CN101502772B - Colophony-based sulphonate type gemini surfactant and method for preparing the same - Google Patents
Colophony-based sulphonate type gemini surfactant and method for preparing the same Download PDFInfo
- Publication number
- CN101502772B CN101502772B CN2009100303234A CN200910030323A CN101502772B CN 101502772 B CN101502772 B CN 101502772B CN 2009100303234 A CN2009100303234 A CN 2009100303234A CN 200910030323 A CN200910030323 A CN 200910030323A CN 101502772 B CN101502772 B CN 101502772B
- Authority
- CN
- China
- Prior art keywords
- colophony
- diamines
- gemini surfactant
- type gemini
- sulphonate type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a rosinyl sulphonate gemini surfactant, the general structure thereof is shown in the right formula, R represents rosinyl tricyclic diterpene group and is an integer less than or equal to 1 and greater than or equal to 5. The preparation method is as follows: nucleophilic reaction is carried out on dehydro-abietylamine or disproportionated rosin and dibromoalkane to obtainan active intermediate N, N'-didehydro-abietylamine base alpha, omega-diamine which is then used to react with 2-bromoethyl sodium sulfonate to obtain the rosinyl sulphonate gemini surfactant. The surfactant prepared by the invention has better water solubility, very high surface activity and ability of reducing oil/water interfacial tension, excellent solubilization, salt-resistance, anti-deposition and wetting properties for oil, cheap and accessible raw materials and low toxicity, and is biodegradable.
Description
Technical field
The present invention relates to a kind of sulphonate type gemini surfactant and its production and use, relate in particular to a kind of colophony-based sulphonate type gemini surfactant and its production and use.
Background technology
Rosin is a kind of abundant, cheap renewable forest products resource, it contains the resin acid of the luxuriant and rich with fragrance structure of alkyl hydrogenation, huge in its molecular structure, nonpolar tricyclic structure has excellent hydrophobic property, and the carboxy moiety possess hydrophilic property of polarity, therefore rosin belongs to typical amphiphile, amphiphilic molecule, after different reagent modifications, can obtain anionic, cationic and nonionic surface active agent, in national economy, have important use and be worth.For example sodium abietate has good foaming effect and emulsifying capacity as a kind of anion surfactant, is mainly used in the flotation agent of soap foam improver, wetting agent, anticorrisive agent, elastomeric emulsifying agent and some materials.The rosin sugar surfactant that the reaction of rosin and glucose or sucrose obtains has very strong wetability and emulsifiability and does not have toxicity, and skin and eyes are not stimulated, and is a kind of tempting, renewable material with prospect.There is lack of raw materials at surfactant at present, rise in price, under the strict day by day condition of environmental requirement, exploitation rosin based surfactant, has resources advantage undoubtedly, can enrich the kind of surfactant series products on the one hand, also search out an effective way on the other hand for the rosin raw material enlarges to utilize.
Gemini surface active agent is the novel surfactant of a class, because distinctive molecular structure and multiple specific character are arranged itself, over nearly 30 years, becomes the research focus of international interdisciplinary science and association area just gradually.Traditional surfactant is to have single head base (hydrophilic group), a class amphiphile of single tail base (hydrophobic grouping is generally long carbochain).And Gemini surface active agent is to be connected by chemical bond through spacer group by the ion head base of two parents' molecules to form, this particular structure has stoped the basic separating force in the orderly accumulation process of surfactant, greatly improved surface-active, show significantly easier absorption on the gas/liquid surface, more effectively reduce surface tension, composite cooperative effect, lower Kraft point, easier gathering generate micelle, the better unique advantage that do not possess of wetability and good conventional surfactants such as lime soap dispersing power better.Therefore, Gemini surface active agent can extensively be brought into play its important function in more areas.Wherein sulphonate type gemini surfactant has good infiltration dispersive property and wettability, have broad application prospects and market value, particularly the grease proofing and waterproof of mineral floating, fabric, agricultural chemicals use and the active water displacement of reservoir oil aspect all need wettability preferably surfactant producing and life in reach application purpose.Many survey article system introductions have been arranged both at home and abroad this molecular geometry, structure, SOLUTION PROPERTIES, various association aggregation and application, a lot of surfactant raw materials that use are from nonrenewable resourceses such as oil at present, and are unfavorable to sustainable development.Simultaneously, adopt the lipophilic constituent of linear paraffin, the product price height as Gemini surface active agent.
At present, in oil extraction, use various oil displacement agents for improving reservoir recovery, active water is exactly one of them, it is a kind of water that is added with surfactant, wettability is better, has the stronger reduction oil-water interfacial tension and the ability of moistening counter-rotating, and the representative wetting agent of this respect generally is the surfactant with sulfonate groups.In thickened oil recovery and transportation, add the aqueous solution that contains wetting agent, can form one deck water-wetted surface at the inner surface of oil pipe, sucker rod and oil pipeline, thereby wall is reduced the flow resistance of viscous crude, be beneficial to the exploitation and the conveying of viscous crude.
Summary of the invention
In order to solve product price height that prior art exists, to be difficult for biodegradable shortcoming, the invention provides a kind of colophony-based sulphonate type gemini surfactant and preparation method thereof.Have better water solubility, very high surface-active and reduce the ability of oil/water termination tension force, crude oil is had good solubilising, anti-salt, anti-deposition and wettability, raw material is cheap and easy to get, low toxicity, biodegradable.
The present invention adopts following technical scheme:
A kind of colophony-based sulphonate type gemini surfactant, its general structure is as follows:
In the formula, R is an abietyl tricyclic diterpene group, the integer in 1≤n≤5.
R is a kind of in the following substituting group:
The tricyclic diterpene group of dehydroabietylamine
Or the tricyclic diterpene group of disproportionated rosin amine.
The preparation method of above-claimed cpd is as follows:
A kind of preparation method of colophony-based sulphonate type gemini surfactant, earlier obtain reactive intermediate N by necleophilic reaction with dehydroabietylamine or disproportionated rosin amine and two bromoalkanes, N '-two dehydrogenation fir base α, ω-diamines, use N again, N '-two dehydrogenation fir base α, ω-diamines and the reaction of 2-bromoethyl sodium sulfonate obtain colophony-based sulphonate type gemini surfactant.
Intermediate N, N '-two dehydrogenation fir base α, the synthetic of ω-diamines may further comprise the steps:
With two bromoalkanes is nucleopilic reagent, is solvent with toluene, and natrium carbonicum calcinatum is made acid binding agent, carries out nucleophilic addition with dehydroabietylamine and obtains N, N '-two dehydrogenation fir base α, ω-diamines.Wherein, the mol ratio of dehydroabietylamine, two bromoalkanes and natrium carbonicum calcinatum is 2.3-2.5: 1-1.1: 1.Described two bromoalkanes are 1,2-Bromofume, 1,4-dibromobutane, 1,6-dibromo-hexane, 1, any one in 8-two bromooctanes
Described N, N '-two dehydrogenation fir base α, ω-diamines and 2-bromoethyl sodium sulfonate sulfonating reaction condition are:
N, N '-two dehydrogenation fir base α, ω-diamines, 2-bromoethyl sodium sulfonate and natrium carbonicum calcinatum are 1～1.5 with mol ratio: 2: 1, and with N, N '-two dehydrogenation fir base α, ω-diamines, 2-bromoethyl sodium sulfonate mix in solvent methanol, stirring condition adds down natrium carbonicum calcinatum, and under 78-85 ℃ of reflux temperature stirring reaction 24-36 hour, steaming desolventized, purifying is recrystallized, and filters the final vacuum drying and obtains colophony-based sulphonate type gemini surfactant.
Reaction equation is as follows:
Beneficial effect:
1. the present invention in the characteristics aspect physics and the chemical property, adopts active group splicing principle in conjunction with Rosinyl diterpene amine, has synthesized a series of novel colophony-based sulphonate type gemini surfactants, and this surfactant has stronger some surface active property.Have lower surface tension and critical micelle concentration, as A product N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1,2-diamines and B product N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1, the surface tension of 4-diamines is below 30mN/m, and the surface tension of conventional sulfonate surfactant is about 35-40mN/m.The critical micelle concentration of product A and B reaches 10
-4The order of magnitude, the critical micelle concentration of conventional surfactants is 10
-3The order of magnitude.
2. lipophilic group and two sulfonate hydrophilic groups of containing two tricyclic diterpene structures in the surfactant molecule with rosin and derivative preparation thereof, closely arrangement of surfactant molecule setting appears in the certain density aqueous solution and make, thereby utilize the stronger hydrophily of sulfonic group, it is water-soluble to give Gemini surface active agent, bring into play the washing detergency ability of surfactant better, have better water solubility, very high surface-active and reduce the ability of oil/water termination tension force.
3. it is raw material that preparation method of the present invention adopts biomass resource, adopt the polar head access method, with two bromoalkanes is that spacer chain is introduced two hydrophobic abietyl tricyclic diterpene structures that connect in the Gemini surface active agent structure earlier, again two sulfonate polar heads are added up, the raw material cheapness, technology is succinct, has improved the added value of rosin resource greatly, toxicity is low, and is little to the harmfulness of environment.
Description of drawings
Fig. 1 is intermediate N of the present invention, N '-two dehydrogenation fir base 1, the 4-diamines
1H NMR spectrogram.
Fig. 2 is intermediate N of the present invention, N '-two dehydrogenation fir base 1, the C NMR spectrogram of 4-diamines.
Fig. 3 is a colophony-based sulphonate type gemini surfactant of the present invention (B)
1H NMR spectrogram.
Fig. 4 is the C NMR spectrogram of colophony-based sulphonate type gemini surfactant of the present invention (B).
Fig. 5 is γ-c curve of colophony-based sulphonate type gemini surfactant of the present invention (A, B, C, D).
Fig. 6 is that the contact angle of colophony-based sulphonate type gemini surfactant of the present invention (A, B, C, D) on slide compared with conventional surfactants with the variation tendency of concentration.
Wherein A is N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1,2-diamines; B is N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1,4-diamines; C is N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1,6-diamines; D is N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1,8-diamines.
The specific embodiment
Below in conjunction with Fig. 1～4, the present invention is elaborated:
With two bromoalkanes is nucleopilic reagent, and stirring condition drips the toluene solution of dehydroabietylamine or disproportionated rosin amine down, adds the acid binding agent natrium carbonicum calcinatum again, carry out nucleophilic addition, temperature 100-110 ℃, reaction time 16-20h, obtain intermediate N, N '-two dehydrogenation fir base α, ω-diamines.Wherein, the mol ratio of dehydroabietylamine, two bromoalkanes and natrium carbonicum calcinatum is 2.3-2.5: 1-1.1: 1.Described two bromoalkanes are 1,2-Bromofume, 1,4-dibromobutane, 1,6-dibromo-hexane, 1, any one in 8-two bromooctanes.
Described N, N '-two dehydrogenation fir base α, ω-diamines and 2-bromoethyl sodium sulfonate sulfonating reaction condition are:
N, N '-two dehydrogenation fir base α, ω-diamines, 2-bromoethyl sodium sulfonate and natrium carbonicum calcinatum are 1～1.5 with mol ratio: 2: 1, with N, N '-two dehydrogenation fir base α, ω-diamines, 2-bromoethyl sodium sulfonate mix in solvent methanol, and stirring condition adds down natrium carbonicum calcinatum, under 78-85 ℃ of reflux temperature stirring reaction 24-36 hour, steaming desolventizes, purifying is recrystallized, and filters the final vacuum drying and obtains colophony-based sulphonate type gemini surfactant, and general structure is as follows:
In the formula, R is an abietyl tricyclic diterpene group, and n is an integer, 1≤n≤5.Described abietyl tricyclic diterpene group is a kind of in the following substituting group:
The tricyclic diterpene base of dehydroabietylamine
Or the tricyclic diterpene group of disproportionated rosin amine.
Embodiment 1
A kind of colophony-based sulphonate type gemini surfactant, its general structure is as follows:
In the formula, R is an abietyl tricyclic diterpene structure, the integer in 1≤n≤5, and for example n can be chosen for 1,2,3,4,5.
In the present embodiment, R is a kind of in the following substituting group:
The tricyclic diterpene group of dehydroabietylamine
Or the tricyclic diterpene group of disproportionated rosin amine.
Embodiment 2
A kind of preparation method of colophony-based sulphonate type gemini surfactant, earlier prepare N with dehydroabietylamine or disproportionated rosin amine, N '-two dehydrogenation fir base α, ω-diamines, use N again, N '-two dehydrogenation fir base α, ω-diamines and 2-bromoethyl sodium sulfonate obtain colophony-based sulphonate type gemini surfactant by sulfonating reaction.
In the present embodiment, N, N '-two dehydrogenation fir base α, the synthetic of ω-diamines may further comprise the steps: with two bromos
To be nucleopilic reagent and dehydroabietylamine carry out nucleophilic addition to alkane in natrium carbonicum calcinatum is made the toluene solution of acid binding agent obtain N, N '-two dehydrogenation fir base α, and ω-diamines, wherein the mol ratio of dehydroabietylamine, two bromoalkanes and natrium carbonicum calcinatum is 2.3: 1: 1.
Described N, N '-two dehydrogenation fir base α, ω-diamines and 2-bromoethyl sodium sulfonate by the sulfonating reaction condition are: N, N '-two dehydrogenation fir base α, the mol ratio of ω-diamines, 2-bromoethyl sodium sulfonate and natrium carbonicum calcinatum is 1.3: 2: 1, is solvent with methyl alcohol, stirring reaction is 24 hours under 80 ℃ of reflux temperatures, steaming desolventizes, and residue is purified with ethyl acetate and is recrystallized, and filters the final vacuum drying.
Embodiment 3
A kind of preparation method of colophony-based sulphonate type gemini surfactant may further comprise the steps:
The first step: N, N '-two dehydrogenation fir base 1,4-diamines synthetic:
Dropping funel, anhydrous CaCl are being housed
2Add 1 in the four-hole bottle of drying tube and reflux condensing tube, 4-dibromobutane and acid binding agent natrium carbonicum calcinatum, mixing speed is the toluene solution that 1500-3000r/min drips dehydroabietylamine down, dehydroabietylamine, 1, the mol ratio of 4-dibromobutane and natrium carbonicum calcinatum is 2.4: 1.1: 1, and the consumption of solvent toluene is 100-250mL.110 ℃ of backflow stirring reactions 20 hours, being cooled to room temperature then filters, filter residue with methanol wash to loose, steam desolventize buff wax shape sticky solid, dissolve with chloroform, solution washing 3 times, dry oil phase steams and desolventizes, and purifies with ether, and filtration drying obtains white solid intermediate N, N '-two dehydrogenation fir base 1, the 4-diamines.
Second step: colophony-based sulphonate type gemini surfactant synthetic:
N, N '-two dehydrogenation fir base 1, the mol ratio of 4-diamines, 2-bromoethyl sodium sulfonate and natrium carbonicum calcinatum is 1.5: 2: 1, with N, N '-two dehydrogenation fir base 1,4-diamines, 2-bromoethyl sodium sulfonate mix in solvent methanol, under the stirring of 1500-3000r/min, add natrium carbonicum calcinatum, reaction is 24 hours under 83 ℃ of reflux temperatures, steaming desolventizes, and the recrystallization of purifying filters the final vacuum drying and obtains colophony-based sulphonate type gemini surfactant.
Embodiment 4
A kind of preparation method of colophony-based sulphonate type gemini surfactant may further comprise the steps:
The first step: N, N '-two dehydrogenation fir base 1,6-diamines synthetic:
Dropping funel, anhydrous CaCl are being housed
2Add 1 in the four-hole bottle of drying tube and reflux condensing tube, 6-dibromo-hexane and acid binding agent natrium carbonicum calcinatum, stirring condition drip the toluene solution of dehydroabietylamine, dehydroabietylamine, 1 down, the mol ratio of 6-dibromo-hexane and natrium carbonicum calcinatum is 2.5: 1: 1, and solvent toluene adopts conventional amount used.105 ℃ of backflow stirring reactions 18 hours are cooled to room temperature and filter after the reaction, filter residue with methanol wash to loose, steaming desolventize buff wax shape sticky solid, with chloroform dissolving, solution washing 2 times, dry oil phase steams and desolventizes, and purifies with ether, and filtration drying gets white solid.
Second step: colophony-based sulphonate type gemini surfactant synthetic:
N, N '-two dehydrogenation fir base 1,6-diamines, 2-bromoethyl sodium sulfonate and natrium carbonicum calcinatum are 1.45: 2: 1 with mol ratio, with N, and N '-two dehydrogenation fir base 1,6-diamines, 2-bromoethyl sodium sulfonate mix in solvent methanol, add natrium carbonicum calcinatum, reaction is 32 hours under 78 ℃ of reflux temperatures, and steaming desolventizes, purifying is recrystallized, and filters the final vacuum drying.
A kind of preparation method of colophony-based sulphonate type gemini surfactant may further comprise the steps:
The first step: N, N '-two dehydrogenation fir base 1,4-diamines synthetic:
Dropping funel, anhydrous CaCl are being housed
2Add 1 in the four-hole bottle of drying tube and reflux condensing tube, 8-two bromooctanes and acid binding agent natrium carbonicum calcinatum, mixing speed is the toluene solution that 1500-3000r/min drips disproportionated rosin amine down, disproportionated rosin amine, 1, the mol ratio of 8-two bromooctanes and natrium carbonicum calcinatum is 2.3: 1: 1, and the consumption of solvent toluene is 200-300mL.100 ℃ of backflow stirring reactions 18 hours, being cooled to room temperature then filters, filter residue with methanol wash to loose, steam desolventize buff wax shape sticky solid, dissolve with chloroform, solution washing 3 times, dry oil phase steams and desolventizes, and purifies with ether, and filtration drying obtains white solid intermediate N, N '-two dehydrogenation fir base 1, the 8-diamines.
Second step: colophony-based sulphonate type gemini surfactant synthetic:
N, N '-two dehydrogenation fir base 1, the mol ratio of 8-diamines, 2-bromoethyl sodium sulfonate and natrium carbonicum calcinatum is 1.5: 2: 1, with N, N '-two dehydrogenation fir base 1,8-diamines, 2-bromoethyl sodium sulfonate mix in solvent methanol, under the stirring of 1500-3000r/min, add natrium carbonicum calcinatum, reaction is 24 hours under 83 ℃ of reflux temperatures, steaming desolventizes, and the recrystallization of purifying filters the final vacuum drying and obtains colophony-based sulphonate type gemini surfactant.
Embodiment 3
A kind of preparation method of colophony-based sulphonate type gemini surfactant may further comprise the steps:
The first step: N, N '-two dehydrogenation fir base 1,2-diamines synthetic:
Dropping funel, anhydrous CaCl are being housed
2Add 1 in the four-hole bottle of drying tube and reflux condensing tube, 2-Bromofume and acid binding agent natrium carbonicum calcinatum, mixing speed is the toluene solution that 1500-3000r/min drips disproportionated rosin amine down, disproportionated rosin amine, 1, the mol ratio of 2-Bromofume and natrium carbonicum calcinatum is 2.3: 1.1: 1, and the consumption of solvent toluene is 100-250mL.100 ℃ of backflow stirring reactions 16 hours, being cooled to room temperature then filters, filter residue with methanol wash to loose, steam desolventize buff wax shape sticky solid, dissolve with chloroform, solution washing 3 times, dry oil phase steams and desolventizes, and purifies with ether, and filtration drying obtains white solid intermediate N, N '-two dehydrogenation fir base 1, the 2-diamines.
Second step: colophony-based sulphonate type gemini surfactant synthetic:
N, N '-two dehydrogenation fir base 1, the mol ratio of 2-diamines, 2-bromoethyl sodium sulfonate and natrium carbonicum calcinatum is 1.3: 2: 1, with N, N '-two dehydrogenation fir base 1,2-diamines, 2-bromoethyl sodium sulfonate mix in solvent methanol, under the stirring of 1500-3000r/min, add natrium carbonicum calcinatum, reaction is 34 hours under 80 ℃ of reflux temperatures, steaming desolventizes, and the recrystallization of purifying filters the final vacuum drying and obtains colophony-based sulphonate type gemini surfactant.
The structural characterization of colophony-based sulphonate type gemini surfactant adopts melting point detector, infrared and nuclear magnetic resonance to intermediate N, N '-two dehydrogenation fir base 1, and 4-diamines and surfactant have carried out structural characterization.The structural analysis of part surface activating agent is as follows, intermediate N, N '-two dehydrogenation fir base 1, the nmr spectrum of 4-diamines as shown in Figure 1, carbon-13 nmr spectra is as shown in Figure 2; The nmr spectrum of surfactant B as shown in Figure 3, carbon-13 nmr spectra as shown in Figure 4:
Intermediate N, N '-two dehydrogenation fir base 1,4-diamines: white solid, mp.:170.3-171.0 ℃.
IR (cm
-1): 2955.42,2868.73 (γ
CH2CH3) 1610.92 (phenyl ring skeletal vibrations), 821.11 (γ
CH)
1H NMR:(DMSO. δ/ppm.300MHz): 6.37-7.08 (6H, C=C
H-), 3.58 (2H,＞C
H-), 2.51-2.94 (4H, N C
H 2CH
2CH
2C
H 2N), 3.39 (2H,
HN CH
2CH
2CH
2CH
2N
H) 1.09-1.511.16-1.57 (24H ,-C
H 3).
13C?NMR(DMSO.δ/ppm.300MHz)：123.7，123.9，126.4，134.0，145.1，146.8(6C，
CH＝CH)，23.9-29.1(8C，-
CH
3)，17.8-57.3(16C，-
CH
2)，36.9-38.7(4C，-C-)，39.2-57.3(4C，＞
CH-)。
B: white solid, mp.:210.3-211.0 ℃.
IR (cm
-1): 2958.40,2870.53,2782.28 (γ
CH2CH3), 1618.93 (phenyl ring skeletal vibrations) 1204.82 (S=O asymmetric stretching vibration) 1171.87,1059.55 (S=0 asymmetric stretching vibration), 796.30 (γ
CH)
1H NMR:(DMSO. δ/ppm.300MHz): 6.35-7.15 (6H, C=C
H-), 3.51 (4H, CH
2C
H 2SO
3Na), 3.12 (2H,＞C
H-), 2.92 (4H, C
H 2CH
2SO
3Na), 2.36 (4H, N C
H 2CH
2CH
2C
H 2N), 1.16-1.57 (24H ,-C
H 3)
13C?NMR(DMSO.δ/ppm.300MHz)：123.1，126.1，126.8，133.7，145.6，145.7(6C，
CH＝CH)，23.9-25.1(8C，-
CH
3)，18.2-56.9(20C，-
CH
2)，36.9-38.9(4C，-C-)，38.6-54.3(4C，＞
CH-)，
Embodiment 6
The some surface active property of colophony-based sulphonate type gemini surfactant is measured, surface tension is the important parameter of surfactant properties, this research is adopted and is hung surface tension and the CMC that the sheet method is measured surfactant, measuring temperature is 25 ℃, the surface tension of the aqueous solution when measuring the variable concentrations of series of products, with the surface tension is ordinate, and concentration is that abscissa is made the relation curve between surface tension and the concentration, obtains the CMC value by point of inflexion on a curve.The γ of surfactant A, B, C-the c curve as shown in Figure 5.
Measurement of contact angle: with product be mixed with 100,200,350,500,1000,1500 respectively, 2500mgL
-1Each product aqueous solution of series concentration 25 ℃ of room temperatures, proves its wettability by measuring the Gemini surface active agent aqueous solution at the lip-deep contact angle of silicate (glass).
The some surface active property of surfactant A, B, C, D is as shown in table 1.
The surface-active of table 1 surfactant A, B, C, D is compared with the activity of conventional surfactant
Table 2A, B, C, the contact angle of D solution on slide are compared with conventional surfactants
Wherein A is N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1,2-diamines; B is N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1,4-diamines; C is N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1,6-diamines; D is N, N '-diethyl sodium sulfonate, N, N '-two dehydrogenation fir base 1,8-diamines.
As shown in Table 1, along with the increase of connecting chain length, the critical micelle concentration of A, B, C, D (CMC) and critical surface tension (δ) roughly are the trend of reduction, and all are lower than conventional surfactant C
12H
25SO
3The critical micelle concentration (CMC) of Na (TLS) and critical surface tension (δ) show higher surface activity.The spacer group of Gemini surface active agent closely connects two parents' molecules, causes the interaction between hydrocarbon chain stronger, has strengthened the hydrophobic effect of hydrocarbon chain.Spacer group has been offset the Coulomb repulsion effect between a base to a great extent simultaneously, makes Gemini surface active agent form micella than the easier gathering of hydrophobic chain surfactant.In addition, all contain the luxuriant and rich with fragrance skeleton of three rings in the molecular structure of A, B, C, D, have excellent hydrophobic property, the ethyl sulfonate group that the hydrophily of introducing is stronger is to such an extent as to whole molecular system has higher surface activity.
As shown in Table 2, along with the increase of the concentration of aqueous solution of A, B, C, D, contact angle reduces gradually.Reason may be that the amphiphile, amphiphilic molecule of Table A, B, C, D is adsorbed in glass surface, forms the adsorption layer that aligns, and reduced interfacial free energy, thereby wetting effectively glass surface is realized spontaneous sprawling.It can also be seen that by table 2 ability that the aqueous solution of A, B, C, D reduces contact angle is bigger than conventional surfactants, this be because of A, B, that C, D reduce capillary ability is bigger than conventional surfactants TLS, so their wettability is better.
Claims (5)
1. colophony-based sulphonate type gemini surfactant is characterized in that general structure is as follows:
In the formula, R is an abietyl tricyclic diterpene group, and n is an integer, 1≤n≤5; Described abietyl tricyclic diterpene group is a kind of in the following substituting group:
The tricyclic diterpene base of dehydroabietylamine
Or the tricyclic diterpene group of disproportionated rosin amine.
2. colophony-based sulphonate type gemini surfactant according to claim 1 is characterized in that: described colophony-based sulphonate type gemini surfactant is to use as the wetting agent that adds in the displacement of reservoir oil active water.
3. the preparation method of colophony-based sulphonate type gemini surfactant as claimed in claim 1, it is characterized in that earlier with dehydroabietylamine or disproportionated rosin amine and two bromoalkane prepared in reaction intermediate N, N '-two dehydrogenation fir base α, ω-diamines, use intermediate N again, N '-two dehydrogenation fir base α, ω-diamines and 2-bromoethyl sodium sulfonate carry out sulfonating reaction and obtain colophony-based sulphonate type gemini surfactant;
Described intermediate N, N '-two dehydrogenation fir base α, synthesizing of ω-diamines, may further comprise the steps: dehydroabietylamine or disproportionated rosin amine in molar ratio: two bromoalkanes: natrium carbonicum calcinatum=2.3-2.5: 1-1.1: 1 ratio is with hybrid reaction in the toluene solution of dehydroabietylamine or disproportionated rosin amine, two bromoalkanes and natrium carbonicum calcinatum, temperature 100-110 ℃, reaction time 16-20h obtains N, N '-two dehydrogenation fir base α, ω-diamines.
4. according to the preparation method of claim 4 or 5 described colophony-based sulphonate type gemini surfactants, it is characterized in that described two bromoalkanes are 1,2-Bromofume, 1,4-dibromobutane, 1,6-dibromo-hexane, 1, any one in 8-two bromooctanes.
5. the preparation method of colophony-based sulphonate type gemini surfactant according to claim 4, it is characterized in that described intermediate N, N '-two dehydrogenation fir base α, ω-diamines and 2-bromoethyl sodium sulfonate carry out the sulfonating reaction condition and are: N in molar ratio, N '-two dehydrogenation fir base α, ω-diamines: 2-bromoethyl sodium sulfonate: natrium carbonicum calcinatum=1～1.5: 2: 1 ratio, with N, N '-two dehydrogenation fir base α, ω-diamines, 2-bromoethyl sodium sulfonate mixes in solvent methanol, add natrium carbonicum calcinatum, at reflux temperature 78-85 ℃ of following stirring reaction 24-36 hour, steaming desolventizes, and the recrystallization of purifying filters the final vacuum drying and obtains colophony-based sulphonate type gemini surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100303234A CN101502772B (en) | 2009-03-11 | 2009-03-11 | Colophony-based sulphonate type gemini surfactant and method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100303234A CN101502772B (en) | 2009-03-11 | 2009-03-11 | Colophony-based sulphonate type gemini surfactant and method for preparing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101502772A CN101502772A (en) | 2009-08-12 |
| CN101502772B true CN101502772B (en) | 2011-05-11 |
Family
ID=40975224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100303234A Expired - Fee Related CN101502772B (en) | 2009-03-11 | 2009-03-11 | Colophony-based sulphonate type gemini surfactant and method for preparing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101502772B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972613B (en) * | 2010-09-25 | 2012-07-04 | 长江大学 | Carboxylate type gemini surfactant and synthesis method thereof |
| CN102814144A (en) * | 2012-09-03 | 2012-12-12 | 山东大学 | Environment-friendly positive ion fluorinated surfactant based on short perfluorocarbon chain and preparation method thereof |
| CN102908937B (en) * | 2012-09-12 | 2015-07-29 | 衢州学院 | Based on the cationic Shuangzi fluorine surfactant and preparation method thereof of perfluorinated nonene and perfluor hexene |
| CN103657514B (en) * | 2012-09-18 | 2015-12-02 | 湖北中科博策新材料研究院 | The preparation method of fluorine-containing nonionic surface active agent and application |
| CN103111229B (en) * | 2013-03-08 | 2014-11-05 | 山东大学 | Gemini type fluorocarbon surfactant containing sulfonic group and preparation method thereof |
| CN103406066B (en) * | 2013-07-26 | 2015-01-21 | 中国林业科学研究院林产化学工业研究所 | Rosinyl polyoxyethylene amine type gemini surfactant and preparation method thereof |
| CN104906996B (en) * | 2015-04-28 | 2017-11-07 | 三明市海斯福化工有限责任公司 | A kind of sulfonate type fluorine-containing surfactant, its synthetic method and application |
| CN105707071B (en) * | 2016-01-21 | 2018-09-18 | 威尔（福建）生物有限公司 | A kind of pesticidal preparations wetting agent and preparation method thereof and the application in pesticidal preparations |
| CN107760295A (en) * | 2017-11-08 | 2018-03-06 | 陕西友邦石油工程技术有限公司 | A kind of small molecule is recycled fracturing fluid and its application method |
| CN109913193B (en) * | 2017-12-13 | 2021-03-30 | 中国石油天然气股份有限公司 | Pressure-reducing and injection-increasing agent for water injection well of low-permeability oil reservoir and preparation method thereof |
| CN112442098B (en) * | 2019-09-03 | 2022-05-17 | 中国石油化工股份有限公司 | Sulfonated modified sophorolipid or salt thereof and preparation method thereof |
| CN111635747B (en) * | 2020-06-05 | 2023-03-31 | 赛科思能源技术(重庆)有限责任公司 | Imbibition displacement agent for developing compact oil |
| CN113522158A (en) * | 2021-07-19 | 2021-10-22 | 深圳建实科技有限公司 | Gemini surfactant containing rosin structure and preparation method thereof |
-
2009
- 2009-03-11 CN CN2009100303234A patent/CN101502772B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101502772A (en) | 2009-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101502772B (en) | Colophony-based sulphonate type gemini surfactant and method for preparing the same | |
| CN100374192C (en) | Surface activator with double-ether bisbensulfosalt and double molecule | |
| CN102688722B (en) | Hydrogenated rosin-based quaternary ammonium salt gemini surfactant and preparation method thereof | |
| CN101745343B (en) | Alkyl group polyoxyethylene ether surface active agent with Guerbet structure and preparation method and application thereof | |
| CN102304069B (en) | Method for synthesizing saturated cardanol sulfonate surfactant for oil displacement | |
| CN103396306A (en) | Cardanol Gemini polyoxyethylene ether carboxylate and preparation method thereof | |
| CN103145568A (en) | Cardanol cationoid quaternary ammonium salt and preparation method thereof | |
| CN101480590B (en) | Sulphonate Gemini surfactant and preparation method thereof | |
| CN103406066B (en) | Rosinyl polyoxyethylene amine type gemini surfactant and preparation method thereof | |
| CN109851530A (en) | N, N, N ', four substituted diphenylamine ether sulfonate anionic gemini surfactant of N '-dodecyl and its synthesis | |
| CN104525044A (en) | Gemini quaternary ammonium salt cationic surfactant and synthesis method thereof | |
| CN101863949B (en) | Structural modification type cameclia oleifera saponin and preparation method and application thereof | |
| CN109679678A (en) | Alkalinity/non basic nitrogen eutectic solvent and method are extracted from analog gasoline | |
| CN104190314A (en) | Fatty amine polyoxyethylene ether diethyl disulfonate surfactant and preparation method thereof | |
| CN102755855A (en) | Alkylaryl sulfonate type hyperbranched polymer surface active agent and preparation method thereof | |
| CN107814755B (en) | Anionic gemini surfactant and preparation method thereof | |
| CN103805155B (en) | Sulfonate type living beings surfactant and synthetic method thereof | |
| CN104817479A (en) | Preparation technology optimization method of biomass surfactant for oil displacement | |
| CN102618242A (en) | Oil-displacing agent as Gemini surfactant | |
| CN106146562B (en) | A kind of production method of phosphorous nitride methyl oleate green lubrication additive | |
| CN102091562B (en) | Surfactant benzyl-dihydroxyethyl-2-hydroxyl lauryl ammonium chloride and preparation method thereof | |
| CN106268497A (en) | One class contains abietyl Gemini surface active agent and the performance thereof of polyoxyethylene ether coupling link | |
| CN106943948A (en) | One class abietyl sulfobetaines amphoteric surfactant and its performance | |
| CN101747185B (en) | Method for separating saturated fatty acid methyl ester from biodiesel | |
| CN102728272A (en) | Cashew-based quaternary ammonium salt cationic surfactant and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Jingdong Li'ao Linchan Group Forestry Chemical Co., Ltd. Assignor: Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry Contract record no.: 2011530000038 Denomination of invention: Colophony-based sulphonate type gemini surfactant and method for preparing the same Granted publication date: 20110511 License type: Exclusive License Open date: 20090812 Record date: 20110705 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110511 Termination date: 20180311 |