CN111057230A - Double-end-group perfluoropolyether silane and preparation method thereof - Google Patents
Double-end-group perfluoropolyether silane and preparation method thereof Download PDFInfo
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- CN111057230A CN111057230A CN201911399562.7A CN201911399562A CN111057230A CN 111057230 A CN111057230 A CN 111057230A CN 201911399562 A CN201911399562 A CN 201911399562A CN 111057230 A CN111057230 A CN 111057230A
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- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 68
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 24
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 15
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 15
- XAKMJUAGVWKMOB-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioyl difluoride Chemical compound FC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)=O XAKMJUAGVWKMOB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002009 diols Chemical class 0.000 claims abstract description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 alkoxy silane compound Chemical class 0.000 claims abstract description 7
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 238000006884 silylation reaction Methods 0.000 claims abstract description 4
- 238000005336 cracking Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- YBMDPYAEZDJWNY-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluorocyclopentene Chemical compound FC1=C(F)C(F)(F)C(F)(F)C1(F)F YBMDPYAEZDJWNY-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000002309 gasification Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 238000002444 silanisation Methods 0.000 abstract description 3
- 150000001265 acyl fluorides Chemical class 0.000 abstract description 2
- 125000002252 acyl group Chemical group 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 230000003666 anti-fingerprint Effects 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- SQEGLLMNIBLLNQ-UHFFFAOYSA-N 1-ethoxy-1,1,2,3,3,3-hexafluoro-2-(trifluoromethyl)propane Chemical compound CCOC(F)(F)C(F)(C(F)(F)F)C(F)(F)F SQEGLLMNIBLLNQ-UHFFFAOYSA-N 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- DJXNLVJQMJNEMN-UHFFFAOYSA-N 2-[difluoro(methoxy)methyl]-1,1,1,2,3,3,3-heptafluoropropane Chemical compound COC(F)(F)C(F)(C(F)(F)F)C(F)(F)F DJXNLVJQMJNEMN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
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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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- 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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/328—Polymers modified by chemical after-treatment with inorganic compounds containing other elements
-
- 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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention belongs to the field of fluorine chemical industry, and particularly relates to double-end-group perfluoropolyether silane and a preparation method thereof. Comprising the steps of 1) preparing perfluoropolyether carboxylic ester; 2) reducing perfluoropolyether carboxylate to prepare perfluoropolyether diol; 3) reacting the obtained perfluoropolyether diol with a silylation reagent to obtain double-end perfluoropolyether siloxane; according to the synthesis method of the double-end-group perfluoropolyether alkoxy silane compound, the double-end-group acyl fluoropolyether is obtained through the reaction of perfluoroglutaryl fluoride and hexafluoropropylene oxide, and then esterification reduction and silanization are carried out on acyl fluoride, so that the perfluoropolyether carboxylate is obtained.
Description
Technical Field
The invention belongs to the field of fluorine chemical industry, and particularly relates to double-end-group perfluoropolyether silane and a preparation method thereof.
Background
The perfluoropolyether silane compound has the good hydrophobic and oleophobic characteristics of perfluoropolyether, and has the characteristic of strong adhesive force of the silane compound on the glass panel, so that the film obtained by coating the surface treatment composition containing the perfluoropolyether silane compound can prevent the surface of the glass panel from being polluted by outside dirt and fingerprints of a user, and can be firmly attached to the glass panel. Therefore, the perfluoropolyether silane which is simple in preparation method, high in siloxane proportion and strong in adhesive force is provided, and the silane has a good application prospect.
Disclosure of Invention
The invention aims to provide a double-end-group perfluoropolyether silane and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of double-end-group perfluoropolyether silane is characterized by adopting the following formula (I):
the preparation method specifically comprises the following steps:
1) preparation of perfluoropolyether carboxylate: adding an aprotic organic solvent and alkali metal fluoride into a pressure-resistant reaction kettle, stirring for 3-30 hours at room temperature, controlling the temperature of the reaction kettle to be-70-40 ℃, adding high-purity perfluoroglutaryl fluoride, stirring for 2-10 hours, controlling the temperature of the reaction kettle to be-50-10 ℃, and slowly introducing dry HFPO into the reaction kettle at the rate of 1-100 mL/min to perform polymerization for 2-20 hours; after the polymerization reaction is finished, introducing methanol or ethanol for esterification reaction, and after the reaction is finished, separating and drying to obtain perfluoropolyether carboxylate;
2) dissolving perfluoropolyether carboxylic ester in an aprotic organic solvent, controlling the temperature of the perfluoropolyether carboxylic ester to be lower than 20 ℃, and slowly adding a reducing agent into the perfluoropolyether carboxylic ester to reduce the carboxylic ester to obtain perfluoropolyether diol with a hydroxyl end group; the molar ratio of the perfluoropolyether carboxylate to the reducing agent is 1: 2-4; separating the product;
3) reacting the obtained perfluoropolyether diol with a silylation reagent to obtain double-end perfluoropolyether siloxane; wherein the molar ratio of the obtained double-end perfluoropolyether siloxane is 1:2-4, and the product is separated to obtain the double-end perfluoropolyether silane.
The reducing agent in the step 2) is sodium borohydride or lithium aluminum hydride.
The silanization reagent in the step 3) is chloropropyl trimethoxy silane or 3-aminopropyl trimethoxy silane.
Wherein, the perfluoroglutaryl fluoride is prepared by the following method: adding perfluorocyclopentene into an activation chamber, introducing ozone, controlling the reaction temperature to be-10-20 ℃, irradiating for 10-90min, opening a liquid discharge valve at the bottom of a storage tank after irradiation is finished, putting the activated perfluorocyclopentene into a gasification chamber for slow gasification, putting the gasified raw material into a cracking chamber, carrying out heating cracking in the presence of oxygen, and controlling the feeding molar ratio of the gasified raw material to the oxygen to be 20:1-1:10 by a gas flowmeter in the cracking process; the contact reaction time is 0.1s to 200 s; the reaction pressure is 0-1 MPa; the reaction temperature is 500 ℃; rectifying and purifying the product obtained after cracking to obtain the high-purity perfluoroglutaryl fluoride.
The application also comprises a double-end-group perfluoropolyether silane prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the synthesis method of the double-end-group perfluoropolyether alkoxy silane compound, the double-end-group acyl fluoropolyether is obtained through the reaction of perfluoroglutaryl fluoride and hexafluoropropylene oxide, and then esterification reduction and silanization are carried out on acyl fluoride, so that the perfluoropolyether carboxylate is obtained.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.
Example 1: the preparation method of the perfluoropentyl diacyl fluoride comprises the following steps: adding perfluorocyclopentene into an activation chamber, introducing ozone, controlling the reaction temperature to be 0 ℃, controlling the irradiation time to be 10-90min, opening a liquid discharge valve at the bottom of a storage tank after irradiation is finished, putting the activated perfluorocyclopentene into a gasification chamber for slow vaporization, allowing the gasified raw material to enter a cracking chamber, carrying out heating cracking under the condition of oxygen, and controlling the feeding molar ratio of the gasified raw material to the oxygen to be 1 by a gas flowmeter in the cracking process: 1; the contact reaction time is 0.1s to 200 s; the reaction pressure is 0-1 MPa; the reaction temperature is 500 ℃; rectifying and purifying the product obtained after cracking to obtain the high-purity diacyl fluoride product.
The preparation method of the perfluoropolyether carboxylic ester specifically comprises the following steps: adding tetraethylene glycol dimethyl ether (aprotic organic solvent) and potassium fluoride into a pressure-resistant reaction kettle, stirring for 3 hours at room temperature, controlling the temperature of the reaction kettle to be-40 ℃, adding high-purity perfluoroglutaryl fluoride, stirring for 5 hours, controlling the temperature of the reaction kettle to be-10 ℃, and slowly introducing dry HFPO into the reaction kettle at the rate of 50mL/min to perform polymerization for 12 hours. And then introducing methanol into the reactants to react to obtain perfluoropolyether carboxylate, separating and drying after the polymerization reaction is finished to obtain the perfluoropolyether carboxylate, and testing by GPC and 19F NMR shows that the perfluoropolyether carboxylate with the average molecular weight of 4000 and narrow molecular weight distribution can be obtained respectively according to different reaction conditions.
Reduction of perfluoropolyether carboxylic acid ester: putting the perfluoropolyether carboxylic ester into a reaction kettle with a jacket, introducing cooling water into the jacket, controlling the temperature of the reaction kettle to be lower than 20 ℃, slowly adding sodium borohydride into the reaction kettle until the reaction is finished, continuing stirring at room temperature for 3 hours, adding two volumes of water, separating a fluorine phase from a water phase, and drying by using a molecular sieve to obtain the perfluoropolyether diol.
Uniformly mixing 30g of perfluoropolyether diol (Mw 3940), 0.51g of potassium hydroxide and 0.10g of dodecyl trimethyl ammonium chloride in a three-neck flask, slowly adding 2.53g of 3-aminopropyl trimethoxy silane into the mixture under the conditions of stirring and nitrogen protection, filtering and washing the mixture after the reaction is finished, and performing rotary evaporation to obtain the product of the double-end-group perfluoropolyether silane.
Dissolving the double-end-group perfluoropolyether siloxane in perfluoroisobutyl methyl ether or perfluoroisobutyl ethyl ether to prepare a solution with the mass concentration of 0.1%, namely the anti-fingerprint agent; soaking the glass slide in absolute ethyl alcohol, performing ultrasonic treatment for 3 minutes, taking out, cleaning for 3 times by using acetone, and drying for 30 minutes in a vacuum drying oven at 50 ℃ for later use; and soaking the pretreated glass slide in the anti-fingerprint agent for 0.5 minute, and drying the glass slide in an oven at 160 ℃ for 1 hour to form a cured film.
The static contact angle between water and the coating layer on the glass slide is measured by using a contact angle tester, the volume of each drop of test liquid is 1 microliter, and the contact angle between the water and the coating layer is 117 ℃ under the room temperature condition. A steel wool friction resistance tester is used for carrying out a friction resistance test by loading 1.0Kg, the friction stroke is 30mm, the friction treatment is carried out for 3000 times of reciprocating, and the contact angle between water and the coating is measured again to be 115 ℃, which shows that the material has good pollution resistance and friction resistance.
Example 2: the preparation method of the perfluoropentyl diacyl fluoride comprises the following steps: adding perfluorocyclopentene into an activation chamber, introducing ozone, controlling the reaction temperature to be 0 ℃, controlling the irradiation time to be 10-90min, opening a liquid discharge valve at the bottom of a storage tank after irradiation is finished, putting the activated perfluorocyclopentene into a gasification chamber for slow vaporization, allowing the gasified raw material to enter a cracking chamber, carrying out heating cracking under the condition of oxygen, and controlling the feeding molar ratio of the gasified raw material to the oxygen to be 1 by a gas flowmeter in the cracking process: 1; the contact reaction time is 0.1s to 200 s; the reaction pressure is 0-1 MPa; the reaction temperature is 500 ℃; rectifying and purifying the product obtained after cracking to obtain the high-purity diacyl fluoride product.
The preparation method of the perfluoropolyether carboxylic ester specifically comprises the following steps: adding tetraethylene glycol dimethyl ether (aprotic organic solvent) and potassium fluoride into a pressure-resistant reaction kettle, stirring for 3 hours at room temperature, controlling the temperature of the reaction kettle to be-40 ℃, adding high-purity perfluoroglutaryl fluoride, stirring for 5 hours, controlling the temperature of the reaction kettle to be-10 ℃, and slowly introducing dry HFPO into the reaction kettle at the rate of 50mL/min to perform polymerization for 12 hours. And then introducing methanol into the reactants to react to obtain perfluoropolyether carboxylate, separating and drying after the polymerization reaction is finished to obtain the perfluoropolyether carboxylate, and testing by GPC and 19F NMR shows that the perfluoropolyether carboxylate with the average molecular weight of 2000 and narrow molecular weight distribution can be obtained respectively according to different reaction conditions.
Reduction of perfluoropolyether carboxylic acid ester: putting the perfluoropolyether carboxylic ester into a reaction kettle with a jacket, introducing cooling water into the jacket, controlling the temperature of the reaction kettle to be lower than 20 ℃, slowly adding sodium borohydride into the reaction kettle until the reaction is finished, continuing stirring at room temperature for 3 hours, adding two volumes of water, separating a fluorine phase from a water phase, and drying by using a molecular sieve to obtain the perfluoropolyether diol.
Uniformly mixing 30g of perfluoropolyether diol (Mw ═ 1940), 1.04g of potassium hydroxide and 0.10g of dodecyl trimethyl ammonium chloride in a three-neck flask, slowly adding 5.14g of 3-aminopropyl trimethoxy silane into the mixture under the conditions of stirring and nitrogen protection, filtering and washing the mixture after the reaction is finished, and performing rotary evaporation to obtain the product of the double-end-group perfluoropolyether silane.
Dissolving the double-end-group perfluoropolyether siloxane in perfluoroisobutyl methyl ether or perfluoroisobutyl ethyl ether to prepare a solution with the mass concentration of 0.2 percent, namely the anti-fingerprint agent; soaking the glass slide in absolute ethyl alcohol, performing ultrasonic treatment for 3 minutes, taking out, cleaning for 3 times by using acetone, and drying for 30 minutes in a vacuum drying oven at 50 ℃ for later use; and soaking the pretreated glass slide in the anti-fingerprint agent for 0.5-2 minutes, and drying the glass slide in a 160 ℃ oven for 1 hour to form a cured film.
And measuring the static contact angle between the water and the coating layer on the glass slide by using a contact angle tester, wherein the volume of each drop of the test liquid is 1 microliter, and the contact angle between the water and the coating layer is 116 ℃ under the room temperature condition. And (3) performing a friction resistance test by using a steel wool friction resistance tester under the load of 1.0Kg, wherein the friction stroke is 30mm, performing friction treatment for 3000 times, and measuring the anti-pollution performance and the friction resistance of the material again, wherein the contact angle between water and the coating is 114 ℃.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (6)
1. A preparation method of double-end-group perfluoropolyether silane is characterized by adopting the following formula (I):
2. the method for preparing the bis-terminal perfluoropolyether silane according to claim 1, comprising the steps of:
1) preparation of perfluoropolyether carboxylate: adding an aprotic organic solvent and alkali metal fluoride into a pressure-resistant reaction kettle, stirring for 3-30 hours at room temperature, controlling the temperature of the reaction kettle to be-70-40 ℃, adding high-purity perfluoroglutaryl fluoride, stirring for 2-10 hours, controlling the temperature of the reaction kettle to be-50-10 ℃, and slowly introducing dry HFPO into the reaction kettle at the rate of 1-100 mL/min to perform polymerization for 2-20 hours; after the polymerization reaction is finished, introducing methanol or ethanol for esterification reaction, and after the reaction is finished, separating and drying to obtain perfluoropolyether carboxylate;
2) dissolving perfluoropolyether carboxylic ester in an aprotic organic solvent, controlling the temperature of the perfluoropolyether carboxylic ester to be lower than 20 ℃, and slowly adding a reducing agent into the perfluoropolyether carboxylic ester to reduce the carboxylic ester to obtain perfluoropolyether diol with a hydroxyl end group; the molar ratio of the perfluoropolyether carboxylate to the reducing agent is 1: 2-4; separating the product;
3) reacting the obtained perfluoropolyether diol with a silylation reagent to obtain double-end perfluoropolyether siloxane; wherein the molar ratio of the obtained double-end perfluoropolyether siloxane is 1:2-4, and the product is separated to obtain the double-end perfluoropolyether silane.
3. The method for preparing the bis-terminal perfluoropolyether silane according to claim 2, wherein the reducing agent in step 2) is sodium borohydride or lithium aluminum hydride.
4. The method for preparing the bis-terminal perfluoropolyether silane according to claim 2, wherein the silylation agent in step 3) is chloropropyltrimethoxysilane or 3-aminopropyltrimethoxysilane.
5. The process for preparing the bis-terminal perfluoropolyether silane according to claim 2, wherein said perfluoroglutaryl fluoride is prepared by: adding perfluorocyclopentene into an activation chamber, introducing ozone, controlling the reaction temperature to be-10-20 ℃, irradiating for 10-90min, opening a liquid discharge valve at the bottom of a storage tank after irradiation is finished, putting the activated perfluorocyclopentene into a gasification chamber for slow gasification, putting the gasified raw material into a cracking chamber, carrying out heating cracking in the presence of oxygen, and controlling the feeding molar ratio of the gasified raw material to the oxygen to be 20:1-1:10 by a gas flowmeter in the cracking process; the contact reaction time is 0.1s to 200 s; the reaction pressure is 0-1 MPa; the reaction temperature is 500 ℃; rectifying and purifying the product obtained after cracking to obtain the high-purity perfluoroglutaryl fluoride.
6. A double-ended perfluoropolyether silane obtained by the process according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911399562.7A CN111057230B (en) | 2019-12-30 | 2019-12-30 | Double-end-group perfluoropolyether silane and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911399562.7A CN111057230B (en) | 2019-12-30 | 2019-12-30 | Double-end-group perfluoropolyether silane and preparation method thereof |
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| Publication Number | Publication Date |
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| CN111057230A true CN111057230A (en) | 2020-04-24 |
| CN111057230B CN111057230B (en) | 2022-07-15 |
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| CN115975177A (en) * | 2023-02-13 | 2023-04-18 | 中国科学院兰州化学物理研究所 | A kind of double-end Z-type perfluoropolyether siloxane and its preparation method and application |
| CN118515934A (en) * | 2024-06-01 | 2024-08-20 | 江西立讯智造有限公司 | Dustproof sweat-proof functional material for Bluetooth headset shell and preparation method thereof |
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