correct.
Embodiment 4, the non-ionic biomass-based surfactant B S-4 of synthesis
Non-ionic biomass-based surfactant is synthesized according to route shown in Fig. 1 (C), the specific steps are as follows:
(1) with embodiment 3.
(2) by bromo isobide shown in Ⅹ II-A of 8.0g formula, 15.6g hexadecylamine, 30mL anhydrous methanol, which is added, to react
Container is warming up to 40 DEG C of stirring 12h, reaction solution is concentrated under reduced pressure after reaction, and it is solid to be recrystallized to give white with acetone/ethanol
Compound shown in Ⅸ-B of body formula, 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).Verified, structure is correct.
Embodiment 5, the non-ionic biomass-based surfactant B S-5 of synthesis
Non-ionic biomass-based surfactant is synthesized according to route shown in Fig. 1 (B), the specific steps are as follows:
(1) 10.1g 1 is added in the reaction vessel, 5- dehydration-D-glucitol is added 50mL Isosorbide-5-Nitrae-dioxane, is placed in
It is stirred in ice bath, 4.8mL acetyl bromide is added dropwise.Reaction temperature is adjusted to 18 DEG C, stirs 12h.Vacuum distillation removes solvent, obtains
Bromo 1 shown in VIII-A, 5- dehydration-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)；Verified, structure is correct.
(2) by bromo 1 shown in VIII-A of 4.0g formula, 5- dehydration-D-glucitol, 6.25g n-Decylamine, the addition of 25mL anhydrous methanol
Reaction vessel is warming up to 40 DEG C of stirring 12h, reaction solution is concentrated under reduced pressure after reaction, is recrystallized with acetone/anhydrous ether
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；Verified, structure is correct.
The evaluation of embodiment 6, the surface-active of non-ionic biomass-based surfactant and emulsifiability
One, surface tension
Instrument: Dataphysics DCAT-21 surface tension measuring instrument (German Dataphysics company)；BX-101 type
It is (25 ± 0.1) DEG C that super constant temperature trough, which controls experimental temperature,.
Measurement method: a series of non-ionic biomass-based surfactant of concentration is measured with Wilhelmy-plate method
Equilibrium surface tension at 25 DEG C.Since low concentration, measurement surface tension value changes with time, and takes value when equalization point
It is then the equilibrium surface tension under the concentration.
Curve is made to concentration by surface tension, obtains γ-logC curve, point of inflexion on a curve is the non-ionic biomass
The critical micelle concentration (CMC) of based surfactants.
Experimental result is as shown in Figure 2.Figure it is seen that the non-ionic biomass-based surfactant of the present invention has
Lower surface tension (10-5~10-6mol/L)。
Two, emulsifiability
Measuring method: it under the conditions of 25 DEG C, weighs the non-ionic biomass-based surfactant of 5mg and is placed in container, add
Enter 15mL normal heptane, 3mL deionized water, both hands fluctuate 5 times simultaneously, and lotion is formed, and stand the property of observation lotion.
Experimental result is as shown in Figure 3 and Figure 4, it can be seen that the non-ionic biological surface activating agent emulsifiability of the present invention
It is good.By being arranged on interface so that the interfacial film of varying strength is formed, so as to stable emulsion.
Embodiment 7, solubilization
Solubilising experiment mainly passes through the polarization index I of measurement solubilising pyrene into surfactant solution1/I3Value is before CMC
Variation afterwards, to obtain surface active agent solubilization effect.The foundation of the method is: hydrophobic fluorescence probe pyrene solubilising to Jie
Fluorescent characteristic corresponding with medium character can be shown in matter.Pyrene solubilising is into surfactant solution, due to aggregation
The microenvironment of body is sensitive, shows before micellization and then different Fluorescence behaviours after micellization.I1And I3It is pyrene fluorescence emission
First (373nm) and third (384nm) electronic vibration peak in spectrum.Fluorescence intensity is surveyed using Hitachi F-4500 luminoscope
It is fixed.The excitation wavelength of pyrene is 335nm, and the scanning range of emission spectrum is 350-500nm.Exciting light and transmitting optical slits are respectively provided with
For 2.5nm, sweep speed selects 240nm/min.With in the fluorescence emission spectrum of pyrene first peak (at 373nm) and third
Intensity ratio (the I at peak (at 384nm)1/I3) evaluation aggregation inside it is micropolar, wherein with I1/I3Surfactant concentration
Make curve, is the CMC of surfactant at point of inflexion on a curve.
Specific experiment method: being 1 × 10 by 4 μ l concentration-3To ethyl alcohol in the ethanol solution injection sample bottle of M fluorescence probe pyrene
It volatilizes, the sample solution of 4ml various concentration is added, stirring measures afterwards for 24 hours.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 the non-ionic 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 H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22, but R1、
R2It is not simultaneously H, R3、R4It is not simultaneously H.
2. the preparation method of compound shown in I-formula of claim 1 Chinese style III, includes the following steps:
(1) selective halogenation of the sorbierite through halide reagent obtains VI institute of compound shown in compound shown in formula IV, formula V or formula
Show compound；
In IV-formula of formula VI, X is halogen；
(2) compound shown in formula IV, compound shown in compound, formula VI shown in formula V obtain respectively with alkylamine through nucleophilic displacement of fluorine
To compound shown in compound shown in compound shown in formula I, formula II, formula III；
In I-formula of formula III, R1、R2、R3、R4It is independently selected from H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22, but R1、
R2It is not simultaneously H, R3、R4It is not simultaneously H；
In step (1), the ratio between amount of substance of the sorbierite and the halide 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 of acid and hydroiodic acid；
The temperature of the selective halogenation is 15~35 DEG C, and the time is 2~24 hours；
In step (2), the substance of compound shown in formula IV, compound and the alkylamine shown in compound or formula VI shown in formula V
The ratio between amount be 1:(1~6)；
The temperature of the nucleophilic displacement of fluorine is 30~50 DEG C, and the time is 5~24 hours.
3. according to the method described in claim 2, it is characterized by: the selective halogenation is in organic solvent I in step (1)
Middle progress, the organic solvent I are any one of Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, chloroform and methylene chloride；
The mass volume ratio of the sorbierite and the organic solvent I is 1g:(3~20) mL；
In step (2), the nucleophilic displacement of fluorine carries out in organic solvent II, the organic solvent II be methanol, ethyl alcohol, acetone,
Any one of methylene chloride and chloroform；
The mass volume ratio of compound shown in formula IV, compound and the organic solvent II shown in compound or formula VI shown in formula V
For 1g:(0.5~20) mL.
4. compound shown in formula VII:
In formula VII, R1、R2It is independently selected from H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22, but R1、R2It is not simultaneously
H。
5. the preparation method of compound shown in claim 4 Chinese style VII, includes the following steps:
Selective halogenation of (1) 1, the 5- dehydration-D-glucitol through halide reagent, obtains compound shown in formula VIII；
In formula VIII, X is halogen；
(2) compound shown in formula VIII and alkylamine obtain compound shown in formula VIII through nucleophilic displacement of fluorine；
In formula VII, R1、R2It is independently selected from H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22, but R1、R2It is not simultaneously
H；
In step (1), the ratio between amount of substance of 1, the 5- dehydration-D-glucitol and the halide 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 of acid and hydroiodic acid；
The temperature of the selective halogenation is 15~35 DEG C, and the time is 2~24 hours；
In step (2), the ratio between amount of substance of compound shown in formula VIII and the alkylamine is 1:(1~6)；
The temperature of the nucleophilic displacement of fluorine is 30~50 DEG C, and the time is 5~24 hours.
6. according to the method described in claim 5, it is characterized by: the selective halogenation is in organic solvent I in step (1)
Middle progress, the organic solvent I are any one of Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, chloroform and methylene chloride；
The mass volume ratio of the 1,5- dehydration-D-glucitol and the organic solvent I is 1g:(3~20) mL；
In step (2), the nucleophilic displacement of fluorine carries out in organic solvent II, the organic solvent II be methanol, ethyl alcohol, acetone,
Any one of methylene chloride and chloroform；
The mass volume ratio of compound shown in formula VIII and the organic solvent II is 1g:(0.5~20) mL.
7. compound shown in Ⅸ-formula of formula Ⅺ:
In Ⅸ-formula of formula Ⅺ, R1、R2、R3、R4It is independently selected from H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22, but
R1、R2It is not simultaneously H, R3、R4It is not simultaneously H.
8. the preparation method of compound shown in Ⅸ-formula of formula Ⅺ as claimed in claim 7, includes the following steps:
(1) isobide obtains compound shown in formula Ⅹ II, compound shown in Ⅹ III or Ⅹ IV 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 shown in Ⅹ III or Ⅹ IV be respectively with alkylamine through nucleophilic displacement of fluorine,
Obtain compound shown in compound shown in formula Ⅸ, formula Ⅹ, compound shown in formula Ⅺ；
In Ⅸ-formula of formula Ⅺ, R1、R2、R3、R4It is independently selected from H, the branched-chain or straight-chain alkyl that carbon atom number is 1~22, but
R1、R2It is not simultaneously H, R3、R4It is not simultaneously H；
In step (1), the ratio between amount of substance of the isobide and the halide 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 of acid and hydroiodic acid；
The temperature of the selective halogenation is 15~35 DEG C, and the time is 2~24 hours；
In step (2), the object of compound shown in formula Ⅹ II, compound and the alkylamine shown in compound shown in Ⅹ III or Ⅹ IV
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.
9. according to the method described in claim 8, it is characterized by: the selective halogenation is in organic solvent I in step (1)
Middle progress, the organic solvent I are any one of Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, chloroform and methylene chloride；
The mass volume ratio of the isobide and the organic solvent I is 1g:(3~20) mL；
In step (2), the nucleophilic displacement of fluorine carries out in organic solvent II, the organic solvent II be methanol, ethyl alcohol, acetone,
Any one of methylene chloride and chloroform；
The quality volume of compound shown in formula Ⅹ II, compound shown in compound shown in Ⅹ III or Ⅹ IV and the organic solvent II
Than for 1g:(0.5~20) mL.
10. compound shown in I-formula of formula III described in claim 1, compound, right shown in formula as claimed in claim 4 VII are wanted
Compound shown in Ⅸ-formula of formula Ⅺ described in asking 7 as or prepare application in surfactant.
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