CN103657514A - Preparation method of fluorine-containing non-ionic surface active agent and application - Google Patents
Preparation method of fluorine-containing non-ionic surface active agent and application Download PDFInfo
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 45
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 31
- 239000011737 fluorine Substances 0.000 title claims abstract description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 perfluoroalkyl sulfuryl fluoride Chemical compound 0.000 claims abstract description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 26
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- KJESGYZFVCIMDE-UHFFFAOYSA-N 1-chloroethanol Chemical compound CC(O)Cl KJESGYZFVCIMDE-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 238000011938 amidation process Methods 0.000 claims description 7
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 6
- 229940124530 sulfonamide Drugs 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 3
- 239000000463 material Substances 0.000 claims 1
- 239000010865 sewage Substances 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000005935 Sulfuryl fluoride Substances 0.000 abstract 1
- 238000007112 amidation reaction Methods 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000005457 ice water Substances 0.000 description 6
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- FUVKFLJWBHVMHX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonamide Chemical compound NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FUVKFLJWBHVMHX-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- HSDJWNJDPDJOEV-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O HSDJWNJDPDJOEV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 231100000704 bioconcentration Toxicity 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- BEPGHZIEOVULBU-UHFFFAOYSA-N n,n'-diethylpropane-1,3-diamine Chemical compound CCNCCCNCC BEPGHZIEOVULBU-UHFFFAOYSA-N 0.000 description 1
- UQUPIHHYKUEXQD-UHFFFAOYSA-N n,n′-dimethyl-1,3-propanediamine Chemical compound CNCCCNC UQUPIHHYKUEXQD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a preparation method of a fluorine-containing non-ionic surface active agent and an application. The preparation method comprises the steps of carrying out amidation reaction on perfluoroalkyl sulfuryl fluoride and N, N'-dimethyl (ethyl)-1, 3-propane diamine to obtain an intermediate 1; after refining, adopting acetone as a solvent to react with ethylene oxide or chlorethyl alcohol to obtain an intermediate 2 (N'-3-(dimethyl(ethyl))-propyl-(N-perfluorobutylsulfonyl-N-epoxy)-amine); carrying out ring-opening reaction on the intermediate 2 and ethylene oxide according to different proportions to obtain the fluorine-containing non-ionic surface active agent. The preparation method disclosed by the invention has the advantages that the production cost of the surface active agent is low, the preparation method is simple, the requirement on production equipment is low, and the production process is simple; the yield is high, the fluorine-containing monomer conversion rate reaches 93%; the surface performance is excellent, the lowest surface tension of certain compound to water is below 20mN/m and the HLB (Hydrophile Lipophile Balance) value of the surface active agent is easily changed.
Description
Technical field
The present invention relates to preparation method and the purposes of fluorine-containing surfactant, relate in particular to the preparation method and application of fluorine nonionic surface active agent.
Background technology
Fluorocarbon surfactant is that a class receives much concern and a lot of special surfactant of achievement in research, and it has the outstanding features such as high surface, high thermal stability and high chemical stability.But perfluoro capryl sulphonyl compounds (PFOS) and perfluoro caprylic acid and its esters (PFOA) are as current application fluorocarbon surfactant the most widely, and it has received people's concern to the potential impact of environmental and human health impacts; Various experiments show: any degraded that can observe can occur hardly under various physico chemical factors for PFOS and PFOA, for current one of organic pollution of difficult degradation in the world, have very high bioconcentration and many internal organs of human body toxicity, various countries have forbidden its use successively.
Nonionic contains fluorocarbon surfactant as a class fluorocarbon surfactant, it is unionization in the aqueous solution, be not vulnerable to the impact that electrolyte and pH value change, than ionic fluorocarbon surfactant, be more soluble in organic solvent, simultaneously with ionic and the good compatibility of amphoteric surfactant.These features determine that it can be used as the stabilizing agent in efficient foam extinguishing chemical, be used as the solid of hydrocarbon or the wetting agent of liquid surface, dispersant, as the emulsifying agent of Fluorine containing olefine emulsion party, the detergent of metal surface, also can be used as the levelling agent of coating, cement, plastering.Easily the short carbon chain fluorine carbon nonionic surface active agent of degraded, becomes the main direction that nonionic surface active agent is researched and developed.
Summary of the invention
The object of the invention is to design the preparation method of fluorine nonionic ionic surface active agent, the substitute as perfluoro capryl sulphonyl compounds (PFOS) and perfluoro caprylic acid and its esters (PFOA), is applied to a plurality of fields.
Fluorine nonionic ionic surface active agent of the present invention, its molecular structural formula is:
Wherein, a is 4 ~ 6, b=1 or 2, r=1 ~ 14.
The preparation method of fluorine nonionic ionic surface active agent of the present invention, it is characterized in that: take carrene as solvent, by perfluoroalkyl sulfonyl fluoride and N, N '-dimethyl (ethyl)-1, 3-propane diamine, carry out amidation process, obtain intermediate 1(N-[3-(dimethyl (ethyl) ammonia)-propyl group] perfluoroalkyl sulfonamide), intermediate 1 be take acetone and is reacted with oxirane or chlorethanol as solvent, obtain intermediate 2(N '-3-(diethyl)-propyl group-(N-perfluoro butyl sulfonyl-N-epoxy radicals)-amine), intermediate 2 be take acetone as solvent, carry out ring-opening reaction with oxirane, the temperature of reaction is 5-60 ℃, obtain nonionic fluorine-containing surfactant.
In preparation method of the present invention, described take carrene as solvent, by perfluoroalkyl sulfonyl fluoride and N, N '-dimethyl (ethyl)-1, after the amidatioon of 3-propane diamine, react with oxirane or chlorethanol again, obtain intermediate 2, again with reacting ethylene oxide, prepare nonionic fluorine-containing surfactant, first step perfluoroalkyl sulfonyl fluoride and N, N '-dimethyl (ethyl)-1, 3-propane diamine amidation process is to make catalyst with triethylamine, catalyst loading is that 0.3 mole of alkyl sulfonyl fluorine is doubly measured, while reacting with oxirane or chlorethanol again, all to add NaOH to adjust PH to 7 ~ 8, in reaction system, the proportion of solvent accounts for the 50%-90% of gross weight.
In preparation method of the present invention, perfluoroalkyl sulfonyl fluoride and N, N '-dimethyl (ethyl)-1, the mol ratio that 3-propane diamine carries out amidation process is 1:1; Intermediate 1 N-[3-(dimethyl (ethyl) ammonia)-propyl group] the perfluoroalkyl sulfonamide mol ratio of reacting with oxirane or chlorethanol is 1:1; Intermediate 2(N '-3-(diethyl)-propyl group-(N-perfluoro butyl sulfonyl-N-epoxy radicals)-amine) be 1:1 ~ 1:13 with the mol ratio of oxirane.
Fluorine-containing nonionic ionic surface active agent of the present invention can be used as the emulsifying agent of chemical field, antistatic additive, the metal surface cleaning agent of mechanical field, the levelling agent of building field, the extinguishing chemical additive of fire-fighting domain, the foam flotation agents of field of metallurgy.
The preparation method of the fluorine-containing nonionic surface active agent of the present invention and the advantage of application are:
1, raw material is easy to get, and preparation method is simple, low to production equipment requirement, the advantages such as concise production process.
2, productive rate is high, and fluorochemical monomer conversion ratio reaches 93%.
3, surface property is excellent, and the surface tension of the aqueous solution of some compound is below 20mN/m.
4, by modifying the length of hydrophobic group, comparatively easily change surfactant HLB value.
5, usining compound of the present invention can obtain high surfaces activity, fluorine-containing surfactant that cost is low as active component, has higher practical value.
The specific embodiment
Below by embodiment, further illustrate the preparation method of fluorine-containing nonionic ionic surface active agent of the present invention, but be not the restriction to both sexes fluoride ion surfactant kind of the present invention.
Embodiment 1
The preparation of nonionic fluoride ion type surfactant.
Get 0.1mol perfluoro butyl sulfonic acid fluoride and 0.1mol N; N '-diethyl-1; 3-propane diamine carries out amidation process; carrene is made solvent; obtain intermediate 1(N-[3-(diethyl amino)-propyl group] perfluoro butyl sulfonamide); intermediate 1 is usingd acetone as solvent; react with oxirane or chlorethanol; obtain intermediate 2(N '-3-(diethyl)-propyl group-(N-perfluoro butyl sulfonyl-N-epoxy radicals)-amine); intermediate 2 is usingd acetone and is carried out ring-opening reaction as solvent and oxirane, obtains nonionic fluorine-containing surfactant.
Embodiment 2
N-[3-in embodiment 1 (diethyl amino)-propyl group] perfluoro butyl sulfonamide synthetic
Synthesis technique is as follows: in being furnished with three neck round-bottomed flasks of magneton, add appropriate carrene, 0.03mol triethylamine and 0.1mol N, N '-diethyl-1,3-propane diamine, under ice-water bath, drips 0.1mol perfluoro butyl sulfonic acid fluoride, then react 8 hours, revolve and steam to obtain yellow oil, with acetone recrystallization, obtain white crystal, its chemical expression is:
MS(412.09)；?F
19NMR：-85.952，-115.049，-123.705，-128.212；H
1NMR：2.322(6H,-CH
3),3.502(2H,-CH
2-),2.617(2H,-CH
2-,),1.766(2H,-CH
2-),3.488(-NH)。
Embodiment 3
Synthesizing of N '-3-in embodiment 1 (diethyl)-propyl group-(N-perfluoro butyl sulfonyl-N-epoxy radicals)-amine
Synthesis technique is as follows: in being furnished with three neck round-bottomed flasks of magneton, add proper amount of acetone, 0.1mol N-[3-(diethyl amino)-propyl group] perfluoro butyl sulfonamide, add a small amount of NaOH to adjust PH to 7 ~ 8, under ice-water bath, drip 0.1mol oxirane, then react 6 hours, continue to toast obtaining faint yellow thick thing after revolving steaming, Product Expression formula is:
MS(456.11);?H
1NMR:?3.60(2H,-CH
2-),?2.74(2H,-CH
2-),?2.55(2H,-CH
2-,),?2.36(2H,-CH
2-),?2.40(4H,-CH
2-),?1.51(2H,-CH
2-),1.02(6H,-CH
3)，2.0(-OH)。
Lowest surface tension: 19.8 mN/m, CMC value 4/1000.
Embodiment 4
Synthesizing of N '-3-in embodiment 1 (diethyl)-propyl group-(N-perfluoro butyl sulfonyl-N-4 epoxy radicals)-amine
Synthesis technique is as follows: in being furnished with three neck round-bottomed flasks of magneton; add proper amount of acetone, 0.1mol N '-3-(diethyl)-propyl group-(N-perfluoro butyl sulfonyl-N-epoxy radicals)-amine; add a small amount of NaOH to adjust PH to 7 ~ 8; under ice-water bath; drip 0.3mol oxirane; then react 6 hours, continue to toast obtaining yellow thick thing after revolving steaming, Product Expression formula is:
MS(584.16);?H
1NMR:?3.60(12H,-CH
2-),?2.65(2H,-CH
2-),?2.36(2H,-CH
2-,),2.40(4H,-CH
2-),?1.00(6H,-CH
3)，2.0(-OH)。
Lowest surface tension: 20.3 mN/m, CMC value: 3/1000.
Embodiment 5
The preparation of nonionic fluoride ion type surfactant.
Get 0.1mol perfluoro hexyl sulfuryl fluoride and 0.1mol N; N '-dimethyl-1; 3-propane diamine carries out amidation process; obtain intermediate 1(N-[3-(dimethylamino)-propyl group] perfluoro butyl sulfonamide); intermediate 1 is usingd acetone as solvent; react with oxirane or chlorethanol; obtain intermediate 2(N '-3-(dimethyl)-propyl group-(N-perfluoro butyl sulfonyl-N-epoxy radicals)-amine); intermediate 2 carries out ring-opening reaction with oxirane, obtains nonionic fluorine-containing surfactant.
Embodiment 6
N-[3-in embodiment 5 (dimethylamino)-propyl group] perfluoro hexyl sulfonamide synthetic
Synthesis technique is as follows: in being furnished with three neck round-bottomed flasks of magneton, add appropriate carrene, 0.03mol triethylamine and 0.1mol N, N '-dimethyl-1,3-propane diamine, under ice-water bath, drips 0.1mol perfluoro hexyl sulfuryl fluoride, then react 8 hours, suction filtration, obtains white crystal by dichloromethane rinse, and its chemical expression is:
MS (484.0);
1hNMR (400M, CDCl
3solvent peak calibration 7.26) δ: 1.791(d, 2H ,-CH
2-), 2.355(s, 6H ,-CH
3), 2.642(d, 2H ,-CH
2-), 3.502(d, 2H ,-CH
2-).
Embodiment 7
Synthesizing of N '-3-in embodiment 5 (dimethyl)-propyl group-(N-perfluoro hexyl sulfonyl-N-epoxy radicals)-amine
Synthesis technique is as follows: in being furnished with three neck round-bottomed flasks of magneton, add proper amount of acetone, 0.1mol N-[3-(dimethylamino)-propyl group] perfluoro hexyl sulfonamide, add a small amount of NaOH to adjust PH to 7 ~ 8, drip 0.1mol chlorethanol, then react 8 hours, revolve steaming, with absolute ethyl alcohol, wash out NaCl, then revolve and steam to obtain product, its expression formula is:
MS(558.4)；?F
19NMR：-85.932，-115.041，-123.694，-128.022；H
1NMR：3.63(2H,-CH
2-)，2.55(2H,-CH
2-),2.36(4H,-CH
2-,),1.49(2H,-CH
2-),2.27(6H,-CH
3),?2.0(-OH)。
Lowest surface tension: 18.1mN/m, CMC value: 2/1000
Embodiment 8
Synthesizing of N '-3-in embodiment 5 (dimethyl)-propyl group-(N-perfluoro hexyl sulfonyl-N-2 epoxy radicals)-amine
Synthesis technique is as follows: in being furnished with three neck round-bottomed flasks of magneton; add proper amount of acetone and 0.1mol N '-3-(dimethyl)-propyl group-(N-perfluoro hexyl sulfonyl-N-epoxy radicals)-amine; add a small amount of NaOH to adjust PH to 7 ~ 8; under ice-water bath; drip 0.1mol oxirane; then react 6 hours, continue to toast obtaining faint yellow thick thing after revolving steaming, Product Expression formula is:
MS(572.1)；?F
19NMR：-85.932，-115.041，-123.694，-128.022；H
1NMR：3.70(2H,-CH
2-)，3.56(2H,-CH
2-)，3.47(2H,-CH
2-)，2.53(2H,-CH
2-)，?2.36(4H,-CH
2-)，?1.49(2H,-CH
2-)，?2.27(6H,-CH
3),?2.0(-OH)。
Lowest surface tension: 21.2 mN/m, CMC value: 4/1000.
Embodiment 9
Synthesizing of N '-3-in embodiment 5 (dimethyl)-propyl group-(N-perfluoro hexyl sulfonyl-N-6 epoxy radicals)-amine
Synthesis technique is as follows: in being furnished with three neck round-bottomed flasks of magneton; add proper amount of acetone and 0.1mol N '-3-(dimethyl)-propyl group-(N-perfluoro hexyl sulfonyl-N-epoxy radicals)-amine; add a small amount of NaOH to adjust PH to 7 ~ 8; under ice-water bath; drip 0.5mol oxirane; then react 6 hours, continue to toast obtaining the thick thing of brown after revolving steaming, Product Expression formula is:
MS(748.21)；?F
19NMR：-85.932，-115.041，-123.694，-128.022；H
1NMR：3.70(2H,-CH
2-)，3.56(2H,-CH
2-)，3.47(2H,-CH
2-)，3.54(16H,-CH
2-)，?2.53(2H,-CH
2-)，?2.36(4H,-CH
2-,)，?1.49(2H,-CH
2-)，?2.27(6H,-CH
3),?2.0(-OH)。
Lowest surface tension: 22.4mN/m, CMC value: 3.5/1000
Fluorine-containing surfactant target product lowest surface tension table
The surface tension of the nonionic ionic surface active agent of low fluorocarbon chain is better than the fluorocarbon surfactant surface tension of same commodity, but current nonionic perfluoro capryl class surfactant, environmental and human health impacts is had to potential impact, and hard degradation, Er Bei various countries ban use of, so the fluorine-containing nonionic ionic surface active agent of low fluorocarbon chain can be used as the substitute of the surfactant of high fluorocarbon chain, use.
Claims (5)
1. the preparation method and application of fluorine-containing nonionic surface active agent, is characterized in that, its molecular structural formula is
Wherein, a is 4 ~ 6, b=1 or 2, r=1 ~ 14.
2. the preparation method and application of a Ju fluorine-containing nonionic surface active agent claimed in claim 1, is characterized in that: prepare new material, emulsifying agent, administer sewage and soil, solubilising disperses, metal surface cleaning agent, extinguishing chemical additive, the levelling agent of coating, cement and plastering.
3. the preparation method and application of a Ju fluorine-containing nonionic surface active agent claimed in claim 1, it is characterized in that: take toluene as solvent, by perfluoroalkyl sulfonyl fluoride and N, N '-dimethyl (ethyl)-1, 3-propane diamine, carry out amidation process, obtain intermediate 1 N-[3-(dimethyl (ethyl) ammonia)-propyl group] perfluoroalkyl sulfonamide, after institute's carrene recrystallization, take acetone as solvent, react with oxirane or chlorethanol again, obtain after intermediate 2 (N '-3-(dimethyl (ethyl))-propyl group-(N-perfluoroalkyl group sulfonyl-N-epoxy ethyl base)-amine), by different proportion, carry out ring-opening reaction with oxirane, obtain pure fluorine-containing nonionic surface active agent.
4. the preparation method and application of a Ju fluorine-containing nonionic surface active agent claimed in claim 2, it is characterized in that: described take toluene as solvent, by perfluoroalkyl sulfonyl fluoride and N, N '-dimethyl (ethyl)-1, after the amidatioon of 3-propane diamine, react with oxirane or chlorethanol again, obtain intermediate 2 and reacting ethylene oxide, prepare nonionic fluorine-containing surfactant, this three-step reaction is made catalyst with triethylamine, catalyst loading is that 1/3 mole of alkyl sulfonyl fluorine is doubly measured, and in reaction system, the proportion of solvent accounts for the 50%-90% of gross weight.
5. the preparation method and application of a Ju fluorine-containing nonionic surface active agent claimed in claim 2, is characterized in that: perfluoroalkyl sulfonyl fluoride and N, and N '-dimethyl (ethyl)-1, the mol ratio that 3-propane diamine carries out amidation process is 1:1; Intermediate 1 N-[3-(dimethyl (ethyl) ammonia)-propyl group] the perfluoroalkyl sulfonamide mol ratio of reacting with oxirane or chlorethanol is 1:1; Intermediate 2(N '-3-(dimethyl (ethyl))-propyl group-(N-perfluoro butyl sulfonyl-N-epoxy radicals)-amine) be 1:1 ~ 1:13 with the mol ratio of oxirane, reaction temperature is 10-60 ℃, obtains fluorine-containing nonionic surface active agent.
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| CN105817177A (en) * | 2015-01-28 | 2016-08-03 | 东莞东阳光科研发有限公司 | Fluorine-containing polyoxyethylene ether non-ionic surface active agent and preparation method thereof |
| CN111303399A (en) * | 2020-03-23 | 2020-06-19 | 东北石油大学 | Preparation method of demulsifier suitable for ternary combination flooding crude oil |
| CN112169693A (en) * | 2020-10-26 | 2021-01-05 | 蒲城驭腾新材料科技有限公司 | Compounding method of fluorocarbon surfactant |
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Cited By (7)
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| CN105817177A (en) * | 2015-01-28 | 2016-08-03 | 东莞东阳光科研发有限公司 | Fluorine-containing polyoxyethylene ether non-ionic surface active agent and preparation method thereof |
| CN104906996A (en) * | 2015-04-28 | 2015-09-16 | 三明市海斯福化工有限责任公司 | Sulfonate-type fluorine-containing surfactant and synthetic method and application thereof |
| CN111303399A (en) * | 2020-03-23 | 2020-06-19 | 东北石油大学 | Preparation method of demulsifier suitable for ternary combination flooding crude oil |
| CN111303399B (en) * | 2020-03-23 | 2022-07-15 | 东北石油大学 | Preparation method of demulsifier suitable for ASP flooding crude oil |
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| CN115340473A (en) * | 2021-04-28 | 2022-11-15 | 南开大学 | Environment-friendly fluorine-containing nonionic Gemini surfactant and preparation method and application thereof |
| CN115340473B (en) * | 2021-04-28 | 2024-05-28 | 南开大学 | Environment-friendly fluorine-containing nonionic Gemini surfactant, and preparation method and application thereof |
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