CN109954449A - Double tail amidino groups surfactants and preparation method thereof - Google Patents
Double tail amidino groups surfactants and preparation method thereof Download PDFInfo
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- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
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Abstract
The invention discloses a kind of double tail amidino groups surfactants and preparation method thereof, with N, N- dimethylacetamide dimethylacetal and chain alkyl amine are raw material, the first step carries out the corresponding double tail alkyl ethanamidines of amide condensed generation, the double tail alkyl ethanamidines of second step double tail alkyl ethanamidine base bicarbonate surfactants corresponding with carbon dioxide reaction generation.Reaction condition of the present invention is mild, eliminates pyroreaction condition, chromatographs the step of purifying using column instead of to first step product with recrystallization, reaction yield can reach 80%；Obtained double tail amidino groups bicarbonate surfactants are relative to low three orders of magnitude of corresponding list tail amidino groups surfactant cmc, the surface tension that can effectively reduce solution has broad application prospects in the chemical industry process such as oil exploitation, crude oil recovery, emulsion polymerization.
Description
Technical field
The present invention relates to organic chemical industries to synthesize field more particularly to a kind of preparation of double tail amidino groups surfactants
Method.
Background technique
In oil exploitation, crude oil recovery, emulsion polymerization, leather weaving and detergent industry etc., in a variety of chemical industry process
90FD needs the stabilising system using surfactant, and (Jiang Qingzhe surfactant science goes out with using [M] Sinopec
Version society, 2006.).And surfactant is generally not involved in reaction, the effects of only serving interface stability, solubilising and emulsify, and
Only work in certain moment.At present due to make it lose surface-active or separate it from system after use
Difficult, therefore all direct emission after use, not only waste of resource also causes some environmental problems (Ying G G.
Fate, behavior and effects of surfactants and their degradation products in
The environment. [J] Environment International, 2006,32 (3): 417-431.).If surface
Activating agent is greatly improved service efficiency, and save the cost also can reduce environmental pressure.
Surfactant can solve the above problems.Surfactant can pass through the ring locating for adjustment and control system
Border come control surface it is active whether there is or not, this process can artificial adjustment, it is reversible and repetitive operation (Qin Yong, Ji Jun can be carried out
The tinkling of pieces of jade, Me Shiping wait progress [J] daily chemical industry of switch surfactant, 2009,39 (3): 191-
195.).People can make it lose surface-active from system after surfactant plays function by certain method
It detaches.In recent years, switch surfactant reported in the literature mainly has soda acid to switch surfactant, electrochemical switch table
Face activating agent, photoswitch surfactant, ionic switch surfactant, CO2/ N2Or Ar switchs surfactant (Ying G
G. Fate, behavior and effects of surfactants and their degradation products
In the environment. [J] Environment International, 2006,32 (3): 417-431.).
CO2/N2 switch surfactant controls the on or off of surfactant surface-active by blasting CO2 or N2.
CO2 switch have many advantages, such as green, cheap, renewable and low energy consumption, oil exploitation, drug controlled release, gene delivery,
Environment remediation, separation engineering and pharmaceutical synthesis etc. need the field of application surface activating agent all to have broad application prospects (Yan
Q, Zhou R, Fu C, et al. CO2-responsive polymeric vesicles that breathe.[J].
Angewandte Chemie, 2011,123 (21): 5025-5029.).The amidine of chain alkyl was not a good table originally
Face activating agent, but bicarbonate can be converted into become an effective earth's surface by being exposed in water or carbon dioxide
Face activating agent.The bigger benefit of amidine system is that product can reduce the active and water-soluble of surfactant by turning off the switch
Property, this is very favorable to environment.Because it does not need that demulsifier demulsification, and recyclable recycling is added, industrially will
Operating cost can be greatlyd save, therefore is had broad application prospects.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of double tail amidino groups surfactants, this method reacts item
Part is mild, and purification step is simple, and the surface tension of solution can be effectively reduced in obtained double tail amidino groups surfactants.
To achieve the goals above, technical scheme is as follows:
Double tail amidino groups surfactant I of the present invention, structure are as follows:
Wherein R base is selected from octyl, decyl, dodecyl.
The method for preparing double tail amidino groups surfactants with structural formula I, described method includes following steps:
A. raw material preparation
Raw material a is n,N-dimethylacetamide dimethylacetal, and raw material b is alkylamine, and raw material c is nafoxidine；
B. primary first-order equation
Raw material a, b, c and methanol are added under heating condition, is stirred to react to obtain reaction mixture, reaction mixture is first revolved
Solvent methanol is evaporated off, adds solvent f and is recrystallized, d is obtained by filtration after recrystallization；
C. raw material secondary response
D is dissolved in solvent g, deionized water is added, is passed through CO2And sustained response is until the reaction is complete, and final production is obtained by filtration
Object e, as double tail amidino groups surfactants.
Further, the mole dosage of raw material a and raw material b mole dosage ratio are 1~1.5:2~3 in step A, c moles of raw material with
Amount is the 0.02 ~ 0.05 of raw material a.
Further, heating temperature is 70 ~ 80 DEG C in step B, and the reaction time is 2 ~ 6h.
Further, it is acetonitrile or acetone that the solvent f used is recrystallized in step B.
Further, step C can be passed through carbon dioxide under condition of ice bath.
Further, dry ice can be used instead of carbon dioxide in step C.
Further, anhydrous ether can be used in solvent g in step C.
Compared with prior art, the invention has the benefit that
(1) nafoxidine, which is added, in the present invention for the first time in the reaction makes reaction yield reach 80%；
(2) temperature of the present invention, which was compared at 70 ~ 80 DEG C with former 120 DEG C of reaction, reduces reaction temperature；
(3) present invention uses recrystallization purifying first step product, simple, easy to operate compared to the purification process chromatographed with front pillar；
(4) double tail amidino groups surfactants that the present invention synthesizes are than corresponding unit amidino groups surfactant
Low three orders of magnitude of cmc.
Detailed description of the invention
Fig. 1 is product N, and the nuclear magnetic data of the bis- dodecyl ethanamidine base bicarbonates of N '-parses schematic diagram.
Fig. 2 is product 1N, and the nuclear magnetic data of the bis- decyl ethanamidine base bicarbonates of N '-parses schematic diagram.
Fig. 3 is product N, and the mass spectrometric data of the bis- dodecyl ethanamidine base bicarbonates of N '-parses schematic diagram.
Fig. 4 is product N, and the mass spectrometric data of the bis- decyl ethanamidine base bicarbonates of N '-parses schematic diagram.
Fig. 5 is product N, and the γ-logC of the bis- dodecyl ethanamidine base bicarbonates of N '-schemes.
Specific embodiment
In the following with reference to the drawings and specific embodiments, to the present invention further illustrate, but the present invention be not limited to it is following
Embodiment.
Embodiment 1
It weighs 1.8535g1- lauryl amine to be dissolved in 20ml methanol, adds 0.66595gN, N- dimethylacetamide
Acetal and 0.1778g nafoxidine react 4h in 80 DEG C of heating, and revolving removes solvent methanol.Acetonitrile is added to be recrystallized, mistake
Filter obtains the bis- dodecyl ethanamidines of the first step product N, N '-.By N, the bis- dodecyl ethanamidines of N '-are dissolved in anhydrous ether, add
Enter a small amount of deionized water, is passed through CO2 reaction, there are a large amount of white solids to occur, be not further added by fully reacting to white solid, filter
Obtain N, the bis- dodecyl ethanamidine base bicarbonate surfactants of N '-.
Embodiment 2
It weighs 1.573g1- decyl amine to be dissolved in 20ml methanol, adds 0.66595gN, N- dimethylacetamide dimethylacetal
With 0.1778g nafoxidine, 4h is reacted in 80 DEG C of heating, revolving removes solvent methanol.Acetonitrile is added to be recrystallized, filters
To the bis- decyl ethanamidines of the first step product N, N '-.By N, the bis- decyl ethanamidines of N '-are dissolved in anhydrous ether, and addition is gone on a small quantity
Ionized water is passed through CO2 reaction, has a large amount of white solids to occur, be not further added by fully reacting to white solid, N is obtained by filtration,
The bis- decyl ethanamidine base bicarbonate surfactants of N '-.
Embodiment 3
It weighs 1.2924g1- octylame to be dissolved in 20ml methanol, adds 0.66595gN, the contracting of N- dimethylacetamide
Aldehyde and 0.1778g nafoxidine react 4h in 80 DEG C of heating, and revolving removes solvent methanol.Acetonitrile is added to be recrystallized, filters
Obtain the bis- octyl ethanamidines of the first step product N, N '-.By N, the bis- octyl ethanamidines of N '-are dissolved in anhydrous ether, are added a small amount of
Deionized water is added dry ice reaction, has a large amount of white solids to occur, be not further added by fully reacting to white solid, be obtained by filtration
N, N '-bis- octyl ethanamidine base bicarbonate surfactants.
Embodiment 4
It weighs 3.707g1- lauryl amine to be dissolved in 50ml methanol, adds 1.3319gN, the contracting of N- dimethylacetamide
Aldehyde and 0.3556g nafoxidine react 4h in 80 DEG C of heating, and revolving removes solvent methanol.Acetonitrile is added to be recrystallized, filters
Obtain the bis- dodecyl ethanamidines of the first step product N, N '-.By N, the bis- dodecyl ethanamidines of N '-are dissolved in anhydrous ether, are added
A small amount of deionized water is passed through CO2 reaction, has a large amount of white solids to occur, be not further added by fully reacting to white solid, filter
To N, the bis- dodecyl ethanamidine base bicarbonate surfactants of N '-.
Embodiment 5
It weighs 1.8535g1- lauryl amine to be dissolved in 20ml methanol, adds 0.66595gN, N- dimethylacetamide
Acetal and 0.1778g nafoxidine react 2h in 70 DEG C of heating, and revolving removes solvent methanol.Acetonitrile is added to be recrystallized, mistake
Filter obtains the bis- dodecyl ethanamidines of the first step product N, N '-.By N, the bis- dodecyl ethanamidines of N '-are dissolved in anhydrous ether, add
Enter a small amount of deionized water, is passed through CO2 reaction, there are a large amount of white solids to occur, be not further added by fully reacting to white solid, filter
Obtain N, the bis- dodecyl ethanamidine base bicarbonate surfactants of N '-.
Embodiment 6
It weighs 1.8535g1- lauryl amine to be dissolved in 20ml methanol, adds 0.66595gN, N- dimethylacetamide
Acetal and 0.1778g nafoxidine react 6h in 70 DEG C of heating, and revolving removes solvent methanol.Acetonitrile is added to be recrystallized, mistake
Filter obtains the bis- dodecyl ethanamidines of the first step product N, N '-.By N, the bis- dodecyl ethanamidines of N '-are dissolved in anhydrous ether, add
Enter a small amount of deionized water, is passed through CO2 reaction, there are a large amount of white solids to occur, be not further added by fully reacting to white solid, filter
Obtain N, the bis- dodecyl ethanamidine base bicarbonate surfactants of N '-.
Embodiment 7
It weighs 1.8535g1- lauryl amine to be dissolved in 20ml methanol, adds 0.66595gN, N- dimethylacetamide
Acetal and 0.1778g nafoxidine react 6h in 70 DEG C of heating, and revolving removes solvent methanol.Acetone is added to be recrystallized, mistake
Filter obtains the bis- dodecyl ethanamidines of the first step product N, N '-.By N, the bis- dodecyl ethanamidines of N '-are dissolved in anhydrous ether, add
Enter a small amount of deionized water, is passed through CO2 reaction, there are a large amount of white solids to occur, be not further added by fully reacting to white solid, filter
Obtain N, the bis- dodecyl ethanamidine base bicarbonate surfactants of N '-.
Embodiment 8
It weighs 1.8535g1- lauryl amine to be dissolved in 20ml methanol, adds 0.66595gN, N- dimethylacetamide
Acetal and 0.1778g nafoxidine react 6h in 70 DEG C of heating, and revolving removes solvent methanol.Acetone is added to be recrystallized, mistake
Filter obtains the bis- dodecyl ethanamidines of the first step product N, N '-.By N, the bis- dodecyl ethanamidines of N '-are dissolved in anhydrous ether, add
Enter a small amount of deionized water, CO2 reaction is passed through under condition of ice bath, there are a large amount of white solids to occur, is not further added by white solid
N, the bis- dodecyl ethanamidine base bicarbonate surfactants of N '-are obtained by filtration in fully reacting.
Embodiment 9
It weighs 1.8535g1- lauryl amine to be dissolved in 20ml methanol, adds 0.66595gN, N- dimethylacetamide
Acetal and 0.1778g nafoxidine react 6h in 70 DEG C of heating, and revolving removes solvent methanol.Acetone is added to be recrystallized, mistake
Filter obtains the bis- dodecyl ethanamidines of the first step product N, N '-.By N, the bis- dodecyl ethanamidines of N '-are dissolved in anhydrous ether, add
Enter a small amount of deionized water, dry ice reaction is added, there are a large amount of white solids to occur, is not further added by fully reacting, mistake to white solid
Filter obtains N, the bis- dodecyl ethanamidine base bicarbonate surfactants of N '-.
Performance measurement
N, the bis- dodecyl ethanamidine base bicarbonates of N '-, N, N are determined using drop-volume method '-bis- decyl ethanamidine base bicarbonates
The surface tension γ of salt, N, N '-bis- octyl ethanamidine base bicarbonates, obtains γ-logC curve graph.According to γ-logC curve graph
Available critical micelle concentration is respectively 7.6535 × 10-5mol/l。
0.01mol/lN, the bis- dodecyl ethanamidine base bicarbonates of N '-, N, N are respectively configured '-bis- decyl ethanamidine base bicarbonates
The aqueous solution of salt, N, N '-bis- octyl ethanamidine base bicarbonates.The aqueous solution of N, N '-bis- dodecyl ethanamidine base bicarbonates is in
The aqueous solution clarification of existing turbid solution, N, N '-bis- decyl ethanamidine base bicarbonates, N, N '-bis- octyl ethanamidine base bicarbonates.Knot
Fruit shows N, the bis- decyl ethanamidine base bicarbonates of N '-, N, N ' water solubilitys of-bis- octyl ethanamidine base bicarbonates is than N, N '-bis- ten
The good water solubility of dialkyl group ethanamidine base bicarbonate.
Attached drawing 1 is that deuterated chloroform makees solvent, N, N ' the nucleus magnetic hydrogen spectrum figures of-bis- dodecyl ethanamidine base bicarbonates.
1H NMR (300 MHz, CDCl3) δ 3.10 (s, 4H), 1.88 (s, 3H), 1.53 (s, 4H),
1.25 (s, 35H), 0.87 (s, 6H).
Attached drawing 2 is that deuterated chloroform makees solvent, N, N ' the nucleus magnetic hydrogen spectrum figures of-bis- decyl ethanamidine base bicarbonates.
1H NMR (300 MHz, CDCl3) δ 3.11 (s, 4H), 1.86 (s, 3H), 1.52 (s, 4H),
1.25 (s, 28H), 0.87 (s, 6H).
Attached drawing 3 is N, the mass spectrogram of the bis- dodecyl ethanamidine base bicarbonates of N '-.
MS(ESI): 395.34 [M-HCO3]+
Attached drawing 4 is N, the mass spectrogram of the bis- decyl ethanamidine base bicarbonates of N '-.
MS(ESI): 339.28[M-HCO3]+
Attached drawing 5 is N, and the γ-logC of the bis- dodecyl ethanamidine base bicarbonates of N '-, available cmc value is 7.6535 × 10- 5mol/l。
Claims (9)
1. couple tail amidino groups surfactant I, which is characterized in that structure is as follows:
Wherein R base is selected from octyl or decyl.
2. the preparation method of couple tail amidino groups surfactant I, which is characterized in that including
(1) after n,N-dimethylacetamide dimethylacetal a and alkylamine b being carried out amide condensed reaction, preparationization is recrystallized
The step of closing object d,
(2) compound d is dissolved in solvent g, water is added dropwise, be passed through excessive CO2 or excess dry ice progress salt-forming reaction preparation is added
The step of target product,
,
Wherein, R base is selected from octyl, decyl, dodecyl.
3. preparation method as claimed in claim 2, which is characterized in that in step (1), amide condensed reaction is deposited in nafoxidine
In lower progress；Nafoxidine mole dosage is 0.02 ~ 0.05 equivalent of DMAC N,N' dimethyl acetamide dimethylacetal.
4. preparation method as claimed in claim 2, which is characterized in that in step (1), the solvent of amide condensed reaction system is adopted
With any one in methanol, chloroform, tetrahydrofuran, acetone.
5. preparation method as claimed in claim 2, which is characterized in that in step (1), the temperature of amide condensed reaction system is
70~90℃；Reaction time is 2 ~ 6 hours.
6. preparation method as claimed in claim 2, which is characterized in that in step (1), the contracting of n,N-dimethylacetamide dimethyl
Molar ratio 1~1.5:2~3 of aldehyde a and alkylamine b.
7. preparation method as claimed in claim 2, which is characterized in that in step (1), recrystallize the solvent that uses be acetonitrile or
Acetone.
8. preparation method as claimed in claim 2, which is characterized in that in step (2), solvent g uses anhydrous ether.
9. preparation method as claimed in claim 2, which is characterized in that in step (2), the volume that water is added dropwise is solvent g volume
1%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112228018A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | CO with amidino compounds2Oil displacement method |
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Application publication date: 20190702 |