CN112691607A - Gemini type fluorine-containing surfactant and preparation method and application thereof - Google Patents
Gemini type fluorine-containing surfactant and preparation method and application thereof Download PDFInfo
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- CN112691607A CN112691607A CN202011570837.1A CN202011570837A CN112691607A CN 112691607 A CN112691607 A CN 112691607A CN 202011570837 A CN202011570837 A CN 202011570837A CN 112691607 A CN112691607 A CN 112691607A
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- perfluoropolyether
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- gemini
- fluorine
- surfactant
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 82
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 47
- 239000011737 fluorine Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 105
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 53
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 40
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 32
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 claims abstract description 20
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- 229920001400 block copolymer Polymers 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 238000012661 block copolymerization Methods 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000012674 dispersion polymerization Methods 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 73
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 12
- 238000009833 condensation Methods 0.000 abstract description 11
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 229910052697 platinum Inorganic materials 0.000 abstract description 6
- 230000005494 condensation Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000004698 Polyethylene Substances 0.000 abstract 1
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- RRRXPPIDPYTNJG-UHFFFAOYSA-N perfluorooctanesulfonamide Chemical compound NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RRRXPPIDPYTNJG-UHFFFAOYSA-N 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 31
- 238000010992 reflux Methods 0.000 description 31
- 239000007864 aqueous solution Substances 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 239000012295 chemical reaction liquid Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 238000001914 filtration Methods 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 239000005046 Chlorosilane Substances 0.000 description 15
- 239000011230 binding agent Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 15
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000004709 Chlorinated polyethylene Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000002274 desiccant Substances 0.000 description 11
- -1 diamine compound Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 7
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical group CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 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 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000002444 silanisation Methods 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001265 acyl fluorides Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000007847 digital PCR Methods 0.000 description 1
- 230000001779 embryotoxic effect Effects 0.000 description 1
- 231100000238 embryotoxicity Toxicity 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000010025 steaming Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- 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
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/26—Tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a gemini fluorine-containing surfactant and a preparation method and application thereof, wherein perfluoro polyether alcohol (PFPE-OH) reacts with halogenated allyl to introduce unsaturated double bonds; then carrying out hydrosilylation reaction with methylhydrogen dichlorosilane under the catalysis of platinum; the obtained intermediate product reacts with carbon magnesium polyethylene glycol monomethyl ether to generate perfluoropolyether-polyethylene glycol-methyl chlorosilane (PFPE-SiCl-PEG); further hydrolytic condensation to obtain the Gemini type fluorine-containing surfactant. The hydrophobic group adopted by the surfactant is perfluoropolyether, so that the problems that the common fluorine surfactants such as perfluorooctyl sulfonamide (PFOS), perfluorooctane sulfonic acid (PFOA) and the like are difficult to degrade and accumulate toxicity due to long carbon chain fluoroalkyl groups are avoided, the hydrophobicity of the surfactant is easy to control by controlling the molecular weight of the segment of the perfluoropolyether, and the surfactant has very high hydrophobic efficiency. The gemini fluorine-containing surfactant is simple and convenient in preparation process, mild in reaction condition, only conventional equipment is needed for production, and the gemini fluorine-containing surfactant is suitable for industrial production.
Description
Technical Field
The invention relates to a Gemini type fluorine-containing surfactant, a preparation method and application thereof, belonging to the field of synthesis of fine chemicals and auxiliaries.
Background
Perfluoropolyethers (PFPE) are discovered at the earliest in the 60 th 20 th century, are relatively special perfluoropolymer compounds, have the average molecular weight of 500-15000, and contain no hydrogen elements and only consist of carbon, fluorine and oxygen elements, so that the product has a series of characteristics of heat resistance, oxidation resistance, radiation resistance, corrosion resistance, non-combustion and the like.
The prior art discloses a perfluoropolyether fluorocarbon surfactant, a preparation method and application thereof, belongs to the technical field of high molecular surfactants, can be used as an oil phase component in a PCR method, and can be applied to liquid drop type digital PCR, the stability of liquid drops can be ensured, and the perfluoropolyether fluorocarbon surfactant has excellent surface performance. The prior art discloses a long-chain perfluoropolyether surfactant and a preparation method thereof, wherein the long-chain perfluoropolyether surfactant comprises the following components: firstly, adding perfluoropolyether acyl fluoride ether and a solvent into a reaction kettle, adding a diamine compound while stirring, heating the reaction kettle, and cooling to room temperature after the reaction is finished; and then carrying out reduced pressure treatment and column chromatography purification, finally adding chloroacetate solution and water into the compound, heating and stirring, and obtaining the long-chain perfluoropolyether surfactant after the reaction is finished.
Perfluoropolyethers can be classified into 4-molecular structures of type K, type Y, type Z, type D, depending on the monomers used and the polymerization process: (1) k type structural formula is CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3) COF, which is a series of branched polymers formed by anionic polymerization of hexafluoropropylene oxide (HFPO) under the catalysis of CsF or KF and the like; (2) y-type structural formula is CF3O(C3F6O)m(CF2O)nCF3The ultraviolet light curing agent is a polymer formed by photo-oxidizing Hexafluoropropylene (HFP) under the action of ultraviolet light, and the molecular weight is generally between 1000 and 10000; (3) z-type structural formula is CF3(C2F4O)m(CF2O)nCF3The polymer is a linear chain polymer formed by photo-oxidation of Tetrafluoroethylene (TFE) under ultraviolet irradiation, and the molecular weight is generally between 1000 and 100000; (4) d type structural formula is C3F7O(CF2CF2CF2O)mC2F5It isA polymer obtained by directly fluorinating a polymerization product of tetrafluorooxetane.
The K-type perfluoropolyether belongs to acyl fluoride oligomers, the terminal group of the K-type perfluoropolyether has reactivity, and can be further reacted to generate various derivatives, such as perfluoropolyether carboxylic acid (PFPE-COOH), perfluoropolyether alcohol (PFPE-OH), perfluoropolyether terminal olefin (PFPE-C = C) and the like, and further reacted to synthesize the corresponding fluorocarbon surfactant. In addition, PFOS/PFOA is a new class of organic pollutants of great interest, with high environmental persistence and bioaccumulation. Environmental epidemiological studies have revealed a high degree of correlation between PFOS/PFOA exposure in humans and a variety of adverse health effects. Although the mechanism of action of toxicity of PFOS/PFOA is not clear at present, numerous animal experiments show that PFOS/PFOA has hepatotoxicity, endocrine disrupting action, embryotoxicity, reproductive toxicity, neurotoxicity, potential carcinogenicity and the like.
Disclosure of Invention
The invention aims to provide a Gemini type fluorine-containing surfactant which is formed by coupling a perfluoropolyether chain segment and a polyethylene glycol chain segment, wherein the fluorine-containing chain segment provides strong hydrophobicity, and the fluorine content and the polymerization degree are adjustable; the polyethylene glycol chain segment provides hydrophilicity; the special Gemini structure can provide excellent surface activity, and the preparation process is simple and convenient, the reaction condition is mild, and the method is suitable for industrial production. The fluorine-containing polyether segment is used as a nonpolar group, has hydrophobic property and unique oleophobic property, has extremely high surface activity and stability, can obviously reduce the surface tension of an aqueous solution under extremely low application content, has the characteristics of directional adsorption and micelle formation in the solution, can be used as an emulsifier in emulsion polymerization, and can prevent monomer droplets or polymer particles from being closely associated to generate coagulation when the molecular weight of a polymer is not too high, thereby stabilizing a dispersion system. The surfactant has the advantages of special performance, small dosage, no toxicity and the like, and is a product with high technical content, high added value and environmental friendliness. Therefore, the fluorine-containing surfactant prepared from the perfluoropolyether has wide development and application prospects. Particularly has outstanding advantages and market prospects when replacing long fluorocarbon chain products such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA).
The invention discloses a Gemini type fluorine-containing surfactant, which has the following structure:
wherein m is 1-30; n is 2 to 20.
The fluorine-containing surfactant provided by the invention has high surface activity and strong dispersion effect, and can be used as an emulsifier, a leveling agent, a wetting agent, a defoaming agent and the like. In particular, the method can be applied to fluoroolefin dispersion polymerization, and fluoroolefin monomers such as tetrafluoroethylene, vinylidene fluoride and vinylidene fluoride are dispersed into a water phase by utilizing surface activity to synthesize corresponding fluoropolyolefin.
The invention discloses a preparation method of the gemini fluorinated surfactant, which comprises the steps of coupling reaction of carbon magnesium polyethylene glycol monomethyl ether and silanized perfluoropolyether to obtain a block copolymerization product; hydrolyzing the block copolymerization product and then carrying out condensation reaction to obtain the Gemini type fluorine-containing surfactant;
the chemical structural formula of the silanized perfluoropolyether is as follows:
the chemical structural formula of the carbon magnesium polyethylene glycol monomethyl ether is as follows:
the chemical structural formula of the block copolymerization product is as follows:
in the structural formula, m is 1-30; n is 2 to 20.
In the invention, perfluoropolyether alcohol is used as an initial raw material, unsaturated double bonds are introduced through substitution reaction to obtain allylated perfluoropolyether, and hydrosilylation reaction is carried out on the alkenylated perfluoropolyether to obtain silanized perfluoropolyether; reacting halogenated polyethylene glycol monomethyl ether with metal magnesium to prepare the carbon-magnesium polyethylene glycol monomethyl ether. Preferably, the perfluoropolyether alcohol is reacted with a halogenated allyl group to obtain an allylated perfluoropolyether; and (3) carrying out addition reaction on the alkenyl perfluoropolyether and the methylhydrogen dichlorosilane to prepare the silanized perfluoropolyether.
In the invention, the coupling reaction is carried out at room temperature for 0.5-12 hours; the hydrolysis is carried out for 0.5 to 12 hours at room temperature; the condensation reaction temperature is the distillation temperature.
In the present invention, the hydrolysis is carried out in isopropanol in the presence of an aqueous hydrochloric acid solution.
The invention discloses the application of the gemini fluorine-containing surfactant in fluoroolefin dispersion polymerization; such as fluoroolefin dispersion polymerization to give a fluoropolyolefin.
The invention further discloses a preparation method of the Gemini type fluorine-containing surfactant, a segmented copolymer is formed by perfluoropolyether and chlorinated polyethylene glycol monomethyl ether through a coupling method, and the segmented copolymer is further subjected to hydrolytic condensation to obtain the Gemini type surfactant, which specifically comprises the following steps:
(1) perfluoropolyether alkenylation
Adding 50-100 parts by weight of perfluoropolyether alcohol, 0.4-1 part by weight of ammonium salt, 50-3000 parts by weight of fluoroalkyl benzene solvent and 4-50 parts by weight of halogenated allyl into a reactor, controlling the temperature to be 20-85 ℃, and dropwise adding an acid-binding agent for 30 minutes-2 hours; after the addition, the reaction is carried out for 1 to 12 hours in a heat preservation way; after the reaction is finished, standing and layering the reaction solution, wherein the upper layer is a water layer and is discarded; adding 1-10 parts of drying agent into the lower oil layer, drying for 1-24 hours, filtering to remove the drying agent to obtain an alkenyl perfluoropolyether solution, and directly putting the alkenyl perfluoropolyether solution into the next step of perfluoropolyether silylation reaction;
preferably, 4-30 parts by weight of inorganic base is dissolved in 8-300 parts by weight of water to obtain an acid-binding agent;
in the technical scheme, the inorganic base is any one of sodium hydroxide and potassium hydroxide; the halogenated allyl is bromopropylene or chloropropene; the fluoroalkyl benzene is any one of trifluorotoluene or bis (trifluoromethyl) benzene; the ammonium salt is tetrabutylammonium bromide; the drying agent is any one of anhydrous sodium sulfate, anhydrous magnesium sulfate and anhydrous calcium chloride.
(2) Perfluoropolyether silylation
Putting the alkenyl perfluoropolyether solution into a reactor, adding 0.05-0.25 part by weight of platinum catalyst, heating to 60-110 ℃, and then dropwise adding 1-25 parts by weight of methylhydrogen dichlorosilane for 30 minutes-2 hours; after the addition, the reaction is carried out for 0.5 to 12 hours in a heat preservation way; then distilling the reaction liquid under reduced pressure to obtain silanized perfluoropolyether;
in the technical scheme, the platinum catalyst is any one of chloroplatinic acid, Karster catalyst and Piermann catalyst.
(3) Carbon magnesium treatment of chlorinated polyethylene glycol monomethyl ether
Adding 20-120 parts by weight of ether solvent, 1-10 parts by weight of chlorinated polyethylene glycol monomethyl ether and 1-10 parts by weight of magnesium chips into a reactor, heating to reflux, adding 1 particle of iodine to initiate a Grignard reaction, and keeping the temperature for continuous reaction for 30 minutes-2 hours after the initiation of the reaction to obtain a light gray carbon magnesium polyethylene glycol monomethyl ether solution;
in the above technical scheme, the ether solvent is any one of diethyl ether and tetrahydrofuran.
(4) Coupling synthesis of block copolymers
And (3) dropwise adding the carbon-magnesium polyethylene glycol monomethyl ether solution synthesized in the step (3) into the solution of the silanized perfluoropolyether in the step (2), wherein the dropwise adding time is 30 minutes to 2 hours, stirring at room temperature for reaction for 0.5 to 12 hours, filtering to remove a precipitated white solid byproduct, and distilling the crude product to remove the solvent to obtain a viscous block copolymerization product.
(5) Hydrolysis-condensation
a. Hydrolysis: dissolving the viscous block copolymerization product in 100-300 parts by weight of isopropanol, adding 0.1-5 parts by weight of dilute hydrochloric acid with the mass concentration of 10% as a catalyst, and carrying out hydrolysis reaction for 0.5-12 hours at room temperature;
b. condensation: after hydrolysis is finished, the hydrolysate is heated while distilling the water/isopropanol azeotrope in the reaction liquid, the distillation time is 30 min-6 h, the temperature of the final reaction liquid is raised to 95-100 ℃, and isopropanol is evaporated to be clean, so that the Gemini type fluorine-containing surfactant prepared by the invention is obtained.
In the preparation method of the Gemini type fluorine-containing surfactant provided by the invention, perfluoropolyether alcohol is used as a starting material, unsaturated double bonds are introduced by substitution reaction with halogenated allyl groups, and allylated perfluoropolyether is obtained, wherein the reaction formula is as follows in the step (1):
wherein m is 1-30; x = Cl or Br.
And (3) carrying out hydrosilylation reaction on the alkenyl perfluoropolyether and methylhydrogen dichlorosilane under the action of a platinum catalyst to prepare the silanized perfluoropolyether, wherein the reaction formula is shown in the step (2) as follows:
reacting chlorinated polyethylene glycol monomethyl ether with magnesium metal in an ether solvent to prepare carbon-magnesium polyethylene glycol monomethyl ether, referring to the step (3), wherein the reaction formula is as follows:
wherein n is 2-20.
And (3) carrying out a coupling method on the carbon magnesium polyethylene glycol monomethyl ether and the silanized perfluoropolyether to prepare the A-B type block copolymer, wherein the reaction formula is shown in the step (4) as follows:
wherein m is 1-30; n is 2 to 20.
The block copolymer contains Si-Cl bonds and is easy to hydrolyze and condense to generate Si-O-Si bonds, so that two block copolymer structures are bonded to generate the Gemini type fluorine-containing surfactant of the invention, which is shown in the step (5) and has the following reaction formula:
wherein m is 1-30; n is 2 to 20.
In the gemini surfactant, the fluoropolyether chain segment is used as a nonpolar group, so that the gemini surfactant has hydrophobic property and unique oleophobic property, has extremely high surface activity and stability, can remarkably reduce the surface tension of an aqueous solution under extremely low application content, has the characteristics of directional adsorption in the solution and micelle formation, can be used as an emulsifier in emulsion polymerization, and can prevent monomer droplets or polymer particles from being closely associated to generate coagulation when the molecular weight of a polymer is not too high, thereby stabilizing a dispersion system. The surfactant has the advantages of special performance, small dosage, no toxicity and the like, is a product with high technical content and high added value, and has wide development and application prospects.
Compared with the prior art, the invention has the advantages that:
1. the gemini fluorinated surfactant synthesized by the invention has very high hydrophobic efficiency because the hydrophobic group adopted by the surfactant is perfluoropolyether, which avoids the difficult degradation and toxicity accumulation of long carbon chains in molecular structures such as common fluorinated surfactants PFOS, PFOA and the like, and is easy to regulate and control the hydrophobicity by controlling the molecular weight of the chain segment of the perfluoropolyether.
2. The Gemini surfactant is formed by directly bonding ether bonds (-O-), and the two hydrophobic chain segments and the two hydrophilic chain segments are tightly coupled to form a compact Gemini surfactant structure, so that the surface activity is very excellent.
3. The gemini fluorine-containing surfactant provided by the invention has the advantages of simple preparation process, mild reaction conditions, production only requiring conventional equipment and suitability for industrial production.
4. The fluorine-containing surfactant provided by the invention is applied to the dispersion polymerization of fluoroolefin, and has the advantages of good dispersion effect of monomer fluoroolefin in a water phase, high solid content in a polymerization single kettle and high productivity.
Drawings
FIG. 1 is an infrared absorption curve of the fluorosurfactants prepared in examples 1 and 2, wherein (a) is the product of example 1 and (b) is the product of example 2.
FIG. 2 is an XPS broad scan spectrum of a fluorosurfactant spin-on film surface prepared in example 1.
FIG. 3 is a surface tension curve of aqueous solutions of fluorosurfactants prepared in example 1 at various concentrations.
Detailed Description
The invention utilizes ether linkage (-O-) to directly bond, so that two hydrophobic chain segments and two hydrophilic chain segments are tightly coupled to form a compact Gemini surfactant structure, thereby providing excellent surface activity. The gemini fluorine-containing surfactant provided by the invention has the advantages of simple preparation process, mild reaction conditions, production only requiring conventional equipment and suitability for industrial production. The fluorine-containing surfactant provided by the invention is applied to fluoroolefin dispersion polymerization, the monomer fluoroolefin has strong dispersion performance in a water phase, the solid content of a polymerization single kettle can reach 25-32%, and the fluorine-containing surfactant has the advantage of high productivity.
The invention further discloses a preparation method of the Gemini type fluorine-containing surfactant, a segmented copolymer is formed by perfluoropolyether and chlorinated polyethylene glycol monomethyl ether through a coupling method, and the segmented copolymer is further subjected to hydrolytic condensation to obtain the Gemini type surfactant, which specifically comprises the following steps:
(1) perfluoropolyether alkenylation
a. Preparing an acid binding agent: dissolving 4-30 parts by weight of inorganic base in 8-300 parts by weight of water to obtain an acid-binding agent;
b. and (3) substitution reaction: adding 50-100 parts by weight of perfluoropolyether alcohol, 0.4-1 part by weight of tetrabutylammonium bromide, 50-3000 parts by weight of a fluoroalkyl benzene solvent and 4-50 parts by weight of halogenated allyl, controlling the temperature to be 20-85 ℃, and dropwise adding a prepared acid-binding agent for 30 minutes-2 hours; after the addition, the reaction is carried out for 1 to 12 hours in a heat preservation way;
c. separation: after the reaction is finished, standing and layering the reaction solution, wherein the upper layer is a water layer and is discarded; adding 1-10 parts of drying agent into the lower oil layer, drying for 1-24 hours, filtering to remove the drying agent to obtain an alkenyl perfluoropolyether solution, and directly putting the alkenyl perfluoropolyether solution into the next reaction;
in the technical scheme, the inorganic base is any one of sodium hydroxide and potassium hydroxide; the halogenated allyl is bromopropylene or chloropropene; the fluoroalkyl benzene is any one of trifluorotoluene or bis (trifluoromethyl) benzene; the drying agent is any one of anhydrous sodium sulfate, anhydrous magnesium sulfate and anhydrous calcium chloride.
(2) Perfluoropolyether silylation
a. Hydrosilylation: putting the alkenyl perfluoropolyether solution into a reactor, adding 0.05-0.25 part by weight of platinum catalyst, heating to 60-110 ℃, and then dropwise adding 1-25 parts by weight of methylhydrogen dichlorosilane for 30 minutes-2 hours; after the addition, the reaction is carried out for 0.5 to 12 hours in a heat preservation way;
b. and (3) distillation: distilling the reaction liquid under reduced pressure to obtain silanized perfluoropolyether;
in the technical scheme, the platinum catalyst is any one of chloroplatinic acid, Karster catalyst and Piermann catalyst.
(3) Carbon magnesium treatment of chlorinated polyethylene glycol monomethyl ether
Adding 20-120 parts by weight of ether solvent, 1-10 parts by weight of chlorinated polyethylene glycol monomethyl ether and 1-10 parts by weight of magnesium chips into a reactor, heating to reflux, adding 1 particle of iodine to initiate a Grignard reaction, and keeping the temperature for continuous reaction for 30 minutes-2 hours after the initiation of the reaction to obtain a light gray carbon magnesium polyethylene glycol monomethyl ether solution;
in the above technical scheme, the ether solvent is any one of diethyl ether and tetrahydrofuran.
(4) Coupling synthesis of block copolymers
Dissolving the silanized perfluoropolyether in a fluorobenzene solvent to obtain a reaction liquid;
and (3) dropwise adding the reaction liquid synthesized in the step (3) into the reaction liquid obtained in the step (2), stirring and reacting for 0.5-12 hours at room temperature, filtering to remove a precipitated white solid by-product, and distilling a crude product to remove a solvent to obtain a viscous block copolymerization product.
(5) Hydrolysis-condensation
a. Hydrolysis: dissolving the viscous block copolymer product in 100-300 parts by weight of isopropanol, adding 0.1-5 parts by weight of dilute hydrochloric acid with the mass concentration of 10% as a catalyst, and performing hydrolysis reaction at room temperature for 0.5-12 hours;
b. condensation: and (3) slowly distilling the water/isopropanol azeotrope in the reaction liquid while heating the hydrolysis liquid, wherein the distillation time is 30 min-6 h until the final reaction liquid is heated to 95-100 ℃, and steaming to remove the isopropanol to obtain the Gemini fluorine-containing surfactant prepared by the invention.
The raw materials involved in the invention are all commercial products, and the involved specific operation method and test method are conventional technologies; the technical solution of the present invention is further described below with reference to the following examples and accompanying drawings.
Example 1
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water to obtain an acid-binding agent for later use;
a 500mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 80g of a number-average perfluoropolyether alcohol (molecular weight 2000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added; after stirring and completely dissolving, heating to 85 ℃, dropwise adding a prepared acid-binding agent for 30 minutes, and then carrying out heat preservation reaction for 4 hours;
after the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution to a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting to release heat, wherein the dropping time is 45 minutes, preserving the temperature for 2 hours after the dropping is finished, carrying out reduced pressure rotary evaporation on the reaction solution, removing unreacted methylhydrogen dichlorosilane, and obtaining 78.5g of chlorosilane perfluoropolyether, wherein the yield is 90.5%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60.5g of the chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene) to prepare the chlorosilane perfluoropolyether solution for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. 6.5g of chlorinated polyethylene glycol monomethyl ether (purchased from carbohydrate technology limited, Guangzhou) and 3g of magnesium chips are added into the reactor, the temperature is raised to reflux, 1g of small-particle iodine (0.1 g) is added to initiate reaction, the reaction liquid is quickly converted into gray suspension, the temperature is kept for continuous reaction for 1 hour, and the carbon magnesium polyethylene glycol monomethyl ether solution is obtained. Under the condition of room temperature, dripping the carbon magnesium polyethylene glycol monomethyl ether solution into the prepared chlorine silanization perfluoropolyether solution, finishing the addition for 1 hour, and stirring at room temperature to continue the reaction for 8 hours;
the reaction was stopped, the precipitated salt was removed by filtration, and the solvent was distilled off from the filtrate to obtain 51.2g of a viscous perfluoropolyether-polyethylene glycol block copolymer with a reaction yield of 76.4%.
(3) Hydrolysis-condensation
A250 mL single-neck flask is provided with a straight distillation head, a thermometer, a reflux condenser tube and a liquid receiving tube, 150 mL of isopropanol is added into the flask, 50g of perfluoropolyether-polyethylene glycol block copolymer and 5g of dilute hydrochloric acid aqueous solution with the mass concentration of 10% are added, after hydrolysis reaction is carried out for 2 hours at room temperature, heating is carried out until the mixture is distilled out to obtain an azeotrope, the distillation time lasts for 2 hours, finally, the temperature is raised to 98 ℃, isopropanol is evaporated, 48.2g of fluorine-containing surfactant is obtained, the yield is 97.1%, and the fluorine-containing surfactant is used for the following application experiments. FIG. 1a shows FT-IR (γ, liquid membrane method) as a product: 1125 cm-1，1188 cm-1，1233 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3Is telescopicAnd (5) vibrating. The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product fluorosurfactant is:
the obtained fluorine-containing surfactant is prepared into aqueous solutions with different concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1wt%, the surface tension of the aqueous solution is 19.814 mN/m; when the concentration of the surfactant is 10wt%, the surface tension of the aqueous solution is as low as 18.792 mN/m; when the concentration of the surfactant is 85wt%, the surface tension of the aqueous solution is as low as 15.001 mN/m. The surface tension curve of the fluorosurfactant in aqueous solution at different mass concentrations is shown in figure 3.
(4) Application experiments
Adding 980g of deionized water, 4g of ammonium persulfate and 5g of fluorine-containing surfactant into a 2-liter autoclave in sequence at room temperature, stirring uniformly by a conventional method to form a nearly transparent solution, heating to 100 ℃ after 30min, increasing the stirring speed to 60rpm, filling a tetrafluoroethylene/nitrogen mixed gas (volume ratio of 1: 1), slowly increasing the pressure in the autoclave, increasing the pressure in the autoclave to 0.3 MPa after 1 hour, stopping filling the tetrafluoroethylene/nitrogen mixed gas, keeping the temperature and reacting for 3 hours, and stopping the reaction. And (3) cooling the reaction solution to room temperature, discharging gas, opening the reaction kettle after the pressure in the kettle is reduced to normal pressure, pouring out the materials in the kettle, and filtering to obtain 307g of granular polytetrafluoroethylene resin, wherein the solid content of a single polymerization kettle reaches 31.6%, and the particle size of the product is 500-510 nm (D90).
Example 2
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water to obtain an acid-binding agent for later use;
a500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 120g of a number-average perfluoropolyether alcohol (molecular weight 3000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added. After stirring and completely dissolving, heating to 85 ℃, dropwise adding a prepared acid-binding agent for 30 minutes, and then carrying out heat preservation reaction for 4 hours;
after the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution into a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting for heat release, wherein the dropping time is 45 minutes, and preserving the heat for 2 hours after the dropping is finished. And (3) carrying out reduced pressure rotary evaporation on the reaction liquid to remove unreacted methylhydrogen dichlorosilane to obtain 109.5g of chlorosilane perfluoropolyether with the yield of 87.4%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60.5g of the chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene) to prepare the chlorosilane perfluoropolyether solution for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. 6.5g of chlorinated polyethylene glycol monomethyl ether and 3.1g of magnesium chips are additionally added into the reactor, after the temperature is raised to reflux, 1g of small-particle iodine (0.1 g) is added to initiate the reaction, the reaction liquid is quickly converted into a gray suspension, and the temperature is kept for continuous reaction for 1 hour to obtain the carbon magnesium polyethylene glycol monomethyl ether solution. And (3) dropwise adding the solution into the prepared chlorinated silanization perfluoropolyether solution at room temperature, finishing the addition for 1 hour, and stirring at room temperature after the addition is finished to continue the reaction for 8 hours.
The reaction was stopped, the precipitated salt was removed by filtration, and the solvent was distilled off from the filtrate to obtain 51.5g of a viscous perfluoropolyether-polyethylene glycol block copolymer with a reaction yield of 76.6%.
(3) Hydrolysis-condensation
A250 mL single-neck flask is provided with a straight distillation head, a thermometer, a reflux condenser tube and a liquid receiving tube, 150 mL of isopropanol is added into the flask, 50g of perfluoropolyether-polyethylene glycol block copolymer and 5g of dilute hydrochloric acid aqueous solution with the mass concentration of 10% are added, after hydrolysis reaction is carried out for 2 hours at room temperature, heating is carried out until the mixture boils, an azeotrope is distilled out, the distillation time lasts for 2 hours totally, finally, the temperature is raised to 98 ℃, and the isopropanol is evaporated to obtain 45.1g of fluorine-containing surfactant, wherein the yield is 90.2%. FIG. 1b shows FT-IR (γ, liquid membrane method) as a product: 1125 cm-1，1188 cm-1，1233 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3The stretching vibration of (2). The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product is as follows:
the surface activity of the surfactant is tested, the obtained fluorine-containing surfactant is prepared into aqueous solutions with different mass concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1%, the surface tension of the aqueous solution is 19.245 mN/m; when the concentration of the surfactant is 10 percent, the surface tension of the aqueous solution is as low as 18.113 mN/m.
(4) Application experiments
980g of deionized water, 4g of ammonium persulfate and 5g of fluorine-containing surfactant are sequentially added into a 2 liter high-pressure autoclave, and the mixture is uniformly stirred to form a nearly transparent solution. After 30min, the temperature is raised to 90 ℃, the stirring speed is increased to 60rpm, tetrafluoroethylene/nitrogen mixed gas (the volume ratio is 1: 1) is filled, the pressure in the kettle is slowly increased, after 1 hour, the pressure in the kettle is increased to 0.3 MPa, and at the moment, the filling of the tetrafluoroethylene/nitrogen mixed gas is stopped. After the reaction was maintained for 3 hours, the reaction was stopped. And (3) cooling the reaction liquid to room temperature, discharging gas, opening the reaction kettle after the pressure in the kettle is reduced to normal pressure, pouring out the materials in the kettle, and filtering to obtain 288g of granular polytetrafluoroethylene resin with the particle size of 470-480 nm (D90).
Example 3
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water in advance to obtain an acid-binding agent, and cooling for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 80g of a number-average perfluoropolyether alcohol (molecular weight 2000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added. After stirring and dissolving completely, heating to 85 ℃, dripping the prepared acid-binding agent for 30 minutes, and keeping the temperature for reaction for 4 hours after the dripping is finished.
After the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution into a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting for heat release, wherein the dropping time is 45 minutes, and preserving the heat for 2 hours after the dropping is finished. And (3) carrying out reduced pressure rotary evaporation on the reaction liquid to remove unreacted methylhydrogen dichlorosilane to obtain 78.8g of chlorosilane perfluoropolyether with the yield of 90.7%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60g of chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene) to prepare a chlorosilane perfluoropolyether solution for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. Adding 8.2g of chlorinated polyethylene glycol monomethyl ether (purchased from carbohydrate technology limited, Guangzhou) and 3g of magnesium chips into the reactor, heating to reflux, adding 1g of small-particle iodine (0.1 g) to initiate reaction, quickly converting the reaction liquid into a gray suspension, keeping the temperature, and continuing the reaction for 1 hour to obtain the carbon magnesium polyethylene glycol monomethyl ether solution. And (3) dropwise adding the solution into the prepared chlorinated silanization perfluoropolyether solution at room temperature, finishing the addition for 1 hour, and stirring at room temperature after the addition is finished to continue the reaction for 8 hours.
The reaction was stopped, the precipitated salt was removed by filtration, and the filtrate was distilled to remove the solvent to obtain 55.1g of a viscous perfluoropolyether-polyethylene glycol block copolymer with a reaction yield of 82.2%.
(3) Hydrolysis-condensation
A250 mL single-neck flask is provided with a straight distillation head, a thermometer, a reflux condenser tube and a liquid receiving tube, 150 mL of isopropanol is added into the flask, 50g of perfluoropolyether-polyethylene glycol block copolymer and 5g of dilute hydrochloric acid aqueous solution with the mass concentration of 10% are added, after hydrolysis reaction is carried out for 2 hours at room temperature, heating is carried out until the mixture boils, an azeotrope is distilled out, the distillation time lasts for 2 hours totally, finally, the temperature is raised to 98 ℃, and the isopropanol is evaporated to obtain 48.2g of fluorine-containing surfactant, wherein the yield is 97.1%. Product FT-IR (γ, liquid membrane process): 1125 cm-1，1188 cm-1，1233 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3The stretching vibration of (2). The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product is as follows:
the surface activity of the surfactant is tested, the obtained fluorine-containing surfactant is prepared into aqueous solutions with different mass concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1%, the surface tension of the aqueous solution is 19.886 mN/m; when the concentration of the surfactant is 10 percent, the surface tension of the aqueous solution is as low as 19.023 mN/m.
Example 4
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water in advance to obtain an acid-binding agent, and cooling for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 80g of a number-average perfluoropolyether alcohol (molecular weight 2000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added. After stirring and dissolving completely, heating to 85 ℃, dripping the prepared acid-binding agent for 30 minutes, and keeping the temperature for reaction for 4 hours after the dripping is finished.
After the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution into a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting for heat release, wherein the dropping time is 45 minutes, and preserving the heat for 2 hours after the dropping is finished. And (3) carrying out reduced pressure rotary evaporation on the reaction liquid to remove unreacted methylhydrogen dichlorosilane to obtain 78.8g of chlorosilane perfluoropolyether with the yield of 90.7%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60g of chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene) to prepare a chlorosilane perfluoropolyether solution for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. 4.8g of chlorinated polyethylene glycol monomethyl ether (purchased from carbohydrate technology limited, Guangzhou) and 3g of magnesium chips are added into the reactor, the temperature is raised to reflux, 1g of small-particle iodine (0.1 g) is added to initiate reaction, the reaction liquid is quickly converted into gray suspension, the temperature is kept for continuous reaction for 1 hour, and the carbon magnesium polyethylene glycol monomethyl ether solution is obtained. And (3) dropwise adding the solution into the prepared chlorinated silanization perfluoropolyether solution at room temperature, finishing the addition for 1 hour, and stirring at room temperature after the addition is finished to continue the reaction for 8 hours.
The reaction was stopped, the precipitated salt was removed by filtration, and the filtrate was distilled to remove the solvent to obtain 45.3g of a viscous perfluoropolyether-polyethylene glycol block copolymer with a reaction yield of 76.8%.
(3) Hydrolysis-condensation
A250 mL single-neck flask is provided with a straight distillation head, a thermometer, a reflux condenser tube and a liquid receiving tube, 150 mL of isopropanol is added into the flask, 50g of perfluoropolyether-polyethylene glycol block copolymer and 5g of dilute hydrochloric acid aqueous solution with the mass concentration of 10% are added, after hydrolysis reaction is carried out for 2 hours at room temperature, heating is carried out until the mixture boils, an azeotrope is distilled out, the distillation time lasts for 2 hours totally, finally, the temperature is raised to 98 ℃, and the isopropanol is evaporated to obtain 48.0g of fluorine-containing surfactant, wherein the yield is 96.8%. Product FT-IR (γ, liquid membrane process): 1125 cm-1，1188 cm-1，1233 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3The stretching vibration of (2). The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product is as follows:
the surface activity of the surfactant is tested, the obtained fluorine-containing surfactant is prepared into aqueous solutions with different mass concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1%, the surface tension of the aqueous solution is 27.886 mN/m; when the surfactant concentration was 10%, the surface tension of its aqueous solution was 24.623 mN/m.
Comparative example 1
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water in advance to obtain an acid-binding agent, and cooling for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 80g of a number-average perfluoropolyether alcohol (molecular weight 2000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added. After stirring and dissolving completely, heating to 85 ℃, dripping the prepared acid-binding agent for 30 minutes, and keeping the temperature for reaction for 4 hours after the dripping is finished.
After the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution into a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting for heat release, wherein the dropping time is 45 minutes, and preserving the heat for 2 hours after the dropping is finished. And (3) carrying out reduced pressure rotary evaporation on the reaction liquid to remove unreacted methylhydrogen dichlorosilane to obtain 74.1g of chlorosilane perfluoropolyether, wherein the yield is 85.4%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60.4g of chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene), and the solution is prepared into perfluoropolyether solution for later use through chlorosilane reaction.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. 6.5g of chlorinated polyethylene glycol monomethyl ether (purchased from carbohydrate technology limited, Guangzhou) and 3g of magnesium chips are added into the reactor, the temperature is raised to reflux, 1g of small-particle iodine (0.1 g) is added to initiate reaction, the reaction liquid is quickly converted into gray suspension, the temperature is kept for continuous reaction for 1 hour, and the carbon magnesium polyethylene glycol monomethyl ether solution is obtained. And (3) dropwise adding the solution into the prepared chlorinated silanization perfluoropolyether solution at room temperature, finishing the addition for 1 hour, and stirring and reacting at room temperature for 6 hours after the addition is finished.
After the reaction is finished, the ethyl ether solution (the mass concentration is 10%) of the ethyl magnesium bromide Grignard reagent is added dropwise, the reaction is continued for 4 hours after the addition is finished, the reaction is stopped, and insoluble substances are removed by filtration. The filtrate was rotary evaporated to remove the solvent to give 50.1g of the final product in 82.9% yield for the following application experiments. Product FT-IR (γ, liquid membrane process): 1121 cm-1，1189 cm-1，1232 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3The stretching vibration of (2). The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product is as follows:
the surface activity of the surfactant is tested, the obtained fluorine-containing surfactant is prepared into aqueous solutions with different mass concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1%, the surface tension of the aqueous solution is 28.432 mN/m; when the surfactant concentration is 10%, the surface tension of the aqueous solution is as low as 25.333mN/m, and the surface activity is inferior to that of gemini type fluorine-containing surfactants.
(3) Application experiments
980g of deionized water, 4g of ammonium persulfate and 5g of fluorine-containing surfactant are sequentially added into a 2 liter autoclave, and the mixture is stirred uniformly by a conventional method to form a nearly transparent solution. After 30min, the temperature is raised to 100 ℃, the stirring speed is increased to 60rpm, tetrafluoroethylene/nitrogen mixed gas (the volume ratio is 1: 1) is filled, the pressure in the kettle is slowly increased, after 1 hour, the pressure in the kettle is increased to 0.3 MPa, and at the moment, the filling of the tetrafluoroethylene/nitrogen mixed gas is stopped. After the reaction was maintained for 3 hours, the reaction was stopped. And (3) cooling the reaction liquid to room temperature, deflating, opening the reaction kettle after the pressure in the kettle is reduced to normal pressure, pouring out the materials in the kettle, and filtering to obtain 211g of polytetrafluoroethylene resin, wherein the resin particles are uneven and have micron-sized particles and blocky materials.
Claims (10)
1. The gemini fluorinated surfactant is characterized by having the following chemical structural formula:
wherein m is 1-30; n is 2 to 20.
2. The preparation method of the gemini type fluorosurfactant of claim 1 is characterized by comprising the following steps: coupling reaction of carbon-magnesium polyethylene glycol monomethyl ether and silanized perfluoropolyether to obtain a block copolymerization product; hydrolyzing the block copolymerization product and then carrying out condensation reaction to obtain the Gemini type fluorine-containing surfactant;
the chemical structural formula of the silanized perfluoropolyether is as follows:
the chemical structural formula of the carbon magnesium polyethylene glycol monomethyl ether is as follows:
the chemical structural formula of the block copolymerization product is as follows:
in the structural formula, m is 1-30; n is 2 to 20.
3. The preparation method of the Gemini type fluorinated surfactant according to claim 2, wherein perfluoropolyether alcohol is used as a starting material, unsaturated double bonds are introduced through substitution reaction to obtain allylated perfluoropolyether, and the allylated perfluoropolyether is subjected to hydrosilylation reaction to obtain silanized perfluoropolyether; reacting halogenated polyethylene glycol monomethyl ether with metal magnesium to prepare the carbon-magnesium polyethylene glycol monomethyl ether.
4. The method for preparing gemini fluorinated surfactant according to claim 3, wherein perfluoropolyether alcohol is reacted with halogenated allyl group to obtain allylated perfluoropolyether; and (3) carrying out addition reaction on the alkenyl perfluoropolyether and the methylhydrogen dichlorosilane to prepare the silanized perfluoropolyether.
5. The preparation method of the gemini fluorinated surfactant according to claim 2, wherein the coupling reaction is carried out at room temperature for 0.5-12 hours; the hydrolysis is carried out for 0.5 to 12 hours at room temperature; the condensation reaction temperature is the distillation temperature.
6. The method for preparing gemini fluorosurfactants according to claim 2, wherein the hydrolysis is performed in isopropanol in the presence of aqueous hydrochloric acid.
7. The use of gemini fluorosurfactants as claimed in claim 1 in fluoroolefin dispersion polymerization.
8. Use according to claim 8, wherein the fluoroolefin is dispersion polymerized to give a fluoropolyolefin.
9. The fluorine-containing block copolymer is characterized in that the chemical structural formula of the fluorine-containing block copolymer is as follows:
wherein m is 1-30; n is 2 to 20.
10. Use of the fluorine-containing block copolymer according to claim 9 for producing a fluorosurfactant.
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