CN104437239A - Perfluorous-nonene-containing amphoteric surfactant and preparation method thereof - Google Patents
Perfluorous-nonene-containing amphoteric surfactant and preparation method thereof Download PDFInfo
- Publication number
- CN104437239A CN104437239A CN201410647872.7A CN201410647872A CN104437239A CN 104437239 A CN104437239 A CN 104437239A CN 201410647872 A CN201410647872 A CN 201410647872A CN 104437239 A CN104437239 A CN 104437239A
- Authority
- CN
- China
- Prior art keywords
- surfactant
- perfluorinated nonene
- solvent
- oxygen base
- amphoteric
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a perfluorous-nonene-containing amphoteric surfactant and a preparation method of the perfluorous nonene containing amphoteric surfactant. According to the perfluorous-nonene-containing amphoteric surfactant, perfluorous nonenoxy benzene sulfonamide tertiary amine is subjected to condensation quaternization reaction with halogeno salt or sultone in a solvent to obtain the amphoteric fluorine-containing surfactant under the existence of an acid-binding agent. The preparation process of the amphoteric fluorine-containing surfactant is simple and the surface property is excellent; and besides, the fluorine-containing chain is a perfluoroalkyl group chain with short carbon chain and multiple branched chains, and meets the current international environmental requirement for the surfactant.
Description
Technical field
The present invention relates to surfactant field, be specifically related to a kind of amphoteric surfactant containing perfluorinated nonene base and preparation method thereof.
Background technology
Surfactant is containing hydrophilic and material that is hydrophobic grouping.According to the difference of hydrophobic grouping, hc-surfactant, organic silicon surfactant, fluorine-containing surfactant etc. can be divided into.Difference according to hydrophilic radical can be divided into again cationic, anionic, nonionic and amphoteric.Fluorine-containing surfactant is the compound containing hydrophobic long-chain perfluoroalkyl or PFPE and hydrophilic radical.Compared with general hc-surfactant, fluorine-containing surfactant has the hydrophobic and lyophobic property of higher surface-active, higher heat endurance, higher chemical stability and excellence, i.e. so-called " three is high " and " two hate " characteristic, be applicable to the various occasions that common hc-surfactant can not meet use, have a wide range of applications in fields such as daily life, industrial production, science and techniques of defence.
Model ylid bloom action power between fluorine-containing surfactant and solvent molecule is less, and easy strong adsorption in solvent and Air Interface, thus presents high surface-active.Because C-F bond energy is higher than c h bond, and the shielding action of fluorine atom, the perfluoroalkyl chain in fluorine-containing surfactant molecule has the physical and chemical stability of height.Especially the fluorine-containing surfactant containing long perfluoroalkyl chain, there is the biological metabolism stability of height, remote migrate attribute, high bioconcentration and potential bio-toxicity (Journal of Fluorine Chemistry 2001,107,337-354), the extensive concern of international community is caused.The international Convention of Stockholm of such as perfluoro octyl sulfonic acid (PFOS) and derivative Yi Bei thereof is classified as one of lasting organic pollution (POPs), is restricted and prohibits the use.Other the surfactant containing long perfluoroalkyl chain as the application of perfluoro caprylic acid (PFOA) and derivative thereof the Environmental and ecological problems that brings also be subject to great attention (the Journal of Fluorine Chemistry 2009 of people, 130,1192 – 1199).Therefore development of new fluorine-containing surfactant, substitutes the fluorine-containing surfactant containing long perfluoroalkyl chain, has important economic and social benefit.
Be the fluorine-containing surfactant that raw material can synthesize short carbon chain, highly branched chain with hexafluoropropylene trimer, have that synthesis is simple, cost is low, cost performance high.Chinese patent CN101293860A for raw material with phenol and hexafluoropropylene trimer, has prepared phenyl ether, has then been obtained by reacting tertiary amine intermediate with chlorosulfonic acid, propane diamine successively, finally quaternary ammoniatedly obtains cationic fluorosurfactants activating agent; The hair people such as fur coat that continue have synthesized N-(2H, 2H-perfluor 11 carbonic acyl radical amine propyl group)-N, N, N-trimethyl iodate amine (Organic fluoride industry, 1996, (1), 1-5), have very high surfactant, may be used for ocean oil-collecting; A series of fluorine-containing surfactants containing hexafluoropropylene trimer base that Chinese patent CN103432959A synthesizes, the lowest surface tension of most compound reaches 19mN/m, and surface property is superior, can be used for the field such as fire-fighting, oil field.But there is no document at present and relate to amphoteric fluorotensides containing benzenesulfonyl.
Summary of the invention
The defect of fluorine-containing surfactant deficiency of the present invention in order to overcome existing perfluorinated nonene base and derive, according to the theory and design method of amphoteric surfactant, design and prepared a kind of amphoteric fluorine-containing surfactant based on perfluorinated nonene base (hexafluoropropylene trimer), this amphoteric fluorine-containing surfactant has good dispersiveness, foaming characteristic, levelability, wetability and higher surface-active, and lower critical micelle concentration and lower toxicity.
Technical scheme of the present invention provides a kind of amphoteric surfactant containing hexafluoropropylene trimer base, and the general structure of this amphoteric fluorine-containing surfactant is as follows:
Wherein C
9f
17for perfluorinated nonene base, R
-for CH
2cOO
-, CH
2cH
2cOO
-, CH
2cH
2sO
3 -, CH
2cH
2cH
2sO
3 -, CH
2cH
2cH
2cH
2sO
3 -, CH
2cH
2cH
2cH
2cH
2sO
3 -or CH
2cH (OH) SO
3 -.
Another technical scheme of the present invention provides a kind of preparation method of above-mentioned amphoteric surfactant, comprises the following steps:
1), under acid binding agent existence, after perfluorinated nonene oxygen base benzene sulfonyl chloride passes through amidation process with N, N-dimethyl-1,3-propane diamine in solvent a, perfluorinated nonene oxygen base benzsulfamide tertiary amine intermediate is obtained through cooling, filtration, washing, drying and precipitation;
2) perfluorinated nonene oxygen base benzsulfamide tertiary amine intermediate is under acid binding agent exists, in solvent b with halogeno salt or sultones condensation quaterisation after, through cooling, the fluorine-containing surfactant obtaining amphoteric after precipitation;
The solvent a of reaction is selected from chloroform, oxolane or carbon tetrachloride;
The solvent b of reaction is selected from methyl alcohol, ethanol, DNF, acetonitrile, ketone.
In technical schemes more provided by the invention, halogeno salt or sultones are selected from sodium chloroacetate, chloropropionic acid sodium, chloroethyl sodium sulfonate, 1,3-propane sultone, Isosorbide-5-Nitrae-butane sultones, 1,5-pentanesulfonic acid lactone or 2-hydroxy chloride ethylsulfonic acid sodium.
In technical schemes more provided by the invention, acid binding agent is selected from triethylamine, pyridine, potash, triethylamine, sodium carbonate or NaOH.
In technical schemes more provided by the invention, step 1) described in perfluorinated nonene oxygen base benzene sulfonyl chloride, solvent a and N, N-dimethyl-1,3-propane diamine mass ratio be 5-10:20-40:1.
In technical schemes more provided by the invention, step 2) described in perfluorinated nonene oxygen base benzsulfamide tertiary amine, acid binding agent, the mass ratio of halogeno salt/sultones is 1-10:1-10:1 in solvent b.
In technical schemes more provided by the invention, the temperature of amidation process is 20-100 DEG C, and the reaction time is 0.5-8h.
In technical schemes more provided by the invention, the temperature of quaterisation is 20-100 DEG C, and the reaction time is 0.5-8h.
In technical schemes more of the present invention, perfluorinated nonene oxygen base benzene sulfonyl chloride is prepared from via once step:
1) under acid binding agent exists, the hexafluoropropylene trimer in phenol and solvent a is obtained by reacting intermediate perfluorinated nonene oxygen base phenyl ether;
2) perfluorinated nonene oxygen base phenyl ether is obtained by reacting intermediate perfluorinated nonene oxygen base benzene sulfonyl chloride in solvent b with chlorosulfonic acid;
Wherein said solvent a is oxolane, acetonitrile or carrene; Described solvent b is selected from chloroform, oxolane or carbon tetrachloride.
In some embodiments of the invention, chemical raw material used, solvent etc. are technical grade.
Drying of the present invention, refers to and to make in material water or solvent gasification by means of energy, and take away the process of generated steam.The drying mode that embodiments more of the present invention adopt is bake drying.It should be pointed out that the drying means that can reach same effect also includes but not limited to oven dry, vacuum drying, freeze drying, pneumatic conveying drying, microwave drying, infrared drying and dielectric dry etc.In certain embodiments of the present invention, baking temperature≤100 DEG C.
The term " filtration " that the present invention uses represents the operation be separated with nonfluid by fluid by medium under gravity or other External Force Actings, described medium includes but not limited to filter paper, gauze, filter core, pellicle, filter screen etc., in theory, the material containing loose structure can become the medium of filtration; The equipment filtered includes but not limited to vacuum or decompressor, pressue device, centrifugal device etc.
The water used in embodiments of the present invention is deionized water.
Unless explicitly stated otherwise in contrast, otherwise all scopes that the present invention quotes comprise end value.Such as, " temperature of described amidation process is 20-100 DEG C ", represents that the scope of temperature T is 20 DEG C≤T≤100 DEG C.
Beneficial effect of the present invention is:
Prepared by the present invention containing hexafluoropropylene trimer base amphoteric surfactant with perfluorinated nonene oxygen base benzene be oleophilic moiety, amphiprotic group is for hydrophilic segment.Between both sexes hydrophilic radical with methylene, ethylidene, propylidene, butylidene, pentylidene and 2-hydroxypropyl for connect bridge; Oleophilic moiety is connected by sulfonamide key with hydrophilic segment.Owing to having possessed above architectural feature, this amphoteric surfactant has had very high surface-active and lower critical micelle concentration, and wherein, surface tension can reach 19mN/m-20.5mN/m, significantly lower than the surface tension of the fluorine-containing surfactant of other type; Critical micelle concentration can reach 3.5 × 10
-5-6.7 × 10
-5mol/L, lower than the critical micelle concentration of the fluorine-containing surfactant of other type of similar structures.
The amphoteric surfactant of the perfluorinated nonene base obtained by the present invention has higher surface-active, and the surface tension of the aqueous solution of mass concentration 0.01% is at about 23mN/m.Decontamination and the washability of product are high, have better dispersiveness, foaming characteristic, levelability, wetability, lower toxicity etc., can be used for washing, fire-fighting, oil field, coating, textile finishing etc. than general anion, cationic surfactant.
Detailed description of the invention
The following stated be the preferred embodiment of the present invention, what the present invention protected is not limited to following preferred embodiment.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, the some distortion made and improvement, all belong to protection scope of the present invention.Raw material used in embodiment all can be obtained by commercial sources.
Embodiment 1
The first step: the synthesis (A) of perfluorinated nonene oxygen base phenyl ether
39g (0.5mol) phenol is added in 1000mL there-necked flask, 21g (0.5mol) potash, 500mL oxolane, heats 60 DEG C of backflows, slow dropping 225g (0.5mol) hexafluoropropylene trimer, drip off and continue reaction 4h, cooling, filter, washing, drying, precipitation obtains weak yellow liquid 243.7g, and yield is 93%.
Second step:
The synthesis (B) of perfluorinated nonene oxygen base benzene sulfonyl chloride
52.5g (0.1mol) perfluorinated nonene oxygen base phenyl ether is added in 500mL there-necked flask, 150mL ethyl, be warmed up to 20-80 DEG C, slowly drip 35g (0.3mol) chlorosulfonic acid, drip off and continue reaction 4h, cooling, filter, washing, dry, precipitation obtains brown liquid 60.5g, and yield is 97%.
3rd step
The synthesis (C) of perfluorinated nonene oxygen base benzsulfamide intermediate
311g (0.5mol) perfluorinated nonene oxygen base benzene sulfonyl chloride is added, 20g (0.5mol) NaOH, 500mL oxolane in 500mL there-necked flask, be heated to 70 DEG C, slowly drip 66.5g (0.65mol) N, N-dimethyl-1,3-propane diamine, drip off and continue reaction 6h, cooling, filter, washing, drying, precipitation obtains dark brown liquid 311.7g, and yield is 90.6%.
Embodiment 2
The condensation (D1) of perfluorinated nonene oxygen base benzsulfamide intermediate and sodium chloroacetate
6.88g (10mmol) perfluorinated nonene oxygen base benzsulfamide intermediate is added in 100mL there-necked flask, 25mL ethanol, be heated to 20 DEG C, the aqueous solution of slow dropping 1.39g (12mmol) sodium chloroacetate, drip off and continue reaction 6h, cooling, precipitation, vacuum drying obtains faint yellow solid 6.93g, and yield is 92.9%.
Embodiment 3
The condensation (D2) of perfluorinated nonene oxygen base benzsulfamide intermediate and chloropropionic acid sodium
6.88g (10mmol) perfluorinated nonene oxygen base benzsulfamide intermediate is added in 100mL there-necked flask, 25mL ethanol, be heated to 40 DEG C, the aqueous solution of slow dropping 1.73g (12mmol) sodium chloroacetate, drip off and continue reaction 8h, cooling, precipitation, vacuum drying obtains faint yellow solid 6.81g, and yield is 89.6%.
Embodiment 4
The condensation (D3) of perfluorinated nonene oxygen base benzsulfamide intermediate and chloroethyl sodium sulfonate
6.88g (10mmol) perfluorinated nonene oxygen base benzsulfamide intermediate is added in 100mL there-necked flask, 25mL methyl alcohol, be heated to 60 DEG C, the aqueous solution of slow dropping 1.99g (12mmol) chloroethyl sodium sulfonate, drip off and continue reaction 6h, cooling, precipitation, vacuum drying obtains faint yellow solid 7.05g, and yield is 88.6%.
Embodiment 5
The condensation (D4) of perfluorinated nonene oxygen base benzsulfamide intermediate and 1,3-propane sultone
6.88g (10mmol) perfluorinated nonene oxygen base benzsulfamide intermediate is added in 100mL there-necked flask, 25mL methyl alcohol, be heated to 60 DEG C, the methanol solution of slow dropping 1.34g (11mmol) 1,3-propane sultone, drips off and continues reaction 8h, cooling, precipitation, vacuum drying obtains faint yellow solid 6.79g, and yield is 83.8%.
Embodiment 6
The condensation (D5) of perfluorinated nonene oxygen base benzsulfamide intermediate and Isosorbide-5-Nitrae-butane sultones
6.88g (10mmol) perfluorinated nonene oxygen base benzsulfamide intermediate is added in 100mL there-necked flask, 25mL methyl alcohol, be heated to 60 DEG C, the methanol solution of slow dropping 1.50g (11mmol) Isosorbide-5-Nitrae-butane sultones, drips off and continues reaction 6h, cooling, precipitation, vacuum drying obtains faint yellow solid 6.43g, and yield is 78%.
Embodiment 7
The condensation (D6) of perfluorinated nonene oxygen base benzsulfamide intermediate and 1,5-pentanesulfonic acid lactone
6.88g (10mmol) perfluorinated nonene oxygen base benzsulfamide intermediate is added in 100mL there-necked flask, 25mL methyl alcohol, be heated to 80 DEG C, the methanol solution of slow dropping 1.65g (11mmol) 1,5-pentanesulfonic acid lactone, drips off and continues reaction 4h, cooling, precipitation, vacuum drying obtains faint yellow solid 6.24g, and yield is 74.5%.
Embodiment 8
The condensation (D7) of perfluorinated nonene oxygen base benzsulfamide intermediate and 2-hydroxy chloride ethylsulfonic acid sodium
6.88g (10mmol) perfluorinated nonene oxygen base benzsulfamide intermediate is added in 100mL there-necked flask, 25mL methyl alcohol, be heated to 60 DEG C, the aqueous solution of slow dropping 2.18g (12mmol) 2-hydroxy chloride ethylsulfonic acid sodium, drip off and continue reaction 6h, cooling, precipitation, vacuum drying obtains faint yellow solid 6.61g, and yield is 81.4%.
Embodiment 9
Take the amphoteric fluorine-containing surfactant of perfluorinated nonene base prepared in embodiment 2-8 respectively, be configured to the aqueous solution that mass concentration is 0.001%, 0.01%, 0.05%, 0.1%, 0.5% successively, leave standstill 1-10h, measure its surface tension respectively with surface tension apparatus.Below lowest surface tension and the critical micelle concentration data of the fluorine-containing surfactant synthesized by the present invention.
| Compound numbers | Lowest surface tension (mN/m) | Critical micelle concentration (mol/L) |
| D1 | 19.8 | 6.7×10 -5 |
| D2 | 19.4 | 3.1×10 -5 |
| D3 | 20.1 | 8.2×10 -5 |
| D4 | 19.7 | 7.7×10 -5 |
| D5 | 20.3 | 5.6×10 -5 |
| D6 | 20.0 | 4.2×10 -5 |
| D7 | 19.4 | 2.4×10 -5 |
Lowest surface tension below 20.2mN/m of all compounds prepared by the present invention, most of kind is at below 20mN/m, and minority can reach 19mN/m.The surface property of the perfluoroalkyl class surfactant (17mN/m) of this and straight chain type is suitable.Compared to the surface property of the perfluorinated nonene base class fluorine-containing surfactant of other report, the amphoteric surfactant surface-active synthesized by the present invention is higher.Visible, effectively can improve surface-active by the amphoterisation of perfluorinated nonene type surfactant.
Claims (8)
1., containing an amphoteric surfactant for perfluorinated nonene base, it is characterized in that, the general structure of described amphoteric fluorine-containing surfactant is as follows:
Wherein C
9f
17for perfluorinated nonene base, R
-for CH
2cOO
-, CH
2cH
2cOO
-, CH
2cH
2sO
3 -, CH
2cH
2cH
2sO
3 -, CH
2cH
2cH
2cH
2sO
3 -, CH
2cH
2cH
2cH
2cH
2sO
3 -or CH
2cH (OH) SO
3 -.
2. prepare a method for amphoteric surfactant as claimed in claim 1, it is characterized in that, comprise the following steps:
1), under acid binding agent existence, after perfluorinated nonene oxygen base benzene sulfonyl chloride passes through amidation process with N, N-dimethyl-1,3-propane diamine in solvent a, perfluorinated nonene oxygen base benzsulfamide tertiary amine intermediate is obtained through cooling, filtration, washing, drying and precipitation;
2) perfluorinated nonene oxygen base benzsulfamide tertiary amine intermediate is under acid binding agent exists, in solvent b with halogeno salt/sultones condensation quaterisation after, through cooling, the fluorine-containing surfactant obtaining amphoteric after precipitation;
The solvent a of described reaction is selected from chloroform, oxolane or carbon tetrachloride;
The solvent b of described reaction is selected from methyl alcohol, ethanol, DNF, acetonitrile, ketone.
3. method according to claim 2, it is characterized in that, described halogeno salt or sultones are selected from sodium chloroacetate, chloropropionic acid sodium, chloroethyl sodium sulfonate, 1,3-propane sultone, 1,4-butane sultones, 1,5-pentanesulfonic acid lactone or 2-hydroxy chloride ethylsulfonic acid sodium.
4. method according to claim 2, is characterized in that, described acid binding agent is selected from triethylamine, pyridine, potash, triethylamine, sodium carbonate or NaOH.
5. method according to claim 2, is characterized in that, step 1) described in perfluorinated nonene oxygen base benzene sulfonyl chloride, solvent a and N, N-dimethyl-1,3-propane diamine mass ratio be 5-10:20-40:1.
6. method according to claim 2, is characterized in that, step 2) described in perfluorinated nonene oxygen base benzsulfamide tertiary amine, acid binding agent, the mass ratio of halogeno salt/sultones is 1-10:1-10:1 in solvent b.
7. method according to claim 2, is characterized in that, the temperature of described amidation process is 20-100 DEG C, and the reaction time is 0.5-8h.
8. method according to claim 2, is characterized in that, the temperature of described quaterisation is 20-100 DEG C, and the reaction time is 0.5-8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410647872.7A CN104437239A (en) | 2014-11-14 | 2014-11-14 | Perfluorous-nonene-containing amphoteric surfactant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410647872.7A CN104437239A (en) | 2014-11-14 | 2014-11-14 | Perfluorous-nonene-containing amphoteric surfactant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104437239A true CN104437239A (en) | 2015-03-25 |
Family
ID=52884451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410647872.7A Pending CN104437239A (en) | 2014-11-14 | 2014-11-14 | Perfluorous-nonene-containing amphoteric surfactant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437239A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112351967A (en) * | 2018-07-02 | 2021-02-09 | 美利肯公司 | Method for preparing high-purity cis-cyclohexane-1, 2-diformate |
| CN114404859A (en) * | 2021-12-21 | 2022-04-29 | 程潇 | Preparation method of lithium battery fire extinguishing agent and lithium battery fire extinguishing test device |
| CN117486685A (en) * | 2023-10-30 | 2024-02-02 | 台州氟乐新材料合伙企业(有限合伙) | Preparation method of high-efficiency perfluorinated nonenyl ether |
-
2014
- 2014-11-14 CN CN201410647872.7A patent/CN104437239A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 王辉等: "羧基甜菜碱型两性氟表面活性剂的合成和表面活性", 《合成化学》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112351967A (en) * | 2018-07-02 | 2021-02-09 | 美利肯公司 | Method for preparing high-purity cis-cyclohexane-1, 2-diformate |
| KR20210028670A (en) * | 2018-07-02 | 2021-03-12 | 밀리켄 앤드 캄파니 | Method for producing a high purity salt of cis-cyclohexane-1,2-dicarboxylic acid |
| CN112351967B (en) * | 2018-07-02 | 2023-08-22 | 美利肯公司 | Process for preparing high purity cis-cyclohexane-1,2-dicarboxylic acid salts |
| KR102595570B1 (en) | 2018-07-02 | 2023-10-27 | 밀리켄 앤드 캄파니 | Method for preparing high purity salts of cis-cyclohexane-1,2-dicarboxylic acid |
| CN114404859A (en) * | 2021-12-21 | 2022-04-29 | 程潇 | Preparation method of lithium battery fire extinguishing agent and lithium battery fire extinguishing test device |
| CN117486685A (en) * | 2023-10-30 | 2024-02-02 | 台州氟乐新材料合伙企业(有限合伙) | Preparation method of high-efficiency perfluorinated nonenyl ether |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105983370B (en) | Saturated cardanol betaine surfactant, and preparation method and application thereof | |
| CN103865026B (en) | A kind of preparation method of the organic fluorinated silicone modified polyaminoester emulsion containing short fluorocarbon chain | |
| CN103446943B (en) | Gemini perfluoroalkylsulfonyloxybenzyl cationic surfactant as well as preparation and application thereof | |
| CN104437239A (en) | Perfluorous-nonene-containing amphoteric surfactant and preparation method thereof | |
| CN103270021A (en) | Derivatives of perfluoroalkoxy sulfosuccinates as surface-active surfactants | |
| CN105419958A (en) | Anti-staining soaping agent for acid dyes as well as preparation method and application of soaping agent | |
| CN102755855B (en) | Alkylaryl sulfonate type hyperbranched polymer surface active agent and preparation method thereof | |
| CN103111229A (en) | Gemini type fluorocarbon surfactant containing sulfonic group and preparation method thereof | |
| CN104190314B (en) | Aliphatic amine polyoxyethylene ether diethyl disulfonate surfactant and preparation method thereof | |
| CN103992247A (en) | Fatty alcohol polyoxypropylene ether sulfobetaine and alkali-free composite oil displacement composition | |
| CN106634894A (en) | Dual-cation fluorocarbon surfactant and preparation method thereof, application of dual-cation fluorocarbon surfactant as hydrophobic and oleophobic wetting reversal agent, as well as drilling fluid and application thereof | |
| CN104826543A (en) | Preparation method of quaternary ammonium salt Gemini surfactant containing alkyl amide ethyl | |
| CN102908937A (en) | Cationic type gemini fluorinated surfactant based on perfluorinated nonene and perfluorinated hexene and preparation method of cationic type gemini fluorinated surfactant | |
| CN106867405B (en) | A kind of hydrophobic coating and preparation method thereof based on polyamide-amide dendrimer | |
| CN103432959B (en) | Surface active agent containing hexafluoropropylene tripolymer group and preparation method thereof | |
| CN102924345A (en) | Preparation method and application of branched fluorine-containing cationic surfactant | |
| CA2469242A1 (en) | (per) fluoropolyether carboxylic acids and use thereof for the oleo-repellent paper sizing | |
| CN110818890A (en) | Super-spreading wetting agent and preparation method thereof | |
| CN103657512B (en) | One class perfluor ene-type anionic gemini surfactant and preparation method thereof | |
| CN102872751B (en) | Sulfonic acid dimeric surfactant based on perfluoroolefine and preparation method thereof | |
| CN103240034A (en) | Sulfonate type and sulfonate inner salt type fluorocarbon surfactant as well as preparation and applications thereof | |
| CN105504153A (en) | Fluorine-containing hydrophobic-associating surface-active polyacrylamide and preparation method thereof | |
| CN106566514B (en) | Alkali-free binary composite flooding composition and application thereof in high-temperature high-salinity oil reservoir | |
| CN103464049A (en) | Perfluorohexyl sulfonyloxy benzyl cation surfactant as well as preparation method and application thereof | |
| CN103657514A (en) | Preparation method of fluorine-containing non-ionic surface active agent and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150325 |