CN113583231A - Preparation method of perfluoropolyether siloxane compound and fingerprint resisting agent - Google Patents
Preparation method of perfluoropolyether siloxane compound and fingerprint resisting agent Download PDFInfo
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- CN113583231A CN113583231A CN202110778093.0A CN202110778093A CN113583231A CN 113583231 A CN113583231 A CN 113583231A CN 202110778093 A CN202110778093 A CN 202110778093A CN 113583231 A CN113583231 A CN 113583231A
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- perfluoropolyether
- carbon
- amine
- siloxane compound
- alcohol
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- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 147
- -1 siloxane compound Chemical class 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 30
- 150000001265 acyl fluorides Chemical class 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 230000003666 anti-fingerprint Effects 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000012650 click reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 51
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 16
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 claims description 14
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 230000003373 anti-fouling effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 3
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
- 239000006116 anti-fingerprint coating Substances 0.000 description 3
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- 239000002335 surface treatment layer Substances 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 241000252506 Characiformes Species 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
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- 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
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
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- 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
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33317—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group heterocyclic
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a preparation method of a perfluoropolyether siloxane compound and an anti-fingerprint agent, belonging to the technical field of fine fluorine chemical industry. Under the protection of inert gas, under the catalytic action of an alkaline catalyst A, perfluoropolyether acyl fluoride reacts with alcohol or amine containing carbon-carbon double bonds to obtain a perfluoropolyether intermediate M containing carbon-carbon double bonds; and then carrying out sulfydryl-olefin click reaction on the perfluoropolyether intermediate M and a sulfydryl-containing silane coupling agent under the catalytic action of a catalyst B to obtain a perfluoropolyether siloxane compound. According to the invention, a series of perfluoropolyether siloxane compounds containing 1-4 siloxane groups can be efficiently prepared by reacting acyl fluoride with alcohol or amine compounds containing different numbers of double bonds, the prepared siloxane compounds have controllable structures and high purity, and can be applied to the surface of a workpiece coated with the fingerprint inhibitor to obtain a hydrophobic and oleophobic coating with excellent wear resistance.
Description
Technical Field
The invention relates to the technical field of new chemical materials and surface treatment of base materials, in particular to a preparation method of a perfluoropolyether siloxane compound and an anti-fingerprint agent.
Background
In recent years, the touch panel of a screen has been rapidly developed, as represented by a display of a mobile phone. However, the glass surface which is often touched is easily contaminated with fingerprints, sweat, cosmetics, and the like, and once contaminated, it is not easily removed, and the appearance and use thereof are affected. Due to the unique chemical stability, temperature resistance, low friction coefficient, low surface tension and the like of the perfluoropolyether structure, the perfluoropolyether is widely applied to the fingerprint-resistant coating on the surface of the touch screen. However, the currently used anti-fingerprint agents have the problems of complex preparation route, high production cost and poor effect, and are mostly monopolized by foreign companies.
CN106085227A discloses a preparation method of a high-performance anti-fingerprint agent, which comprises the steps of reacting hydroxyl-terminated perfluoropolyether with allyl bromide to obtain allyl-terminated perfluoropolyether; carrying out hydrosilylation reaction on allyl-terminated perfluoropolyether and hydrogen-containing silicone oil to obtain perfluoropolyether hydrogen-containing silicone oil; and continuously carrying out hydrosilylation on the obtained product and allyl silica, thereby obtaining the target product. The patent uses lachrymatory allyl bromide as a raw material to finally obtain the comb-shaped perfluoropolyether siloxane. However, the preparation route of the fingerprint inhibitor in the patent is complex, and the wear-resistant effect is poor.
JP2017048375 discloses a high-performance anti-fingerprint agent, which discloses a method for preparing perfluoropolyether trichlorosilane by hydrosilylation reaction of allyl-terminated perfluoropolyether, and then reacting the perfluoropolyether trichlorosilane with allyl bromide to prepare a perfluoropolyether triallyl silane compound; then carrying out hydrosilylation reaction to prepare the perfluoropolyether chlorosilane compound. The patent has long synthesis route, and uses trichlorosilane with strong corrosivity and low boiling point as a raw material, so that the requirement on equipment is high.
CN109851775 discloses a preparation method of an anti-fingerprint agent with high perfluoro content, which comprises the steps of utilizing perfluoropolyether acyl fluoride to react with hydroxyethyl acrylate to prepare PFPE with an end group of acrylate, and then adding a silane coupling agent with secondary amine to prepare silane with two PFPE chains on one molecule. Although the patent has branched chains with high fluorine content and good water and oil repellency, the patent has relatively low silicon content and poor wear resistance.
Therefore, it is necessary to develop a low-cost fingerprint resisting agent which has high water and oil repellency and high wear resistance and can be prepared under the mild conditions of economy, greenness and easy production.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art. Therefore, the invention provides a preparation method of a perfluoropolyether siloxane compound and an anti-fingerprint agent, aiming at efficiently preparing the perfluoropolyether siloxane compound, wherein the method is not limited by the molecular weight of perfluoropolyether, and the number of terminal siloxane is adjustable.
Based on the above purpose, the invention provides a preparation method of a perfluoropolyether siloxane compound, which comprises the steps of firstly reacting perfluoropolyether acyl fluoride with alcohol or amine containing carbon-carbon double bonds under the protection of inert gas and the catalysis of a basic catalyst A to obtain a perfluoropolyether intermediate M containing carbon-carbon double bonds; and then carrying out sulfydryl-olefin click reaction on the perfluoropolyether intermediate M and a sulfydryl-containing silane coupling agent under the catalytic action of a catalyst B to obtain a perfluoropolyether siloxane compound.
Preferably, the preparation method comprises the following steps:
(1) under the protection of inert gas, dropwise adding a solution consisting of perfluoropolyether acyl fluoride and a solvent D into a system consisting of alcohol or amine containing carbon-carbon double bonds, a basic catalyst A and a solvent C, and after the reaction is finished, filtering, washing, standing for layering and concentrating to obtain a perfluoropolyether intermediate M with carbon-carbon double bonds;
(2) and (2) under the protection of inert gas, adding the perfluoropolyether intermediate M obtained in the step (1), a solvent E, a catalyst B and a mercapto silane coupling agent into a reactor, uniformly mixing, and carrying out heating reaction at room temperature to 150 ℃ for 4-12 h to obtain a perfluoropolyether siloxane compound.
Preferably, the perfluoropolyether acyl fluoride is one of K type, Z type and Y type.
Preferably, the mole ratio of the perfluoropolyether acyl fluoride, the alcohol or amine containing carbon-carbon double bonds and the basic catalyst A is 1: 1-2. More preferably, the molar ratio of the perfluoropolyether acyl fluoride, the alcohol or amine containing carbon-carbon double bonds and the basic catalyst A is 1: 1-1.2.
Preferably, the reaction temperature of the perfluoropolyether acyl fluoride, the alcohol or amine containing the carbon-carbon double bond and the alkaline catalyst A for preparing the perfluoropolyether intermediate M containing the carbon-carbon double bond is not more than 80 ℃, and the reaction time is 2-12 h. More preferably, the reaction temperature for preparing the perfluoropolyether intermediate M containing carbon-carbon double bonds is room temperature, and the reaction time is 4-6 hours.
Preferably, the basic catalyst A is an organic base catalyst or an inorganic base catalyst, and the organic base catalyst comprises one or more of triethylamine, tri-N-butylamine, diisopropylethylamine, N-methylmorpholine, N-dimethylaniline, 4-dimethylaminopyridine, imidazole, pyridine and 1, 8-diazabicycloundecen-7-ene (DBU); the inorganic base catalyst comprises one or more of potassium carbonate, sodium hydroxide, potassium phosphate and potassium hydrogen phosphate.
More preferably, the basic catalyst A is triethylamine or pyridine.
Preferably, the alcohol or amine containing the carbon-carbon double bond is an alcohol or amine compound containing 1-4 carbon-carbon double bonds, the alcohol is a primary alcohol or a secondary alcohol, and the amine is a primary amine or a secondary amine; preferably, the carbon-carbon double bond is a carbon-carbon double bond from an olefin, vinyl ether, allyl amine, acrylate, methacrylate, or maleate structure.
Preferably, the washing in step (1) is carried out for 2 times by using one or more mixed solvents of methanol, ethanol, ethyl acetate and the like.
Preferably, the molar ratio of the perfluoropolyether intermediate M, the mercapto-containing silane coupling agent and the catalyst B is n (1-1.5) xn (0.01-0.5) xn, wherein n is the number of double bonds contained in the perfluoropolyether intermediate M and is a positive integer of 1-4; preferably, the catalyst B is one of a free radical initiator, organic amine or organic phosphorus; preferably, the mercapto-containing silane coupling agent is one of mercaptopropyltrimethoxysilane or mercaptopropyltriethoxysilane. Preferably, the radical initiator includes an azo-type initiator, a peroxide initiator or a photo-radical initiator.
Preferably, in the step (2), the combination of the catalyst B and the perfluoropolyether intermediate M having a carbon-carbon double bond is: the electron-rich carbon-carbon double bond (such as olefin, vinyl ether, allyl amine) is initiated by a free radical initiator, more preferably, an azo initiator and a photo-free radical initiator; organic amine or organic phosphorus catalyst is used for electron-deficient carbon-carbon double bond (such as acrylate, methacrylate and maleate).
Preferably, the solvent D in the step (1) is a fluorocarbon solvent, a perfluorinated cyclic ether or a perfluorinated alkane; and (3) in the step (2), the solvent E is one of hydrofluoroether, F113, a fluorocarbon solvent or 1, 3-bis (trifluoromethyl) benzene. More preferably, the solvent D is a perfluorocyclic ether or a perfluoroalkane.
The invention also provides an anti-fingerprint agent, which comprises the perfluoropolyether siloxane compound.
The perfluoropolyether derivative belongs to a polymer, the higher the molecular weight is, the lower the reactivity is, the more difficult the reaction is to complete, the product is difficult to purify, and efficient reaction is needed to prepare the perfluoropolyether compound with a controllable structure. The initial raw materials of various derivatives of perfluoropolyether are all prepared from perfluoropolyether acyl fluoride, therefore, the invention directly adopts the high-efficiency reaction of direct esterification or amidation of acyl fluoride and alcohol or amine to prepare the perfluoropolyether intermediate derivative M, and then uses the high-efficiency mercapto-alkene click reaction to prepare the perfluoropolyether siloxane compound, the number of siloxane end groups is adjustable, and the invention is also high-efficiency aiming at the reaction of high molecular weight perfluoropolyether. Meanwhile, the molecular weight of the perfluoropolyether and the number of siloxane end groups are improved, and the antifouling property and the high wear resistance can be improved simultaneously.
The invention has the beneficial effects that:
1. the invention provides a simple, convenient and efficient method for preparing perfluoropolyether siloxane. The reaction condition is mild, green, environment-friendly, wide in raw material source and low in production cost. Only two steps of reaction are needed, each step of reaction is very efficient, and the target product can be prepared simply, conveniently and efficiently in a controllable structure mode.
2. The preparation method of the perfluoropolyether siloxane provided by the invention is not limited by the molecular weight of perfluoropolyether, the number of the end group siloxane is adjustable (containing 1-4 siloxane groups), the molecular weight of the perfluoropolyether and the number of the siloxane end groups can be simultaneously improved, and the antifouling and wear-resisting properties are simultaneously improved. The anti-fingerprint coating has excellent anti-fingerprint effect and wear resistance when being applied to the anti-fingerprint coating (the anti-fingerprint agent is coated on the surface of a workpiece).
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a reaction scheme according to an embodiment of the present invention;
FIG. 2 is a drawing showing the preparation of intermediate M3-3 in example 9 of the present invention1An H-NMR spectrum;
FIG. 3 is the product TM3-3 of example 9 of the present invention1An H-NMR spectrum;
FIG. 4 is a drawing showing a scheme for preparing intermediate M4-3 in example 12 of the present invention1An H-NMR spectrum;
FIG. 5 is the product TM4-3 of example 12 of the present invention1H-NMR spectrum.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments below.
It is to be noted that technical terms or scientific terms used in the embodiments of the present invention should have the ordinary meanings as understood by those having ordinary skill in the art to which the present disclosure belongs, unless otherwise defined.
The perfluoropolyether acyl fluorides useful in the present invention are well known in the art and can be obtained by any conventional method.
For better comparison, the perfluoropolyether acid fluorides mentioned in the examples are all perfluoropolyether acid fluorides of type K, obtained from shanghai organic institute, alcohols or amines with carbon-carbon double bonds, commercially or homemade.
Example 1
(1) Preparation of Single double bond terminated perfluoropolyether intermediate M1-1
Under the protection of nitrogen, 6.15g of ethylene glycol monoallyl ether (60mmol) and 6.1g of triethylamine (60mmol) are added into a 250ml three-neck flask, after uniform stirring, a perfluoro cyclic ether solution of perfluoropolyether acyl fluoride (91.5 g of perfluoropolyether amine acyl fluoride (molecular weight 1829.5g/mol, 50mmol) is dropwise added into the flask at room temperature, the dropwise addition temperature is controlled not to exceed 40 ℃, after the dropwise addition is finished, the reaction is carried out for 3h, filtering is carried out, filtrate is washed for 2 times by 50ml of methanol, and concentration is carried out, thus obtaining an intermediate M1-1.
(2) Preparation of monosubstituted perfluoropolyether siloxanes TM1-1
Under the protection of nitrogen, 9.56g M1-1 intermediate (5mmol), 1.05g of mercaptopropyltrimethoxysilane (5.3mmol), 0.08g of azodiisobutyronitrile (0.5mmol) and 20ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, after uniform mixing, the mixture reacts for 6 hours at 70 ℃, and after the reaction is completed, the volatile component is removed by concentration, and the mono-substituted perfluoropolyether siloxane TM1-1 is obtained.
Example 2
(1) Preparation of Single double bond terminated perfluoropolyether intermediate M1-2
Under the protection of nitrogen, 3.08g of ethylene glycol monoallyl ether (30mmol) and 3.05g of triethylamine (30mmol) are added into a 250ml three-neck flask, after uniform stirring, at room temperature, a perfluoro cyclic ether solution of perfluoropolyether acyl fluoride (112 g of perfluoropolyether amine acyl fluoride (molecular weight 4500g/mol, 25mmol) is dropwise added into the flask, dissolved in 120ml of perfluoro cyclic ether, the dropwise adding temperature is controlled not to exceed 40 ℃, after the dropwise adding is finished, the reaction is carried out for 5h, the filtrate is washed for 2 times by 60ml of methanol, and the intermediate M1-2 is obtained after concentration.
(2) Preparation of monosubstituted perfluoropolyether siloxanes TM1-2
Under the protection of nitrogen, 22.9g M1-2 intermediate (5mmol), 1.2g of mercaptopropyltrimethoxysilane (6mmol), 0.08g of azobisisobutyronitrile (0.5mmol) and 50ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, after uniform mixing, the mixture reacts for 8 hours at 70 ℃, and after the reaction is completed, the mixture is concentrated to remove volatile components, thus obtaining the mono-substituted perfluoropolyether siloxane TM 1-2.
Example 3
(1) Preparation of Single double bond terminated perfluoropolyether intermediate M1-3
Under the protection of nitrogen, 3.08g of ethylene glycol monoallyl ether (30mmol) and 3.05g of triethylamine (30mmol) are added into a 500ml three-neck flask, after uniform stirring, at room temperature, a perfluoro cyclic ether solution of perfluoropolyether acyl fluoride (194 g of perfluoropolyether amine acyl fluoride (molecular weight of 7760g/mol, 25mmol) is dropwise added into the flask, the solution is dissolved in 250ml of perfluoro cyclic ether, the dropwise adding temperature is controlled not to exceed 40 ℃, after the dropwise adding is finished, the reaction is carried out for 5h, the filtrate is washed for 2 times by 150ml of methanol and concentrated, and an intermediate M1-3 is obtained.
(2) Preparation of monosubstituted perfluoropolyether siloxanes TM1-3
Under the protection of nitrogen, 39.2g M1-3 intermediate (5mmol), 1.2g of mercaptopropyltrimethoxysilane (6mmol), 0.08g of azobisisobutyronitrile (0.5mmol) and 100ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, after uniform mixing, the mixture reacts for 8 hours at 70 ℃, and after the reaction is completed, the mixture is concentrated to remove volatile components, thus obtaining the mono-substituted perfluoropolyether siloxane TM 1-3.
Example 4
(1) Preparation of two double bond terminated perfluoropolyether intermediate M2-1
Under the protection of nitrogen, 12.9g trimethylolpropane diallyl ether (60mmol) and 6.1g triethylamine (60mmol) are added into a 250ml three-neck flask, evenly stirred, at room temperature, perfluoro cyclic ether solution of perfluoropolyether acyl fluoride (91.5 g perfluoropolyether amine acyl fluoride (molecular weight 1829.5g/mol, 50mmol) is dropwise added into the flask, the dropwise adding temperature is controlled not to exceed 40 ℃, after the dropwise adding is finished, the reaction is carried out for 3h, the filtration is carried out, filtrate is washed for 2 times by 60ml methanol, and the intermediate M2-1 is obtained after concentration.
(2) Preparation of disubstituted perfluoropolyether siloxanes TM2-1
Under the protection of nitrogen, 10.1g of M2-1 intermediate (5mmol), 2.1g of mercaptopropyltrimethoxysilane (10.6mmol), 0.16g of azodiisobutyronitrile (1.0mmol) and 25ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, after uniform mixing, the mixture reacts at 70 ℃ for 6 hours, and after complete reaction, the mixture is concentrated to remove volatile components, thus obtaining the disubstituted perfluoropolyether siloxane TM 2-1.
Example 5
(1) Preparation of two double bond terminated perfluoropolyether intermediate M2-2
Under the protection of nitrogen, 6.5g trimethylolpropane diallyl ether (30mmol) and 3.1g triethylamine (30mmol) are added into a 250ml three-neck flask, stirred uniformly, at room temperature, a perfluoro cyclic ether solution of perfluoropolyether acyl fluoride (112 g perfluoropolyether amine acyl fluoride (molecular weight 4500g/mol, 25mmol) is dropwise added into the flask, the dropwise adding temperature is controlled not to exceed 40 ℃, after the dropwise adding is finished, the reaction is carried out for 3h, the filtration is carried out, the filtrate is washed for 2 times by 60ml methanol, and the intermediate M2-2 is obtained after concentration.
(2) Preparation of disubstituted perfluoropolyether siloxanes TM2-2
Under the protection of nitrogen, 23.5g M2-2 intermediate (5mmol), 2.1g of mercaptopropyltrimethoxysilane (10.6mmol), 0.16g of azobisisobutyronitrile (1.0mmol) and 75ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, after uniform mixing, the mixture reacts for 8 hours at 70 ℃, and after the reaction is completed, the volatile component is removed by concentration, thus obtaining the disubstituted perfluoropolyether siloxane TM 2-2.
Example 6
(1) Preparation of two double bond terminated perfluoropolyether intermediate M2-3
Under the protection of nitrogen, 6.5g trimethylolpropane diallyl ether (30mmol) and 3.1g triethylamine (30mmol) are added into a 500ml three-neck flask, stirred evenly, at room temperature, perfluoro cyclic ether solution of perfluoropolyether acyl fluoride [ 194g perfluoropolyether amine acyl fluoride (molecular weight 7760g/mol, 25mmol) is added dropwise into the flask, the dropping temperature is controlled not to exceed 40 ℃, after the dropping is finished, the reaction is carried out for 3h, the filtration is carried out, the filtrate is washed for 2 times by 150ml methanol, and the intermediate M2-3 is obtained after concentration.
(2) Preparation of disubstituted perfluoropolyether siloxanes TM2-3
39.8g of 39.8g M2-3 intermediate (5mmol), 2.1g of mercaptopropyltrimethoxysilane (10.6mmol), 0.16g of azobisisobutyronitrile (1.0mmol) and 100ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle under the protection of nitrogen, and after uniform mixing, the mixture reacts at 70 ℃ for 8 hours, and after the reaction is completed, the mixture is concentrated to remove volatile components, thus obtaining the disubstituted perfluoropolyether siloxane TM 2-3.
Example 7
(1) Preparation of three double bond terminated perfluoropolyether intermediate M3-1
Under the protection of nitrogen, 15.4g of pentaerythritol triallyl ether (60mmol) and 6.1g of triethylamine (60mmol) are added into a 250ml three-neck flask, after uniform stirring, perfluoro cyclic ether solution of perfluoropolyether acyl fluoride (91.5 g of perfluoropolyether amine acyl fluoride (molecular weight 1829.5g/mol, 50mmol) is dropwise added into the flask at room temperature, the dropwise adding temperature is controlled not to exceed 40 ℃, after the dropwise adding is finished, the reaction is carried out for 3h, filtering is carried out, filtrate is washed for 2 times by 60ml of methanol, and concentration is carried out, thus obtaining an intermediate M3-1.
(2) Preparation of trisubstituted perfluoropolyether siloxanes TM3-1
10.33g 10.33g M3-1 intermediate (5mmol), 3.15g mercaptopropyltrimethoxysilane (15.9mmol), 0.24g azobisisobutyronitrile (1.5mmol) and 25ml 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle under the protection of nitrogen, after uniform mixing, the mixture reacts for 6 hours at 70 ℃, and after the reaction is completed, the volatile component is removed by concentration to obtain the tri-substituted perfluoropolyether siloxane TM 3-1.
Example 8
(1) Preparation of three double bond terminated perfluoropolyether intermediate M3-2
Under the protection of nitrogen, 7.7g of pentaerythritol triallyl ether (30mmol) and 3.1g of triethylamine (30mmol) are added into a 250ml three-neck flask, after uniform stirring, at room temperature, a perfluoro cyclic ether solution of perfluoropolyether acyl fluoride (112 g of perfluoropolyether amine acyl fluoride (molecular weight is 4500g/mol, 25mmol) is dropwise added into the flask, the dropwise adding temperature is controlled not to exceed 40 ℃, after the dropwise adding is finished, the reaction is carried out for 3h, the filtrate is washed for 2 times by 70ml of methanol and concentrated, and an intermediate M3-2 is obtained.
(2) Preparation of trisubstituted perfluoropolyether siloxanes TM3-1
Under the protection of nitrogen, 23.7g M3-2 intermediate (5mmol), 3.15g of mercaptopropyltrimethoxysilane (15.9mmol), 0.24g of azobisisobutyronitrile (1.5mmol) and 75ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, after uniform mixing, the mixture reacts for 8 hours at 70 ℃, and after the reaction is completed, the volatile component is removed by concentration to obtain the trisubstituted perfluoropolyether siloxane TM 3-2.
Example 9
(1) Preparation of three double bond terminated perfluoropolyether intermediate M3-3
Adding 7.7g pentaerythritol triallyl ether (30mmol) and 3.1g triethylamine (30mmol) into a 250ml three-neck flask under the protection of nitrogen, stirring uniformly, dropwise adding a perfluorinated cyclic ether solution of perfluoropolyether acyl fluoride (194 g perfluoropolyetheramine acyl fluoride (molecular weight 7660g/mol, 25 mmol)) into the mixture at room temperature, controlling the dropwise adding temperature to be not more than 40 ℃, reacting for 3h after dropwise adding, filtering, washing the filtrate for 2 times by 150ml methanol, and concentrating to obtain an intermediate M3-3 and an intermediate M3-31The H-NMR spectrum is shown in figure 2, wherein peaks at delta 4.57-4.16 are characteristic peaks of the compound and are asymmetric AB peaks formed by splitting due to large steric hindrance. And (3) data characterization:1H NMR(400MHz,Chloroform-d):δ5.76(ddt,J＝17.3,10.7,5.5Hz,3H),5.25–4.92(m,6H),4.57–4.16(m,2H),3.84(dt,J＝5.5,1.5Hz,6H),3.46–3.23(m,6H)。
(2) preparation of trisubstituted perfluoropolyether siloxanes TM3-3
Under the protection of nitrogen, 40g M3-3 intermediate (5mmol), 3.15g of mercaptopropyltrimethoxysilane (15.9mmol), 0.24g of azobisisobutyronitrile (1.5mmol) and 120ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, uniformly mixed, reacted at 70 ℃ for 8 hours, and concentrated to remove volatile components after complete reaction to obtain the product of the tri-substituted perfluoropolyether siloxane TM3-3, TM3-31The H-NMR spectrum is shown in FIG. 3, in which the characteristic peak at delta 4.32-the asymmetric AB peak is still present, but the position is shifted in the new compound. And (3) data characterization:1H NMR(400MHz,Chloroform-d):δ4.32(d,J＝60.4Hz,2H),3.49(d,J＝4.0Hz,27H),3.36(d,J＝6.3Hz,6H),3.30(s,6H),2.45(q,J＝7.6Hz,12H),1.72(t,J＝6.8Hz,6H),1.62(t,J＝8.2Hz,6H),0.68(t,J＝8.3Hz,6H)。
example 10
(1) Preparation of four double bond substituted starting materials
Adding 200ml of toluene into a 500ml reaction bottle, precooling to-5 ℃, adding 25g of cyanuric chloride, uniformly stirring, dropwise adding equivalent diallylamine, controlling the temperature to be not more than 10 ℃, after dropwise adding, heating to 45-50 ℃ and reacting for 3 hours. Then cooling to 0 ℃, dropwise adding an equivalent sodium hydroxide solution, controlling the temperature not to exceed 20 ℃, reacting for 1h after dropwise adding, filtering, separating liquid from filtrate, washing to be neutral, and drying. Adding 2 times of equivalent of hexamethylenediamine into the filtrate, heating to the reflux temperature of toluene, reacting for 1h, filtering, washing the filtrate to be neutral, drying the filtrate, and concentrating to obtain a compound with the following structure:
(2) preparation of four double bond terminated perfluoropolyether intermediate M4-1
Under the protection of nitrogen, 23.2g of the compound with the structure (60mmol) and 6.2g of triethylamine (60mmol) are added into a 250ml three-neck flask, after uniform stirring, perfluorinated cyclic ether solution of perfluoropolyether acyl fluoride (91.5 g of perfluoropolyether amine acyl fluoride (molecular weight 1829.5g/mol, 50mmol) is dropwise added into the mixture at room temperature, the dropwise adding temperature is controlled not to exceed 40 ℃, after the dropwise adding is finished, the reaction is carried out for 3h, the filtration is carried out, the filtrate is washed for 2 times by 70ml of methanol, and the concentration is carried out, thus obtaining an intermediate M4-1.
(3) Preparation of tetra-substituted perfluoropolyether siloxanes TM4-1
Under the protection of nitrogen, 11g M4-1 intermediate (5mmol), 4.2g of mercaptopropyltrimethoxysilane (21.2mmol), 0.32g of azobisisobutyronitrile (2.0mmol) and 40ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, the mixture is uniformly mixed, the mixture reacts for 8 hours at 70 ℃, and after the reaction is completed, the volatile component is removed by concentration, so that the tetra-substituted perfluoropolyether siloxane TM4-1 is obtained.
Example 11
(1) Preparation of four double bond terminated perfluoropolyether intermediate M4-2
Under the protection of nitrogen, 11.6g of the compound with the structure (30mmol) and 3.1g of triethylamine (60mmol) are added into a 250ml three-neck flask, after uniform stirring, a perfluoro cyclic ether solution of perfluoropolyether acyl fluoride (112 g of perfluoropolyether amine acyl fluoride (molecular weight is 4500g/mol, 25mmol) is dropwise added into the flask at room temperature, the dropwise adding temperature is controlled not to exceed 40 ℃, after the dropwise adding is finished, the reaction is carried out for 3h, the filtrate is washed for 2 times by 90ml of methanol, and the intermediate M4-2 is obtained after concentration.
(2) Preparation of tetra-substituted perfluoropolyether siloxanes TM4-2
Under the protection of nitrogen, 24.3g M4-2 intermediate (5mmol), 4.2g of mercaptopropyltrimethoxysilane (21.2mmol), 0.32g of azodiisobutyronitrile (2.0mmol) and 60ml of 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, after uniform mixing, the mixture reacts for 8 hours at 70 ℃, and after the reaction is completed, the volatile component is removed by concentration, thus obtaining the tetra-substituted perfluoropolyether siloxane TM 4-2.
Example 12
(1) Preparation of four double bond terminated perfluoropolyether intermediate M4-3
Under the protection of nitrogen, 11.6g of the compound with the structure (30mmol) and 3.1g of triethylamine (60mmol) are added into a 250ml three-neck flask, after uniform stirring, a perfluoro cyclic ether solution of perfluoropolyether acyl fluoride (194 g of perfluoropolyether amine acyl fluoride (molecular weight of 7760g/mol, 25mmol) is dropwise added into the flask at room temperature, the dropwise adding temperature is controlled not to exceed 40 ℃, after the dropwise adding is finished, the reaction is carried out for 3h, the filtrate is washed for 2 times by 120ml of methanol and concentrated, and the intermediate M4-3 and the intermediate M4-3 are obtained1The H-NMR spectrum is shown in figure 4. And (3) data characterization:1H NMR(400MHz,Chloroform-d):δ6.52(s,1H),5.72(ddt,J＝16.6,11.1,6.0Hz,4H),4.99(t,J＝13.3Hz,8H),4.00(d,J＝6.0Hz,8H),3.29(ddt,J＝26.6,13.2,6.7Hz,4H),1.51(dq,J＝14.0,7.1Hz,4H),1.33(q,J＝4.7,4.2Hz,4H),1.14(d,J＝11.7Hz,1H)。
(2) preparation of tetra-substituted perfluoropolyether siloxanes TM4-3
Under the protection of nitrogen, 41g M4-3 intermediate (5mmol), 4.2g mercaptopropyltrimethoxysilane (21.2mmol), 0.32g azobisisobutyronitrile (2.0mmol) and 90ml 1, 3-bis (trifluoromethyl) benzene are added into a reaction bottle, uniformly mixed, reacted at 70 ℃ for 8 hours, and concentrated to remove volatile components after complete reaction to obtain tetra-substituted perfluoropolyether siloxane TM4-3 and a product TM4-31The H-NMR spectrum is shown in figure 5. And (3) data characterization:1H NMR(400MHz,Chloroform-d):δ3.82(m,1H),3.65(d,J＝1.6Hz,1H),3.47(m,44H),3.40–3.20(m,4H),2.44(dd,J＝8.8,6.3Hz,16H),1.76–1.52(m,16H),1.19(m,J＝4.5Hz,8H),0.66(dd,J＝9.8,6.8Hz,8H)。
example 13
(1) Preparation of four double bond terminated perfluoropolyether intermediate M4-3
See example 12, except that the basic catalyst was replaced with sodium hydroxide, solvent C was water, and the other steps were the same as in example 12.
(2) Preparation of tetra-substituted perfluoropolyether siloxanes TM4-3
See example 12 above.
Comparative example 1
The anti-fingerprint agent product of a certain foreign brand is sold in the market and is directly prepared for use.
Applications and Performance
Diluting the perfluoropolyether siloxane compound in the embodiment by using hydrofluoroether 7100, 7200 or 7300 of 3M company to prepare a diluent with the mass concentration of 0.3 percent, namely the anti-fingerprint agent; treating the high-alumina-silica glass sheet by using piranha washing liquor in advance, washing with water, and drying by using nitrogen for later use; and (3) soaking the pretreated high-alumina-silicon glass sheet in the anti-fingerprint agent for 30min, taking out, and drying in an oven at 150 ℃ for 1h to form the anti-fingerprint cured film.
The above-mentioned glass sheet having the fingerprint-resistant cured film formed thereon was subjected to the following performance tests as they were, and the test results are shown in the following table.
(1) Contact Angle testing
The contact angle of the water static state was measured using a contact angle tester. The measurement was carried out at room temperature, and the glass sample to be measured was laid flat on the horizontal stage of the contact angle measuring instrument and fixed, and the droplet size was 5. mu.l.
(2) Durability test and analysis of results of initial angle with water static state
First, in a state where the surface treatment layer is not formed yet in any contact (i.e., the number of times of rubbing is zero), the measured angle is an initial angle. Then, evaluation of the abrasion durability of the steel wool was carried out by contacting 0000# steel wool (size 5mmx5mmx2mm) with the surface treatment layer, applying a load of 1kg thereto, reciprocating the steel wool 3000 times at a speed of 65 times/minute in the contact state with the load applied thereto, and measuring the static contact angle of water at the contact surface as shown in table 1.
(3) Antifouling Property test
And (3) putting the treated glass sheet into artificial simulated sweat to be soaked for 48 hours, taking out the glass sheet, sequentially cleaning the glass sheet by using deionized water and ethanol, and testing the water static contact angle according to the method after drying the glass sheet by using nitrogen. The higher the contact angle, the better the antifouling property. The results are shown in Table 1.
TABLE 1 anti-fingerprint agent abrasion resistance and antifouling Property test results
As can be seen from Table 1, the more the number of siloxane groups in the molecular structure of the perfluoropolyether with the same molecular weight is, the better the wear resistance and antifouling property are; at the same time, the higher the molecular weight of the perfluoropolyether for the same number of silanes, the higher the initial contact angle is expected to be, while the better the abrasion and stain resistance properties are. The molecular weight of the perfluoropolyether is increased, the number of siloxane groups in molecules is increased, and the wear-resistant effect and the antifouling effect of the anti-fingerprint coating can be improved simultaneously. This result is in accordance with the original intention of the present invention.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The embodiments of the invention are intended to embrace all such alternatives, modifications and variances that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A preparation method of perfluoropolyether siloxane compound is characterized in that under the protection of inert gas, under the catalytic action of a basic catalyst A, perfluoropolyether acyl fluoride reacts with alcohol or amine containing carbon-carbon double bonds to obtain a perfluoropolyether intermediate M containing carbon-carbon double bonds; and then carrying out sulfydryl-olefin click reaction on the perfluoropolyether intermediate M and a sulfydryl-containing silane coupling agent under the catalytic action of a catalyst B to obtain a perfluoropolyether siloxane compound.
2. The method for producing a perfluoropolyether siloxane compound according to claim 1, comprising the steps of:
(1) under the protection of inert gas, dropwise adding a solution consisting of perfluoropolyether acyl fluoride and a solvent D into a system consisting of alcohol or amine containing carbon-carbon double bonds, a basic catalyst A and a solvent C, and after the reaction is finished, filtering, washing, standing for layering and concentrating to obtain a perfluoropolyether intermediate M with carbon-carbon double bonds;
(2) and (2) under the protection of inert gas, adding the perfluoropolyether intermediate M obtained in the step (1), a solvent E, a catalyst B and a mercapto silane coupling agent into a reactor, uniformly mixing, and carrying out heating reaction at room temperature to 150 ℃ for 4-12 h to obtain a perfluoropolyether siloxane compound.
3. The method of claim 1 or 2, wherein the perfluoropolyether acid fluoride is one of type K, type Z, and type Y.
4. The method for producing a perfluoropolyether siloxane compound according to claim 1 or 2, wherein the molar ratio of the perfluoropolyether acid fluoride, the carbon-carbon double bond-containing alcohol or amine, and the basic catalyst a is 1:1 to 2.
5. The method for preparing perfluoropolyether siloxane compound according to claim 1 or 2, wherein the reaction temperature of the perfluoropolyether acyl fluoride, the alcohol or amine containing the carbon-carbon double bond, and the alkaline catalyst A for preparing the perfluoropolyether intermediate M containing the carbon-carbon double bond is not more than 80 ℃ and the reaction time is 2-12 h.
6. The method for preparing a perfluoropolyether siloxane compound according to claim 1 or 2, wherein the basic catalyst a is an organic base catalyst or an inorganic base catalyst, and the organic base catalyst comprises one or more of triethylamine, tri-N-butylamine, diisopropylethylamine, N-methylmorpholine, N-dimethylaniline, 4-dimethylaminopyridine, imidazole, pyridine, and 1, 8-diazabicycloundece-7-ene (DBU); the inorganic base catalyst comprises one or more of potassium carbonate, sodium hydroxide, potassium phosphate and potassium hydrogen phosphate.
7. The method for producing a perfluoropolyether siloxane compound according to claim 1 or 2, characterized in that the alcohol or amine containing a carbon-carbon double bond is an alcohol or amine compound containing 1 to 4 carbon-carbon double bonds, the alcohol is a primary alcohol or a secondary alcohol, and the amine is a primary amine or a secondary amine; the carbon-carbon double bond is a carbon-carbon double bond in a structure of olefin, vinyl ether, allyl amine, acrylate, methacrylate or maleate.
8. The method for producing a perfluoropolyether siloxane compound according to claim 1 or 2, wherein the molar ratio of the perfluoropolyether intermediate M, the mercapto group-containing silane coupling agent, and the catalyst B is n (1 to 1.5) xn (0.01 to 0.5) xn, where n is the number of double bonds contained in the perfluoropolyether intermediate M and is a positive integer of 1 to 4; the catalyst B is one of a free radical initiator, organic amine or organic phosphorus; the mercapto silane coupling agent is one of mercapto propyl trimethoxy silane or mercapto propyl triethoxy silane.
9. The method for producing a perfluoropolyether siloxane compound according to claim 2, wherein the solvent D in step (1) is a fluorocarbon solvent, a perfluorocyclic ether, or a perfluoroalkane; in the step (2), the solvent E is one of hydrofluoroether, F113, fluorocarbon solvent or 1, 3-bis (trifluoromethyl) benzene.
10. An anti-fingerprint agent comprising the perfluoropolyether siloxane compound of claim 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672054A (en) * | 2022-04-20 | 2022-06-28 | 江苏铁锚玻璃股份有限公司 | Super-hydrophobic and wear-resistant acrylic and preparation method thereof |
| CN115125047A (en) * | 2022-07-07 | 2022-09-30 | 西安交通大学 | Preparation method of modified silicon dioxide used as perfluoropolyether lubricant additive |
| CN115448610A (en) * | 2022-08-17 | 2022-12-09 | 江苏铁锚玻璃股份有限公司 | Anti-fingerprint glass and preparation method thereof |
| CN118359801A (en) * | 2024-06-19 | 2024-07-19 | 东华大学 | Perfluoropolyether grafted modified compound and preparation method and application thereof |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3382221A (en) * | 1961-04-19 | 1968-05-07 | Formica Corp | Thermoset resins containing the s-triazine ring |
| US6127498A (en) * | 1997-04-08 | 2000-10-03 | Ausimont S.P.A. | Modified hydrogenated polymers |
| US20080314287A1 (en) * | 2007-06-20 | 2008-12-25 | 3M Innovative Properties Company | Fluorochemical urethane-silane compounds and aqueous compositions thereof |
| CN101501046A (en) * | 2006-08-28 | 2009-08-05 | 3M创新有限公司 | Perfluoropolyether silanes and use thereof |
| CN101501045A (en) * | 2006-08-28 | 2009-08-05 | 3M创新有限公司 | Antireflective article |
| WO2014062652A1 (en) * | 2012-10-17 | 2014-04-24 | 3M Innovative Properties Company | Vehicle member |
| CN105482099A (en) * | 2015-12-24 | 2016-04-13 | 天津科技大学 | Catalyst-free method for preparing polysiloxane perfluoropolyether |
| CN105524353A (en) * | 2016-01-20 | 2016-04-27 | 清远市一丞阻燃材料有限公司 | Fire retardant containing allyl substituted triazine carbon-forming agent and preparation method of same |
| CN105693949A (en) * | 2016-03-25 | 2016-06-22 | 中科院广州化学有限公司南雄材料生产基地 | Fluorine-containing anti-fingerprint oil polymer and preparation thereof, and application of polymer in field of super-amphiphobic materials |
| CN105778693A (en) * | 2016-03-10 | 2016-07-20 | 中科院广州化学有限公司南雄材料生产基地 | Self-cleaning coating material polymer and preparation method and application thereof |
| CN107129557A (en) * | 2017-04-21 | 2017-09-05 | 中科院广州化学有限公司南雄材料生产基地 | A kind of fluorine-containing automatically cleaning polymer and its application in hydrophobic anti-pollution paint |
| US20180282578A1 (en) * | 2015-09-23 | 2018-10-04 | 3M Innovative Properties Company | Composition including silanes and methods of making a treated article |
| CN109851775A (en) * | 2019-02-21 | 2019-06-07 | 浙江诺诚技术发展有限公司 | A kind of anti-fingerprint agent and preparation method thereof of high perfluoropolyether content |
| CN110248983A (en) * | 2017-02-03 | 2019-09-17 | 大金工业株式会社 | Compound containing perfluor (poly-) ether, surface treating agent and article containing it |
| CN110922582A (en) * | 2018-09-20 | 2020-03-27 | 东莞东阳光科研发有限公司 | Perfluoropolyether siloxane compound and preparation method and application thereof |
| CN110997851A (en) * | 2017-08-22 | 2020-04-10 | 阿科玛法国公司 | Allyl-functionalized urethane oligomers and related compositions for coatings and adhesives |
| CN111057231A (en) * | 2019-12-31 | 2020-04-24 | 山东华夏神舟新材料有限公司 | High-wear-resistance perfluoropolyether type fingerprint-resistant agent and preparation method thereof |
| WO2020111138A1 (en) * | 2018-11-30 | 2020-06-04 | ダイキン工業株式会社 | Polyether group-containing compound |
| CN111278640A (en) * | 2017-10-31 | 2020-06-12 | 大金工业株式会社 | Wearable terminal member |
| CN111334188A (en) * | 2020-03-13 | 2020-06-26 | 东莞市永益诚电子有限公司 | Antistatic anti-fingerprint oil for toughened film and preparation method thereof |
-
2021
- 2021-07-09 CN CN202110778093.0A patent/CN113583231A/en active Pending
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3382221A (en) * | 1961-04-19 | 1968-05-07 | Formica Corp | Thermoset resins containing the s-triazine ring |
| US6127498A (en) * | 1997-04-08 | 2000-10-03 | Ausimont S.P.A. | Modified hydrogenated polymers |
| CN101501046A (en) * | 2006-08-28 | 2009-08-05 | 3M创新有限公司 | Perfluoropolyether silanes and use thereof |
| CN101501045A (en) * | 2006-08-28 | 2009-08-05 | 3M创新有限公司 | Antireflective article |
| US20080314287A1 (en) * | 2007-06-20 | 2008-12-25 | 3M Innovative Properties Company | Fluorochemical urethane-silane compounds and aqueous compositions thereof |
| WO2014062652A1 (en) * | 2012-10-17 | 2014-04-24 | 3M Innovative Properties Company | Vehicle member |
| US20180282578A1 (en) * | 2015-09-23 | 2018-10-04 | 3M Innovative Properties Company | Composition including silanes and methods of making a treated article |
| CN105482099A (en) * | 2015-12-24 | 2016-04-13 | 天津科技大学 | Catalyst-free method for preparing polysiloxane perfluoropolyether |
| CN105524353A (en) * | 2016-01-20 | 2016-04-27 | 清远市一丞阻燃材料有限公司 | Fire retardant containing allyl substituted triazine carbon-forming agent and preparation method of same |
| CN105778693A (en) * | 2016-03-10 | 2016-07-20 | 中科院广州化学有限公司南雄材料生产基地 | Self-cleaning coating material polymer and preparation method and application thereof |
| CN105693949A (en) * | 2016-03-25 | 2016-06-22 | 中科院广州化学有限公司南雄材料生产基地 | Fluorine-containing anti-fingerprint oil polymer and preparation thereof, and application of polymer in field of super-amphiphobic materials |
| CN110248983A (en) * | 2017-02-03 | 2019-09-17 | 大金工业株式会社 | Compound containing perfluor (poly-) ether, surface treating agent and article containing it |
| CN107129557A (en) * | 2017-04-21 | 2017-09-05 | 中科院广州化学有限公司南雄材料生产基地 | A kind of fluorine-containing automatically cleaning polymer and its application in hydrophobic anti-pollution paint |
| CN110997851A (en) * | 2017-08-22 | 2020-04-10 | 阿科玛法国公司 | Allyl-functionalized urethane oligomers and related compositions for coatings and adhesives |
| CN111278640A (en) * | 2017-10-31 | 2020-06-12 | 大金工业株式会社 | Wearable terminal member |
| CN110922582A (en) * | 2018-09-20 | 2020-03-27 | 东莞东阳光科研发有限公司 | Perfluoropolyether siloxane compound and preparation method and application thereof |
| WO2020111138A1 (en) * | 2018-11-30 | 2020-06-04 | ダイキン工業株式会社 | Polyether group-containing compound |
| CN109851775A (en) * | 2019-02-21 | 2019-06-07 | 浙江诺诚技术发展有限公司 | A kind of anti-fingerprint agent and preparation method thereof of high perfluoropolyether content |
| CN111057231A (en) * | 2019-12-31 | 2020-04-24 | 山东华夏神舟新材料有限公司 | High-wear-resistance perfluoropolyether type fingerprint-resistant agent and preparation method thereof |
| CN111334188A (en) * | 2020-03-13 | 2020-06-26 | 东莞市永益诚电子有限公司 | Antistatic anti-fingerprint oil for toughened film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 冯裕智: "有机硅改性全氟聚醚涂覆剂的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672054A (en) * | 2022-04-20 | 2022-06-28 | 江苏铁锚玻璃股份有限公司 | Super-hydrophobic and wear-resistant acrylic and preparation method thereof |
| CN115125047A (en) * | 2022-07-07 | 2022-09-30 | 西安交通大学 | Preparation method of modified silicon dioxide used as perfluoropolyether lubricant additive |
| CN115448610A (en) * | 2022-08-17 | 2022-12-09 | 江苏铁锚玻璃股份有限公司 | Anti-fingerprint glass and preparation method thereof |
| CN115448610B (en) * | 2022-08-17 | 2023-08-25 | 江苏铁锚玻璃股份有限公司 | Fingerprint-proof glass and preparation method thereof |
| CN118359801A (en) * | 2024-06-19 | 2024-07-19 | 东华大学 | Perfluoropolyether grafted modified compound and preparation method and application thereof |
| CN118359801B (en) * | 2024-06-19 | 2024-10-11 | 东华大学 | Perfluoropolyether grafted modified compound and preparation method and application thereof |
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