CN112047976B - Fluorine-containing organosilicon quaternary ammonium salt and preparation method and application thereof - Google Patents
Fluorine-containing organosilicon quaternary ammonium salt and preparation method and application thereof Download PDFInfo
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- CN112047976B CN112047976B CN202010950867.9A CN202010950867A CN112047976B CN 112047976 B CN112047976 B CN 112047976B CN 202010950867 A CN202010950867 A CN 202010950867A CN 112047976 B CN112047976 B CN 112047976B
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- quaternary ammonium
- ammonium salt
- fluorine
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 31
- 239000011737 fluorine Substances 0.000 title claims abstract description 31
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- 239000013067 intermediate product Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 14
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 12
- 229960002887 deanol Drugs 0.000 claims description 12
- 239000012972 dimethylethanolamine Substances 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 229960004624 perflexane Drugs 0.000 claims description 8
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005507 spraying Methods 0.000 abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000000304 alkynyl group Chemical group 0.000 abstract description 2
- 150000001408 amides Chemical class 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract description 2
- 230000003115 biocidal effect Effects 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000010702 perfluoropolyether Substances 0.000 description 3
- 229940086542 triethylamine Drugs 0.000 description 3
- 230000003666 anti-fingerprint Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- -1 silicon quaternary ammonium salt Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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Abstract
The invention relates to a fluorine-containing organosilicon quaternary ammonium salt and a preparation method and application thereof, wherein the chemical structural formula of the organosilicon quaternary ammonium salt is as follows:wherein R is 1 Is CH 3 、CH 2 CH 3 、CH(CH 3 ) 2 Or CH 2 CH 2 CH 3 (ii) a Y is a chain segment containing alkyl, ether, thioether, amide, carbonyl, ester, alkenyl or alkynyl; rf has the formula: f- (CF) 2 ) a ‑(OC 3 F 6 ) b ‑(OC 2 F 4 ) c ‑(OCF 2 ) d ‑(CH 2 ) e -, a is any integer of 1 to 3, b, c, d are each 1 to 100Any integer, e is 1 or 2; x is Cl, br or I. The fluorine-containing organosilicon quaternary ammonium salt is used for spraying and coating a film on the surface of glass, so that the surface of the glass has the performances of antibiosis, hydrophobicity, oleophobicity, wear resistance and the like.
Description
Technical Field
The invention relates to the technical field of glass surface modification, in particular to a fluorine-containing organosilicon quaternary ammonium salt and a preparation method and application thereof.
Background
With the continuous improvement of living standard and the development of science and technology, people have increasingly strengthened health care consciousness, and health becomes an important factor for measuring quality of life. And the germs seriously harm the life and health of the masses in the actual life. In order to reduce these hazards, research on antibacterial materials has become a focus of research.
Glass uses very extensively in daily life, and from the smart mobile phone screen of private application to the various intelligent touch equipment of public place, mostly be the glass material at present, these equipment are attached to by the sweat on the fingerprint very easily in the use, leave the fingerprint trace, influence visual effect. In recent years, in order to improve user experience, most touch screens are coated with an anti-fingerprint film layer, and the film layer has a hydrophobic and oleophobic function and can effectively prevent the residue of fingerprint prints. But the anti-fingerprint film layer does not have obvious antibacterial property and can not meet the antibacterial requirement of customers at the same time. Most of the currently reported antibacterial glass is prepared by adding nano-silver into a matching material, and the product has the defects of low light transmittance, low strength, high cost, non-lasting sterilization, single function and the like. Therefore, a new solution is needed to be found, and the dual requirements of antifouling and antibacterial properties are met on the premise of not influencing the inherent characteristics of glass products.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the defect that the existing glass surface coating does not have antifouling and antibacterial properties at the same time, the invention provides the fluorine-containing organosilicon quaternary ammonium salt and the preparation method and application thereof.
The technical scheme is as follows: a fluorine-containing organosilicon quaternary ammonium salt has a chemical structural formula as follows:
wherein R is 1 Is CH 3 、CH 2 CH 3 、CH(CH 3 ) 2 Or CH 2 CH 2 CH 3 ;
Y is a chain segment containing alkyl, ether, thioether, amide, carbonyl, ester, alkenyl or alkynyl;
rf has the formula: f- (CF) 2 ) a -(OC 3 F 6 ) b -(OC 2 F 4 ) c -(OCF 2 ) d -(CH 2 ) e A is any integer from 1 to 3, b, c, d are each any integer from 1 to 100, e is 1 or 2;
x is Cl, br or I.
Rf is C 14 ~C 20 Y is a segment comprising an ester group or an alkane chain.
The preparation method of the fluorine-containing organosilicon quaternary ammonium salt comprises the following steps:
step 1: mixing a monomer and an acyl chlorination reagent in a reaction container, heating to 50-100 ℃ under the protection of inert gas, then dropwise adding dimethylformamide into the reaction container, and reacting for 2-4 hours under the condition of 50-100 ℃ to obtain an intermediate product a, wherein the structural formula of the monomer is Rf-COOH, the molar ratio of the monomer to the acyl chlorination reagent is (1-2): 1, and the weight of the dimethylformamide is 0.1-1% of the weight of the acyl chlorination reagent;
and 2, step: mixing dimethylethanolamine, an acid-binding agent and perfluorohexane, and cooling to 0 to 10 ℃ to obtain a reaction system, wherein the molar ratio of the dimethylethanolamine to the intermediate product a obtained in the step (1 to 1.2) to 1, the molar ratio of the acid-binding agent to the intermediate product a obtained in the step (1 to 3) to 1, and the volume ratio of the perfluorohexane to the dimethylethanolamine is 50;
and step 3: slowly dropwise adding the intermediate product a obtained in the step 1 into the reaction system obtained in the step 2, and reacting at room temperature for 1-2h;
and 4, step 4: after the reaction in the step 3 is finished, extracting with methanol, and then purifying to obtain an intermediate product b;
and 5: heating gamma-chloropropyltrimethoxysiloxane, an intermediate product b, potassium iodide and a solvent to 50-150 ℃ under the protection of inert gas, reacting for 12-48h, and purifying after the reaction is finished to obtain the fluorine-containing organosilicon quaternary ammonium salt, wherein the molar ratio of the intermediate product b to the gamma-chloropropyltrimethoxysiloxane is 1 (1-1.5), the weight of potassium iodide is 0.5-1% of that of the gamma-chloropropyltrimethoxysiloxane, the solvent is a mixed solution of m-benzotrifluoride and dimethylformamide, the volume ratio of the m-benzotrifluoride to the dimethylformamide is 1 (0.5-1), and the volume of the solvent to the intermediate product b is 50.
The acyl chloride reagent in the step 1 is oxalyl chloride or thionyl chloride.
The acid-binding agent in the step 2 is triethylamine or diisopropylethylamine.
The purification methods in step 4 and step 5 are both decompression rotary evaporation of solvent.
The fluorine-containing organosilicon quaternary ammonium salt is applied to the preparation of glass coatings.
Has the advantages that: the fluorine-containing organosilicon quaternary ammonium salt and the preparation method and the application thereof have the following beneficial effects: the silicon-oxygen radical of the organic silicon quaternary ammonium salt can be chemically bonded with the hydroxyl on the surface of the glass, so that the glass has excellent water and oil repellency and antibacterial performance, and the functional coating formed on the surface of the glass has excellent wear resistance. In addition, the coating can be formed only by adopting a heating and curing mode, the operation is simple, the feasibility is high, and the formed coating is a transparent coating layer and does not influence the attractiveness of the glass.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples, but it will be understood that these examples are intended to illustrate further features and advantages of the invention, and are not intended to limit the scope of the claims. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.
Example 1
A preparation method of fluorine-containing organosilicon quaternary ammonium salt comprises the following steps:
step 1: mixing a monomer and oxalyl chloride in a reaction vessel, heating to 50-60 ℃ under the protection of inert gas, then dropwise adding dimethylformamide into the reaction vessel, and reacting for 2h at 50-60 ℃ to obtain a light green solution intermediate product a, wherein the monomer is perfluoropolyether acid with the average molecular weight of 1500, and the structural formula of the intermediate product is CF 3 CF 2 CF 2 -(OCF 2 CF 2 CF 2 )n-O-CF 2 CF 2 -COOH, the molar ratio of monomer to oxalyl chloride is 1, the weight of dimethylformamide is 0.1% of the weight of oxalyl chloride;
step 2: mixing dimethylethanolamine, triethylamine and perfluorohexane, and cooling to 0-10 ℃ to obtain a reaction system, wherein the molar ratio of the dimethylethanolamine to the intermediate product a obtained in the step 1 to the triethylamine is 1;
and step 3: slowly dropwise adding the intermediate product a obtained by the reaction in the step 1 into the reaction system obtained in the step 2, and then reacting for 1h at room temperature;
and 4, step 4: after the reaction in the step 3 is finished, adding methanol for extraction and purification, and then carrying out reduced pressure rotary evaporation at 70 ℃ to remove the solvent to obtain a colorless transparent viscous liquid intermediate product b;
and 5: heating gamma-chloropropyltrimethoxysiloxane, an intermediate product b, potassium iodide and a solvent to 50-60 ℃ under the protection of inert gas, reacting for 18h, and performing reduced pressure rotary evaporation to remove the solvent after the reaction is finished to obtain a light yellow viscous liquid, namely the fluorine-containing organosilicon quaternary ammonium salt, wherein the molar ratio of the intermediate product b to the gamma-chloropropyltrimethoxysiloxane is 1:1, the weight of potassium iodide is 0.5% of the weight of the gamma-chloropropyltrimethoxysiloxane, the solvent is a mixed solution of m-ditrifluoromethane and dimethylformamide, the volume ratio of the m-ditrifluoromethane to dimethylformamide is 1:1, and the volume of the solvent to the intermediate product b is 50.
Example 2
A preparation method of fluorine-containing organosilicon quaternary ammonium salt comprises the following steps:
step 1: mixing a monomer and thionyl chloride in a reaction vessel, heating to 60-70 ℃ under the protection of inert gas, then dropwise adding dimethylformamide into the reaction vessel, and reacting for 3 hours at 60-70 ℃ to obtain a light green solution intermediate product a, wherein the monomer is perfluoropolyether acid with the average molecular weight of 3000, the structural formula of the perfluoropolyether acid is CF3CF2CF2- (OCF 2CF2CF 2) n-O-CF2CF2-COOH, the molar ratio of the monomer to oxalyl chloride is 1.2, and the weight of the dimethylformamide is 0.1 percent of the weight of the thionyl chloride;
step 2: mixing dimethylethanolamine, triethylamine and perfluorohexane, and cooling to 0-10 ℃ to obtain a reaction system, wherein the molar ratio of the dimethylethanolamine to the intermediate product a obtained in the step (1) to the triethylamine is 1.1;
and step 3: slowly dropwise adding the intermediate product a obtained in the step 1 into the reaction system obtained in the step 2, and reacting at room temperature for 1.5h;
and 4, step 4: after the reaction in the step 3 is finished, adding methanol for extraction and purification, and then carrying out reduced pressure rotary evaporation at 70 ℃ to remove the solvent to obtain a colorless transparent viscous liquid intermediate product b;
and 5: heating gamma-chloropropyltrimethoxysiloxane, an intermediate product b, potassium iodide and a solvent to 85-95 ℃ under the protection of inert gas, reacting for 24h, and performing reduced pressure rotary evaporation to remove the solvent after the reaction is finished to obtain a yellow viscous liquid, namely the fluorine-containing organosilicon quaternary ammonium salt, wherein the molar ratio of the intermediate product b to the gamma-chloropropyltrimethoxysiloxane is 1:1.2, the weight of potassium iodide is 0.5 percent of the weight of the gamma-chloropropyltrimethoxysiloxane, the solvent is a mixed solution of m-ditrifluoromethane and dimethylformamide, the volume ratio of the m-ditrifluoromethane to the dimethylformamide is 1: 0.5, and the volume of the solvent to the intermediate product b is 50.
Example 3
A preparation method of fluorine-containing organosilicon quaternary ammonium salt comprises the following steps:
step 1: mixing a monomer and thionyl chloride in a reaction vessel, heating to 70-80 ℃ under the protection of inert gas, then dropwise adding dimethylformamide into the reaction vessel, and reacting for 2 hours at 70-80 ℃ to obtain a light green solution intermediate product a, wherein the monomer is perfluorinated polyether acid with the average molecular weight of 4000, the structural formula of which is CF3CF2CF2- (OCF 2CF2CF 2) n-O-CF2CF2-COOH, the molar ratio of the monomer to oxalyl chloride is 1.5, and the weight of the dimethylformamide is 0.1% of the weight of the thionyl chloride;
step 2: mixing dimethylethanolamine, triethylamine and perfluorohexane, and cooling to 0-10 ℃ to obtain a reaction system, wherein the molar ratio of the dimethylethanolamine to the intermediate product a obtained in the step 1 to the triethylamine is 1.2;
and step 3: slowly dropwise adding the intermediate product a obtained by the reaction in the step 1 into the reaction system obtained in the step 2, and then reacting for 2 hours at room temperature;
and 4, step 4: after the reaction in the step 3 is finished, adding methanol for extraction and purification, and then carrying out reduced pressure rotary evaporation at 70 ℃ to remove the solvent to obtain a colorless transparent viscous liquid intermediate product b;
and 5: heating gamma-chloropropyltrimethoxysiloxane, an intermediate product b and a solvent to 100-120 ℃ under the protection of inert gas, reacting for 36h, and removing the solvent through reduced pressure rotary evaporation after the reaction is finished to obtain a reddish brown viscous liquid, namely the fluorine-containing organosilicon quaternary ammonium salt, wherein the molar ratio of the intermediate product b to the gamma-chloropropyltrimethoxysiloxane is 1:1.2, the solvent is a mixed solution of m-ditrifluoromethane and dimethylformamide, the volume ratio of the m-ditrifluoromethane to the dimethylformamide is 1:1, and the volume ratio of the solvent to the intermediate product b is 50.
The chemical structural formulas of the fluorine-containing organosilicon quaternary ammonium salts prepared in examples 1 to 3 are as follows:
wherein n is any integer from 7 to 22.
The method for plating the film on the surface of the glass by adopting the fluorine-containing organosilicon quaternary ammonium salt comprises the following steps: preparing a 0.1% solution of fluorine-containing organosilicon quaternary ammonium salt by using a fluorine-containing solvent, spraying the solution on the surface of glass in a spraying manner, and drying and curing the solution for 30 minutes at 120 ℃; the fluorine-containing solvent is perfluorohexane or m-ditrifluorotoluene.
The fluorine-containing organosilicon quaternary ammonium salts obtained in the embodiments 1 to 3 are respectively coated on the surfaces of glass, the surfaces are respectively marked as modified glass 1, modified glass 2 and modified glass 3, then blank glass without being coated, the modified glass 1, the modified glass 2 and the modified glass 3 are subjected to performance test, and the antibacterial test method refers to a method in appendix A (a film pasting method) of GB 21551.2-2010 (Special requirements for antibacterial, degerming and purifying functional antibacterial materials of household and similar-purpose electric appliances) issued by the Ministry of public health of the people's republic of China. The test strains selected for the experiment were: e.coli (AS 1.90) and Staphylococcus aureus (ATCC 6538). The test results are given in table 1 below.
TABLE 1
As can be seen from Table 1, when the fluorine-containing organosilicon quaternary ammonium salt is used for coating, the coating is bonded with the glass surface through chemical bonds, the coated glass surface has high antibacterial performance and antifouling performance, and the steel wool friction resistance of the coated glass surface is more than 2000 times.
While the embodiments of the present invention have been described in detail, those skilled in the art will recognize that the embodiments of the present invention can be practiced without departing from the spirit and scope of the claims.
Claims (6)
2. The method for preparing the fluorine-containing organosilicon quaternary ammonium salt according to claim 1, characterized by comprising the following steps:
step 1: mixing a monomer and an acyl chlorination reagent in a reaction container, heating to 50-100 ℃ under the protection of inert gas, then dropwise adding dimethylformamide into the reaction container, and reacting for 2-4 hours under the condition of 50-100 ℃ to obtain an intermediate product a, wherein the structural formula of the monomer is CF3CF2CF2- (OCF 2CF2CF 2) n-O-CF2CF2-COOH, n is any integer from 7 to 22, the molar ratio of the monomer to the acyl chlorination reagent is (1-2): 1, and the weight of the dimethylformamide is 0.1-1% of the weight of the acyl chlorination reagent;
step 2: mixing dimethylethanolamine, an acid-binding agent and perfluorohexane, and cooling to 0-10 ℃ to obtain a reaction system, wherein the molar ratio of the dimethylethanolamine to the intermediate product a obtained in the step (1-1.2) to 1, the molar ratio of the acid-binding agent to the intermediate product a obtained in the step (1-3) to 1, and the volume ratio of the perfluorohexane to the dimethylethanolamine (25-50) to 1;
and step 3: slowly dropwise adding the intermediate product a obtained by the reaction in the step 1 into the reaction system obtained in the step 2, and then reacting for 1-2h at room temperature;
and 4, step 4: after the reaction in the step 3 is finished, adding methanol for extraction, and then purifying to obtain an intermediate product b;
and 5: heating gamma-chloropropyltrimethoxysiloxane, an intermediate product b, potassium iodide and a solvent to 50-150 ℃ under the protection of inert gas, reacting for 12-48h, and purifying after the reaction is finished to obtain the fluorine-containing organosilicon quaternary ammonium salt, wherein the molar ratio of the intermediate product b to the gamma-chloropropyltrimethoxysiloxane is 1 (1-1.5), the weight of potassium iodide is 0.5-1% of that of the gamma-chloropropyltrimethoxysiloxane, the solvent is a mixed solution of m-benzotrifluoride and dimethylformamide, the volume ratio of the m-benzotrifluoride to the dimethylformamide is 1 (0.5-1), and the volume of the solvent to the intermediate product b is 50.
3. The method for preparing fluorine-containing organosilicon quaternary ammonium salt according to claim 2, characterized in that: the acyl chlorination reagent in the step 1 is oxalyl chloride or thionyl chloride.
4. The method for preparing the fluorine-containing organosilicon quaternary ammonium salt according to claim 2, characterized in that: and the acid-binding agent in the step 2 is triethylamine or diisopropylethylamine.
5. The method for preparing fluorine-containing organosilicon quaternary ammonium salt according to claim 2, characterized in that: the purification method in the step 4 and the purification method in the step 5 are decompression rotary evaporation of the solvent.
6. The use of the quaternary ammonium salt of fluorine-containing organosilicon according to claim 1 for preparing glass coatings.
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