CN114957646B - Perfluoro polyether amino compound and preparation method and application thereof - Google Patents
Perfluoro polyether amino compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN114957646B CN114957646B CN202210356412.3A CN202210356412A CN114957646B CN 114957646 B CN114957646 B CN 114957646B CN 202210356412 A CN202210356412 A CN 202210356412A CN 114957646 B CN114957646 B CN 114957646B
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- China
- Prior art keywords
- perfluoropolyether
- compound
- fluorine
- amino compound
- cyano
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- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 81
- -1 amino compound Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 31
- 239000011737 fluorine Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229920003023 plastic Polymers 0.000 claims abstract description 19
- 239000004033 plastic Substances 0.000 claims abstract description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 8
- 238000010791 quenching Methods 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 11
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 claims description 10
- 239000002335 surface treatment layer Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- FNUBKINEQIEODM-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentanal Chemical compound FC(F)(F)C(F)(F)C(F)(F)CC=O FNUBKINEQIEODM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229960004624 perflexane Drugs 0.000 claims description 2
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 125000000101 thioether group Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 4
- 229920000570 polyether Polymers 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 18
- 229920000728 polyester Polymers 0.000 description 17
- 238000005507 spraying Methods 0.000 description 15
- 239000012756 surface treatment agent Substances 0.000 description 15
- 239000002985 plastic film Substances 0.000 description 12
- 229920006255 plastic film Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000003666 anti-fingerprint Effects 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- REXUYBKPWIPONM-UHFFFAOYSA-N 2-bromoacetonitrile Chemical compound BrCC#N REXUYBKPWIPONM-UHFFFAOYSA-N 0.000 description 2
- PYNYHMRMZOGVML-UHFFFAOYSA-N 2-bromopropanenitrile Chemical compound CC(Br)C#N PYNYHMRMZOGVML-UHFFFAOYSA-N 0.000 description 2
- UMLFTCYAQPPZER-UHFFFAOYSA-N 4-(bromomethyl)benzonitrile Chemical compound BrCC1=CC=C(C#N)C=C1 UMLFTCYAQPPZER-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution 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
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- JNAYPRPPXRWGQO-UHFFFAOYSA-N 2-chloropropanenitrile Chemical compound CC(Cl)C#N JNAYPRPPXRWGQO-UHFFFAOYSA-N 0.000 description 1
- VODKOOOHHCAWFR-UHFFFAOYSA-N 2-iodoacetonitrile Chemical compound ICC#N VODKOOOHHCAWFR-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001233 Poly-4-hydroxybenzoate Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006116 anti-fingerprint coating Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- 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
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33365—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group
- C08G65/33368—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group acyclic
-
- 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
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33365—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group
- C08G65/33375—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group cyclic
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention relates to the technical field of high molecular compound synthesis, in particular to a perfluoropolyether amino compound and a preparation method and application thereof. The invention relates to a preparation method of a perfluoropolyether amino compound, which specifically comprises the following steps: dissolving perfluoropolyether alcohol with a fluorine-containing solvent, and adding a strong base, a phase transfer catalyst and a cyano compound to obtain the perfluoropolyether cyano compound; dissolving the perfluor polyether cyano compound with a fluorine-containing solvent, adding tetrahydrofuran for mixing, adding a reducing agent for reaction, quenching by inorganic acid, and extracting to obtain the perfluor polyether amino compound. The synthetic route is simple and easy to realize. The perfluoropolyether amino compound prepared by the method has high hydrophobicity and oleophobicity. The perfluoro polyether amine compound is applied to obtain a surface treating agent, and the compound is used for being deposited on the surface of a plastic substrate, so that the substrate has good fingerprint resistance and wear resistance and good adhesive force.
Description
Technical Field
The invention relates to the technical field of high molecular compound synthesis, in particular to a perfluoropolyether amino compound and a preparation method and application thereof.
Background
The perfluoropolyether is a perfluoro compound having an ether bond (-C-O-C-) in the molecular chain, has high lubricity, water repellency, oil repellency, etc., and is therefore very suitable for surface treatment agents, particularly for anti-fingerprint treatment of the surface of a glass substrate. In the prior art, the anti-fingerprint oil product obtained by combining the perfluoropolyether and the silane coupling agent can be subjected to dehydration condensation reaction with Si-OH on the surface of glass, so that a firm perfluoropolyether protective coating is formed on the surface of the glass, and excellent anti-fingerprint performance is provided for the surface of the glass. Currently, such products are commercially available as Japanese Dajin OPTOOL UD509, xinyue X-71-197, etc.
In recent years, transparent plastics (such as polycarbonate PC, polyacrylic resin PAA, polyethylene terephthalate PET, etc.) have been increasingly replaced with conventional inorganic glass materials due to their light weight, ease of processing, safety and environmental protection. However, the conventional anti-fingerprint oil products containing perfluoropolyether siloxane series cannot be applied due to the few surface active groups of plastics, especially the absence of Si-OH.
In the prior art, a perfluoropolyether acrylate compound is generally adopted to modify the surface of plastic, CN105121517A reports a fluorosilicone polymer surface treating agent containing a plurality of acrylate groups, and the water contact angle on a polycarbonate substrate reaches 109 degrees and has better surface smoothness. However, the perfluoro polyether acrylic ester surface modification treatment agent has the defects of complicated synthetic route and inconvenient use, and ultraviolet light is used for initiating the solidification when the plastic surface is solidified into a film, so that the application of the material is greatly limited.
Analysis of influence factors of adhesion of a polycarbonate surface organosilicon abrasion-resistant coating [ J ]. Coating technology and abstract, 2016, 37 (2): 14-17 mentions that an amino silane coupling agent such as gamma-aminopropyl trimethoxy silane, gamma-aminoethyl aminopropyl trimethoxy silane and the like is adopted to modify the surface of the plastic, so that a layer of Si-OH active groups is formed on the surface of the plastic, and the anti-fingerprint modification can be carried out on the surface of the plastic on the basis of a Si-OH buffer layer, but on one hand, the amino silane coupling agent has poorer solubility in the traditional anti-fingerprint fluorine-containing diluent, so that the method is adopted to carry out two procedures on the surface of the plastic, namely, silanization treatment is carried out on the surface of the plastic first, then anti-fingerprint treatment is carried out, the process is complicated, the method is not suitable for mass production and use, and on the other hand, the number of Si-OH formed by the buffer layer is limited, and the bonding with perfluoropolyether siloxane is less, so that the performance of the anti-fingerprint coating can be influenced.
Accordingly, there is a need for a compound for preparing a surface treatment agent capable of forming a surface treatment layer having water repellency, oil repellency and stain resistance and excellent surface smoothness on a plastic substrate, thereby improving the fingerprint resistance of the plastic substrate.
Disclosure of Invention
Based on this, the object of the present invention is to provide a perfluoropolyether amine-based compound which has high hydrophobicity and oleophobicity and has good solubility in an organic solvent, and can be widely used for preparing a surface treatment agent. The invention further aims to provide a preparation method of the perfluoropolyether amino compound, which is simple in synthetic route and easy to realize. Another object of the present invention is to provide the use of a perfluoropolyether amine-based compound, which is applied to the surface of a plastic substrate, so that the substrate maintains good fingerprint and abrasion resistance, and at the same time has good adhesion.
The preparation method of the perfluoropolyether amino compound is characterized by comprising the following steps:
(1) Dissolving perfluoropolyether alcohol in a fluorine-containing solvent, adding strong alkali and a phase transfer catalyst, heating to 50-80 ℃ and stirring for reaction for 1-3h, then adding a cyano compound, continuing to react for 3-6h, then sequentially extracting with water and ethanol, and removing the solvent under reduced pressure to obtain an intermediate product of the perfluoropolyether cyano compound.
(2) Dissolving the perfluor polyether cyano compound obtained in the step (1) by using a fluorine-containing solvent, adding tetrahydrofuran, uniformly mixing, adding a reducing agent under ice bath cooling, reacting for 3-6 hours at room temperature, adding an inorganic acid to quench the reaction, regulating the pH of a system to 8-9 by using an inorganic base, extracting by using a mixture of water and isobutanol (mass ratio of 10/3), and removing the solvent under reduced pressure to obtain the perfluor polyether amino compound.
Further, the fluorine-containing solvent in the step (1) is one or more of m-xylene (HFX), methyl nonafluorobutyl ether (HFE-7100), ethyl nonafluorobutyl ether (HFE-7200), perfluorohexane, tridecafluorooctane (AC-6000), 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether (AE-3000) and trifluorotrichloroethane.
Further, the strong base in the step (1) is one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, potassium tert-butoxide, N-Diisopropylethylamine (DIPEA) and 1, 3-tetramethylguanidine.
Preferably, the strong base is sodium hydroxide and potassium hydroxide.
Further, the amount of the strong base to be used is 1.05 to 6 times the amount of the perfluoropolyether alcohol substance (hereinafter referred to as molar equivalent equ).
Preferably, the amount of strong base used is 3 to 4 molar equivalents of the perfluoropolyether alcohol.
Further, the phase transfer catalyst in the step (1) is a quaternary ammonium salt compound, and may specifically be one or more compounds selected from benzyl triethyl ammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethyl ammonium chloride, dodecyl trimethyl ammonium chloride, and tetradecyl trimethyl ammonium chloride.
Further, the phase transfer catalyst is used in an amount of 0.05 to 20wt% of the perfluoropolyether alcohol. Preferably, the phase transfer catalyst is used in an amount of 0.5 to 2wt% of the perfluoropolyether alcohol.
Further, the cyano compound described in the above step (1) is a cyano compound containing a halogeno group, including, but not limited to, bromoacetonitrile, chloroethyl, iodoacetonitrile, bromopropionitrile, chloropropionitrile, 4- (bromomethyl) benzonitrile, and the like.
Further, the cyano compound is used in an amount of 1.05 to 6 molar equivalents of the perfluoropolyether alcohol. Preferably, the cyano compound is used in an amount of 2 to 3 molar equivalents of the perfluoropolyether alcohol.
Further, the reducing agent in the step (2) is preferably one of lithium aluminum hydride or sodium borohydride.
Further, the reducing agent is used in an amount of 1.05 to 6 molar equivalents of the cyano compound of the perfluoropolyether. Preferably, the reducing agent is used in an amount of 1.5 to 2 molar equivalents of the perfluoropolyether cyano compound.
Further, the inorganic acid in the step (2) is preferably one of hydrochloric acid, phosphoric acid, nitric acid and sulfuric acid.
Further, the concentration of the inorganic acid is 0.05M to 10M. Preferably, the concentration of the mineral acid is 0.1M-2M.
Further, the inorganic base in the step (2) is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate and sodium carbonate.
Further, the concentration of the inorganic base is 0.05M to 10M. Preferably, the concentration of the inorganic base is 0.1M to 2M.
The structural formula of the perfluoropolyether amino compound prepared by the method is as follows:
wherein Rf is F- (CF) 2 ) m -(OC 4 F 8 ) n -(OC 3 F 6 ) s -(OC 2 F 4 ) p -(OCF 2 ) q -O(CF 2 ) u Where n, s, p and q are each an integer of 0 or more and 100 or less, the sum of n, s, p and q is at least 1, and the order of presence of the repeating units with m, n, s, p and q and bracketed by brackets is arbitrary in the formula: m and u are integers of 0 to 20 inclusive; rf has a molecular weight of 69-20000; preferably, rf has a molecular weight of 800-10000;
x is fluorine-containing or fluorine-free alkyl, phenyl, ether, thioether chain segment, which can be selected from the following groups: -CH 2 -、-CHCH 3 -、-(CH 2 ) 2 -、-(CH 2 ) 3 -、-(CH 2 ) 4 -、-(CH 2 ) 5 -etc., the H atom of the above group may be incompletely substituted with an F atom.
Further, the repeating unit-OC 3 F 6 -comprising-OCF 2 CF 2 CF 2 -and/or-OCF (CF) 3 )CF 2 -。
The preparation method of the perfluoropolyether amine compound surface modifier comprises the following steps: the perfluoropolyether amino compound is dissolved in an organic solvent, and then a transesterification catalyst is added.
Further, the organic solvent is only used to dissolve the perfluoropolyether amine-based compound and does not react with the perfluoropolyether amine-based compound. Preferably, the organic solvent includes a fluorine-containing solvent, which may be a fluorine-containing alkane, fluorine-containing haloalkane, hydrofluoroether, etc., such as methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, tridecafluorooctane, 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether.
Further, the perfluoropolyether amine-based compound is 0.01-30wt% of the surface treating agent. Preferably, the perfluoropolyether amine-based compound is 0.05 to 20wt% of the surface treating agent. Optimally, the perfluoropolyether amine-based compound is 0.1 to 20wt% of the surface treating agent.
Further, the transesterification catalyst refers to an organic base compound capable of promoting the transesterification reaction, including but not limited to N, N-Diisopropylethylamine (DIPEA), 1, 3-tetramethylguanidine, potassium t-butoxide, triethylamine, dicyclohexylcarbodiimide (DCC), dimethylaminopyridine (DMAP), 1, 8-diazabicycloundec-7-ene (DBU), and the like.
Further, the transesterification catalyst is used in an amount of 0.002 to 0.05wt% of the treating agent. Preferably, the transesterification catalyst is used in an amount of 0.005-0.02wt% of the treating agent.
The perfluoropolyether amino compound surface modifier is used for carrying out surface modification treatment on polyester plastics. Preferably, the surface modification treatment is performed on a polyester plastic substrate containing ester groups (-O-c=o), wherein the polyester plastic is a polymer obtained by polycondensation of a polyhydric alcohol and a polybasic acid, such as surface modification of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-p-hydroxybenzoate, polycarbonate (PC), polyacrylic resin (PAA), and the like.
A preparation method of a perfluoropolyether amine compound surface modification treatment layer comprises a wet coating method and a dry coating method. Wet coating methods include, but are not limited to, dip coating, spin coating, flow coating, spray coating, and roll coating; dry coating methods include, but are not limited to, vacuum evaporation, sputtering, CVD, and the like.
The invention has the beneficial effects that:
(1) A perfluoropolyether amine-based compound is provided which has high hydrophobicity and oleophobicity and good solubility in a fluorine-containing solvent.
(2) The preparation method of the perfluoropolyether amino compound is simple in synthetic route and easy to realize.
(3) The compound is used for being deposited on the surface of a plastic substrate, so that the substrate has good fingerprint resistance and wear resistance and good adhesive force.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
Example 1
Step 1: into a three-necked flask equipped with stirring 100mL was charged 10g (2.86 mmol) of a composition having an average CF 3 (OCF 2 CF 2 ) p (OCF 2 ) q OCF 2 CH 2 OH perfluoropolyether alcohol (p, q: 36 sum, number average molecular weight: 3500, produced by SOLVAY Co.), 15mL of m-xylene, 1.61g of 30% by weight potassium hydroxide (8.61 mmol,3 equ) solution, 0.1g (1% by weight of the perfluoropolyether alcohol) of tetrabutylammonium bromide, heating to 60℃and stirring for reaction for 1 hour, then dropwise adding 0.69g (5.75 mmol,2 equ) of bromoacetonitrile, continuing to react at 60℃for 6 hours, extracting with water and ethanol in sequence and distilling under reduced pressure to obtain 9.71g of colorless transparent product, the yield of which is 96%, namely perfluoropolyether cyano compound A 1 。
Step 2: 9.71g (2.74 mmol) of the perfluoropolyether cyano compound obtained in the step 1 and 15mL of m-xylene are added into a three-necked flask with stirring of 100mL, after the mixture is fully dissolved, 15mL of tetrahydrofuran is added, the mixture is stirred and mixed uniformly in an ice bath, and the mixture is slowly added0.16g (4.21 mmol,1.5 equ) of lithium aluminum hydride, then stirring and reacting for 4h at room temperature, adding 10mL of 0.1M hydrochloric acid to quench the reaction, stirring fully, removing a non-fluorine phase (namely an upper solution), adjusting the pH of a lower fluorine phase to 8 by using 0.1M sodium hydroxide solution, removing the upper non-fluorine phase, extracting the fluorine phase by water/isobutanol (mass ratio of 10/3) and distilling under reduced pressure to obtain 8.84g of pale yellow transparent product, wherein the yield is 91%, namely the perfluoropolyether amino compound B 1 。
Step 3: the above compound B 1 The surface treatment agent (1) was prepared by preparing 0.4% by mass of ethyl nonafluorobutyl ether (Novec 7200, 3M Co.) and adding 0.005% by mass of N, N-Diisopropylethylamine (DIPEA), and sufficiently dissolving, and then uniformly spray-coating the surface treatment agent (1) on the surface of a polyethylene terephthalate (PET) film at a flow rate of 50mg/sec and a transport line speed of 13mm/sec using a commercially available spray coating apparatus. Before coating, plasma activating treatment is carried out on the surface of the plastic film, and after spraying, the plastic film is baked for 30min at the constant temperature of 60 ℃ to form a surface treatment layer C 1 。
Example 2
Step 1: into a three-necked flask equipped with stirring 100mL was charged 10g (2.50 mmol) of CF having an average composition 3 (OCF 2 CF 2 ) p (OCF 2 ) q OCF 2 CH 2 OH perfluoropolyether alcohol (p, q: 40; number average molecular weight 4000; SOLVAY Co.), 15mL of m-xylene, 1.34g of 30wt% sodium hydroxide (10.05 mmol,4 equ) solution, 0.15g (1.5 wt% in perfluoropolyether alcohol) of tetrabutylammonium hydrogen sulfate, heating to 50℃and stirring to react for 1 hour, then dropwise adding 0.57g (7.50 mmol,3 equ) of chloroacetonitrile, continuing to react at 50℃for 5 hours, and sequentially extracting with water, ethanol and distilling under reduced pressure to obtain 9.59g of colorless transparent product, the yield being 95% which is the perfluoropolyether cyano compound A 2 。
Step 2: 9.59g (2.37 mmol) of the perfluoropolyether cyano compound obtained in the above step 1 and 15mL of m-xylene were put into a three-necked flask equipped with stirring 100mL, and after the mixture was sufficiently dissolved, 15mL of tetrahydrofuran was added thereto, and the mixture was stirred and mixed uniformly in an ice bath, and 0.18g (4.75 mmol,2.0 equ), then heating to room temperature, stirring and reacting for 6h, adding 10mL of 0.1M hydrochloric acid to quench the reaction, stirring fully, removing a non-fluorine phase (namely an upper solution), adjusting the pH of a lower fluorine phase to 9 by using 0.1M sodium hydroxide solution, removing the upper non-fluorine phase, extracting the fluorine phase by water/isobutanol (mass ratio of 10/3) and distilling under reduced pressure to obtain 8.55g of pale yellow transparent product, wherein the yield is 89%, namely the perfluoropolyether amino compound B 2 。
Step 3: the above compound B 2 The Polycarbonate (PC) film was uniformly spray-coated with the surface treating agent (2) prepared by preparing the polycarbonate film to have a mass concentration of 0.4% with ethyl nonafluorobutyl ether (Novec 7200, 3M Co., ltd.) and adding 1, 3-tetramethylguanidine having a mass concentration of 0.01% thereto, and sufficiently dissolving the mixture to obtain the surface treating agent (2), and then uniformly spray-coating the surface treating agent (2) on the Polycarbonate (PC) film surface at a flow rate of 50mg/sec and a transport line speed of 13mm/sec using a commercially available spray-coating apparatus. Before coating, plasma activating treatment is carried out on the surface of the plastic film, and after spraying, the plastic film is baked for 30min at the constant temperature of 60 ℃ to form a surface treatment layer C 2 。
Example 3
Step 1: into a 100mL three-necked flask equipped with stirring, 10g (2.24 mmol) of CF having an average composition 3 CF 2 CF 2 (OCF(CF 3 )CF 2 ) s OCF(CF 3 )CH 2 OH perfluoropolyether alcohol (s 25, number average molecular weight 4460, manufactured by Su Ku mu New Material Co., ltd.), 15mL of m-xylene, 1.05g of 30wt% sodium hydroxide (7.88 mmol,3.5 equ) solution, 0.20g (2 wt% in perfluoropolyether alcohol) of dodecyltrimethylammonium chloride, heating to 70℃and stirring to react for 1 hour, then dropwise adding 0.90g (6.72 mmol,3 equ) of bromopropionitrile, continuing to react for 4 hours at 70℃and sequentially extracting with water and ethanol and distilling under reduced pressure to obtain 9.82g of colorless transparent product, the yield of which is 97%, namely perfluoropolyether cyano compound A 3 。
Step 2: into a three-necked flask equipped with 100mL of stirring, 9.82g (2.17 mmol) of the perfluoropolyether cyano compound obtained in the above step 1 and 15mL of m-xylene are added, after the mixture is sufficiently dissolved, 15mL of tetrahydrofuran is added, and the mixture is stirred and mixed uniformly in an ice bath, and 0.17g (4.48 mmol,2.0 equ) of hydrogenation is slowly addedLithium aluminum, then heating to room temperature, stirring and reacting for 4h, adding 10mL of 0.1M hydrochloric acid to quench the reaction, stirring fully, removing a non-fluorine phase (namely an upper solution), adjusting the pH of a lower fluorine phase to 8 by using 0.1M sodium hydroxide solution, removing the upper non-fluorine phase, extracting the fluorine phase by water/isobutanol (mass ratio of 10/3) and distilling under reduced pressure to obtain 9.03g of pale yellow transparent product, wherein the yield is 92%, namely the perfluoropolyether amino compound B 3 。
Step 3: the above compound B 3 The surface treatment agent (3) was prepared by preparing 0.4% by mass of ethyl nonafluorobutyl ether (Novec 7200, 3M Co.) and adding 0.015% by mass of Dimethylaminopyridine (DMAP), and after sufficient dissolution, the surface treatment agent (3) was applied by spraying uniformly on the surface of a polybutylene terephthalate (PBT) film at a flow rate of 50mg/sec and a feed line speed of 13mm/sec using a commercially available spray coating apparatus. Before coating, plasma activating treatment is carried out on the surface of the plastic film, and after spraying, the plastic film is baked for 30min at the constant temperature of 60 ℃ to form a surface treatment layer C 3 。
Example 4
Step 1: into a 100mL three-necked flask equipped with stirring, 10g (2.03 mmol) of a composition having an average CF 3 (OCF 2 CF 2 ) p (OCF 2 ) q OCF 2 CH 2 OH perfluoropolyether alcohol (p, q: 49, number average molecular weight: 4930, produced by SOLVAY Co.), 15mL of m-xylene, 1.14g of 30wt% potassium hydroxide (6.10 mmol,3 equ) solution, 0.10g (1 wt% in perfluoropolyether alcohol) of tetrabutylammonium bromide, heating to 80 ℃ and stirring for reaction for 1h, then dropwise adding 1.00g (5.10 mmol,2.5 equ) of 4- (bromomethyl) benzonitrile, continuing to react for 3h at 80 ℃, and sequentially extracting with water, ethanol and distilling under reduced pressure to obtain 9.52g of colorless transparent product, the yield of which is 93%, namely perfluoropolyether cyano compound A 4 。
Step 2: 9.52g (1.89 mmol) of the perfluoropolyether cyano compound obtained in the step 1 and 15mL of m-xylene are added into a three-necked flask with stirring of 100mL, after the mixture is fully dissolved, 15mL of tetrahydrofuran is added, the mixture is stirred and mixed uniformly in an ice bath, 0.13g (3.42 mmol,1.8 equ) of lithium aluminum hydride is slowly added, and thenStirring at room temperature for 5h, adding 10mL of 0.1M hydrochloric acid to quench the reaction, stirring thoroughly, removing a non-fluorine phase (namely an upper solution), regulating the pH of a lower fluorine phase to 8 by using 0.1M sodium hydroxide solution, removing the upper non-fluorine phase, extracting the fluorine phase by water/isobutanol (mass ratio of 10/3) and distilling under reduced pressure to obtain 8.30g of pale yellow transparent product, wherein the yield is 87%, namely the perfluoropolyether amino compound B 4 。
Step 3: the above compound B 4 The surface treatment agent (4) was prepared by preparing 0.4% by mass of ethyl nonafluorobutyl ether (Novec 7200, 3M Co.) and then adding Dicyclohexylcarbodiimide (DCC) at a concentration of 0.02% by mass, and after sufficient dissolution, the surface treatment agent (4) was applied by spraying uniformly on the surface of a polyacrylic resin (PAA) film at a flow rate of 50mg/sec and a transport line speed of 13mm/sec using a commercially available spray coater. Before coating, plasma activating treatment is carried out on the surface of the plastic film, and after spraying, the plastic film is baked for 30min at the constant temperature of 60 ℃ to form a surface treatment layer C 4 。
Comparative example 1
The surface treatment agent OPTOOL UD509 (manufactured by Dain industries Co., ltd.) was prepared to have a concentration of 0.4% by mass with ethyl nonafluorobutyl ether (Novec 7200, 3M company), N-Diisopropylethylamine (DIPEA) having a concentration of 0.005% by mass was added thereto, and the mixture was sufficiently dissolved to obtain a surface treatment agent (5), and the surface treatment agent (5) was uniformly spray-coated on the surface of a polyethylene terephthalate (PET) film at a flow rate of 50mg/sec and a transport line speed of 13mm/sec using a commercially available spray coating apparatus. Before coating, plasma activating treatment is carried out on the surface of the plastic film, and after spraying, the plastic film is baked for 30min at the constant temperature of 60 ℃ to form a surface treatment layer C 5 。
Comparative example 2
The surface treatment agent X-71-197 (manufactured by Xinyue chemical industry Co., ltd.) was prepared with ethyl nonafluorobutyl ether (Novec 7200, 3M company) to a concentration of 0.4% by mass, 1, 3-tetramethylguanidine was added to a concentration of 0.01% by mass, and the mixture was sufficiently dissolved to obtain the surface treatment agent (6), and the surface treatment agent (6) was applied by a commercially available spray coater at a flow rate of 50mg/sec and a conveyor line speed13mm/sec, a Polycarbonate (PC) film surface was uniformly spray coated. Before coating, plasma activating treatment is carried out on the surface of the plastic film, and after spraying, the plastic film is baked for 30min at the constant temperature of 60 ℃ to form a surface treatment layer C 6 。
The films prepared in the examples and comparative examples were tested for water repellency, oil repellency, slip property, and abrasion resistance.
Hydrophobic oleophobic test: the contact angle of the surface treatment layer with water and the contact angle of n-hexadecane were measured by using a contact angle measuring instrument (Shenzhen Xin He Jib instruments, inc., XHS-CAZ 1), then the surface of the sample was cleaned with Novec 7200, and after drying, the contact angle of water on the surface of the sample was measured to make a comparison. The test results are shown in Table 1.
Slip test: the dynamic coefficient of friction against paper for public use (dab) was tested using a coefficient of friction meter (CV-3009, dongguan-sika precision instruments limited) under the following conditions: contact area: 20mm by 20mm; load: 200g; linear velocity: 200mm/min; travel: 35mm. The test results are shown in Table 1.
Steel wool abrasion resistance test: the water contact angle of the surface-treated layer after abrasion was evaluated using a multifunctional abrasion resistance tester (HG-9600, a company of Ward precision instruments, inc.) under the following conditions: steel wool: BONSTAR #0000; load: 1kg; friction area: 2cm x 2cm; and (3) moving travel: 40mm; speed of movement: 60rpm. The number of rubs was 2000 times back and forth, and the water contact angle was measured. The test results are shown in Table 2.
Resistance to rubber abrasion test: and (3) an eraser: minoan MB006004,6.0mm; load is as follows: 1kg; and (3) moving travel: 40mm; speed of movement: 40rpm; the number of rubs was 1000 back and forth, and the water contact angle was measured. The test results are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from Table 1, after Novec 7200 cleaning, the surface treatment layer obtained by adding the perfluoropolyether amine-based compound in examples 1-4 has almost no influence on the hydrophobicity, while the surface hydrophobicity of the perfluoropolyether amine-based compound in the proportion 1-2 is obviously deteriorated, which indicates that the perfluoropolyether amine-based compound of the invention has better adhesion to plastic substrates in addition to maintaining good hydrophobic and oleophobic properties compared with the commercially available products.
As can be seen from Table 2, the surface-treated layers obtained by adding the perfluoropolyether amine-based compound of examples 1 to 4 exhibited excellent abrasion resistance as compared with comparative examples 1 to 2.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and the invention is intended to encompass such modifications and improvements.
Claims (7)
1. The application of the perfluoropolyether amino compound is characterized in that: firstly dissolving a perfluoropolyether amino compound in an organic solvent, then adding an ester exchange catalyst, and coating the mixture on a plastic substrate to form a surface treatment layer;
the structural formula of the perfluoropolyether amino compound is as follows:
wherein Rf is F- (CF) 2 ) m -(OC 4 F 8 ) n -(OC 3 F 6 ) s -(OC 2 F 4 ) p -(OCF 2 ) q -O(CF 2 ) u Where n, s, p and q are each integers of 0 to 100, the sum of n, s, p and q being at least 1, with m, n, s, p and q being used in combinationThe order of presence of the repeating units in brackets is arbitrary in the formula: m and u are integers of 0 to 20 inclusive; rf has a molecular weight of 69-20000;
x is fluorine-containing or fluorine-free alkyl, phenyl, ether group, thioether group chain segment;
the repeating unit-OC 3 F 6 -comprising-OCF 2 CF 2 CF 2 -and/or-OCF (CF) 3 )CF 2 -。
2. The preparation method of the perfluoropolyether amino compound is characterized by comprising the following steps:
(1) Dissolving perfluoropolyether alcohol in a fluorine-containing solvent, adding strong base and a phase transfer catalyst, heating to 50-80 ℃, stirring and reacting for 1-3h, adding a cyano compound, continuously reacting for 3-6h, extracting, and removing the solvent under reduced pressure to obtain the perfluoropolyether cyano compound;
(2) Dissolving the perfluoropolyether cyano compound obtained in the step (1) by using a fluorine-containing solvent, adding tetrahydrofuran, uniformly mixing, adding a reducing agent under ice bath cooling, and reacting for 3-6 hours at room temperature; adding inorganic acid to quench reaction, regulating the pH value of the system to 8-9 by using inorganic alkali, extracting, decompressing and removing the solvent to obtain the perfluoropolyether amino compound;
the reducing agent in the step (2) is sodium borohydride;
the ratio of the amounts of the materials of the raw materials in the steps is as follows: perfluoropolyether alcohol: and (3) strong alkali: cyano compound: reducing agent = 1:
(1.05～6)：(1.05～6)：(1.05～6)。
3. the method for producing a perfluoropolyether amine-based compound according to claim 2, characterized in that: the fluorine-containing solvent in the step 1 and the step 2 is one or more than two of m-benzotrifluoride, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, perfluorohexane, tridecafluorooctane, 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether and trifluorotrichloroethane.
4. A process for the preparation of a perfluoropolyether amine-based compound as claimed in claim 3, characterized in that: the strong base in the step 1 is one or more than two compounds of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, potassium tert-butoxide, N-diisopropylethylamine and 1, 3-tetramethylguanidine.
5. The method for producing a perfluoropolyether amine-based compound according to claim 4, characterized in that: the phase transfer catalyst in the step 1 is a quaternary ammonium salt compound.
6. The method for producing a perfluoropolyether amine-based compound according to claim 5, characterized by: the cyano compound in step 1 is a cyano compound containing a halo group.
7. A process for the preparation of a perfluoropolyether amine-based compound as claimed in any one of claims 2 to 6, characterized in that: the use amount of the phase transfer catalyst is 0.05-20wt% of the perfluoropolyether alcohol.
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