CN104815590B - A kind of synthetic method of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant - Google Patents
A kind of synthetic method of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant Download PDFInfo
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Abstract
The synthetic method of a kind of diethyl three [(1 alkyl 3 carbamoylmethyl) imidazole salts] surfactant, it relates to the synthetic method of a kind of surfactant.Present invention aim to address that conventional surfactant molecule exists surface activity poor, adsorptivity and autohemagglutination are weak, and existing process for synthesizing surfactant uses solvent as reaction media, causes production cost high, post processing difficulty, the problem of harm production safety.Synthetic method: one, synthesizing trichloroacetyl base diethylenetriamine；Two, synthesis N alkyl imidazole；Three, synthetic surfactant, i.e. obtains diethyl three [(1 alkyl 3 carbamoylmethyl) imidazole salts] surfactant.Present invention is mainly used for synthesizing diethyl three [(1 alkyl 3 carbamoylmethyl) imidazole salts] surfactant.
Description
Technical field
The present invention relates to the synthetic method of a kind of surfactant.
Background technology
Conventional surfactant molecule is made up of a hydrophobic group and a hydrophilic group, and critical micelle concentration is higher, pC20Value and
γcmcIt is worth bigger.Therefore, conventional surfactant surface activity is poor, and adsorptivity and autohemagglutination are weak, the solubilising power shown
And wettability is low.And, single ionic head based structures makes the krafft point of surfactant higher, at reality application neck
There is the biggest limitation in territory.
During conventional method synthetic surfactant, generally need to not only improve cost during commercial production with solvent as reaction media,
Increase post processing difficulty, and equipment, people and environment can be worked the mischief.The most existing process for synthesizing surfactant is adopted
With solvent as reaction media, improve production cost, and post processing difficulty, endanger production safety.
Summary of the invention
Present invention aim to address that conventional surfactant molecule exists surface activity poor, adsorptivity and autohemagglutination are weak, performance
The solubilising power and the wettability that go out are low, and krafft point is higher, and existing process for synthesizing surfactant uses solvent to make
For reaction media, cause production cost high, post processing difficulty, the problem of harm production safety；And provide a kind of diethyl-
The synthetic method of three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant.
A kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant, its general structure is as follows:Wherein n is 6,8,10,12 or 14；X is Cl.
A kind of synthetic method of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant, specifically by with
Lower step completes:
One, synthesizing trichloroacetyl base diethylenetriamine: 1., chloracetyl chloride is dissolved in dichloromethane, obtain chloracetyl chloride/
Dichloromethane solution, step one 1. described in chloracetyl chloride/dichloromethane solution in the concentration of chloracetyl chloride be
2.0mmol/mL～3.0mmol/mL；2., diethylenetriamine and triethylamine are added in dichloromethane, and under condition of ice bath
Stirring, mixing speed is 600rpm～800rpm, then uses constant pressure funnel with constant rate of addition
2mL/min～4mL/min instills chloracetyl chloride/dichloromethane solution, drips and complete follow-up continuous with mixing speed is
600rpm～800rpm stirring reaction 5h～7h, obtain product, step one 2. described in diethylenetriamine and triethylamine
Mol ratio be (0.22～0.25): 1, step one 2. described in the volume ratio of amount and dichloromethane of material of diethylenetriamine
For 0.01mol:60mL, step one 2. described in diethylenetriamine and chloracetyl chloride in chloracetyl chloride/dichloromethane solution
Mol ratio is (0.22～0.25): 1；3., utilize to rotate and steam dichloromethane in instrument decompression removal product, obtain except solvent is anti-
Answering product, be subsequently adding distilled water and carry out cancellation, the described volume ratio except solvent reaction product with distilled water is
1:(10～15), obtain product after cancellation, then extract 3～5 times for extractant with ethyl acetate, single extraction acetic acid second
After ester and cancellation, the volume ratio of product is (1～1.5): 1, merges the organic facies being obtained by extraction, then utilizes Rotary Evaporators
Carry out the rotary evaporation removing solvent ethyl acetate that reduces pressure, obtain product after rotation is steamed, with use ethanol as recrystallization solvent pair
After rotation is steamed, product at room temperature carries out recrystallization, obtains crystal, is 0.09MPa～0.1MPa and temperature in vacuum
Crystal is dried under conditions of being 40～45 DEG C by degree, and drying time is 2h～3h, obtains white powdery solids, in vain
Color pulverulent solids is tribromo-acetyl base diethylenetriamine；
Two, synthesis N-alkyl imidazole: the most successively imidazoles and NaOH are added in dimethyl sulfoxide, be stirred at room temperature
1h～2h, mixing speed is 800rpm～1200rpm, obtains mixed solution, with rate of addition as 3mL/min～5mL/min
In mixed solution, add 1-bromoalkane, and low whipping speed is reaction 4h～6h under 800rpm～1200rpm, is reacted
Liquid, adds distilled water in reactant liquor, then extracts 3～5 times for extractant with chloroform, single extraction chloroform and reactant liquor
Volume ratio be (0.18～0.27): 1, combined chloroform layer, and use distilled water wash chloroform layer 4～5 times, then use anhydrous
Na2SO4Being dried 2h～4h, dried product exhibited filters, and obtains organic facies, then utilizes Rotary Evaporators to reduce pressure
Rotary evaporation removes solvent chloroform, obtains except reactant after solvent, is 0.09MPa～0.1MPa and temperature is in vacuum
Under conditions of 50～60 DEG C to except after solvent reactant be dried, drying time is 3h～5h, obtains weak yellow liquid, light
Yellow liquid is N-alkyl imidazole；Described imidazoles is (1.0～1.2) with the mol ratio of NaOH: 1, the material of described imidazoles
The volume ratio of amount and dimethyl sulfoxide be (16.5～19.8) mmol:20mL, described distilled water with the volume ratio of dimethyl sulfoxide is
(1～1.2): 1, the mol ratio of described imidazoles and 1-bromoalkane is (1.0～1.2): 1, described 1-bromoalkane be 1-bromooctane,
1-bromodecane, Dodecyl Bromide, 1-bromotetradecane or 1-bromohexadecane；
Three, synthetic surfactant: tribromo-acetyl base diethylenetriamine and N-alkyl imidazole are added in reactor, from room
Temperature is heated with stirring to 120 DEG C～140 DEG C, continues reaction 1h～2h, uses chloroform/acetone mixed liquor to carry out recrystallization after cooling,
Described chloroform/acetone mixed liquor is (2～4) by chloroform and acetone by the volume ratio of chloroform Yu acetone: 1 mixes, and is tied
Brilliant product, is dried crystallized product under conditions of vacuum is 0.09MPa～0.1MPa and temperature is 35～45 DEG C,
Drying time is 2h～4h, obtains white powdery solids, and white powdery solids is diethyl-three [(1-alkyl-3-carbamyl
Methyl) imidazole salts] surfactant；Described tribromo-acetyl base diethylenetriamine with the mol ratio of N-alkyl imidazole is
(0.25～0.35): 1.
The invention have the advantages that one, diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surface activity of present invention synthesis
Containing multiple amido links and multiple imidazole ring nitrogen cation head in agent, there is higher surface activity, more preferable water solublity, suction
Attached property, oil-soluble and corrosion inhibition etc..The molecular structure feature of such surfactant makes it not only have biological degradability but also have
There is bactericidal properties.Two, course of reaction raw material of the present invention is easy to get, and reaction condition gentleness is easily controllable, and step 3 building-up process is
Carry out under condition of no solvent, simplify last handling process, shorten the response time, reduce reaction cost, improve product
The yield of thing, this reaction meets the requirement of Green Chemistry.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of tribromo-acetyl base diethylenetriamine；
Fig. 2 is the infrared spectrum of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant；
Fig. 4 is the hydrogen spectrogram of N-octylimidazole；
Fig. 3 is the hydrogen spectrogram of tribromo-acetyl base diethylenetriamine；
Fig. 5 is the hydrogen spectrogram of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant；
Fig. 6 is the carbon spectrogram of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant；
Fig. 7 is that diethyl-three [(1-octyl group-3-carbamoylmethyl) imidazole salts] aqueous surfactant solution electrical conductivity becomes with concentration
Change curve.
Detailed description of the invention
Detailed description of the invention one: present embodiment is a kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surface
Activating agent, its general structure is as follows:Wherein n be 6,8,10,12 or
14；X is Cl.
Containing many in diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant described in present embodiment
Individual amido link and multiple imidazole ring nitrogen cation head, have higher surface activity, more preferable water solublity, adsorptivity, oil soluble
Property and corrosion inhibition etc..The molecular structure feature of such surfactant makes it not only have biological degradability but also have bactericidal properties.
Detailed description of the invention two: present embodiment is a kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surface
The synthetic method of activating agent, is specifically realized by the following steps:
One, synthesizing trichloroacetyl base diethylenetriamine: 1., chloracetyl chloride is dissolved in dichloromethane, obtain chloracetyl chloride/
Dichloromethane solution, step one 1. described in chloracetyl chloride/dichloromethane solution in the concentration of chloracetyl chloride be
2.0mmol/mL～3.0mmol/mL；2., diethylenetriamine and triethylamine are added in dichloromethane, and under condition of ice bath
Stirring, mixing speed is 600rpm～800rpm, then uses constant pressure funnel with constant rate of addition
2mL/min～4mL/min instills chloracetyl chloride/dichloromethane solution, drips and complete follow-up continuous with mixing speed is
600rpm～800rpm stirring reaction 5h～7h, obtain product, step one 2. described in diethylenetriamine and triethylamine
Mol ratio be (0.22～0.25): 1, step one 2. described in the volume ratio of amount and dichloromethane of material of diethylenetriamine
For 0.01mol:60mL, step one 2. described in diethylenetriamine and chloracetyl chloride in chloracetyl chloride/dichloromethane solution
Mol ratio is (0.22～0.25): 1；3., utilize to rotate and steam dichloromethane in instrument decompression removal product, obtain except solvent is anti-
Answering product, be subsequently adding distilled water and carry out cancellation, the described volume ratio except solvent reaction product with distilled water is
1:(10～15), obtain product after cancellation, then extract 3～5 times for extractant with ethyl acetate, single extraction acetic acid second
After ester and cancellation, the volume ratio of product is (1～1.5): 1, merges the organic facies being obtained by extraction, then utilizes Rotary Evaporators
Carry out the rotary evaporation removing solvent ethyl acetate that reduces pressure, obtain product after rotation is steamed, with use ethanol as recrystallization solvent pair
After rotation is steamed, product at room temperature carries out recrystallization, obtains crystal, is 0.09MPa～0.1MPa and temperature in vacuum
Crystal is dried under conditions of being 40～45 DEG C by degree, and drying time is 2h～3h, obtains white powdery solids, in vain
Color pulverulent solids is tribromo-acetyl base diethylenetriamine；
Two, synthesis N-alkyl imidazole: the most successively imidazoles and NaOH are added in dimethyl sulfoxide, be stirred at room temperature
1h～2h, mixing speed is 800rpm～1200rpm, obtains mixed solution, with rate of addition as 3mL/min～5mL/min
In mixed solution, add 1-bromoalkane, and low whipping speed is reaction 4h～6h under 800rpm～1200rpm, is reacted
Liquid, adds distilled water in reactant liquor, then extracts 3～5 times for extractant with chloroform, single extraction chloroform and reactant liquor
Volume ratio be (0.18～0.27): 1, combined chloroform layer, and use distilled water wash chloroform layer 4～5 times, then use anhydrous
Na2SO4Being dried 2h～4h, dried product exhibited filters, and obtains organic facies, then utilizes Rotary Evaporators to reduce pressure
Rotary evaporation removes solvent chloroform, obtains except reactant after solvent, is 0.09MPa～0.1MPa and temperature is in vacuum
Under conditions of 50～60 DEG C to except after solvent reactant be dried, drying time is 3h～5h, obtains weak yellow liquid, light
Yellow liquid is N-alkyl imidazole；Described imidazoles is (1.0～1.2) with the mol ratio of NaOH: 1, the material of described imidazoles
The volume ratio of amount and dimethyl sulfoxide be (16.5～19.8) mmol:20mL, described distilled water with the volume ratio of dimethyl sulfoxide is
(1～1.2): 1, the mol ratio of described imidazoles and 1-bromoalkane is (1.0～1.2): 1, described 1-bromoalkane be 1-bromooctane,
1-bromodecane, Dodecyl Bromide, 1-bromotetradecane or 1-bromohexadecane；
Three, synthetic surfactant: tribromo-acetyl base diethylenetriamine and N-alkyl imidazole are added in reactor, from room
Temperature is heated with stirring to 120 DEG C～140 DEG C, continues reaction 1h～2h, uses chloroform/acetone mixed liquor to carry out recrystallization after cooling,
Described chloroform/acetone mixed liquor is (2～4) by chloroform and acetone by the volume ratio of chloroform Yu acetone: 1 mixes, and is tied
Brilliant product, is dried crystallized product under conditions of vacuum is 0.09MPa～0.1MPa and temperature is 35～45 DEG C,
Drying time is 2h～4h, obtains white powdery solids, and white powdery solids is diethyl-three [(1-alkyl-3-carbamyl
Methyl) imidazole salts] surfactant；Described tribromo-acetyl base diethylenetriamine with the mol ratio of N-alkyl imidazole is
(0.25～0.35): 1.
Bull based surfactants molecule is made up of two or more parents' groups, and more parents' group makes it have
Higher surface activity.Diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant of synthesis in the present invention
Molecular structure there are three hydrophilic groups and three hydrophobic groups couple by coupling base, there is higher surface activity, more preferable water
The performance such as dissolubility and adsorptivity.The critical micelle concentration of such surfactant is minimum up to 0.6 × 10-4Mol/L, is formed
Micelle more stable.It addition, compared with tertiary amines surfactant, ion head base introduces imidazoles circulus, it is possible to
Strengthening its heat stability, decomposition temperature can reach 230 DEG C, and thermostability is preferable.
Containing many in diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant of present embodiment synthesis
Individual amido link and multiple imidazole ring nitrogen cation head, have higher surface activity, more preferable water solublity, adsorptivity, oil soluble
Property and corrosion inhibition etc..The molecular structure feature of such surfactant makes it not only have biological degradability but also have bactericidal properties.
Present embodiment course of reaction raw material is easy to get, and reaction condition gentleness is easily controllable, and step 3 building-up process is without molten
Carry out under the conditions of agent, simplify last handling process, shorten the response time, reduce reaction cost, improve the receipts of product
Rate, this reaction meets the requirement of Green Chemistry.
Detailed description of the invention three: the present embodiment difference from detailed description of the invention two is: step one 3. at rotating speed 60
Rev/min～100 revs/min, bath temperature is room temperature and vacuum is to utilize under the conditions of 0.08MPa～0.09MPa to rotate to steam instrument and subtract
Pressure removes dichloromethane in product, obtains except solvent reaction product.Other are identical with detailed description of the invention two.
Detailed description of the invention four: present embodiment with one of detailed description of the invention two or three difference is: step one 3. in turn
Speed 60 revs/min～100 revs/min, bath temperature are 40 DEG C and vacuum is to utilize rotation under the conditions of 0.08MPa～0.09MPa
Turn evaporimeter and carry out the rotary evaporation removing solvent ethyl acetate that reduces pressure, obtain product after rotation is steamed.Other and specific embodiment party
Formula two or three is identical.
Detailed description of the invention five: present embodiment with one of detailed description of the invention two to four difference is: at rotating speed in step 2
60 revs/min～100 revs/min, bath temperature is 30 DEG C and vacuum is to utilize to rotate under the conditions of 0.08MPa～0.09MPa to steam
Send out instrument and carry out the rotary evaporation removing solvent chloroform that reduces pressure, obtain except reactant after solvent.Other are with detailed description of the invention two to four
Identical.
Detailed description of the invention six: present embodiment with one of detailed description of the invention two to five difference is: step one is 1. middle will
45mmol chloracetyl chloride is dissolved in 20mL dichloromethane, obtains chloracetyl chloride/dichloromethane solution.Other be embodied as
Mode two to five is identical.
Detailed description of the invention seven: present embodiment with one of detailed description of the invention two to six difference is: step one is 2. middle will
10mmol diethylenetriamine and 45mmol triethylamine add in 60mL dichloromethane, and stir under condition of ice bath, stir
Mixing speed is 600rpm～800rpm, then uses constant pressure funnel to instill chloroethene with constant rate of addition 3mL/min
Acyl chlorides/dichloromethane solution, drips complete follow-up continuous with mixing speed as 600rpm～800rpm stirring reaction 5h, obtains anti-
Answer product, step one 2. described in diethylenetriamine with the mol ratio of chloracetyl chloride in chloracetyl chloride/dichloromethane solution be
1:4.5.Other are identical with detailed description of the invention two to six.
Detailed description of the invention eight: present embodiment with one of detailed description of the invention two to seven difference is: step one 3. in turn
Speed 60 revs/min～100 revs/min, bath temperature are room temperature and vacuum is to utilize to rotate under the conditions of 0.08MPa to steam instrument decompression
Remove dichloromethane in product, obtain except solvent reaction product, be subsequently adding distilled water and carry out cancellation, described except molten
Agent product is 1:12 with the volume ratio of distilled water, obtains product after cancellation, then extracts for extractant with ethyl acetate
Taking 4 times, after single extraction ethyl acetate and cancellation, the volume ratio of product is 1.2:1, merges the organic facies being obtained by extraction,
Then Rotary Evaporators is utilized to carry out under the conditions of rotating speed 80 revs/min, bath temperature are 40 DEG C and vacuum is 0.08MPa
Decompression rotary evaporation removes solvent ethyl acetate, obtains product after rotation is steamed, steams rotation with use ethanol as recrystallization solvent
Rear product at room temperature carries out recrystallization, obtains crystal, in the condition that vacuum is 0.1MPa and temperature is 45 DEG C
Under crystal is dried, drying time is 3h, obtains white powdery solids, and white powdery solids is three chloroethenes
Acyl group diethylenetriamine.Other are identical with detailed description of the invention two to seven.
Detailed description of the invention nine: present embodiment with one of detailed description of the invention two to eight difference is: first depend in step 2
Secondary by 16.5mmol imidazoles and 16.5mmol NaOH addition 20mL dimethyl sulfoxide, it is stirred at room temperature 2h, stirring
Speed is 800rpm～1200rpm, obtains mixed solution, adds with rate of addition for 4mL/min in mixed solution
15mmol 1-bromoalkane, and low whipping speed be under 800rpm～1200rpm reaction 5h, obtain reactant liquor, to reactant liquor
Middle addition 30mL distilled water, then extracts 4 times with chloroform for extractant, and single extraction chloroform with the volume ratio of reactant liquor is
0.2:1, combined chloroform layer, and use distilled water wash chloroform layer 5 times, then use anhydrous Na2SO4It is dried 3h, is dried
Afterproduct filters, and obtains organic facies, is then 30 DEG C and true at rotating speed 60 revs/min～100 revs/min, bath temperature
Reciprocal of duty cycle is to utilize under the conditions of 0.08MPa the Rotary Evaporators rotary evaporation that carries out reducing pressure to remove solvent chloroform, after obtaining except solvent
Reactant, under conditions of vacuum is 0.1MPa and temperature is 60 DEG C to except solvent after reactant be dried, be dried
Time is 4h, obtains weak yellow liquid, and weak yellow liquid is N-alkyl imidazole.Other and detailed description of the invention two to eight phase
With.
Detailed description of the invention ten: present embodiment with one of detailed description of the invention two to nine difference is: will in step 3
5.0mmol tribromo-acetyl base diethylenetriamine and 16.5mmol N-alkyl imidazole add in reactor, from heating is stirred at room temperature
To 120～140 DEG C, continue reaction 1h～2h, after cooling, use chloroform/acetone mixed liquor to carry out recrystallization, described chloroform/
Acetone mixture is that 3:1 mixes by chloroform and acetone by the volume ratio of chloroform with acetone, obtains crystallized product, in vacuum
Crystallized product is dried under conditions of being 40 DEG C for 0.1MPa and temperature by degree, and drying time is 3h, obtains white powder
Powder solid, white powdery solids is diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant.Its
He is identical with detailed description of the invention two to nine.
Use following verification experimental verification effect of the present invention
Test one: the synthetic method of a kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant, tool
Body completes according to the following steps:
One, synthesizing trichloroacetyl base diethylenetriamine: 1., 45mmol chloracetyl chloride is dissolved in 20mL dichloromethane,
Obtain chloracetyl chloride/dichloromethane solution；2., 10mmol diethylenetriamine and 45mmol triethylamine are added 60mL bis-
In chloromethanes, and stirring under condition of ice bath, mixing speed is 700rpm, then uses constant pressure funnel with constant
Rate of addition 3mL/min instills chloracetyl chloride/dichloromethane solution, drips complete follow-up continuous with mixing speed as 700rpm
Stirring reaction 5h, obtains product, step one 2. described in diethylenetriamine and chloracetyl chloride/dichloromethane solution in
The mol ratio of chloracetyl chloride is 1:4.5；3., it is room temperature and vacuum is 0.08MPa at rotating speed 80 revs/min, bath temperature
Under the conditions of utilize to rotate and steam instrument decompression and remove dichloromethane in product, obtain, except solvent reaction product, being subsequently adding distillation
Water carries out cancellation, and the described volume ratio except solvent reaction product Yu distilled water is 1:12, obtains product after cancellation,
Extracting 4 times with ethyl acetate for extractant, after single extraction ethyl acetate and cancellation, the volume ratio of product is 1.2:1 again,
Merge the organic facies that is obtained by extraction, be then 40 DEG C and vacuum is 0.08MPa bar at rotating speed 80 revs/min, bath temperature
Utilize Rotary Evaporators to carry out the rotary evaporation removing solvent ethyl acetate that reduces pressure under part, obtain product after rotation is steamed, utilize second
After rotation is steamed by alcohol as recrystallization solvent, product at room temperature carries out recrystallization, obtains crystal, in vacuum is
Crystal is dried under conditions of being 45 DEG C by 0.1MPa and temperature, and drying time is 3h, obtains white powdery solids,
White powdery solids is tribromo-acetyl base diethylenetriamine；
Two, synthesis N-octylimidazole: the most successively 16.5mmol imidazoles and 16.5mmol NaOH are added 20mL bis-
In first sulfoxide, being stirred at room temperature 2h, mixing speed is 1000rpm, obtains mixed solution, with rate of addition as 4mL/min
In mixed solution, add 15mmol 1-bromooctane, and low whipping speed is reaction 5h under 1000rpm, is reacted
Liquid, adds 30mL distilled water in reactant liquor, then extracts 4 times for extractant with chloroform, single extraction chloroform and reaction
The volume ratio of liquid is 0.2:1, combined chloroform layer, and uses distilled water wash chloroform layer 5 times, then uses anhydrous Na2SO4
Being dried 3h, dried product exhibited filters, and obtains organic facies, then rotating speed 80 revs/min, bath temperature be 30 DEG C and
Vacuum is to utilize under the conditions of 0.08MPa the Rotary Evaporators rotary evaporation that carries out reducing pressure to remove solvent chloroform, obtains except solvent
Rear reactant, under conditions of vacuum is 0.1MPa and temperature is 60 DEG C to except solvent after reactant be dried, dry
The dry time is 4h, obtains weak yellow liquid, and weak yellow liquid is N-octylimidazole；
Three, synthetic surfactant: 5.0mmol tribromo-acetyl base diethylenetriamine and 16.5mmol N-octylimidazole are added
Enter in reactor, be heated to 130 DEG C from being stirred at room temperature, continue reaction 2h, after cooling, use chloroform/acetone mixed liquor to carry out
Recrystallization, described chloroform/acetone mixed liquor is that 3:1 mixes by chloroform and acetone by the volume ratio of chloroform with acetone,
Obtain crystallized product, under conditions of vacuum is 0.1MPa and temperature is 40 DEG C, crystallized product is dried, when being dried
Between be 3h, obtain white powdery solids, white powdery solids is diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazoles
Salt] surfactant.
The synthetic route of this test is as follows:
Step one synthetic route:
Step 2 synthetic route:
Step 3 synthetic route:
The tribromo-acetyl base diethylenetriamine of this test procedure one synthesis is detected, as shown in figures 1 and 3, Fig. 1
Being the infrared spectrum of tribromo-acetyl base diethylenetriamine, Fig. 3 is the hydrogen spectrogram of tribromo-acetyl base diethylenetriamine.
IR(KBr),ν/cm-1: 3299cm-1For the N-H stretching vibration absworption peak in amido link, 1672cm-1For amido link
In C=O stretching vibration absworption peak, 1552cm-1For the N-H bending vibration absworption peak in amido link, 1399cm-1For
-CH2-bending vibration absworption peak, 1228cm-1For the stretching vibration absworption peak of C-C, 787cm-1Stretching for C-Cl
Vibration absorption peak.
1H nmr chemical displacement (600MHz, DMSO-d6,ppm)δH:8.38(1H),8.28(1H),4.35(2H),4.08
(2H),4.03(2H),3.37-3.22(8H).
Infrared spectrum according to tribromo-acetyl base diethylenetriamine and hydrogen spectrogram understand the structure of tribromo-acetyl base diethylenetriamine
Formula is
Detecting the N-octylimidazole of this test procedure two synthesis, as shown in Figure 4, Fig. 4 is the hydrogen of N-octylimidazole
Spectrogram.
1H nmr chemical displacement (400MHz, CDCl3,ppm)δH:7.62(1H),7.08(1H),6.92(1H),3.95
(2H),1.78(2H),1.29-1.25(10H),0.89(3H).
Hydrogen spectrogram according to N-octylimidazole understands the structural formula of N-octylimidazole
Diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant of this test synthesis is detected, as
Shown in Fig. 2, Fig. 5 and Fig. 6, Fig. 2 is diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant
Infrared spectrum, Fig. 5 is the hydrogen spectrogram of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant, Fig. 6
It it is the carbon spectrogram of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant.
IR(KBr),ν/cm-1: 3221cm-1For the N-H stretching vibration absworption peak in amido link, 3143cm-1For imidazole ring
Upper C-H stretching vibration absworption peak, 2956cm-1、2927cm-1And 2856cm-1It is respectively-CH3、-CH2-symmetry and
Antisymmetric stretching vibration absworption peak, 1687cm-1For the C=O stretching vibration absworption peak in amido link, 1 564cm-1Amido link
In N-H bending vibration absworption peak, 1467cm-1And 1259cm-1For imidazole ring skeletal vibration absworption peak, 1377cm-1
For-CH3Bending vibration absworption peak, 721cm-1For long alkyl chain-(CH2)n-bending vibration absworption peak.
1H nmr chemical displacement (600MHz, CDCl3,ppm)δH:10.03(2H),9.88(1H),9.51(1H),9.41
(1H),8.18(1H),7.68(1H),7.50(1H),7.38(1H),7.32(1H),7.27(1H),5.86(2H),5.49(2H),
5.25(2H),4.33-4.28(6H),3.59-3.48(8H),1.90(6H),1.34-1.26(30H),0.88(9H).
13C NMR(150MHz,CDCl3,ppm)δ:166.7,165.7,165.3,138.2,138.0,125.3,124.1,
123.7,121.5,121.2,120.6,51.8,51.5,50.4,50.3,46.9,45.1,37.1,36.9,31.7,30.3,30.2,29.0,
29.0,29.0,26.3,22.6,14.1.
According to diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] infrared spectrum of surfactant, hydrogen spectrogram and carbon
Spectrogram understand this test synthesize diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant be diethyl-
Three [(1-octyl group-3-carbamoylmethyl) imidazole salts] surfactant, its structural formula is
Detect the critical glue of diethyl-three [(1-octyl group-3-carbamoylmethyl) imidazole salts] surfactant of this test preparation
Bundle concentration:
With DDS-IIA type electric conductivity instrument (electrode is DSJ-1 type platinum black electrode), under the conditions of 25 DEG C, measure variable concentrations
The conductivity value of aqueous surfactant solution, with concentration C as abscissa, electrical conductivity κ be vertical coordinate mapping, draw C-κ
Curve, the concentration corresponding at point of inflexion on a curve is critical micelle concentration (cmc).Concrete assay method is as follows:
It is the water-soluble of 2.00g/L by diethyl-three [(1-octyl group-3-carbamoylmethyl) imidazole salts] surfactant formulatory concentration
Liquid 5mL, is put in the constant temperature water bath of 25 DEG C insulation, surveys its conductivity value record with DSJ-1 type platinum black electrode, then
Add a certain amount of redistilled water, solution is diluted to 1.95g/L, measure conductivity value the record of now solution.Depend on
Secondary analogize, measure respectively concentration be 1.90,1.85,1.80,1.75,1.70,1.65,1.60,1.55,1.50,1.45,
1.40、1.35、1.30、1.25、1.20、1.15、1.10、1.05、1.00、0.95、0.90、0.85、0.80、0.75、
0.70,0.65,0.60,0.55,0.50,0.45,0.40,0.35,0.30,0.25,0.20,0.15,0.10 and 0.05g/L
Time the conductivity value of solution record.Above-mentioned each mass concentration is converted into substance withdrawl syndrome C, with substance withdrawl syndrome C
For abscissa, with the corresponding conductivity value κ of record as vertical coordinate, make C-κ curve chart, as it is shown in fig. 7, Fig. 7 is two
Aqueous surfactant solution electrical conductivity is with concentration curve, from figure for ethyl-three [(1-octyl group-3-carbamoylmethyl) imidazole salts]
Middle curve break obtains critical micelle concentration value (cmc).Diethyl-three [(1-octyl group-3-carbamoylmethyl) imidazole salts] surface
Activating agent has relatively low critical micelle concentration, and critical micelle concentration is 0.6 × 10-4mol/L。
Claims (9)
1. a synthetic method for diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant, its feature exists
Synthetic method in diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant completes according to the following steps:
One, synthesizing trichloroacetyl base diethylenetriamine: 1., chloracetyl chloride is dissolved in dichloromethane, obtains chloracetyl chloride/bis-
Chloromethanes solution, step one 1. described in chloracetyl chloride/dichloromethane solution in the concentration of chloracetyl chloride be
2.0mmol/mL～3.0mmol/mL；2., diethylenetriamine and triethylamine are added in dichloromethane, and under condition of ice bath
Stirring, mixing speed is 600rpm～800rpm, then uses constant pressure funnel with constant rate of addition
2mL/min～4mL/min instills chloracetyl chloride/dichloromethane solution, drips and complete follow-up continuous with mixing speed is
600rpm～800rpm stirring reaction 5h～7h, obtain product, step one 2. described in diethylenetriamine and triethylamine
Mol ratio be (0.22～0.25): 1, step one 2. described in the amount of material of diethylenetriamine with the volume ratio of dichloromethane be
0.01mol:60mL, step one 2. described in diethylenetriamine and chloracetyl chloride/dichloromethane solution in chloracetyl chloride mole
Than being (0.22～0.25): 1；3., utilize to rotate and steam dichloromethane in instrument decompression removal product, obtain except solvent reaction product,
Being subsequently adding distilled water and carry out cancellation, the described volume ratio except solvent reaction product Yu distilled water is 1:(10～15), quenched
Product after going out, then extract 3～5 times with ethyl acetate for extractant, product after single extraction ethyl acetate and cancellation
Volume ratio be (1～1.5): 1, merge the organic facies that is obtained by extraction, then utilize the Rotary Evaporators rotary evaporation that carries out reducing pressure to remove
Removing solvent ethyl acetate, obtain product after rotation is steamed, after steaming rotation with use ethanol as recrystallization solvent, product is in room
Carry out recrystallization under temperature, obtain crystal, under conditions of vacuum is 0.09MPa～0.1MPa and temperature is 40～45 DEG C
Being dried crystal, drying time is 2h～3h, obtains white powdery solids, and white powdery solids is three chloroethenes
Acyl group diethylenetriamine；
Two, synthesis N-alkyl imidazole: the most successively imidazoles and NaOH are added in dimethyl sulfoxide, be stirred at room temperature 1h～2h,
Mixing speed is 800rpm～1200rpm, obtains mixed solution, with rate of addition as 3mL/min～5mL/min to mixing molten
Liquid adds 1-bromoalkane, and low whipping speed is reaction 4h～6h under 800rpm～1200rpm, obtains reactant liquor, to reaction
Adding distilled water in liquid, then extract 3～5 times for extractant with chloroform, single extraction chloroform with the volume ratio of reactant liquor is
(0.18～0.27): 1, combined chloroform layer, and use distilled water wash chloroform layer 4～5 times, then use anhydrous Na2SO4It is dried
2h～4h, dried product exhibited filters, and obtains organic facies, then utilizes Rotary Evaporators to carry out decompression rotary evaporation and removes molten
Agent chloroform, obtains except reactant after solvent, under conditions of vacuum is 0.09MPa～0.1MPa and temperature is 50～60 DEG C
To except after solvent reactant be dried, drying time is 3h～5h, obtains weak yellow liquid, and weak yellow liquid is N-alkyl
Imidazoles；Described imidazoles is (1.0～1.2) with the mol ratio of NaOH: 1, the amount of the material of described imidazoles and the body of dimethyl sulfoxide
Long-pending is (1～1.2) than the volume ratio for (16.5～19.8) mmol:20mL, described distilled water and dimethyl sulfoxide: 1, described imidazoles
Being (1.0～1.2) with the mol ratio of 1-bromoalkane: 1, described 1-bromoalkane is 1-bromooctane, 1-bromodecane, 1-bromo ten
Dioxane, 1-bromotetradecane or 1-bromohexadecane；
Three, synthetic surfactant: tribromo-acetyl base diethylenetriamine and N-alkyl imidazole are added in reactor, from room temperature
It is heated with stirring to 120 DEG C～140 DEG C, continues reaction 1h～2h, after cooling, use chloroform/acetone mixed liquor to carry out recrystallization, institute
The chloroform/acetone mixed liquor stated is (2～4) by chloroform and acetone by the volume ratio of chloroform Yu acetone: 1 mixes, and obtains crystallization and produces
Thing, is dried crystallized product under conditions of vacuum is 0.09MPa～0.1MPa and temperature is 35～45 DEG C, is dried
Time is 2h～4h, obtains white powdery solids, and white powdery solids is diethyl-three [(1-alkyl-3-carbamoylmethyl)
Imidazole salts] surfactant；Described tribromo-acetyl base diethylenetriamine with the mol ratio of N-alkyl imidazole is
(0.25～0.35): 1；
The general structure of described diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant is as follows:
Wherein n is 6,8,10,12 or 14；X is Cl.
A kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant the most according to claim 1
Synthetic method, it is characterised in that step one 3. in be room temperature and vacuum at rotating speed 60 revs/min～100 revs/min, bath temperature
Steam dichloromethane in instrument decompression removal product for utilizing under the conditions of 0.08MPa～0.09MPa to rotate, obtain except solvent is anti-
Answer product.
A kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant the most according to claim 1
Synthetic method, it is characterised in that step one 3. in be 40 DEG C and vacuum at rotating speed 60 revs/min～100 revs/min, bath temperature
Degree removes solvent ethyl acetate for utilizing Rotary Evaporators to carry out decompression rotary evaporation under the conditions of 0.08MPa～0.09MPa,
Product after steaming to rotation.
A kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant the most according to claim 1
Synthetic method, it is characterised in that step 2 is 30 DEG C and vacuum at rotating speed 60 revs/min～100 revs/min, bath temperature
The rotary evaporation that reduces pressure for utilizing Rotary Evaporators to carry out under the conditions of 0.08MPa～0.09MPa removes solvent chloroform, obtains except molten
Reactant after agent.
A kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant the most according to claim 1
Synthetic method, it is characterised in that 45mmol chloracetyl chloride is dissolved in 20mL dichloromethane by step one, obtains chloroethene
Acyl chlorides/dichloromethane solution.
A kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant the most according to claim 1
Synthetic method, it is characterised in that step one 2. in 10mmol diethylenetriamine and 45mmol triethylamine are added 60mL bis-
In chloromethanes, and under condition of ice bath stir, mixing speed is 600rpm～800rpm, then use constant pressure funnel with
Constant rate of addition 3mL/min instills chloracetyl chloride/dichloromethane solution, drips and complete follow-up continuous with mixing speed is
600rpm～800rpm stirring reaction 5h, obtains product, step one 2. described in diethylenetriamine and chloracetyl chloride/
In dichloromethane solution, the mol ratio of chloracetyl chloride is 1:4.5.
A kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant the most according to claim 1
Synthetic method, it is characterised in that step one 3. in be room temperature and vacuum at rotating speed 60 revs/min～100 revs/min, bath temperature
Steam dichloromethane in instrument decompression removal product for utilizing under the conditions of 0.08MPa to rotate, obtain except solvent reaction product, so
Rear addition distilled water carries out cancellation, and the described volume ratio except solvent reaction product Yu distilled water is 1:12, anti-after obtaining cancellation
Answer product, then extract 4 times for extractant with ethyl acetate, the volume ratio of product after single extraction ethyl acetate and cancellation
For 1.2:1, merge the organic facies being obtained by extraction, be then 40 DEG C and vacuum is at rotating speed 80 revs/min, bath temperature
Utilize Rotary Evaporators to carry out the rotary evaporation removing solvent ethyl acetate that reduces pressure under the conditions of 0.08MPa, obtain reaction after rotation is steamed and produce
Thing, after steaming rotation with use ethanol as recrystallization solvent, product at room temperature carries out recrystallization, obtains crystal, very
Reciprocal of duty cycle be 0.1MPa and temperature be 45 DEG C under conditions of crystal is dried, drying time is 3h, obtains white powder
Shape solid, white powdery solids is tribromo-acetyl base diethylenetriamine.
A kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant the most according to claim 1
Synthetic method, it is characterised in that 16.5mmol imidazoles and 16.5mmol NaOH are added 20mL by step 2 the most successively
In dimethyl sulfoxide, being stirred at room temperature 2h, mixing speed is 800rpm～1200rpm, obtains mixed solution, to drip speed
Degree adds 15mmol 1-bromoalkane for 4mL/min in mixed solution, and low whipping speed is anti-under 800rpm～1200rpm
Answer 5h, obtain reactant liquor, in reactant liquor, add 30mL distilled water, then extract 4 times for extractant with chloroform, single
Extraction chloroform is 0.2:1 with the volume ratio of reactant liquor, combined chloroform layer, and uses distilled water wash chloroform layer 5 times, then adopts
Use anhydrous Na2SO4Be dried 3h, dried product exhibited filters, and obtains organic facies, then rotating speed 60 revs/min～100 turns/
Point, bath temperature is 30 DEG C and vacuum is to utilize under the conditions of 0.08MPa the Rotary Evaporators rotary evaporation that carries out reducing pressure to remove molten
Agent chloroform, obtains except reactant after solvent, under conditions of vacuum is 0.1MPa and temperature is 60 DEG C to except solvent after anti-
Answering thing to be dried, drying time is 4h, obtains weak yellow liquid, and weak yellow liquid is N-alkyl imidazole.
A kind of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant the most according to claim 1
Synthetic method, it is characterised in that by 5.0mmol tribromo-acetyl base diethylenetriamine and 16.5mmol N-alkyl in step 3
Imidazoles adds in reactor, is heated to 120～140 DEG C from being stirred at room temperature, and continues reaction 1h～2h, uses chloroform/the third after cooling
Ketone mixed liquor carries out recrystallization, and described chloroform/acetone mixed liquor is 3:1 by chloroform and acetone by the volume ratio of chloroform Yu acetone
Mix, obtain crystallized product, under conditions of vacuum is 0.1MPa and temperature is 40 DEG C, crystallized product is done
Dry, drying time is 3h, obtains white powdery solids, and white powdery solids is diethyl-three [(1-alkyl-3-carbamyl
Methyl) imidazole salts] surfactant.
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