CN107022072A - A kind of readily soluble side chain fluorochemical polyether glycol by perfluor substituted epoxy ethane and polynary cyclic ethers copolymerization - Google Patents
A kind of readily soluble side chain fluorochemical polyether glycol by perfluor substituted epoxy ethane and polynary cyclic ethers copolymerization Download PDFInfo
- Publication number
- CN107022072A CN107022072A CN201710155883.7A CN201710155883A CN107022072A CN 107022072 A CN107022072 A CN 107022072A CN 201710155883 A CN201710155883 A CN 201710155883A CN 107022072 A CN107022072 A CN 107022072A
- Authority
- CN
- China
- Prior art keywords
- oxirane
- glycol
- side chain
- fluorine
- subsituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 63
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract description 16
- 150000004292 cyclic ethers Chemical class 0.000 title abstract description 15
- 229920000570 polyether Polymers 0.000 title abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 46
- 239000011737 fluorine Substances 0.000 claims abstract description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 150000002921 oxetanes Chemical class 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000012071 phase Substances 0.000 claims description 20
- 238000013517 stratification Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- -1 BFEE Chemical compound 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical class [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000014121 butter Nutrition 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 235000013305 food Nutrition 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Chemical class 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical class Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical class OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 abstract description 7
- 230000002940 repellent Effects 0.000 abstract description 6
- 239000005871 repellent Substances 0.000 abstract description 6
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- LKMRAOVVQDGQBL-UHFFFAOYSA-N 2-(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-nonadecafluorononyl)oxirane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1CO1 LKMRAOVVQDGQBL-UHFFFAOYSA-N 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 2
- MVZODTFBTJNDMW-UHFFFAOYSA-N 2-[(2-methylphenyl)-[(2-methylphenyl)-(oxiran-2-yl)methoxy]methyl]oxirane Chemical class CC1=CC=CC=C1C(C1OC1)OC(C=1C(=CC=CC=1)C)C1OC1 MVZODTFBTJNDMW-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- GXOYTMXAKFMIRK-UHFFFAOYSA-N 2-heptyloxirane Chemical compound CCCCCCCC1CO1 GXOYTMXAKFMIRK-UHFFFAOYSA-N 0.000 description 1
- QBJWYMFTMJFGOL-UHFFFAOYSA-N 2-hexadecyloxirane Chemical compound CCCCCCCCCCCCCCCCC1CO1 QBJWYMFTMJFGOL-UHFFFAOYSA-N 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XXCRKUPYARMPDQ-UHFFFAOYSA-N [F].CCCCCCCCCCCCCC Chemical class [F].CCCCCCCCCCCCCC XXCRKUPYARMPDQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical class CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing 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
- C08G65/04—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 from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
-
- 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
- C08G65/04—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 from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
-
- 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
- C08G65/04—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 from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a kind of by perfluor substituted epoxy ethane and the readily soluble side chain fluorochemical polyether glycol of polynary cyclic ethers copolymerization, copolyreaction is carried out by perfluoroalkyl substituted epoxy ethane, subsituted oxirane and oxetanes or tetrahydrofuran and is prepared from.The present invention can synthesize the fluorine-containing copolyether glycol of side chain of different Oil repellents by feed change ratio, make full use of fluorine raw material；The subsituted oxirane of different substituents can be selected according to the fluorine-containing copolyether glycol subsequent reactions purposes of side chain simultaneously, the defect of the serious inconvenience processing of organofluorine compound process split-phase is solved；Furthermore, the fluorine-containing copolyether glycol of such side chain is soluble in industrial general, cheap nontoxic or low toxicity solvent, and this can largely reduce processing cost, reduces processing environment pollution.In a word, the fluorine-containing copolyether glycol of side chain that the present invention is provided extremely convenient in follow-up various uses, has also expanded the use space of such PTMEG to a great extent.
Description
Technical field
The invention belongs to the intermediate technical field of high polymer material, and in particular to it is a kind of by perfluor substituted epoxy ethane with
Readily soluble side chain fluorochemical polyether glycol of polynary cyclic ethers copolymerization and preparation method thereof.
Background technology
Element fluorine due to 4.0 electronegativity, and atomic radius be it is minimum in addition to hydrogen in all elements periodic table,
So the carbon-fluorine bond in fluoropolymer possesses shorter bond distance and larger bond energy.This causes fluoropolymer has good
Chemical stability and to heat endurance.For polymer containing perfluorinated side chains, fluorine atom is along side chain carbon-carbon bond in close-packed arrays, crowd
Many perfluorinated side chains are migrated to the gas-solid interface of main chain due to immiscible with main chain, effectively protect main chain not by extraneous factor
The direct effect of such as ultraviolet, chemical attack and ozone, improves the weatherability of this kind of compound, inoxidizability and corrosion-resistant
Property.Moreover, because perfluoroalkyl has extremely low surface free energy, if it is covered in the surface of polymer, it can assign
Polymer is with excellent water repellency, oil repellent, wearability, low-friction coefficient and soil repellency energy.Patent US5100569 is by perfluor alkane
The substitute that hexadecyl ethylene oxide generates low molecular CFC with oxirane copolymerization is used for air-conditioning and the heat exchange of refrigerator is situated between
Matter.In fact, important component of the both-end hydroxy polyethers glycol as polymer such as synthesizing polyester and polyurethane, in daily life and
The various aspects of high-tech sector have obtained many important applications.And the introducing of fluorine-containing side base then being permitted organic fluorine material
In the PTMEG that many excellent properties are brought into so that related material is on the basis of original excellent properties are retained, grafting
There are the various performances of organic fluorine material.- CF in the alkyl of perfluor substitution2- and-CF3In the effect for the surface energy for playing reduction material
On also differ, if all by-CF3Close bed is arranged in, such skin surface tension force low can arrive 6mN/m, equivalent to
Contact angle with water is more than 130 degree, and all-CF2- by being arranged in close bed, its surface tension then high will arrive 18mN/m, quite
In with the contact angle of water be 100 degree or so.When designing side chain fluorochemical polyether, it is necessary to as far as possible by more-CF3Design enters
In side chain, while realization can play fluorine element superior function using less fluorine-containing side chain, additionally it is possible to have more-CF3End
Base produces bigger efficiency.Patent CN2013107367731 and patent CN201310738875.7 are reported with different in size
Perfluoroalkyl substitution ternary cyclic ethers and quaternary or five-membered ring ether four kinds of monomers polynary ring opening copolymer.Above-mentioned various sides
The fluorine-containing homopolymerization of chain, the polynary fluorinated copolymer of the open loop of binary copolymerization or a variety of cyclic ether monomers, exist and make two to some extent
The deficiency of aspect：(1) the side chain fluorine-containing polyether glycol prepared by controls Oil repellent certain difficulty；(2) prepared by
Side chain fluorine-containing polyether glycol is not easily dissolved in industrially general, cheap nontoxic or low toxicity solvent.This two side
The factor in face result in：1) expensive fluorine element can not make the best use of everything, and cause the waste of efficient resource；2) it is this kind of fluorine-containing poly-
The raw material that further reacting or mixing with it occur in post-processing in ether glycol is miscible difficult, harsh to required solvent, enters
And cause use cost to rise and bring the pollution of processing environment.
The content of the invention
Present invention aims to overcome that the deficiencies in the prior art there is provided a kind of fluorine-containing copolyether glycol of readily soluble side chain and its
Preparation method, the fluorine-containing copolyether glycol of the side chain is by subsituted oxirane, perfluoroalkyl ethylene oxide and quaternary cyclic ethers oxa- ring
Butane or five-membered ring ether tetrahydrofuran carry out triple cationic copolymerization and formed, and the side chain that can obtain expected different Oil repellents is fluorine-containing
Copolyether glycol, and the fluorine-containing copolyether glycol dissolubility of the side chain is outstanding, it is readily soluble in general, nontoxic or low poison solvent.
The above-mentioned purpose of the present invention is achieved by following technical scheme：
What a kind of subsituted oxirane, perfluoroalkyl substituted epoxy ethane and oxetanes or tetrahydrofuran copolymerization were obtained
The fluorine-containing copolyether glycol of side chain, with the molecular structure as shown in structural formula I：
Wherein：
P is any number in 1 or 2；N is any number in 0 or 1；M is any one natural number in 4~13；Q is 0 or 3 liang
Any number in person；X, y and z are any one natural number in 1~100；
y：(x+z) it is 5~1：In the range of 1；x：Z is 20~1：In the range of 1；
R is any one in hydrogen, saturated alkyl, saturation alkoxy, phenoxy group, benzyloxy.
Its number-average molecular weight is 1000~10000g/mol, is colourless or pale yellow transparent viscous liquid.
The preparation method of above-mentioned copolyether glycol, by perfluoroalkyl substituted epoxy ethane, subsituted oxirane and oxa- ring
Butane or tetrahydrofuran carry out copolyreaction and are prepared from, and its reaction equation is expressed from the next：
Wherein：
P is any number in 1 or 2；N is any number in 0 or 1；M is any one natural number in 4~13；Q is 0 or 3 liang
Any number in person；X, y and z are any one natural number in 1~100；
y：(x+z) it is 5~1：In the range of 1；x：Z is 20~1：In the range of 1；
R is any one in hydrogen, saturated alkyl, saturation alkoxy, phenoxy group, benzyloxy.
Preferably, any one of the perfluoroalkyl substituted epoxy ethane in following structural compounds：
Wherein, n is any number in 0 or 1；M is any one natural number in 4~13.
Preferably, any one of the subsituted oxirane in following structural compounds：
Wherein, L is any natural number in 0 to 10.
Described preparation method specifically includes the following steps：
(1) raw material prepares：Subsituted oxirane and perfluoroalkyl substituted epoxy ethane, both molal quantity sums and oxa-
The ratio between molal quantity of one of cyclobutane or tetrahydrofuran is 1：In the range of 5~1, wherein subsituted oxirane and perfluoroalkyl
Substituted epoxy ethane mol ratio is 20~1：1, the amount that cationic initiator discharges cationic substance accounts for total monomer total material
Amount 2%~7%, glycol initiator accounts for the 2.5%~7% of the amount of total monomer material；By subsituted oxirane and perfluor alkane
Base substituted epoxy ethane is dissolved into solvent, and solute concentration is 1~20 mol/L in solution；
(2) solvent, oxetanes or tetrahydrofuran, cation are added in reactor of the anhydrous and oxygen-free equipped with agitator
Initiator and glycol initiator, at a temperature of -10 DEG C~15 DEG C, substitution ring in above-mentioned steps (1) is slowly added dropwise into kettle simultaneously
Ethylene Oxide and perfluoroalkyl substituted epoxy ethane solution, then at -10 DEG C~15 DEG C, polymerisation is added after 5~15 hours
The deionized water terminating reaction of the amount of 3~10 times of glycol starter substances；
(3) after terminating reaction, steam and reclaim the organic solvent in reactor, then add 1.5 of mixture after distillation
The distilled water of~2.5 times of volumes, with the alkali compounds such as sodium carbonate, sodium acid carbonate, ammonium carbonate, Ammonium bicarbonate food grade or sodium hydroxide
With pH value to 7, agitator treating, stratification separate aqueous phase, and oil phase washed once with distilled water again, stratification, oil phase
After dehydrating, the fluorine-containing copolyether glycol of side chain is produced through removing solvent.
Preferably, subsituted oxirane and perfluoroalkyl substituted epoxy ethane solution dripped in 1~6 hour in step (2)
Add into.
Preferably, the solvent of step (1) dissolving subsituted oxirane and perfluoroalkyl substituted epoxy ethane is selected from dichloromethane
One kind in alkane, Isosorbide-5-Nitrae-dioxane, ether, tetrahydrofuran, dibutyl ethers, acetone, butanone.
Preferably, oleum of the cationic initiator selected from mass fraction 20%, perchloric acid, trifluoroacetic acid, three
Methyl fluoride sulfonic acid, BFEE, trichloroacetic acid, phosphoric acid, alchlor, titanium tetrachloride, butter of tin, zinc chloride, five
One kind in antimony chloride.
Preferably, the one kind of glycol initiator in ethylene glycol, 1,2-PD, 1,3-PD, BDO
Or it is a variety of.
Beneficial effects of the present invention：
The present invention uses subsituted oxirane and perfluoroalkyl substituted epoxy ethane and quaternary cyclic ethers or five-membered ring ether wherein
One of carry out copolymerization, the beneficial effect with so several aspects：(1) can by change perfluoroalkyl substituted epoxy ethane with
Three's material rate of subsituted oxirane and one of quaternary cyclic ethers or five-membered ring ether, synthesizes expected different Oil repellents
The fluorine-containing copolyether glycol of side chain, expensive fluorine raw material is made full use of to greatest extent；(2) because various structures group can
To be substituted on expoxy propane, so can according to the fluorine-containing copolyether glycol of side chain carry out next step reaction raw material mix,
Selection carries out copolymerization with the propylene oxide monomer that the same or like substituted radical of reaction raw materials solubility parameters is participated in next step,
So when synthesized side chain fluorochemical polyether glycol and next step raw material react, it is possible to easily solve organofluorine compound
Serious split-phase in processing, it is immiscible the problem of；(3) the fluorine-containing copolyether glycol of such side chain is industrially general, cheap
Nontoxic or low toxicity solvent in be easy to dissolving, this can largely reduce processing cost, reduce the pollution of processing environment.Always
It, the fluorine-containing copolyether glycol of side chain that the present invention is provided extremely convenient in follow-up various uses is also expanded to a great extent
The use space of such PTMEG.
Embodiment
The essentiality content of the present invention is specifically introduced with reference to embodiment, but the protection model of the present invention is not limited with this
Enclose.The routine test operation that the test operation not being described in detail in experiment is well known to the skilled person.
Embodiment 1
By 0.95 mole of 0.05 mole of 2- (27 fluorine myristyl) oxirane and 2- methylphenylglycidyl ethers
It is dissolved in together and uses 100mL dichloromethane, forms the dichloromethane solution of ternary cyclic ethers.
Then, the oxetanes of 5 moles of addition, 50mL dichloromethane, 0.15 mole of 98% dense sulphur into 1000mL kettles
Acid and 0.18 mole of ethylene glycol, cool to -10 DEG C, after stirring 20 minutes and maintain this temperature, and 2- (the 27 fluorine tetradecanes are added dropwise
Base) 0.95 mole of 0.05 mole of oxirane and 2- methylphenylglycidyl ethers dichloromethane solution, control in 2 hours
Drip off.- 10 DEG C are maintained, is reacted 10 hours.20ml deionized water terminating reactions are added, solvent is steamed, uses sodium bicarbonate solution
Neutralize neutrality.200mL deionized waters stirring washing 20 minutes is added, stratification, the rotated evaporimeter of oil phase removes solvent,
Obtain the fluorine-containing thick PTMEG of side chain.Add 100mL deionized waters again to wash 20 minutes, stratification, oil phase is used again
Distilled water washed once, stratification.Oil phase is dried in vacuo at 120 DEG C, under 5mm mercurypressures again, obtains product colourless viscous
Thick liquid, yield is 72%, is determined through gpc analysis instrument,Gram/mol,Fluorinated volume 7.1%,
Side chain fluorochemical polyether glycol numbering is HFJM-1.
Embodiment 2
0.5 mole of 0.1 mole of 2- (17 fluorine nonyl) oxirane and benzyl glycidyl ether are dissolved in use together
200mL ether, the diethyl ether solution of formation.
In the kettle of the 1000mL equipped with agitator, after air in pure nitrogen gas displacement kettle, -5 DEG C of addition 100mL are cooled to
Ether adds 1.8 moles of oxetanes, 0.072 mole and 0.12 mole butanediol of perchloric acid as solvent.Be added dropwise it is above-mentioned by
What the 0.5 mole of dissolving of 2- (17 fluorine nonyl) 0.1 mole of oxirane and benzyl glycidyl ether was formed with 200mL ether
Diethyl ether solution, control is added dropwise to be completed in 3 hours.Kept for -5 DEG C, reacted 8 hours, added 30ml deionized waters terminating reaction and steam
Go out solvent, neutralized with sodium carbonate liquor to neutrality.Add 200mL deionized waters to wash 20 minutes, stratification, oil phase is used again
Distilled water washed once, stratification.Oil phase is dried in vacuo at 120 DEG C, under 5mm mercurypressures again, obtains product colourless viscous
Thick liquid, yield is 84%, is determined through gpc analysis instrument,Gram/mol,Fluorinated volume
16.4%, side chain fluorochemical polyether glycol numbering is HFJM-2.
Embodiment 3
0.3 mole of 0.15 mole of 2- perfluoropentyls oxirane and benzyl glycidyl ether are dissolved in 250mL third together
Ketone, forms the acetone soln of ternary cyclic ethers.
In the kettle of the 1000mL equipped with agitator, after air in pure nitrogen gas displacement kettle, -0 DEG C of addition 100mL is cooled to
Acetone adds 0.45 mole of tetrahydrofuran, 0.0225 mole and 0.027 mole butanediol of perchloric acid as solvent.It is added dropwise above-mentioned
250mL acetone is formed third is dissolved in by 0.3 mole of 0.15 mole of 2- perfluoropentyls oxirane and benzyl glycidyl ether
Ketone solution, control is added dropwise to be completed in 3 hours.Kept for 0 DEG C, reacted 10 hours, added 50ml deionized water terminating reactions, steam
Solvent, is neutralized to neutrality with carbonic acid amine aqueous solution.Add 200mL deionized waters to wash 20 minutes, stratification, oil phase is used again
Distilled water washed once, stratification.Oil phase is dried in vacuo at 120 DEG C, under 5mm mercurypressures again, obtains product colourless viscous
Thick liquid, yield is 89%, is determined through gpc analysis instrument,Gram/mol,Fluorinated volume
29.6%, side chain fluorochemical polyether glycol numbering is HFJM-3.
Embodiment 4
0.2 mole of 0.1 mole of 2- perfluor heptyl oxirane and butyl glycidyl ether are dissolved in together and use 200mL tetrahydrochysenes
Furans, the tetrahydrofuran solution of formation.
In the kettle of the 1000mL equipped with agitator, after air in pure nitrogen gas displacement kettle, 5 DEG C of addition oxa- rings are cooled to
0.9 mole of butane, 0.024 mole and 0.072 mole 1,2- propane diols of trifluoroacetic acid.It is added dropwise above-mentioned by 2- perfluor heptyl epoxies
0.2 mole of 0.1 mole of ethane and butyl glycidyl ether are dissolved in the solution formed with 200mL tetrahydrofurans, control drop together
It is added in 2 hours and completes.Kept for 5 DEG C, 6 hours, add 30mL deionized water terminating reactions, steam solvent, use sodium carbonate liquor
Neutralize neutrality.200mL deionized waters stirring washing 20 minutes is added, stratification, oil phase washed once with distilled water again,
Stratification.It is dried in vacuo again at 120 DEG C, under 5mm mercurypressures, obtains product colorless viscous shape liquid, yield is 69%,
Determined through gpc analysis instrument,Gram/mol,Fluorinated volume 34.5%, the side chain fluorochemical polyether glycol
Numbering is HFJM-4.
Embodiment 5
1 mole of 0.25 mole of 2- (ten trifluoro heptyl) oxirane and butyl glycidyl ether are dissolved in together and use 150mL
Tetrahydrofuran, forms the tetrahydrofuran solution of ternary cyclic ethers.
In the kettle of the 1000mL equipped with agitator, after air in pure nitrogen gas displacement kettle, 2 DEG C of addition tetrahydrochysene furans are cooled to
Mutter 1.9 moles, 0.25 mole and 0.25 mole 1,2- propane diols of BFEE.It is added dropwise above-mentioned by 2- (ten trifluoro heptyl) ring
1 mole of 0.25 mole of oxidative ethane and butyl glycidyl ether are dissolved in the solution formed with 150mL tetrahydrofurans, and control is added dropwise
Completed in 3 hours.Kept for 2 DEG C, reacted 5 hours, added 50ml deionized water terminating reactions, steam solvent, it is molten with sodium acid carbonate
Liquid is neutralized to neutrality.250mL deionized waters stirring washing 20 minutes is added, stratification, oil phase uses distillation water washing one again
Secondary, stratification obtains the fluorine-containing thick PTMEG of side chain.Oil phase is dried in vacuo at 120 DEG C, under 5mm mercurypressures again, is obtained
To product colorless viscous shape liquid, yield is 72%, is determined through gpc analysis instrument,Gram/mol,
Fluorinated volume 19.7%, side chain fluorochemical polyether glycol numbering is HFJM-5.
Embodiment 6
0.5 mole of 0.1 mole of 2- (perfluoro capryl) oxirane and 1,2- 7-oxa-bicyclo[4.1.0s are dissolved in together and use 200mL1,
4- dioxane, forms Isosorbide-5-Nitrae-dioxane solution.
In the kettle of the 1000mL equipped with agitator, replaced with pure nitrogen gas in kettle after air, cool to 10 DEG C, add Isosorbide-5-Nitrae-
Dioxane 100mL makees solvent, adds 2.4 moles of oxetanes, 0.09 mole and 0.165 mole second two of BFEE
Alcohol.Dropwise addition is above-mentioned by the 0.5 mole of dissolving of 0.1 mole of 2- (perfluoro capryl) oxirane and 1,2- 7-oxa-bicyclo[4.1.0s and 200mL1,
4- dioxane forms Isosorbide-5-Nitrae-dioxane solution of ternary, and control is added dropwise to be completed in 5 hours.Keep 10 DEG C, reaction 15
Hour, 60mL deionized water terminating reactions are added, solvent is steamed, are neutralized with sodium bicarbonate solution to neutrality.Add 200mL go from
Sub- water stirring washing 20 minutes, stratification, oil phase washed once with distilled water again, and stratification obtains side chain fluorine-containing
Thick PTMEG.Oil phase, then be dried in vacuo at 120 DEG C, under 5mm mercurypressures, obtain product colorless viscous shape liquid, yield
For 76%, determined through gpc analysis instrument,Gram/mol,Fluorinated volume 26.3%, the side chain is fluorine-containing poly-
Ether glycol numbering is HFJM-6.
Comparative example 7 is synthesized according to the embodiments of granted patent ZL 201310736773.1
150mL dichloromethane is added in the autoclave pressure of the 500mL equipped with agitator as solvent, kettle is replaced with pure nitrogen gas
Middle air 20 minutes.Then according to 2- (perfluor nonyl) oxirane：2- (perfluorododecyl) oxirane：Tetrahydrofuran：
Boron trifluoride etherate：The mol ratio of ethylene glycol is 0.1：0.25：0.65：0.06：0.06 ratio gets out each reactant.
Take two kinds of perfluor substituted epoxy ethane：0.1 mole of 2- (perfluor nonyl) oxirane and 2- (perfluorododecyl)
0.25 mole of oxirane, while being dissolved in 50mL dichloromethane, the dichloromethane solution for obtaining perfluor substituted epoxy ethane is standby
With.
0.06mol boron trifluoride etherates and 0.06mol ethylene glycol are added first into kettle, 20 points are stirred at 5 DEG C
Zhong Hou, cools to -10 DEG C and maintains this temperature, while disposably adding 0.65 mole of tetrahydrofuran, above-mentioned perfluor is then added dropwise
The dichloromethane solution of substituted epoxy ethane.The dichloromethane solution of tetrahydrofuran and perfluor substituted epoxy ethane is at 3 hours
Inside drip off.Maintain -10 DEG C to react 1 hour, be then warming up to 5 DEG C and react 4 hours, continue to be warming up to room temperature reaction 40 hours.
20mL deionized water terminating reactions, are neutralized to neutrality with aqueous sodium carbonate.Distilling off solvent.200mL deionized waters are added to stir
Mix 20 minutes, stratification, separate aqueous phase, oil phase is again with distillation water washing.Then removed under 120 DEG C of oil phase, 2mm mercury column pressure
Decontamination, obtains the copolyether glycol resin that side chain contains different perfluor substituted epoxy ethane and cyclic ethers.Yield is 72%.Through end
Base analytic approach confirms that the equal mean molecule quantity of number is 4480 grams/mol, and fluorine mass content is 53.4%.The side chain fluorochemical polyether two
Alcohol numbering is HFJM-7.
The effect example of embodiment 8
The fluorine-containing copolyether glycol of side chain synthesized to embodiment 1-7 carries out different solvents dissolution experiment, specific experiment side
Method is：Take eight 50mL single-necked flask, added respectively in eight flasks 40mL ether, 40mL dibutyl ethers, 40mL acetone,
40mL butanone, 40mL cyclohexanone, 40mL dichloromethane, 40mL ethyl acetate, 40mL butyl acetates and 40mL tetrahydrofurans, then
It is added in the fluorine-containing copolyether glycol of side chain for weighing 10 grams of above example in each solvent bottle, adds magneton and stir 30 points
Clock, then by ultrasonic disperse 10 minutes, place 24 hours, the dissolving situation in observation each sample flask.Experimental result such as table 1.
Dissolving result table of each embodiment sample of table 1 in common solvent
The present invention uses subsituted oxirane and perfluoroalkyl substituted epoxy ethane and quaternary cyclic ethers or five-membered ring ether wherein
One of carry out copolymerization, the beneficial effect with so several aspects：(1) can by change perfluoroalkyl substituted epoxy ethane with
Three's material rate of subsituted oxirane and one of quaternary cyclic ethers or five-membered ring ether, synthesizes expected different Oil repellents
The fluorine-containing copolyether glycol of side chain, expensive fluorine raw material is made full use of to greatest extent；(2) because various structures group can
To be substituted on expoxy propane, so can according to the fluorine-containing copolyether glycol of side chain carry out next step reaction raw material mix,
Selection carries out copolymerization with the propylene oxide monomer that the same or like substituted radical of reaction raw materials solubility parameters is participated in next step,
So when synthesized side chain fluorochemical polyether glycol and next step raw material react, it is possible to easily solve organofluorine compound
Serious split-phase in processing, it is immiscible the problem of；(3) the fluorine-containing copolyether glycol of such side chain is industrially general, cheap
Nontoxic or low toxicity solvent in be easy to dissolving, this can largely reduce processing cost, reduce the pollution of processing environment.Always
It, the fluorine-containing copolyether glycol of side chain of the present invention extremely convenient in follow-up various uses has also expanded such to a great extent
The use space of PTMEG.
The effect of above-described embodiment is the specific essentiality content for introducing the present invention, but those skilled in the art should know
Protection scope of the present invention, should not be confined to the specific embodiment by road.
Claims (10)
1. the side that a kind of subsituted oxirane, perfluoroalkyl substituted epoxy ethane and oxetanes or tetrahydrofuran copolymerization are obtained
The fluorine-containing copolyether glycol of chain, it is characterised in that with the molecular structure as shown in structural formula I：
Wherein：
P is any number in 1 or 2；N is any number in 0 or 1；M is any one natural number in 4~13；Q is 0 or 3 in both
Any number；X, y and z are any one natural number in 1~100；
y：(x+z) it is 5~1：In the range of 1；x：Z is 20~1：In the range of 1；
R is any one in hydrogen, saturated alkyl, saturation alkoxy, phenoxy group, benzyloxy.
2. copolyether glycol according to claim 1, it is characterised in that：Its number-average molecular weight is 1000~10000g/
mol。
3. the preparation method of copolyether glycol described in claim 1 or 2, it is characterised in that by perfluoroalkyl substituted epoxy ethane,
Subsituted oxirane and oxetanes or tetrahydrofuran carry out copolyreaction and are prepared from, and its reaction equation is expressed from the next：
Wherein：
P is any number in 1 or 2；N is any number in 0 or 1；M is any one natural number in 4~13；Q is 0 or 3 in both
Any number；X, y and z are any one natural number in 1~100；
y：(x+z) it is 5~1：In the range of 1；x：Z is 20~1：In the range of 1；
R is any one in hydrogen, saturated alkyl, saturation alkoxy, phenoxy group, benzyloxy.
4. preparation method according to claim 3, it is characterised in that the perfluoroalkyl substituted epoxy ethane is selected from as follows
Any one in structural compounds：
Wherein, n is any number in 0 or 1；M is any one natural number in 4~13.
5. preparation method according to claim 3, it is characterised in that the subsituted oxirane is selected from following structure chemical combination
Any one in thing：
Wherein, L is any natural number in 0 to 10.
6. preparation method according to claim 3, it is characterised in that comprise the following steps：
(1) raw material prepares：Subsituted oxirane and perfluoroalkyl substituted epoxy ethane, both molal quantity sums and oxa- ring fourth
The ratio between molal quantity of one of alkane or tetrahydrofuran is 1：In the range of 5~1, wherein subsituted oxirane and perfluoroalkyl replace
Molar ratio is 20~1：1, the amount that cationic initiator discharges cationic substance accounts for the amount of total monomer total material
2%~7%, glycol initiator accounts for the 2.5%~7% of the amount of total monomer material；Subsituted oxirane and perfluoroalkyl are taken
It is dissolved into for oxirane in solvent, solute concentration is 1~20 mol/L in solution；
(2) solvent, oxetanes or tetrahydrofuran, cation is added in reactor of the anhydrous and oxygen-free equipped with agitator to trigger
Agent and glycol initiator, at a temperature of -10 DEG C~15 DEG C, substituted epoxy third in above-mentioned steps (1) is slowly added dropwise into kettle simultaneously
Alkane and perfluoroalkyl substituted epoxy ethane solution, then at -10 DEG C~15 DEG C, polymerisation is after 5~15 hours, add 3~
The deionized water terminating reaction of the amount of 10 times of glycol starter substances；
(3) after terminating reaction, steam and reclaim the organic solvent in reactor, then add 1.5~2.5 of mixture after distillation
The distilled water of times volume, with alkali compounds and pH value is to 7, agitator treating, stratification separate aqueous phase, and oil phase is used again
Distilled water be washed once, stratification, after oil phase is dehydrated, and the fluorine-containing copolyether glycol of side chain is produced through removing solvent.
7. preparation method according to claim 6, it is characterised in that：Subsituted oxirane and perfluor alkane in step (2)
Base substituted epoxy ethane solution should be added dropwise to complete in 1~6 hour.
8. preparation method according to claim 6, it is characterised in that：Step (1) dissolves subsituted oxirane and perfluor alkane
The solvent of base substituted epoxy ethane is selected from dichloromethane, Isosorbide-5-Nitrae-dioxane, ether, tetrahydrofuran, dibutyl ethers, acetone, fourth
One kind in ketone.
9. preparation method according to claim 6, it is characterised in that：The cationic initiator is selected from mass fraction 20%
Oleum, perchloric acid, trifluoroacetic acid, trifluoromethane sulfonic acid, BFEE, trichloroacetic acid, phosphoric acid, tri-chlorination
One kind in aluminium, titanium tetrachloride, butter of tin, zinc chloride, Antimony pentachloride；Alkali compounds described in step (3) is selected from carbonic acid
Sodium, sodium acid carbonate, ammonium carbonate, Ammonium bicarbonate food grade or sodium hydroxide.
10. preparation method according to claim 6, it is characterised in that：The glycol initiator is selected from ethylene glycol, 1,2- third
One kind in glycol, 1,3- propane diols, 1,4- butanediols.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018166413A1 (en) * | 2017-03-16 | 2018-09-20 | 南京信息工程大学 | Easily soluble fluorine-containing side chain copolyether glycol copolymerised from perfluoroalkyl glycidyl ether and polycyclic ether |
| CN109277269A (en) * | 2018-10-24 | 2019-01-29 | 江苏菲沃泰纳米科技有限公司 | A kind of epoxy nano coating and preparation method thereof |
| CN110003433A (en) * | 2019-04-23 | 2019-07-12 | 南京信息工程大学 | A kind of one pack system ambient self-crosslinking fluorochemical urethane coating material and preparation method thereof |
| CN110041818A (en) * | 2019-04-23 | 2019-07-23 | 南京信息工程大学 | A kind of corrosion resistant super-hydrophobic, oleophobic automatic cleaning coating of solvent resistant and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250300A (en) * | 1977-05-12 | 1981-02-10 | Daikin Kogyo Co., Ltd. | Fluorine-containing polyesters, and their production and use |
| EP0094574A2 (en) * | 1982-05-14 | 1983-11-23 | Daikin Kogyo Co., Ltd. | Mold release composition |
| CN103709388A (en) * | 2013-12-27 | 2014-04-09 | 南京信息工程大学 | Perfluor-substituted ethylene oxide and cyclic ether copolymerized glycol and preparation method thereof |
| CN103772692A (en) * | 2013-12-27 | 2014-05-07 | 南京信息工程大学 | Copolymerized glycol of perfluoroalkyl glycidyl ethers and cyclic ether and preparation method of copolymerized glycol |
-
2017
- 2017-03-16 CN CN201710155883.7A patent/CN107022072B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250300A (en) * | 1977-05-12 | 1981-02-10 | Daikin Kogyo Co., Ltd. | Fluorine-containing polyesters, and their production and use |
| EP0094574A2 (en) * | 1982-05-14 | 1983-11-23 | Daikin Kogyo Co., Ltd. | Mold release composition |
| CN103709388A (en) * | 2013-12-27 | 2014-04-09 | 南京信息工程大学 | Perfluor-substituted ethylene oxide and cyclic ether copolymerized glycol and preparation method thereof |
| CN103772692A (en) * | 2013-12-27 | 2014-05-07 | 南京信息工程大学 | Copolymerized glycol of perfluoroalkyl glycidyl ethers and cyclic ether and preparation method of copolymerized glycol |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018166413A1 (en) * | 2017-03-16 | 2018-09-20 | 南京信息工程大学 | Easily soluble fluorine-containing side chain copolyether glycol copolymerised from perfluoroalkyl glycidyl ether and polycyclic ether |
| CN109277269A (en) * | 2018-10-24 | 2019-01-29 | 江苏菲沃泰纳米科技有限公司 | A kind of epoxy nano coating and preparation method thereof |
| CN110003433A (en) * | 2019-04-23 | 2019-07-12 | 南京信息工程大学 | A kind of one pack system ambient self-crosslinking fluorochemical urethane coating material and preparation method thereof |
| CN110041818A (en) * | 2019-04-23 | 2019-07-23 | 南京信息工程大学 | A kind of corrosion resistant super-hydrophobic, oleophobic automatic cleaning coating of solvent resistant and preparation method thereof |
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