CN106540630A - A kind of carboxylic acid type anionic Gemini surfactant and preparation method thereof - Google Patents
A kind of carboxylic acid type anionic Gemini surfactant and preparation method thereof Download PDFInfo
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- CN106540630A CN106540630A CN201610908127.2A CN201610908127A CN106540630A CN 106540630 A CN106540630 A CN 106540630A CN 201610908127 A CN201610908127 A CN 201610908127A CN 106540630 A CN106540630 A CN 106540630A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Abstract
The invention discloses a kind of carboxylic acid type anionic Gemini surfactant and preparation method thereof, belongs to surfactant science and applied technical field.The synthesis of the surfactant of the present invention includes that 2 decyl diethyl malonates sequentially pass through bilateral substitution reaction, saponification, acidifying, deacidification and acid-base neutralization reaction with dibromoalkane and obtain final carboxylic acid type anionic Gemini surfactant with diethyl malonate and bromo n-decane as 2 decyl diethyl malonate of initiation material synthesis first step product.Such surfactant has extremely low cmc, shows that surface activity is very high.The surfactant of said structure contributes to the relevant knowledge of abundant Gemini surface active self-organizing, and its special performance is also beneficial to the application in commercial production.
Description
Technical field
The present invention relates to a kind of carboxylic acid type anionic Gemini surfactant and preparation method thereof, belongs to surface activity
Agent science and applied technical field.
Background technology
Gemini surface active, also known as Gemini surface active agent, Anionic Gemini Surfactant, geminal surfactant or idol
Connection surfactant, is that in its hydrophilic head base or two conventional surfactant molecules are close to hydrophilic head by a connection base
The class novel surfactant that Ji Chu links together and formed.Due to the particularity of its structure, Gemini surface active agent table
Reveal the special performance not available for many conventional surfactants, thus with very strong application potential.Gemini surfaces
Activating agent has preferable solubilization, wetting action, foaming effect and saponification dispersibility, can be widely applied to each neck
Domain, in addition, in some special dimensions, such as can be used as the template and anti-adhesive agent, improvement sewage for preparing nano material
Transfect, suppress metal erosion, oil recovery and fine chemistry industry etc. with soil, sterilizing effect, gene.
As conventional surfactant, Gemini surface active is also classified into anionic, cationic, nonionic
And amphoteric surfactant.Wherein, it is many with regard to the report of the Gemini surface active of cation, it is typical that m-s-m
Type quaternary cationicses.The Gemini surface active of anionic is more difficult due to its synthesis and purification,
That what is studied and report is relatively fewer.Have been reported and synthesized carboxylate anion's surfactant, but which mainly have studied
How the performances such as liquid crystal property, its critical micelle concentration, surface tension are unknown；And, its carboxylate anion surface is lived
The synthesis step of property agent is loaded down with trivial details, purification process is not easy to operate etc..In addition, compared with cationic surfactant, anionic surface
More preferably, toxicity is lower, can not replace with cation in many applications (such as tertiary oil recovery) for the biological degradability of activating agent
The advantage in generation, so the property of research anionic Gemini surfactant and application are particularly important.
The content of the invention
For these reasons, the invention provides a class novel carboxylic acid salt form anionic Gemini surfactant, this is
Surfactant has abnormal low cmc, and cmc is the critical micelle concentration of surfactant, can weigh surfactant
Ability of aggregation in the solution, is the important parameter for characterizing surfactant surface activity, and its value is lower, shows that its activity is got over
It is high.In the series, spacer group is the surfactant of 10 methylene, its cmc as little as 1.0 × 10-5Mol/L, its corresponding biography
The cmc of system surfactant sodium laurate is 26 × 10-3Mol/L, 2600 times of surfactant cmc about in the present invention, because
The surfactant synthesized in this present invention has high surface activity.
First purpose of the present invention is to provide a kind of new carboxylic acid type anionic Gemini surfactant, structure
Formula is as follows：
Wherein n=3～10.
In one embodiment of the invention, the n is 3,6 or 10.
In one embodiment of the invention, the cation portion of the carboxylic acid type anionic Gemini surfactant
(M+), can be Na+、K+、Li+Or NH4 +。
Second object of the present invention is to provide the preparation method of the carboxylic acid type anionic Gemini surfactant,
With diethyl malonate and halo n-decane as initiation material synthesis 2- decyl diethyl malonates (compound 1), 2- decyls third
Final carboxylic obtained and bilateral replacement, saponification, acidifying, deacidification and acid-base neutralization reaction successively with saturated dihalide in diethyl adipate there is
Hydrochlorate type anionic Gemini surfactant SL-n-SL.
In one embodiment of the invention, the mol ratio of the diethyl malonate and halo n-decane is 1:2～
2:1。
In one embodiment of the invention, the mol ratio of the diethyl malonate and halo n-decane is 1.2:1.
In one embodiment of the invention, the reaction of the diethyl malonate and halo n-decane, is to contain
Carry out in the THF mixed solutions of NaH.
In one embodiment of the invention, the reaction condition of the diethyl malonate and halo n-decane is 65 DEG C
～75 DEG C of 18～20h of reaction.
In one embodiment of the invention, the bilateral substitution reaction, 2- decyls diethyl malonate and dihalo
The mol ratio of alkane is 2:1～3:1.
In one embodiment of the invention, the saturated dihalide is 1,3- dihalopropanes, 1,6- dihalo hexanes
Or 1,10- dihalo decane.
In one embodiment of the invention, the condition of the bilateral substitution reaction be 65 DEG C～75 DEG C reaction 15～
18h。
In one embodiment of the invention, the bilateral substitution reaction, is in the THF mixed solutions containing NaH
Carry out.
In one embodiment of the invention, the saponification, is the compound and potassium tert-butoxide for obtaining bilateral replacement
Reacted, both mol ratios are 1:12～1:20.
In one embodiment of the invention, the compound that bilateral replacement is obtained is 1 with the mol ratio of potassium tert-butoxide:
16。
In one embodiment of the invention, the reaction condition of the saponification is 55 DEG C～70 DEG C 15～18h of reaction.
In one embodiment of the invention, the saponification, is carried out in THF solution.
In one embodiment of the invention, the acidifying, is to add concentrated hydrochloric acid acidifying.
In one embodiment of the invention, deacidification reaction, is to make catalyst with LiCl, at 180 DEG C～220 DEG C or so
3～5h of reaction.
In one embodiment of the invention, acid-base neutralization, is added in the compound that previous step deacidification reaction is obtained
Enter NaOH and be neutralized reaction, reaction condition is 75～85 DEG C of 2～4h of reaction.
In one embodiment of the invention, in acid-base neutralization, the deacidification compound that obtains of reaction and NaOH mole
Than for 1:1.5～1:3.
In one embodiment of the invention, the compound that deacidification reaction is obtained is 1 with the mol ratio of NaOH:2.
In one embodiment of the invention, the concrete reaction equation of the preparation method is as follows：
The synthetic route of SL-n-SL (n=3～10)：
In one embodiment of the invention, the halo n-decane and saturated dihalide are respectively bromo n-decane and two
Bromoalkane.
In one embodiment of the invention, the bromo n-decane and dibromoalkane are commercially available.
Third object of the present invention is to provide the application of the carboxylic acid type anionic Gemini surfactant.
The application, there is anion surfactant mature production technology, raw material to be easy to get, applied widely etc. many excellent
Point.Therefore, carboxylic acid type anionic Gemini surfactant of the invention can be widely applied to environmental conservation, oil field and open
Adopt, medicine, textile printing and dyeing, industry cleaning link, the numerous areas such as household chemicalss.Such as higher surface activity, can be used to give birth to
Detergent and emulsifying agent are produced, is applied and agriculturally, can be used for cleaning soil；Preferable foam stability and stability of emulsion, can
It is used as cleaning agent, detergent and cosmetics additive；Vesicle is formed easily, can be used as biomembrane, pharmaceutical carrier and special reaction
Catalyst etc..
Beneficial effects of the present invention：
(1) novel carboxylic acid salt form anionic Gemini surfactant of the invention contains flexible connected chain, and which has pole
Low critical micelle concentration cmc, cmc are respectively 2.9 × 10-4Mol/L (n=3), 5.8 × 10-5Mol/L (n=6) and 1.2 ×
10-5Mol/L (n=10).The cmc of corresponding conventional surfactant moon sodium silicate is 26 × 10-3Mol/L, about in the present invention
90,448 and 2600 times of surfactant cmc.The novel carboxylic acid salt synthesized in the present invention is can be seen that by result above
The ability of aggregation of Gemini surface active SL-n-SL (n=3～10) is very strong, is the Gemini surfaces of a class function admirable
Activating agent, can be widely used in the research of surfactant self-organizing system.
(2) with diethyl malonate, bromo n-decane as raw material, it is cloudy that five steps of Jing are synthesized novel carboxylic acid salt form to the present invention
Ion Gemini surface active, explores the actual conditions of reaction.By rationally controlling response time and reaction condition, favorably
In reaction yield is improved, the difficulty of final products purification is reduced.
Description of the drawings
Nuclear magnetic resonance, NMR of the Fig. 1 for embodiment product SL-3-SL (compound 9)1HNMR spectrograms；
Nuclear magnetic resonance, NMR of the Fig. 2 for embodiment product SL-6-SL (compound 13)1HNMR spectrograms；
Nuclear magnetic resonance, NMR of the Fig. 3 for embodiment product SL-10-SL (compound 17)1HNMR spectrograms；
Fig. 4 is surface tension curve of embodiment product SL-n-SL (n=3,6,10) at 25 DEG C.
Specific embodiment
Embodiment 1：SL-3-SL synthetic routes
Carboxylic acid type anionic Gemini surfactant SL-3-SL, structural formula are as follows：
The synthetic route of SL-3-SL is as follows：
Compound 1, compound 1 and 1,3- dibromopropane are synthesized as initiation material with diethyl malonate, bromo n-decane
The bilateral substitution reaction of generation, generates compound 6, and compound 6 sequentially passes through saponification, acidifying, deacidification and acid-base neutralization reaction again and obtains
To final compound 9 (carboxylic acid type anionic Gemini surfactant SL-3-SL).
Embodiment 2：The synthesis of compound 1
By diethyl malonate and bromo n-decane according to mol ratio 1.2:1 mixing, is added to the mixing of the THF containing NaH
In solution, 18h is stirred at 70 DEG C, after cooling, revolving removes THF, extracted with the saturated citric acid solution of petroleum ether and ice, it is quiet
10min is put, upper strata organic liquid layer is taken, is used MgSO4It is dried, sucking filtration, Rotary Evaporators remove petroleum ether, the liquid for obtaining continues to subtract
Pressure distillation (170 DEG C -174 DEG C/5mmHg), obtains first step product compound 1, yield：71.6%.
Embodiment 3：The synthesis of compound 6
Compound 1 and 1,3- dibromopropanes are according to mol ratio 2.4:1 mixing, is added to the THF mixed solutions containing NaH
In, 15h or so is stirred at 70 DEG C, after cooling, revolving removes THF, is extracted with the saturated citric acid solution of petroleum ether and ice, quiet
10min is put, upper strata organic liquid layer is taken, is used MgSO4It is dried, sucking filtration, Rotary Evaporators remove petroleum ether, the liquid for obtaining continues logical
Cross silicagel column (silica gel：300～400 mesh, eluant are pure petroleum ether) separating-purifying is carried out, second step product compound 6 is obtained,
Yield：54.3%.
Embodiment 4：The synthesis of compound 7
Potassium tert-butoxide and compound 6 are according to mol ratio 16:1 mixing, is added in THF solution, stirs 15h at 70 DEG C,
After cooling, reacted with water quenching, form biphase, remove water phase, concentrated hydrochloric acid acidifying, ether are extracted 3 times, MgSO4It is dried, sucking filtration,
Revolving removes solvent, and ethanol/water recrystallization obtains compound 7, yield after vacuum drying：78.6%.
Embodiment 5：The synthesis of compound 9
Compound 7 is added in the water phase containing catalyst LiCl, and 5h is stirred at 200 DEG C, and stopped reaction obtains chemical combination
Thing 8.By compound 8 and NaOH according to mol ratio 1：2 mixing, add ethanol solution, after stirring 4h at 80 DEG C, after cooling, rotation
Turn evaporating ethanol, then with ethanol and re-crystallizing in ethyl acetate 3 times, it is vacuum dried after obtain final product compound 9, produce
Rate：46.7%.
Embodiment 6：The nuclear magnetic resonance, NMR of SL-3-SL1HNMR is composed and property
The end-product nuclear magnetic resonance, NMR that embodiment 5 is obtained1HNMR spectrums are shown in Fig. 1.
According to Fig. 1 nuclear magnetic resoance spectrum map analysis, final product SL-3-SL CD3OD dissolves, and measures1HNMR is composed.In FIG
It is CD at δ=3.31 and 4.873The solvent peak of OD.Remaining proton displacement δ is：2.16(d,2H),1.61-1.46(m,4H),
1.40-1.22(m,39H),0.89(t,6H).From the data cases analysis of spectrogram process, final product and design object can be learnt
Product is consistent.
The capillary measure of carboxylic acid type anionic Gemini surfactant SL-3-SL, using surface tension method pair
The surface tension of the reaction mixture of variable concentrations is measured, and at making 25 DEG C, SL-3-SL aqueous solution surface tension is with solution concentration
Change curve, see Fig. 4.
In Fig. 4, the corresponding concentration of curve break is critical micelle concentration cmc of the surfactant, the curve from figure
The corresponding vertical coordinate of turning point can obtain surface tension γ of the surfactantcmc.Experiment discovery, carboxylic acid type anion
The critical micelle concentration of Gemini surface active SL-3-SL is relatively low, and cmc is 2.9 × 10-4Mol/L, under critical micelle concentration
Surfactant SL-6-SL surface tension γcmcFor 31.96mNm-1。
Embodiment 7：SL-6-SL synthetic routes
Carboxylic acid type anionic Gemini surfactant SL-6-SL, structural formula are as follows：
The synthetic route of SL-6-SL：
Compound 1, compound 1 and 1,3- dibromopropane are synthesized as initiation material with diethyl malonate, bromo n-decane
The bilateral substitution reaction of generation, generates compound 10, and compound 10 sequentially passes through saponification, acidifying, deacidification and acid-base neutralization reaction again
Obtain final compound 13 (carboxylic acid type anionic Gemini surfactant SL-6-SL).
Embodiment 8：The synthesis of compound 10
Raw material be 2- decyl diethyl malonates (63g, 0.21mol), 1,6- dibromo-hexanes (20.46g, 0.084mol),
NaH (7.7g, 0.19mol), other synthesis steps with compound 6, by silicagel column purification obtain compound 10 (34.65g,
60.4%).
Embodiment 9：The synthesis of compound 11
Raw material be compound 10 (14.4g, 0.02mol), potassium tert-butoxide (35.9g, 0.32mol), water (1.44mL,
0.08mol), other synthesis steps are with compound 7, purification obtain compound 11 (10.48g, 79.7%).
Embodiment 10：The synthesis of compound 13
Raw material be compound 11 (10.48g, 0.02mol), NaOH (1.6g, 0.04mol), the same chemical combination of other synthesis steps
Thing 9, purification obtain compound 13 (6.45g, 61.2%).
Embodiment 11：The nuclear magnetic resonance, NMR of SL-6-SL1HNMR is composed and property
The end-product nuclear magnetic resonance, NMR that embodiment 10 is obtained1HNMR spectrums are shown in Fig. 1.
According to Fig. 2 nuclear magnetic resoance spectrum map analysis, final product SL-6-SL CD3OD dissolves, and measures1HNMR is composed.In fig. 2
It is CD at δ=3.31 and 4.873The solvent peak of OD.Remaining proton displacement δ is：δ2.18(d,2H),1.60-1.48(m,4H),
1.39-1.21(m,44H),0.89(t,6H).From the data cases analysis of spectrogram process, final product and design object can be learnt
Product is consistent.
The capillary measure of carboxylic acid type anionic Gemini surfactant SL-6-SL, using surface tension method pair
The surface tension of the reaction mixture of variable concentrations is measured, and at making 25 DEG C, SL-6-SL aqueous solution surface tension is with solution concentration
Change curve, see Fig. 4.
In Fig. 4, the corresponding concentration of curve break is critical micelle concentration cmc of the surfactant, the curve from figure
The corresponding vertical coordinate of turning point can obtain surface tension γ of the surfactantcmc.Experiment discovery, carboxylic acid type anion
The critical micelle concentration of Gemini surface active SL-6-SL is relatively low, and cmc is 5.8 × 10-5Mol/L, under critical micelle concentration
Surfactant SL-6-SL surface tension γcmcFor 36.18mNm-1。
Embodiment 12：SL-10-SL synthetic routes
Carboxylic acid type anionic Gemini surfactant SL-10-SL, structural formula are as follows：
Synthetic route is as follows：
The synthetic route of SL-10-SL
Compound 1, compound 1 and 1,3- dibromopropane are synthesized as initiation material with diethyl malonate, bromo n-decane
The bilateral substitution reaction of generation, generates compound 14, and compound 14 sequentially passes through saponification, acidifying, deacidification and acid-base neutralization reaction again
Obtain final compound 17 (carboxylic acid type anionic Gemini surfactant SL-10-SL).
Embodiment 13：The synthesis of compound 14
Raw material is 2- decyl diethyl malonates (36g, 0.12mol), 1,10- dibromo-decanes (15g, 0.05mol), NaH
(4.6g, 0.115mol), other synthesis steps with compound 6, by silicagel column purification obtain compound 14 (27.65g,
74.48%).
Embodiment 14：The synthesis of compound 15
Raw material be compound 10 (20g, 0.03mol), potassium tert-butoxide (48.58g, 0.43mol), water (18mL, 0.1mol),
Other synthesis steps with compound 7, purification obtain compound 15 (13.34g, 82.5%).
Embodiment 15：The synthesis of compound 17
Raw material be compound 15 (13.34g, 0.02mol), NaOH (1.6g, 0.04mol), the same chemical combination of other synthesis steps
Thing 9, purification obtain compound 17 (8.56g, 73.4%).
Embodiment 16：The nuclear magnetic resonance, NMR of SL-n-SL (n=3,6,10)1HNMR is composed
The end-product nuclear magnetic resonance, NMR that embodiment 15 is obtained1HNMR spectrums are shown in Fig. 3.
According to Fig. 3 nuclear magnetic resoance spectrum map analysis, final product SL-10-SL CD3OD dissolves, and measures1HNMR is composed.In Fig. 3
It is CD at middle δ=3.31 and 4.873The solvent peak of OD.Remaining proton displacement δ is：δ2.17(d,2H),1.59-1.48(m,4H),
1.38-1.18(m,39H),0.89(t,6H).From the data cases analysis that three spectrograms are processed, final product and design can be learnt
Target product is consistent.
The capillary measure of carboxylic acid type anionic Gemini surfactant SL-10-SL, using surface tension method pair
The surface tension of the reaction mixture of variable concentrations is measured, and at making 25 DEG C, SL-10-SL aqueous solution surface tension is with solution concentration
Change curve, see Fig. 4.
In Fig. 4, the corresponding concentration of curve break is critical micelle concentration cmc of the surfactant, the curve from figure
The corresponding vertical coordinate of turning point can obtain surface tension γ of the surfactantcmc.Experiment discovery, carboxylic acid type anion
The critical micelle concentration of Gemini surface active SL-10-SL is relatively low, and cmc is 1.2 × 10-5Mol/L, in critical micelle concentration
Under surfactant SL-10-SL surface tension γcmcFor 36.27mNm-1。
Although the present invention is disclosed as above with preferred embodiment, which is not limited to the present invention, any to be familiar with this skill
The people of art, without departing from the spirit and scope of the present invention, can do various changes and modification, therefore the protection model of the present invention
Enclosing should be by being defined that claims are defined.
Claims (10)
1. a kind of carboxylic acid type anionic Gemini surfactant, it is characterised in that carboxylic acid type anion Gemini
The structural formula of surfactant is as follows：
Wherein n=3～10.
2. carboxylic acid type anionic Gemini surfactant according to claim 1, it is characterised in that the n is 3,6
Or 10.
3. carboxylic acid type anionic Gemini surfactant according to claim 1, it is characterised in that the carboxylate
The cation portion of type anionic Gemini surfactant is Na+、K+、Li+Or NH4 +。
4. the preparation method of the carboxylic acid type anionic Gemini surfactant described in a kind of claim 1, it is characterised in that
Methods described is first to synthesize 2- decyl diethyl malonate, 2- decyl as initiation material with diethyl malonate and halo n-decane
There is bilateral replacement, saponification, acidifying, deacidification and acid-base neutralization reaction successively with saturated dihalide and obtain final in diethyl malonate
Carboxylic acid type anionic Gemini surfactant SL-n-SL.
5. method according to claim 4, it is characterised in that the mol ratio of the diethyl malonate and halo n-decane
For 1:2～2:1.
6. method according to claim 4, it is characterised in that the bilateral substitution reaction, 2- decyl diethyl malonates
Mol ratio with saturated dihalide is 2:1～3:1；The condition of the bilateral substitution reaction is 65 DEG C～75 DEG C 15～18h of reaction.
7. method according to claim 4, it is characterised in that the saturated dihalide is 1,3- dihalopropanes, 1,6- bis-
Halo hexane or 1,10- dihalo decane.
8. the application of the arbitrary described carboxylic acid type anionic Gemini surfactant of claims 1 to 3.
9. application according to claim 8, the application are to be applied to environmental area, field of textiles, chemical field, preparation
Drug world, industry cleaning link, household chemicalss.
10. application according to claim 9, the application include：Be applied to environmental conservation, oilfield exploitation, textile printing and dyeing,
Industry cleaning link, household chemicalss.
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| CN107824119A (en) * | 2017-11-24 | 2018-03-23 | 江南大学 | A kind of emulsion-stabilizing system with pH response type Gemini surface actives |
| CN108097159A (en) * | 2017-12-17 | 2018-06-01 | 江南大学 | The viscoelastic system and preparation method that a kind of Gemini type cationic and anionic surfactant is constructed |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107551952A (en) * | 2017-09-15 | 2018-01-09 | 浩力森涂料（上海）有限公司 | Carboxylic acid type plant oil base gemini surfactant and preparation method thereof |
| CN107824119A (en) * | 2017-11-24 | 2018-03-23 | 江南大学 | A kind of emulsion-stabilizing system with pH response type Gemini surface actives |
| CN107824119B (en) * | 2017-11-24 | 2020-01-07 | 江南大学 | Emulsion stabilizing system with pH response type Gemini surfactant |
| CN108097159A (en) * | 2017-12-17 | 2018-06-01 | 江南大学 | The viscoelastic system and preparation method that a kind of Gemini type cationic and anionic surfactant is constructed |
| CN110079290A (en) * | 2019-05-16 | 2019-08-02 | 长江大学 | Low surface tension increasing stick carboxylate gemini surfactant and preparation method |
| CN110079290B (en) * | 2019-05-16 | 2021-10-29 | 长江大学 | Low surface tension viscosity-increasing carboxylate gemini surfactant and preparation method thereof |
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