CN105504153A - Fluorine-containing hydrophobic-associating surface-active polyacrylamide and preparation method thereof - Google Patents
Fluorine-containing hydrophobic-associating surface-active polyacrylamide and preparation method thereof Download PDFInfo
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- CN105504153A CN105504153A CN201510996066.5A CN201510996066A CN105504153A CN 105504153 A CN105504153 A CN 105504153A CN 201510996066 A CN201510996066 A CN 201510996066A CN 105504153 A CN105504153 A CN 105504153A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 47
- 239000011737 fluorine Substances 0.000 title claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 29
- 238000003786 synthesis reaction Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 230000002209 hydrophobic effect Effects 0.000 claims description 25
- -1 perfluoroalkyl sulfonyl fluoride Chemical compound 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 19
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004422 alkyl sulphonamide group Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- HMRWGKIZOBXNRB-UHFFFAOYSA-N octane-1-sulfonyl fluoride Chemical compound CCCCCCCCS(F)(=O)=O HMRWGKIZOBXNRB-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005553 drilling Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract description 2
- 230000015784 hyperosmotic salinity response Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RMSHYQAVCSUECE-UHFFFAOYSA-N hexane-1-sulfonamide Chemical compound CCCCCCS(N)(=O)=O RMSHYQAVCSUECE-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011218 binary composite Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
Abstract
The invention discloses fluorine-containing hydrophobic-associating surface-active polyacrylamide which has the following molecular structure (please see the structure in the description), wherein x=100, y=10-20, z=0.05-1.5, n=4 or 6 or 8, and R and R' represent alkyl. The prepared polyacrylamide has the advantages that the excellent tackifying property, heat resistance and salt tolerance are achieved, the surface tension of water can be reduced to 24-32 mN/m, and the good application prospect on tertiary oil recovery, drilling fluid and paint is achieved.
Description
Technical field
The present invention relates to water-soluble polymer technical field, specifically a kind of fluorine-containing hydrophobic association surfactivity polyacrylamide and preparation method thereof.
Background technology
Tertiary oil recovery is the major measure improving oil recovery factor, wherein relies on polymer flooding to account for critical role.Polymkeric substance used for tertiary oil recovery is at present mainly PAM, but the PAM heatproof of routine, salt tolerant and anti-shear ability are poor, thus causes the recovery ratio of oil unsatisfactory.In order to raising recovery ratio that can be larger, existing many scholars propose to adopt complex oil displacing, i.e. binary and ternary composite driving.Such as: Chinese patent " binary combination flooding composition and method of making the same " CN102220120A; Chinese patent " improve recovery ratio composition and method of making the same " CN102277148A; Chinese patent " composition and method of making the same of recovery ratio can be increased substantially " CN102277146A; Chinese patent " displacement composition used for tertiary oil recovery and preparation method thereof " CN102220124A etc.The recovery ratio comparatively polymer flooding successful of binary and ternary composite driving, also there is certain defect simultaneously, desk research shows, polymkeric substance binary drive and ternary composite driving time, because there is migration velocity difference between different components, so can there is chromatographic separation phenomenon, cause the synergy between different oil-displacing agent to weaken, oil displacement efficiency is deteriorated.
Meanwhile, when synthesizing fluorine-containing polyacrylamide, water-soluble poor due to fluorine-containing hydrophobic monomer, generally adopts micellar copolymerization.But in preparation process, also there is a lot of shortcoming, first, in micellar copolymerization process, water-soluble poor due to fluorine-containing hydrophobic monomer, even if add tensio-active agent to form micella, the polyacrylamide fluorine content of synthesis is also little; Secondly, the last handling process removing tensio-active agent by complexity is needed after synthesis.
Summary of the invention
The object of the invention is: for the technical deficiency in the chromatographic fractionation effect of above-mentioned combination flooding and polymer synthesis process, provide and there is better tackifying and compared with fluorine-containing hydrophobic association polyacrylamide of the one of low surface tension and preparation method thereof simultaneously.
In order to achieve the above object, a kind of fluorine-containing hydrophobic association surfactivity polyacrylamide, has following molecular structure:
Wherein, x=100, y=10-20, z=0.05-1.5, n=4,6,8, R, R ' is alkyl.
A preparation method for fluorine-containing hydrophobic association surfactivity polyacrylamide, specifically comprises the following steps:
The first step: the synthesis of surfactivity fluorine-containing polymerisable macromolecule monomer HAPS
1., the synthesis of N-dialkyl group perfluorinated alkyl sulfonamide
Organic amine, triethylamine and organic solvent are uniformly mixed, then add perfluoroalkyl sulfonyl fluoride, be then warming up to 30 ~ 60 DEG C, continue reaction 4 ~ 10h; Reaction mixture obtains product N-dialkyl group perfluorinated octyl sulfuryl amine through washing, drying, underpressure distillation.
Wherein, raw materials used mol ratio is as follows:
Perfluoroalkyl sulfonyl fluoride: organic amine: triethylamine is 1:1 ~ 2:1.2 ~ 2;
Preferably, described washing successively through washing, 0.5% aqueous hydrochloric acid washes, saturated common salt washing, drying anhydrous sodium sulphate;
Preferably, described organic amine is one or more in dimethylamine, diethylamine, dipropyl amine, Di-n-Butyl Amine, methylethyl amine;
Preferably, described organic solvent is one or more in toluene, Virahol, isopropyl ether, acetone or dimethylbenzene;
Preferably, described perfluoroalkyl sulfonyl fluoride is one or more in perfluoro butyl sulfonic acid fluoride, perfluoro hexyl sulfonic acid fluoride, full-fluorine octyl sulfuryl fluoride.
2., the synthesis of β-chloroacrylic acid hydroxypropyl acrylate
By Propylene glycol monoacrylate and organic solvent mixing, 20 ~ 35 DEG C, pass into condition of nitrogen gas under, add thionyl chloride, under 40 DEG C ~ 60 DEG C conditions react 4 ~ 10h; Cooling, washing, drying, underpressure distillation obtains β-chloroacrylic acid hydroxypropyl acrylate;
Wherein, raw materials used mol ratio is as follows:
Propylene glycol monoacrylate: thionyl chloride is 1:1.5 ~ 2;
Described organic solvent is one or more in Virahol, acetone, methylene dichloride, pyridine or tetrahydrofuran (THF);
Adopt NaOH solution washing to neutral during washing; Drying anhydrous sodium sulphate.
3., the synthesis of macromonomer HAPS
By N-dialkyl group perfluorinated alkyl sulfonamide, organic solvent mixing, under passing into condition of nitrogen gas, add β-chloroacrylic acid hydroxypropyl acrylate, at 30 ~ 50 DEG C, after reaction 20 ~ 48h, cooling, washing, drying, underpressure distillation obtain surfactivity fluorine-containing polymerisable macromolecule monomer HAPS;
Wherein, raw materials used mol ratio is as follows:
β-chloroacrylic acid hydroxypropyl acrylate: N-dialkyl group perfluorinated alkyl sulfonamide is 1.5 ~ 2:1;
Described washing successively through 0.05%HCl, saturated common salt water washing, drying anhydrous sodium sulphate;
Wherein, described organic solvent is one or more in toluene, Virahol, isopropyl ether, acetone or dimethylbenzene.
Second step: the synthesis of fluorine-containing hydrophobic association polyacrylamide
Add HAPS monomer, AM at configuration pH in the AMPS aqueous solution of 7, control AMPS, AM and HAPS monomer total mass number is 5 ~ 25%, and wherein the mol ratio of AM, AMPS and HAPS monomer is 100:10 ~ 20:0.05 ~ 1.5; Ultrasonic rear stirring, passes into nitrogen, adds the initiator accounting for monomer total mass 0.2% ~ 1%, and control temperature is at 30 ~ 50 DEG C; After reaction 4 ~ 10h, obtain colloidal product, washing, obtains white depositions, dries and pulverizes, obtain fluorine-containing hydrophobic association polyacrylamide;
Ammonium persulphate and the S-WAT of described initiator to be mass ratio be 1:1, or mass ratio is Potassium Persulphate and the sodium bisulfite of 1:1.
A kind of fluorine-containing hydrophobic association surfactivity polyacrylamide and preparation method thereof, its advantage is:
1., fluorine-containing surface active monomer is introduced in the molecule, fluorocarbon chain has extremely strong thermostability and chemical stability, therefore the polyacrylamide synthesized has stronger heat-resisting property, the surface tension of water can be reduced to 24 ~ 32mN/m, all have a good application prospect in tertiary oil recovery, drilling fluid and coating;
2., fluorine carbon hydrophobic grouping has lower internal cohesive energy and surface energy, makes the polymkeric substance synthesized have stronger thickening property and lower surface tension;
3., do not add other tensio-active agent in polymer preparation process, cost is low.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the fluorine-containing hydrophobic association polyacrylamide of embodiment one gained;
Embodiment
A kind of fluorine-containing hydrophobic association surfactivity polyacrylamide, producing principle is: first synthesis has surface-active fluorine-containing polymerisable macromolecule monomer HAPS, then adopts emulsifier-free emulsion polymerization to obtain fluorine-containing hydrophobic association polyacrylamide HAPS and acrylamide, AMPS.
Below in conjunction with example, the present invention is further illustrated:
Example one
The first step: the synthesis of surfactivity fluorine-containing polymerisable macromolecule monomer HAPS
1., the synthesis of N-dimethyl perfluoro alkyl sulfonamide
0.1mol dimethylamine, 0.08mol triethylamine and 100mL Virahol are joined spherical reflux condensing tube is housed, temperature takes into account in the there-necked flask of agitator, be uniformly mixed, in reaction system, slowly 0.05mol full-fluorine octyl sulfuryl fluoride is dripped by constant pressure funnel, then be warming up to 40 DEG C, continue reaction 6h.Reaction mixture is washed successively, 0.5% aqueous hydrochloric acid is washed, saturated common salt washing, and then use anhydrous sodium sulfate drying, underpressure distillation obtains product N-dimethyl perfluoro octyl group sulphonamide.
2., the synthesis of β-chloroacrylic acid hydroxypropyl acrylate
The Propylene glycol monoacrylate of 0.1mol and 100mL methylene dichloride are joined spherical reflux condensing tube is housed, temperature takes into account in the there-necked flask of agitator, under agitation pass into nitrogen, in reaction system, slowly dripped the thionyl chloride of 0.15mol by constant pressure funnel under 25 DEG C of conditions, after being added dropwise to complete, 8h is reacted, the tail gas alkali liquor absorption produced in reaction process under 40 DEG C of conditions.After having reacted, system is cooled to room temperature, add NaOH solution washing to neutral, anhydrous sodium sulfate drying, underpressure distillation, finally obtains β-chloroacrylic acid hydroxypropyl acrylate.
3., the synthesis of macromonomer HAPS
In there-necked flask, add 0.01molN-dimethyl perfluoro alkyl sulfonamide, 150ml Virahol, vigorous stirring also passes into nitrogen, is slowly added drop-wise in there-necked flask by 0.02mol β-chloroacrylic acid hydroxypropyl acrylate, reacts 28h after dropwising.Cooled by product after having reacted, use 0.05%HCl, saturated common salt water washing respectively, with anhydrous sodium sulfate drying, underpressure distillation obtains surfactivity fluorine-containing polymerisable macromolecule monomer HAPS.
Second step: the synthesis of fluorine-containing hydrophobic association polyacrylamide
Add HAPS monomer, AM at preparation pH in the AMPS aqueous solution of 7, control AMPS, AM and HAPS monomer total mass number is 20%, and wherein the mol ratio of AM, AMPS and HAPS monomer is 100:10:0.1; Rapid stirring after ultrasonic 30min, passes into nitrogen 30min, and add the ammonium persulphate-S-WAT accounting for monomer total mass 0.05% and make initiator, control temperature is at 40 DEG C; After reaction 6h, obtain colloidal product, repeatedly wash on a small quantity with ethanol, obtain white depositions, dry and pulverize, obtain fluorine-containing hydrophobic association polyacrylamide.
Infrared spectrum analysis is carried out to the fluorine-containing hydrophobic association polyacrylamide finally obtained, obtains the infrared spectrum of Fig. 1.
Wherein, 3430.36cm
-1, 3203.91cm
-1place is the N-H stretching vibration peak of acid amides, 1655.15cm
-1for carbonylic stretching vibration absorption peak, 2933.03cm
-1and 2869.6cm
-1place is-CH
2c-H symmetrical stretching vibration peak, 1452.75cm
-1for the flexural vibration of C-H, 1307.91cm
-1for C-N stretching vibration, 1185.18and1115.18cm
-1wei – CF
2, CF
3obtain stretching vibration absorption peak, 1040.49cm
-1wei – SO
3-stretching vibration absorption peak.
The performance evaluation of fluorine-containing surfactants polymkeric substance: the surface-active polymer aqueous solution of preparation 0.2%, the surface tension recording polymkeric substance with JK99B type Full-automatic tension instrument is 30.2mN/m; The viscosity recording polymkeric substance with the BROOKFIELD III type viscometer of Brookfield company of the U.S. is 518.2mpa.s;
Example two
The first step: the synthesis of surfactivity fluorine-containing polymerisable macromolecule monomer HAPS
1., the synthesis of N-diethyl perfluorobutylsulfonamide
0.2mol diethylamine, 0.2mol triethylamine and 100ml isopropyl ether are joined spherical reflux condensing tube is housed, temperature takes into account in the there-necked flask of agitator, be uniformly mixed, in reaction system, slowly 0.1mol full-fluorine octyl sulfuryl fluoride is dripped by constant pressure funnel, then be warming up to 60 DEG C, continue reaction 10h.Reaction mixture is washed successively, 0.5% aqueous hydrochloric acid is washed, saturated common salt washing, and then use anhydrous sodium sulfate drying, underpressure distillation obtains product N-diethyl perfluorobutylsulfonamide.
2., the synthesis of β-chloroacrylic acid hydroxypropyl acrylate
0.5mol Propylene glycol monoacrylate and 150ml acetone are joined spherical reflux condensing tube is housed, temperature takes into account in the there-necked flask of agitator, under agitation pass into nitrogen, under 20 DEG C of conditions, in reaction system, slowly 1mol thionyl chloride is dripped by constant pressure funnel after completing, after being added dropwise to complete, 6h is reacted, the tail gas alkali liquor absorption produced in reaction process under 50 DEG C of conditions.After having reacted, system is cooled to room temperature, add NaOH solution washing to neutral, anhydrous sodium sulfate drying, underpressure distillation, finally obtains β-chloroacrylic acid hydroxypropyl acrylate.
3., the synthesis of macromonomer HAPS
In there-necked flask, add N-diethyl perfluorobutylsulfonamide, the 150ml Virahol of 0.1mol, vigorous stirring also passes into nitrogen, is slowly added drop-wise in there-necked flask by the β-chloroacrylic acid hydroxypropyl acrylate of 0.2mol, reacts 48h after dropwising.Cooled by product, use 0.05%HCl, saturated common salt water washing respectively, with anhydrous sodium sulfate drying, underpressure distillation obtains surfactivity fluorine-containing polymerisable macromolecule monomer HAPS.
Second step: the synthesis of fluorine-containing hydrophobic association polyacrylamide
Add HAPS monomer, AM at preparation pH in the AMPS aqueous solution of 8, control AMPS, AM and HAPS monomer total mass number is 10%, and wherein the mol ratio of AM, AMPS and HAPS monomer is 100:15:1.5; Rapid stirring after ultrasonic 30min, passes into nitrogen 30min, and add the Potassium Persulphate-sodium bisulfite accounting for monomer total mass 0.3% and make initiator, control temperature is at 45 DEG C; After reaction 10h, obtain colloidal product, repeatedly wash on a small quantity with ethanol, obtain white depositions, dry and pulverize, obtain fluorine-containing hydrophobic association polyacrylamide.
The performance evaluation of fluorine-containing surfactants polymkeric substance: the surface-active polymer aqueous solution of preparation 0.4%, the surface tension recording polymkeric substance with JK99B type Full-automatic tension instrument is 23.9mN/m; The viscosity recording polymkeric substance with the BROOKFIELD III type viscometer of Brookfield company of the U.S. is 7429.5mpa.s;
Example three
The first step: the synthesis of surfactivity fluorine-containing polymerisable macromolecule monomer HAPS
1., N-methyl, the synthesis of ethylperfluoro hexyl sulphonamide
The N-methyl ethyl-amine of 0.6mol, the triethylamine of 0.75mol and 150ml acetone are joined spherical reflux condensing tube is housed, temperature takes into account in the there-necked flask of agitator, be uniformly mixed, in reaction system, slowly dripped the perfluoro hexyl sulfonic acid fluoride of 0.4mol by constant pressure funnel; Then be warming up to 35 DEG C, continue reaction 5h.Reaction mixture is washed successively, 0.5% aqueous hydrochloric acid is washed, saturated common salt washing, and then use anhydrous sodium sulfate drying, underpressure distillation obtains product N-methyl, ethylperfluoro hexyl sulphonamide.
2., the synthesis of β-chloroacrylic acid hydroxypropyl acrylate
The Propylene glycol monoacrylate of 0.5mol and the tetrahydrofuran (THF) of 130ml are joined spherical reflux condensing tube is housed, temperature takes into account in the there-necked flask of agitator, under agitation pass into nitrogen, under 25 DEG C of conditions, in reaction system, slowly dripped the thionyl chloride of 0.75mol by constant pressure funnel after completing, after being added dropwise to complete, 80h is reacted, the tail gas alkali liquor absorption produced in reaction process under 50 DEG C of conditions.After having reacted, system is cooled to room temperature, add NaOH solution washing to neutral, anhydrous sodium sulfate drying, underpressure distillation, finally obtains β-chloroacrylic acid hydroxypropyl acrylate.
3., the synthesis of macromonomer HAPS
In there-necked flask, add the N-methyl of 0.1mol, ethylperfluoro hexyl sulphonamide, 80ml Virahol, vigorous stirring also passes into nitrogen, is slowly added drop-wise in there-necked flask by the β-chloroacrylic acid hydroxypropyl acrylate of 0.15mol, reacts 40h after dropwising; Cooled by product, use 0.05%HCl, saturated common salt water washing respectively, with anhydrous sodium sulfate drying, underpressure distillation obtains surfactivity fluorine-containing polymerisable macromolecule monomer HAPS.
Second step: the synthesis of fluorine-containing hydrophobic association polyacrylamide
Add HAPS monomer, AM at preparation pH in the AMPS aqueous solution of 7.5, control AMPS, AM and HAPS monomer total mass number is 25%, and wherein the mol ratio of AM, AMPS and HAPS monomer is 100:20:0.3; Rapid stirring after ultrasonic 30min, passes into nitrogen 30min, and add the Potassium Persulphate-sodium bisulfite accounting for monomer total mass 0.8% and make initiator, control temperature is at 400 DEG C; After reaction 6h, obtain colloidal product, repeatedly wash on a small quantity with ethanol, obtain white depositions, dry and pulverize, obtain fluorine-containing hydrophobic association polyacrylamide.
The performance evaluation of fluorine-containing surfactants polymkeric substance: the surface-active polymer aqueous solution of preparation 0.3%, the surface tension recording polymkeric substance with JK99B type Full-automatic tension instrument is 27.4.2mN/m; The viscosity recording polymkeric substance with the BROOKFIELD III type viscometer of Brookfield company of the U.S. is 3273.3mpa.s;
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a fluorine-containing hydrophobic association surfactivity polyacrylamide, it is characterized in that, molecular structure is as follows:
Wherein, x=100, y=10-20, z=0.05-1.5, n=4,6,8, R, R ' is alkyl.
2. the preparation method of fluorine-containing hydrophobic association surfactivity polyacrylamide as claimed in claim 1, is characterized in that: comprise the steps:
The first step: the synthesis of surfactivity fluorine-containing polymerisable macromolecule monomer HAPS
1., the synthesis of N-dialkyl group perfluorinated alkyl sulfonamide
Organic amine, triethylamine and organic solvent are mixed, then adds perfluoroalkyl sulfonyl fluoride, be then warming up to 30 ~ 60 DEG C, continue reaction 4 ~ 10h; Reaction mixture obtains product N-dialkyl group perfluorinated octyl sulfuryl amine through washing, drying, underpressure distillation;
Wherein, raw materials used mol ratio is as follows:
Perfluoroalkyl sulfonyl fluoride: organic amine: triethylamine is 1:1 ~ 2:1.2 ~ 2;
2., the synthesis of β-chloroacrylic acid hydroxypropyl acrylate
By Propylene glycol monoacrylate and organic solvent mixing, 20 ~ 35 DEG C, pass into condition of nitrogen gas under, add thionyl chloride, under 40 DEG C ~ 60 DEG C conditions react 4 ~ 10h; Cooling, washing, drying, underpressure distillation obtains β-chloroacrylic acid hydroxypropyl acrylate;
Wherein, raw materials used mol ratio is as follows:
Propylene glycol monoacrylate: thionyl chloride is 1:1.5 ~ 2;
3., the synthesis of macromonomer HAPS
By N-dialkyl group perfluorinated alkyl sulfonamide, organic solvent mixing, under passing into condition of nitrogen gas, add β-chloroacrylic acid hydroxypropyl acrylate, at 30 ~ 50 DEG C, after reaction 20 ~ 48h, cooling, washing, drying, underpressure distillation obtain surfactivity fluorine-containing polymerisable macromolecule monomer HAPS;
Wherein, raw materials used mol ratio is as follows:
β-chloroacrylic acid hydroxypropyl acrylate: N-dialkyl group perfluorinated alkyl sulfonamide is 1.5 ~ 2:1;
Second step: the synthesis of fluorine-containing hydrophobic association polyacrylamide
HAPS monomer, AM is added in the AMPS aqueous solution of 7 ~ 8 at preparation pH; Control AMPS, AM and HAPS monomer total mass number is 5 ~ 25%; Ultrasonic rear stirring, passes into nitrogen, adds the initiator accounting for monomer total mass 0.2% ~ 1%, and control temperature is at 30 ~ 50 DEG C; After reaction 4 ~ 10h, obtain colloidal product, washing, obtains white depositions, dries and pulverizes, obtain fluorine-containing hydrophobic association polyacrylamide;
Wherein, the mol ratio of AM, AMPS and HAPS monomer is 100:10 ~ 20:0.05 ~ 1.5.
3. method as claimed in claim 2, is characterized in that: the step of the described the first step 1. in, described washing is washed through washing, 0.5% aqueous hydrochloric acid successively, saturated common salt washing, drying anhydrous sodium sulphate.
4. method as claimed in claim 2, is characterized in that: described step 2. in, adopt NaOH solution washing to neutral during washing; Drying anhydrous sodium sulphate.
5. method as claimed in claim 2, is characterized in that: described step 3. in, described washing is successively through 0.05%HCl, saturated common salt water washing.
6. method as claimed in claim 2, is characterized in that: the step of the described the first step 1. in, described organic amine is one or more in dimethylamine, diethylamine, dipropyl amine, Di-n-Butyl Amine, methylethyl amine.
7. method as claimed in claim 2, is characterized in that: the step of the described the first step 1., step 3. in, described organic solvent is one or more in toluene, Virahol, isopropyl ether, acetone or dimethylbenzene.
8. method as claimed in claim 2, is characterized in that: described step 2. in, described organic solvent is one or more in Virahol, acetone, methylene dichloride, pyridine or tetrahydrofuran (THF).
9. method as claimed in claim 2, is characterized in that: the step of the described the first step 1. in, described perfluoroalkyl sulfonyl fluoride is one or more in perfluoro butyl sulfonic acid fluoride, perfluoro hexyl sulfonic acid fluoride, full-fluorine octyl sulfuryl fluoride.
10. method as claimed in claim 2, is characterized in that: in second step, ammonium persulphate and the S-WAT of described initiator to be ratio of quality and the number of copies be 1:1, or ratio of quality and the number of copies is Potassium Persulphate and the sodium bisulfite of 1:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018031512A1 (en) * | 2016-08-10 | 2018-02-15 | 3M Innovative Properties Company | A fluorinated tackifier for pressure sensitive adhesives and pressure sensitive adhesives articles |
| CN109609109A (en) * | 2019-01-17 | 2019-04-12 | 长江大学 | A kind of profile control system and preparation method thereof |
| CN113265023A (en) * | 2021-06-22 | 2021-08-17 | 西南石油大学 | Nano lubricant for drilling fluid and preparation method and application thereof |
| CN113801040A (en) * | 2021-10-11 | 2021-12-17 | 石家庄圣泰化工有限公司 | Synthesis method of N, N-dimethyl trifluoromethanesulfonamide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293860A (en) * | 2008-06-05 | 2008-10-29 | 浙江工业大学 | Quaternary ammonium salt fluorine surfactant preparing method |
| CN102924345A (en) * | 2012-10-11 | 2013-02-13 | 浙江工业大学 | Preparation method and application of branched fluorine-containing cationic surfactant |
| CN103275270A (en) * | 2013-04-17 | 2013-09-04 | 山东大学（威海） | Method for preparing fluorocarbon-modified polyacrylamide by using soap-free emulsion method |
| CN103408443A (en) * | 2013-08-14 | 2013-11-27 | 中国海洋石油总公司 | Water-soluble polymer containing fluorine modified diallylamine and preparation method thereof |
-
2015
- 2015-12-25 CN CN201510996066.5A patent/CN105504153B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293860A (en) * | 2008-06-05 | 2008-10-29 | 浙江工业大学 | Quaternary ammonium salt fluorine surfactant preparing method |
| CN102924345A (en) * | 2012-10-11 | 2013-02-13 | 浙江工业大学 | Preparation method and application of branched fluorine-containing cationic surfactant |
| CN103275270A (en) * | 2013-04-17 | 2013-09-04 | 山东大学（威海） | Method for preparing fluorocarbon-modified polyacrylamide by using soap-free emulsion method |
| CN103408443A (en) * | 2013-08-14 | 2013-11-27 | 中国海洋石油总公司 | Water-soluble polymer containing fluorine modified diallylamine and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HANS-JOACHIM LEHMLER,ETL: "Synthesis and structure of environmentally relevant perfluorinated sulfonamides", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
| SHI-TAO FU,ETL: "N,N-dialkyl perfluoroalkanesulfonamides: Synthesis, characterization and properties", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018031512A1 (en) * | 2016-08-10 | 2018-02-15 | 3M Innovative Properties Company | A fluorinated tackifier for pressure sensitive adhesives and pressure sensitive adhesives articles |
| CN109563383A (en) * | 2016-08-10 | 2019-04-02 | 3M创新有限公司 | Fluorination tackifier and pressure-sensitive adhesive article for contact adhesive |
| CN109563383B (en) * | 2016-08-10 | 2021-02-19 | 3M创新有限公司 | Fluorinated tackifiers for pressure sensitive adhesives and pressure sensitive adhesive articles |
| CN109609109A (en) * | 2019-01-17 | 2019-04-12 | 长江大学 | A kind of profile control system and preparation method thereof |
| CN109609109B (en) * | 2019-01-17 | 2020-11-03 | 长江大学 | Profile control system and preparation method thereof |
| CN113265023A (en) * | 2021-06-22 | 2021-08-17 | 西南石油大学 | Nano lubricant for drilling fluid and preparation method and application thereof |
| CN113265023B (en) * | 2021-06-22 | 2022-03-01 | 西南石油大学 | Nano lubricant for drilling fluid and preparation method and application thereof |
| CN113801040A (en) * | 2021-10-11 | 2021-12-17 | 石家庄圣泰化工有限公司 | Synthesis method of N, N-dimethyl trifluoromethanesulfonamide |
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Denomination of invention: A fluorinated hydrophobic surface active polyacrylamide and its preparation method Granted publication date: 20170620 Pledgee: Fushun Dongzhou sub branch of Bank of China Ltd. Pledgor: FUSHUN DRAGON CHEMICAL PLANT Registration number: Y2024210000041 |