CN112262170A - 全氟聚醚磷酸酯、其制造方法以及以其为有效成分的表面处理剂 - Google Patents
全氟聚醚磷酸酯、其制造方法以及以其为有效成分的表面处理剂 Download PDFInfo
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- CN112262170A CN112262170A CN201980039204.7A CN201980039204A CN112262170A CN 112262170 A CN112262170 A CN 112262170A CN 201980039204 A CN201980039204 A CN 201980039204A CN 112262170 A CN112262170 A CN 112262170A
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- perfluoropolyether
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- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 26
- 239000010452 phosphate Substances 0.000 title claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 21
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 16
- 239000004480 active ingredient Substances 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000021317 phosphate Nutrition 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- -1 alkyl phosphate ester Chemical class 0.000 description 6
- 239000006082 mold release agent Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 3
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- 239000004814 polyurethane Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
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- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
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- 239000007924 injection Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
-
- 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
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
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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
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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Abstract
本发明提供一种通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2PO(OH)(其中，n为1～20的整数)所示的全氟聚醚磷酸酯。通过使通式C3F7O{CF(CF3)CF2O}nCF(CF3)CH2OH所示的全氟聚醚醇与氧氯化磷反应、并对所得到的通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2POCl所示的化合物进行水解来制造该化合物。另外，该全氟聚醚磷酸酯或其盐可形成以其为有效成分的表面处理剂。
Description
技术领域
本发明涉及一种全氟聚醚磷酸酯、其制造方法以及以其为有效成分的表面处理剂。更详细地，涉及一种可有效地用作脱模剂等的全氟聚醚磷酸酯、其制造方法以及以其为有效成分的表面处理剂。
背景技术
专利文献1～3中记载有一种脱模剂，其以不具有(CH2CF2)a单元的全氟烷基烷基磷酸酯(盐)为主要成分，并在其中加入了表面活性剂、硅油、沸点为100℃以上的经高度氟化的有机化合物的至少一种或有机硅清漆。
尽管这些脱模剂显示出良好的脱模性，而且脱模寿命比现有的脱模剂长，然而，随着近来的成型品形状的复杂化，要求更进一步提高作为脱模剂的性能。另外，为了提高脱模性能、延长脱模寿命，需要添加表面活性剂或有机硅系物质。需要说明的是，没有提及磷酸酯的制造方法。
另外，专利文献4中记载有一种全氟聚醚磷酸酯，其是使通式HO(CH2CH2O)nCH2RfCH2(OCH2CH2)mOH(Rf为2价的直链全氟聚醚基，n、m为1或2)所示的二醇化合物与P2O5以1：0.25～0.7的摩尔比反应而得到的，能够对硬质表面赋予针对摩擦或高温高湿环境具有优异的耐久性的防污性。
现有技术文献
专利文献
专利文献1：日本特公昭53-23270号公报
专利文献2：日本特公昭53-23271号公报
专利文献3：日本特公昭57-48035号公报
专利文献4：日本特开2012-201709号公报
专利文献5：WO 2007/080949 A1
发明内容
发明要解决的技术问题
由于含全氟聚醚基的化合物的表面能非常小，因此具有疏水疏油性、耐化学试剂性、润滑性、脱模性、防污性等，且利用这些各种性质而广泛用于设备的防油剂、脱模剂、化妆品、保护膜等。
本发明的目的在于，提供一种全氟聚醚磷酸酯、其制造方法以及以其为有效成分的表面处理剂，所述全氟聚醚磷酸酯的疏油性特别优异，即使在耐久试验后疏油性也未明显降低。
用于解决技术问题的方案
本发明的第一目的可通过通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2PO(OH)(其中，n为1～20的整数)所示的全氟聚醚磷酸酯来实现。
另外，本发明的第二目的可通过使通式C3F7O{CF(CF3)CF2O}nCF(CF3)CH2OH(其中，n为1～20的整数)所示的全氟聚醚醇与氧氯化磷反应、并对所得到的通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2POCl(其中，n为1～20的整数)所示的化合物进行水解来实现。
进而，本发明的第三目的可通过以通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2PO(OH)(其中，n为1～20的整数)所示的全氟聚醚磷酸酯或其盐为有效成分的表面处理剂来实现。
发明的效果
本发明的全氟聚醚磷酸酯可发挥如下效果：通过将其以有机溶剂溶液、优选含氟有机溶剂溶液的形式对各种基材、优选金属表面进行处理，显现出针对油的疏油性，即使在耐久试验后其疏油性也未明显降低。
具体而言，关于树脂成型品从涂布有含氟有机溶剂溶液的金属模具的脱模性，脱模载荷小，如果涂布一次含氟有机溶剂溶液，则在50N以下的脱模载荷下可以进行脱模10次左右。
因而，本发明的全氟聚醚磷酸酯或其盐不仅可有效用作脱模剂，而且可有效用作疏水疏油剂、防污加工剂、润滑性改良剂等。
具体实施方式
全氟聚醚磷酸酯可通过如下方法来得到：使全氟聚醚醇(参见专利文献5)C3F7O{CF(CF3)CF2O}nCF(CF3)CH2OH(n为1～20的整数，优选为3～10)在以相对于其为约1～20摩尔比使用的氯化钙等脱水剂的存在下与氧氯化磷反应，并用水对所得到的〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2POCl进行水解。
〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2PO(OH)
氧氯化磷以使其相对于全氟聚醚为过量、通常为约5～10、优选约7～9的摩尔比的量来使用，接着用水对该中间产物进行水解。最终产物的全氟聚醚磷酸酯含有少许〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕PO(OH)2所示的化合物，将其分离是困难的。
通过在约100～120℃下进行第一段反应约10～30小时左右、并在内部温度90～110℃、减压下去除低沸点物质后进行减压蒸馏来进行反应，接着以使内部温度不超过60℃的方式缓慢地滴加水而进行水解反应。通过在减压下从反应混合物中去除水而得到产物。
对于所得到的全氟聚醚磷酸酯，也可以对其进行中和而以盐的形式来使用。盐的形成通过如下方法来进行：通常一边用pH来确认当量点，一边用例如氢氧化钠、氢氧化铵、硫酸锌、乙酸锌、氧化锌、三乙胺、吗啉、三乙醇胺、三(2-羟乙基)等成盐用反应剂进行滴定，形成酸性的1～3价金属盐、胺盐或铵盐。
作为所得到的全氟聚醚磷酸酯盐，可举出例如：全氟聚醚磷酸酯的钠、钾、锂、钡、镁、钙、锌等的金属盐、铵盐、经单乙基、单异丙基、二乙基、二环己基、三乙基等烷基或环烷基取代而成的铵盐、经单乙醇、二乙醇、三乙醇、二异丙醇等羟烷基取代而成的铵盐等。
通过用有机溶剂稀释全氟聚醚磷酸酯或其盐来制备使用有全氟聚醚磷酸酯或其盐的表面处理剂，以使其成为固体成分浓度为约0.01～30重量％、优选约0.03～3重量％的有机溶剂溶液。作为所使用的有机溶剂，可举出甲醇、乙醇、正丙醇、异丙醇等醇类、丙酮、甲基乙基酮、甲基异丁基酮等酮类、二乙醚、二异丙醚、二噁烷、四氢呋喃等醚类、乙酸乙酯、乙酸丁酯等酯类、甲基溶纤剂、乙基溶纤剂、甲基卡必醇、乙基卡必醇等多元醇衍生物类、四氯化碳、二氯甲烷、三氯乙烯、四氯乙烯、三氯乙烷、三氯氟甲烷、四氯二氟乙烷、三氯三氟乙烷等卤代烃类等的至少一种，优选使用含氟有机溶剂。作为含氟有机溶剂，可使用市售品、例如3M公司产品NOVEC 7200等。
在表面处理剂溶液中，也可以根据需要添加改善表面处理剂的润湿性的离子系、非离子系等的各种表面活性剂、进一步改善脱模性、润滑性的硅油、有机硅清漆等。
向金属模具涂布表面处理剂溶液可以通过浸涂、喷涂、刷涂、气溶胶喷射、基于含浸布的涂布等通常使用的任意的方法来进行。另外，作为通过涂布有表面处理剂的金属模具形成的成型材料，可举出例如：聚氨酯、聚碳酸酯、环氧树脂、酚醛树脂、聚酰亚胺树脂、氯乙烯树脂等树脂类、天然橡胶、氯丁橡胶、含氟橡胶等橡胶类。
作为金属模具以外的基材，可举出：金属(氧化物)、陶器、陶瓷、玻璃、树脂、橡胶等成型品。
实施例
下面，针对实施例来说明本发明。
实施例1
(1)在2L容量的烧瓶中，装入1226g(8.0摩尔)氧氯化磷和5.5g(0.05摩尔)氯化钙，搅拌10分钟后，添加1000g(1.0摩尔)CF3CF2CF2O{CF(CF3)CF2O}4CF(CF3)CH2OH〔PO-6-OH〕，将内部温度升高至110℃，搅拌24小时。通过1H NMR确认PO-6-OH消失了，结束反应。
在内部温度90～110℃、4.5KPa的减压下去除低沸点物质，然后使减压度为0.1KPa，在内部温度160℃下进行减压蒸馏，得到937.9g(收率85％)纯度99.2GC％的〔CF3CF2CF2O{CF(CF3)CF2O}4CF(CF3)CH2O〕2POCl〔PO6PAECl〕。
(2)在1L容量的烧瓶中，装入937.9g所得到的PO6PAECl，以使内部温度不超过60℃的方式缓慢地滴加7.8g水，在内部温度50℃下剧烈地搅拌。在搅拌24小时后，通过1H NMR确认PO6PAECl消失了，结束反应。
在内部温度50℃、0.1KPa的减压下进行脱水，得到808.9g(收率90％)透明的液体。进行1H NMR及19F NMR测定，由谱图归属确认其为目标产物。
〔CF3CF2CF2O{CF(CF3)CF2O}4CF(CF3)CH2O〕2PO(OH)〔PO6PAE〕
〔CF3CF2CF2O{CF(CF3)CF2O}4CF(CF3)CH2O〕PO(OH)2
(〔CF3CF2CF2O{CF(CF3)CF2O}4CF(CF3)CH2O〕PO(OH)2为少量，无法分离)
1H NMR(CDCl3、TMS)：ppm 4.4ppm(CFCH 2)
10.9ppm(OH)
19F NMR(CDCl3、C6F6)：ppm-85.3ppm(CF3 )
-83.0～-85.3ppm(CF3CF2 CF2 )
-83.0～-85.3ppm CH2CFCF3(OCF2CFCF3 )
-83.0～-85.3ppm CH2CFCF3(OCF2 CFCF3)
-83.0～-85.3ppm CH2CFCF3 (OCF2CFCF3)
-132.8ppm(CF3 CF2 )
-137.6ppm CH2 CFCF3(OCF2CFCF3)
-147.5ppm CH2CFCF3(OCF2 CFCF3)
实施例2
(1)在500ml容量的烧瓶中，装入215g(1.4摩尔)氧氯化磷和0.94g(0.0085摩尔)氯化钙，搅拌10分钟后，添加300g(0.17摩尔)CF3CF2CF2O{CF(CF3)CF2O}7CF(CF3)CH2OH〔PO-L-OH〕，将内部温度升高至110℃，搅拌24小时。通过1H NMR确认PO-L-OH消失了，结束反应。
在内部温度90～110℃、4.5KPa的减压下去除低沸点物质，然后使减压度为0.1KPa，在内部温度100℃下进行减压蒸馏，得到255g(收率78％)〔CF3CF2CF2O{CF(CF3)CF2O}7CF(CF3)CH2O〕2POCl〔POLPAECl〕。
(2)在300mL容量的烧瓶中，装入255g(0.13摩尔)所得到的POLPAECl，以使内部温度不超过60℃的方式缓慢地滴加7.8g水，在内部温度50℃下剧烈地搅拌。在搅拌24小时后，通过1H NMR确认POLPAECl消失了，结束反应。
在内部温度50℃、0.1KPa的减压下进行脱水，得到189g(收率77％)褐色并带有白色的浑浊液体。1H NMR及19F NMR测定的谱图的归属与实施例1相同。
〔CF3CF2CF2O{CF(CF3)CF2O}7CF(CF3)CH2O〕2PO(OH)〔POLPAE〕
〔CF3CF2CF2O{CF(CF3)CF2O}7CF(CF3)CH2O〕PO(OH)2
(〔CF3CF2CF2O{CF(CF3)CF2O}7CF(CF3)CH2O〕PO(OH)2为少量，无法分离)
实施例3
在99.5g含氟有机溶剂(3M公司产品NOVEC 7200)中，加入0.5g实施例1中所得到的PO6PAE，搅拌约30分钟，制备了制备液A-1。
在该制备液A-1中，在浸渍时间5秒、上提速度2mm/秒的条件下对镀铬的铜板试验片(25×75×1.2mm)进行浸涂，并在150℃下进行烘烤1小时。
初始性能(用十六烷测定静态接触角)为73°，耐久性能(用含棉100％的布在试验片上施加20g/cm2的载荷，在进行2000次滑动后，用十六烷测定静态接触角)为65°。
实施例4
在实施例3中，使用在实施例2中所得到的POLPAE替代PO6PAE来制备制备液B-2，使用制备液B-2测定初始性能和耐久性能，所得到的值分别为73°和66°。
比较例1
在实施例3中，使用
(CF3CF2CF2CF2CF2CF2CH2CH2O)2PO(OH)〔C6PAE〕
(CF3CF2CF2CF2CF2CF2CH2CH2O)PO(OH)2
((CF3CF2CF2CF2CF2CF2CH2CH2O)PO(OH)2为少量，无法分离)
替代PO6PAE来制备制备液C-3，使用制备液C-3测定初始性能和耐久性能，所得到的值分别为60°和30°。
实施例5
在实施例1所得到的0.1g PO6PAE中加入65g异丙醇和34.7g水，一边进行搅拌一边添加0.2g三乙胺，搅拌约30分钟，制备表面处理剂A-4。
在喷涂该表面处理剂A-4并预热至80℃的铝制金属模具(直径45mm、深度50mm)内，将100重量份加热至80℃的聚氨酯预聚物(日本聚氨酯产品Coronate C-4090)和12.8重量份经加热熔融的亚甲基双邻氯苯胺固化剂(IHARA CHEMICAL产品Ihara Cuamine MT)搅拌混合后注入，同时注意不要夹带气泡。
在加热固化前，在注入部中央设置用于取出固化成型品的钩子。在120℃下将注入物加热固化1小时后，测定拉伸钩子而从金属模具中取出成型品时的脱模载荷，结果为10N。
另外，在如此操作求出金属模具脱模性后，涂布1次脱模剂(表面处理剂A-4)，测定在50N以下的脱模载荷条件下的脱模次数，结果是可以达到9次脱模。
实施例6
在实施例5中，使用利用实施例2中所得到的POLPAE而制备的表面处理剂A-5替代表面处理剂A-4，得到的结果是金属模具脱模性为10N、脱模寿命为11次。
比较例2
在实施例5中，使用利用比较例1中所得到的C6PAE而制备的制备液C-5替代表面处理剂A-4，，得到的结果是金属模具脱模性为15N、脱模寿命为2次。
比较例3
在实施例5中，使用未喷涂表面处理剂的铝制金属模具而进行脱模试验时，聚氨酯成型品密合在金属模具上，无法使其脱模。
权利要求书(按照条约第19条的修改)
1.一种由通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2PO(OH)所示的全氟聚醚磷酸酯的制造方法，通式中，n为1～20的整数，所述制造方法的特征在于，在氯化钙脱水剂的存在下，使通式C3F7O{CF(CF3)CF2O}nCF(CF3)CH2OH所示的全氟聚醚醇与氧氯化磷反应，通式中，n为1～20的整数，并对所得到的通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2POCl所示的化合物进行水解，通式中，n为1～20的整数。
2.一种脱模剂，所述脱模剂以通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2PO(OH)所示的全氟聚醚磷酸酯或其盐为有效成分，通式中，n为1～20的整数。
3.根据权利要求2所述的脱模剂，所述脱模剂以有机溶剂溶液的形式来制备。
4.根据权利要求3所述的脱模剂，其中，有机溶剂溶液为含氟有机溶剂溶液。
Claims (7)
1.一种由通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2PO(OH)所示的全氟聚醚磷酸酯，通式中，n为1～20的整数。
2.一种由通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2PO(OH)所示的全氟聚醚磷酸酯的制造方法，通式中，n为1～20的整数，所述制造方法的特征在于，使通式C3F7O{CF(CF3)CF2O}nCF(CF3)CH2OH所示的全氟聚醚醇与氧氯化磷反应，通式中，n为1～20的整数，并对所得到的通式〔C3F7O{CF(CF3)CF2O}nCF(CF3)CH2O〕2POCl所示的化合物进行水解，通式中，n为1～20的整数。
3.根据权利要求2所述的全氟聚醚磷酸酯的制造方法，其中，在氯化钙脱水剂的存在下进行反应。
4.一种表面处理剂，其以权利要求1所述的全氟聚醚磷酸酯或其盐为有效成分。
5.根据权利要求4所述的表面处理剂，所述表面处理剂用作脱模剂。
6.根据权利要求4或5所述的表面处理剂，所述表面处理剂以有机溶剂溶液的形式来制备。
7.根据权利要求6所述的表面处理剂，其中，有机溶剂溶液为含氟有机溶剂溶液。
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| CN116003770A (zh) * | 2022-12-23 | 2023-04-25 | 湖南柯盛新材料有限公司 | 一种全氟聚醚磷酸酯类化合物及其制备方法和应用 |
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- 2019-05-31 WO PCT/JP2019/021819 patent/WO2019239927A1/ja active Application Filing
- 2019-05-31 CN CN201980039204.7A patent/CN112262170A/zh active Pending
- 2019-05-31 JP JP2020525445A patent/JP7045454B2/ja active Active
- 2019-05-31 US US16/973,970 patent/US20210253610A1/en active Pending
- 2019-05-31 EP EP19819069.6A patent/EP3808791B1/en active Active
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| CN113549211A (zh) * | 2021-06-04 | 2021-10-26 | 广州优尔材料科技有限公司 | 含全氟聚醚的磷酸化合物、表面处理剂及物品 |
| CN113549211B (zh) * | 2021-06-04 | 2024-01-26 | 广州优尔材料科技有限公司 | 含全氟聚醚的磷酸化合物、表面处理剂及物品 |
| CN116003770A (zh) * | 2022-12-23 | 2023-04-25 | 湖南柯盛新材料有限公司 | 一种全氟聚醚磷酸酯类化合物及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
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| WO2019239927A1 (ja) | 2019-12-19 |
| KR20210013174A (ko) | 2021-02-03 |
| KR102610032B1 (ko) | 2023-12-06 |
| JP7045454B2 (ja) | 2022-03-31 |
| EP3808791A4 (en) | 2022-03-02 |
| JPWO2019239927A1 (ja) | 2021-07-08 |
| EP3808791B1 (en) | 2023-01-04 |
| US20210253610A1 (en) | 2021-08-19 |
| EP3808791A1 (en) | 2021-04-21 |
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