CN102597060B - 包含氟乙烯基醚官能化芳族部分的芳族聚酰胺 - Google Patents
包含氟乙烯基醚官能化芳族部分的芳族聚酰胺 Download PDFInfo
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- CN102597060B CN102597060B CN201080049703.3A CN201080049703A CN102597060B CN 102597060 B CN102597060 B CN 102597060B CN 201080049703 A CN201080049703 A CN 201080049703A CN 102597060 B CN102597060 B CN 102597060B
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 34
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 22
- 239000004760 aramid Substances 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000007859 condensation product Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- -1 aromatic diester Chemical class 0.000 description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 229940018564 m-phenylenediamine Drugs 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 0 CC*(C)(*)*(C)*(C)[C@]1(C)N(C(C)(C)C)C1=CC Chemical compound CC*(C)(*)*(C)*(C)[C@]1(C)N(C(C)(C)C)C1=CC 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- CUOVAWBKHRKBJC-UHFFFAOYSA-N 2-[2-bromo-1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]benzene-1,4-dicarbonyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(F)(F)OC(F)(Br)C(F)(F)OC1=CC(C(Cl)=O)=CC=C1C(Cl)=O CUOVAWBKHRKBJC-UHFFFAOYSA-N 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 7
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- CJOJIAKIRLKBOO-UHFFFAOYSA-N dimethyl 2-hydroxybenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(O)=C1 CJOJIAKIRLKBOO-UHFFFAOYSA-N 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OPPVOZSUHMHFLE-UHFFFAOYSA-N 2-(1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-hexadecafluorooctoxy)benzene-1,4-dicarbonyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)C(F)(F)OC1=CC(C(Cl)=O)=CC=C1C(Cl)=O OPPVOZSUHMHFLE-UHFFFAOYSA-N 0.000 description 4
- OCAJMDUKZLHBJM-UHFFFAOYSA-N 2-[1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]benzene-1,4-dicarbonyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(F)(F)OC(F)C(F)(F)OC1=CC(C(Cl)=O)=CC=C1C(Cl)=O OCAJMDUKZLHBJM-UHFFFAOYSA-N 0.000 description 4
- UQRCMBFLQUNDRC-UHFFFAOYSA-N 2-[2-chloro-1,1,2-trifluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)ethoxy]benzene-1,4-dicarbonyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(Cl)C(F)(F)OC1=CC(C(Cl)=O)=CC=C1C(Cl)=O UQRCMBFLQUNDRC-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 4
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 3
- OPBXHJRKMYNOLG-UHFFFAOYSA-N 2-[1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(OC(F)(F)C(F)OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)=C1 OPBXHJRKMYNOLG-UHFFFAOYSA-N 0.000 description 3
- YWYKZFZEJZRNDI-UHFFFAOYSA-N 5-[1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]benzene-1,3-dicarbonyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(F)(F)OC(F)C(F)(F)OC1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 YWYKZFZEJZRNDI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229950005499 carbon tetrachloride Drugs 0.000 description 3
- DOSDTCPDBPRFHQ-UHFFFAOYSA-N dimethyl 5-hydroxybenzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC(O)=CC(C(=O)OC)=C1 DOSDTCPDBPRFHQ-UHFFFAOYSA-N 0.000 description 3
- 239000008241 heterogeneous mixture Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- OUUHCUJQKGUQMY-UHFFFAOYSA-N 2-[2-bromo-1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(OC(F)(F)C(F)(Br)OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)=C1 OUUHCUJQKGUQMY-UHFFFAOYSA-N 0.000 description 2
- QRZMXADUXZADTF-UHFFFAOYSA-N 4-aminoimidazole Chemical class NC1=CNC=N1 QRZMXADUXZADTF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 2
- WHDICJGRTOXHDG-UHFFFAOYSA-N dimethyl 2-[1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]benzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(OC(F)(F)C(F)OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)=C1 WHDICJGRTOXHDG-UHFFFAOYSA-N 0.000 description 2
- BQGDDMMXPRJQHZ-UHFFFAOYSA-N dimethyl 3-hydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=CC(O)=C1C(=O)OC BQGDDMMXPRJQHZ-UHFFFAOYSA-N 0.000 description 2
- JJXVDRYFBGDXOU-UHFFFAOYSA-N dimethyl 4-hydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=C(O)C=C1C(=O)OC JJXVDRYFBGDXOU-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- POJPQMDDRCILHJ-UHFFFAOYSA-N 1,1,1,2,2,2-hexabromoethane Chemical compound BrC(Br)(Br)C(Br)(Br)Br POJPQMDDRCILHJ-UHFFFAOYSA-N 0.000 description 1
- PBWHQPOHADDEFU-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,5-decafluoropent-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F PBWHQPOHADDEFU-UHFFFAOYSA-N 0.000 description 1
- RMHCWMIZBMGHKV-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluorohex-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RMHCWMIZBMGHKV-UHFFFAOYSA-N 0.000 description 1
- CDAVUOSPHHTNBU-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,7-tetradecafluorohept-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDAVUOSPHHTNBU-UHFFFAOYSA-N 0.000 description 1
- YCBPKOZNGFQMPB-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-hexadecafluorooct-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YCBPKOZNGFQMPB-UHFFFAOYSA-N 0.000 description 1
- IMVVEWPCRIJQCA-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-icosafluorodec-1-ene Chemical compound FC(F)=C(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)F IMVVEWPCRIJQCA-UHFFFAOYSA-N 0.000 description 1
- UAFOIVDGAVVKTE-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-octadecafluoronon-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UAFOIVDGAVVKTE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QVJOGIWJNRYULE-UHFFFAOYSA-N 2-[2-chloro-1,1,2-trifluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)ethoxy]terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(OC(F)(F)C(F)(Cl)OC(F)(F)C(F)(F)C(F)(F)F)=C1 QVJOGIWJNRYULE-UHFFFAOYSA-N 0.000 description 1
- LWBNGMUILMIZPL-UHFFFAOYSA-N 2-[2-chloro-1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(OC(F)(F)C(F)(Cl)OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)=C1 LWBNGMUILMIZPL-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- WNKQDGLSQUASME-UHFFFAOYSA-N 4-sulfophthalic acid Chemical compound OC(=O)C1=CC=C(S(O)(=O)=O)C=C1C(O)=O WNKQDGLSQUASME-UHFFFAOYSA-N 0.000 description 1
- WNCKPERCGKWRQY-UHFFFAOYSA-N 5-[1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(OC(F)(F)C(F)OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)=CC(C(O)=O)=C1 WNCKPERCGKWRQY-UHFFFAOYSA-N 0.000 description 1
- UGJVVIACUITOEZ-UHFFFAOYSA-N CC(C1)C2C3C1C2CC3 Chemical compound CC(C1)C2C3C1C2CC3 UGJVVIACUITOEZ-UHFFFAOYSA-N 0.000 description 1
- BHMGQDBTOJCEAJ-UHFFFAOYSA-N CC1OC1c1cc(OC(C(OC(C(C(F)(F)F)(OC(C(C(F)(F)F)(F)F)(F)F)F)(F)F)F)(F)F)cc(C(C)=O)c1 Chemical compound CC1OC1c1cc(OC(C(OC(C(C(F)(F)F)(OC(C(C(F)(F)F)(F)F)(F)F)F)(F)F)F)(F)F)cc(C(C)=O)c1 BHMGQDBTOJCEAJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ALBUJVBOIXVVLS-UHFFFAOYSA-N Dimethyl 4-hydroxyisophthalate Chemical compound COC(=O)C1=CC=C(O)C(C(=O)OC)=C1 ALBUJVBOIXVVLS-UHFFFAOYSA-N 0.000 description 1
- 241001546602 Horismenus Species 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910005948 SO2Cl Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 239000000539 dimer Substances 0.000 description 1
- WFFOTOYJOIXKCA-UHFFFAOYSA-N dimethyl 2,4-dihydroxybenzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=C(O)C(C(=O)OC)=C1O WFFOTOYJOIXKCA-UHFFFAOYSA-N 0.000 description 1
- UCLWRPDMRLGRFG-UHFFFAOYSA-N dimethyl 2,5-dihydroxybenzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC(O)=CC(C(=O)OC)=C1O UCLWRPDMRLGRFG-UHFFFAOYSA-N 0.000 description 1
- MSXSMRUOPCJWDT-UHFFFAOYSA-N dimethyl 2,6-dihydroxynaphthalene-1,5-dicarboxylate Chemical compound OC1=CC=C2C(C(=O)OC)=C(O)C=CC2=C1C(=O)OC MSXSMRUOPCJWDT-UHFFFAOYSA-N 0.000 description 1
- VGXJSPVOAOSWFI-UHFFFAOYSA-N dimethyl 2-[2-chloro-1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]benzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(OC(F)(F)C(F)(Cl)OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)=C1 VGXJSPVOAOSWFI-UHFFFAOYSA-N 0.000 description 1
- IVUYABGPNIFMQC-UHFFFAOYSA-N dimethyl 3,4-dihydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=C(O)C(O)=C1C(=O)OC IVUYABGPNIFMQC-UHFFFAOYSA-N 0.000 description 1
- NVFVMNBLADPUFB-UHFFFAOYSA-N dimethyl 3,6-dihydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=C(O)C=CC(O)=C1C(=O)OC NVFVMNBLADPUFB-UHFFFAOYSA-N 0.000 description 1
- UOXUXFHCADEWIZ-UHFFFAOYSA-N dimethyl 3,7-dihydroxynaphthalene-1,5-dicarboxylate Chemical compound C1=C(O)C=C2C(C(=O)OC)=CC(O)=CC2=C1C(=O)OC UOXUXFHCADEWIZ-UHFFFAOYSA-N 0.000 description 1
- FXPCZDQRACWUBW-UHFFFAOYSA-N dimethyl 4,5-dihydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC(O)=C(O)C=C1C(=O)OC FXPCZDQRACWUBW-UHFFFAOYSA-N 0.000 description 1
- IRPFGKMVQYOSKF-UHFFFAOYSA-N dimethyl 5-[1,1,2-trifluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]ethoxy]benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC(OC(F)(F)C(F)OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)=CC(C(=O)OC)=C1 IRPFGKMVQYOSKF-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000007527 glass casting Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
本发明涉及芳族聚酰胺聚合物以及制备所述芳族聚酰胺聚合物的方法,所述芳族聚酰胺聚合物包含氟乙烯基醚官能化芳族二甲酰氯与芳族二胺的缩合产物重复单元。本发明的聚合物用作高强度纤维或表面不易受油影响的溶液浇铸膜。
Description
发明领域
本发明涉及芳族聚酰胺聚合物以及制备所述芳族聚酰胺聚合物的方法,所述芳族聚酰胺聚合物包含氟乙烯基醚官能化芳族二甲酰氯与芳族二胺的缩合产物重复单元。本发明的聚合物用作高强度纤维或表面不易受油影响的溶液浇铸膜。
发明背景
氟化材料具有许多用途。具体地讲,它们用于聚合物相关产业中,并且更具体地讲用于纤维相关产业中以赋予防垢性和防油性。一般来讲,这些材料作为局部处理物施用,但是由于材料因磨损和清洗而损耗,因此它们的有效性随着时间的推移而降低。
需要提供具有改善的防垢性和防油性的聚合材料。
发明概述
在一个方面,本发明提供了包含氟乙烯基醚官能化芳族重复单元的聚合物,所述重复单元由结构(I)表示
其中,
Ar代表苯基或萘基;
每个R独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;OH、或由结构(II)表示的基团
前提条件是仅一个R可为OH或由结构(II)表示的基团;
每个R1独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;
X为O或CF2;
Z为H、Cl、或Br;
a=0或1;
并且
Q由结构(Ia)表示
其中q=0-10;
Y为O或CF2;
Rf1为(CF2)n,其中n为0-10;
并且
Rf2为(CF2)p,其中p为0-10,前提条件是当p为0时,Y为CF2。
在另一方面,本发明提供了方法,所述方法包括使氟乙烯基醚官能化芳族二甲酰氯与芳族二胺混合以形成反应混合物,在介于约-70℃和所述反应混合物回流温度之间的温度下搅拌所述反应混合物以形成聚合物,所述聚合物包含具有结构(I)的重复单元,其中所述氟乙烯基醚官能化芳族二甲酰氯由结构(III)表示,
其中,
Ar代表苯基或萘基;
每个R独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;OH、或由结构(II)表示的基团
前提条件是仅一个R可为OH或由结构(II)表示的基团;
X为O或CF2;
Z为H、Cl、或Br;
a=0或1;
并且
Q由结构(Ia)表示
其中q=0-10;
Y为O或CF2;
Rf1为(CF2)n,其中n为0-10;
并且
Rf2为(CF2)p,其中p为0-10,前提条件是当p为0时,Y为CF2。
在另一方面,本发明提供了包含聚合物的薄膜,所述聚合物包含氟乙烯基醚官能化芳族重复单元,所述重复单元由结构(I)表示
其中,
Ar代表苯基或萘基;
每个R独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;OH、或由结构(II)表示的基团
前提条件是仅一个R可为OH或由结构(II)表示的基团;
每个R1独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;
X为O或CF2;
Z为H、Cl、或Br;
a=0或1;
并且
Q由结构(Ia)表示
其中q=0-10;
Y为O或CF2;
Rf1为(CF2)n,其中n为0-10;
并且
Rf2为(CF2)p,其中p为0-10,前提条件是当p为0时,Y为CF2。
发明详述
在本发明中,除非另外特别说明,当提供数值范围时,应理解它涵盖范围的端点。应当了解,数值具有提供的有效数字位数的精确度,其遵循ASTM E29-08部分6中所述的化学有效数字标准协定。例如,数字40应理解为涵盖35.0至44.9的范围,而数字40.0应理解为涵盖39.50至40.49的范围。
本文中应当了解,如本文所用的参数n、p和q各自独立地为1-10范围内的整数。
就本发明目的而言,术语“氟乙烯基醚官能化芳族二酯”应是指结构(III)的化合物的亚型,其中R2为C1-C10烷基。术语“氟乙烯基醚官能化芳族二酸”应是指结构(III)化合物的亚型,其中R2为H。此外,就本发明目的而言,术语“全氟乙烯基化合物”应是指由下文结构(VII)表示的烯属不饱和化合物。
就本发明目的而言,术语“共聚物”应是指包含两种或更多种化学上不同的重复单元的聚合物,包括二聚物、三聚物、四聚物等。此外,就本发明目的而言,同时根据本领域的通常做法,术语“均聚物”是指包含多个化学上彼此无差异的重复单元的聚合物。
就本发明目的而言,在本文任何化学结构中存在以“—”示出的末端键,其中未指出末端化学基团,所述末端键“—”应理解为代表基团。例如,-CH3应理解为代表甲基。
在一个方面,本发明提供了包含氟乙烯基醚官能化芳族重复单元的聚合物,所述重复单元由结构(I)表示
其中,
Ar代表苯基或萘基;
每个R独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;OH,或由结构(II)表示的基团
前提条件是仅一个R可为OH或由结构(II)表示的基团;
每个R1独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;
X为O或CF2;
Z为H、Cl、或Br;
a=0或1;
并且
Q由结构(Ia)表示
其中q=0-10;
Y为O或CF2;
Rf1为(CF2)n,其中n为0-10;
并且
Rf2为(CF2)p,其中p为0-10,前提条件是当p为0时,Y为CF2。
在本文聚合物的一个实施方案中,Ar为苯基。
在本文聚合物的一个实施方案中,一个R为OH。
在本文聚合物的一个实施方案中,每个R为H。
在本文聚合物的一个实施方案中,一个R为OH,并且所述剩余的两个R各为H。
在本文聚合物的一个实施方案中,一个R由结构(II)表示,并且剩余的两个R各为H。
在本文聚合物的一个实施方案中,每个R1为H。
在本文聚合物的一个实施方案中,X为O。在可供选择的实施方案中,X为CF2。
在本文聚合物的一个实施方案中,Y为O。在可供选择的实施方案中,Y为CF2。
在本文聚合物的一个实施方案中,Z为Cl或Br。在另一个实施方案中,Z为Cl。在可供选择的实施方案中,一个R由结构(II)表示,并且一个Z为H。在另一个实施方案中,一个R由结构(II)表示,一个Z为H,并且一个Z为Cl。
在本文聚合物的一个实施方案中,Rf1为CF2。
在本文聚合物的一个实施方案中,Rf2为CF2。
在本文聚合物的一个实施方案中,Rf2为键(即p=0),并且Y为CF2。
在一个实施方案中,a=0。
在一个实施方案中,a=1,q=0,并且n=0。
在本文聚合物的一个实施方案中,Ar为苯基,每个R为H,Z为Cl,每个R1为H,X为O,Y为O,Rf1为CF2,并且Rf2为全氟丙烯基,并且q=1。
在本文聚合物的一个实施方案中,本发明的聚合物为均聚物。
在本文聚合物的一个实施方案中,本发明的聚合物为共聚物,其重复单元代表由结构(I)表示的重复单元的多个实施方案。在一个实施方案中,由结构(I)表示的重复单元由结构(IVa)进一步表示
其中Z、X、Q和a如上所述。
在一个实施方案中,由结构(I)表示的重复单元由结构(IVb)进一步表示
其中Z、X、Q和a如上所述。
在可供选择的实施方案中,本发明的聚合物为共聚物,所述共聚物包含由结构(IVa)表示的氟乙烯基醚官能化芳族重复单元,和由结构(IVb)表示的氟乙烯基醚官能化芳族重复单元。在一个实施方案中,所述共聚物为无规共聚物。在一个实施方案中,所述共聚物为嵌段共聚物。
在另一个实施方案中,本发明聚合物为共聚物,所述共聚物还包含由结构(V)表示的芳族聚酰胺重复单元
其中每个R2独立地为H或烷基,并且每个R3独立地为H或烷基。在一个实施方案中,所有的R2均为H,并且所述R3均为H。在一个实施方案中,由结构(V)表示的重复单元为对苯二甲酸酯基。在可供选择的实施方案中,由所述结构表示的重复单元为间苯二甲酸酯基。
在可供选择的实施方案中,本发明的聚合物为共聚物,所述共聚物还包含由结构(V)表示的对苯二甲酸酯重复单元和间苯二甲酸酯重复单元。在一个实施方案中,所述共聚物为无规共聚物。在一个实施方案中,所述共聚物为嵌段共聚物。
在另一方面,本发明提供了方法,所述方法包括使氟乙烯基醚官能化芳族二甲酰氯与芳族二胺混合以形成反应混合物,加热至介于180-240℃之间的温度,然后加热至250-300℃,并且通过使所述混合物经历排空来提取挥发性物质;其中所述氟乙烯基醚官能化芳族二甲酰氯由结构(III)表示,
其中,
Ar代表苯基或萘基;
每个R独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;OH、或由结构(II)表示的基团
前提条件是仅一个R能够为OH或由结构(II)表示的基团;
X为O或CF2;
Z为H、Cl、或Br;
a=0或1;
并且
Q由结构(Ia)表示
其中q=0-10;
Y为O或CF2;
Rf1为(CF2)n,其中n为0-10;
并且
Rf2为(CF2)p,其中p为0-10,前提条件是当p为0时,Y为CF2。
在本文方法的一个实施方案中,一个R为OH。
在本文方法的一个实施方案中,每个R为H。
在本文方法的一个实施方案中,一个R为OH,并且所述剩余的两个R各为H。
在本文方法的一个实施方案中,一个R由结构(II)表示,并且所述剩余的两个R各为H。
在本文方法的一个实施方案中,芳族二胺为1,4-二氨基苯。
在本文方法的一个实施方案中,X为O。在可供选择的实施方案中,X为CF2。
在本文方法的一个实施方案中,Y为O。在可供选择的实施方案中,Y为CF2。
在本文方法的一个实施方案中,Z为Cl或Br。在另一个实施方案中,Z为Cl。在可供选择的实施方案中,一个R由结构(II)表示,并且一个Z为H。在另一个实施方案中,一个R由结构(II)表示,一个Z为H,并且一个Z为Cl。
在本文方法的一个实施方案中,Rf1为CF2。
在本文方法的一个实施方案中,Rf2为CF2。
在本文方法的一个实施方案中,Rf2为键(即p=0),并且Y为CF2。
在一个实施方案中,a=0。
在一个实施方案中,a=1,q=0,并且n=0。
在本文方法的一个实施方案中,芳族二胺为1,4-二氨基苯,Ar为苯基,每个R为H,Z为Cl,X为O,Y为O,Rf1为CF2,并且Rf2为全氟丙烯基,并且q=1。
适用于本发明的芳族二胺包括但不限于1,4-二氨基苯、1,3-二氨基苯、或2-(4-氨基苯基)-1H-苯并[d]咪唑-5-胺。
在本文方法的一个实施方案中,通过将上述成分加入到反应容器中形成混合物,在介于约-70℃至所述反应混合物回流温度之间的温度下搅拌所述反应混合物,形成聚合物。由此所得的聚合物可通过真空蒸馏分离以移除过量的胺。
在一个实施方案中,所述反应混合物包含结构(III)所涵盖的多于一种的单体实施方案。在另一个实施方案中,所述反应混合物还包括由结构(VI)表示的芳族二甲酰氯
其中Ar为芳基;每个R独立地为H或C1-C10烷基。在另一个实施方案中,每个R为H。在一个实施方案中,Ar为苯基。在可供选择的实施方案中,Ar为萘基。
具有结构(VI)的适宜芳族二甲酰氯通过用SO2Cl、PCl3、PCI5或草酰氯处理二酯,由相应的二酸获得。具有结构(VI)的适宜芳族二酸包括但不限于间苯二甲酸、对苯二甲酸、2,6-萘二甲酸、4,4’-磺酰基双苯甲酸、4-磺基邻苯二甲酸和联苯-4,4’-二甲酸。在一个实施方案中,所述芳族二酸为对苯二甲酸。在可供选择的实施方案中,所述芳族二酸为间苯二甲酸。
适宜的氟乙烯基醚官能化芳族二酯可通过在介于约-70℃至所述反应混合物回流温度之间的温度下,在溶剂和催化剂的存在下,由结构(VII)表示的全氟乙烯基化合物形成包含羟基芳族二酯的反应混合物来制得,
其中X为O或CF2,a=0或1;并且Q由结构(Ia)表示
其中q=0-10;
Y为O或CF2;
Rf1为(CF2)n,其中n为0-10;
Rf2为(CF2)p,其中p为0-10,前提条件是当p为0时,Y为CF2。
优选地,反应在高于室温但是低于反应混合物回流温度的温度下,采用搅拌来进行。反应后将反应混合物冷却。
当使用卤化溶剂时,由结构(III)表示的所得氟乙烯基醚芳族二酯中表示为“Z”的基团是相应的卤素。适宜的卤化溶剂包括但不限于四氯甲烷、四溴甲烷、六氯乙烷和六溴乙烷。如果溶剂是非卤化的,则Z为H。适宜的非卤化溶剂包括但不限于四氢呋喃(THF)、二氧杂环己烷和二甲基甲酰胺(DMF)。
所述反应由碱催化。可使用多种碱性催化剂,即能够使苯酚去质子的任何催化剂。即适宜的催化剂是pKa大于苯酚pKa(9.95,在25℃下使用水作为参比)的任何催化剂。适宜的催化剂包括但不限于甲醇钠、氢化钙、金属钠、甲醇钾、叔丁醇钾、碳酸钾、或碳酸钠。优选叔丁醇钾、碳酸钾或碳酸钠。
可在任何适宜的点,通过加入酸(如但不限于10%HCl)来终止反应。作为另一种选择,当使用固体催化剂如碳酸盐催化剂时,可将反应混合物过滤以移除催化剂,从而终止反应。
适宜的羟基芳族二酯包括但不限于2-羟基对苯二甲酸1,4-二甲酯、2,5-二羟基对苯二甲酸1,4-二乙酯、4-羟基间苯二甲酸1,3-二甲酯、5-羟基间苯二甲酸1,3-二甲酯、2-羟基间苯二甲酸1,3-二甲酯、2,5-二羟基间苯二甲酸1,3-二甲酯、2,4-二羟基间苯二甲酸1,3-二甲酯、3-羟基邻苯二甲酸二甲酯、4-羟基邻苯二甲酸二甲酯、3,4-二羟基邻苯二甲酸二甲酯、4,5-二羟基邻苯二甲酸二甲酯、3,6-二羟基邻苯二甲酸二甲酯、4,8-二羟基萘-1,5-二甲酸二甲酯、3,7-二羟基萘-1,5-二甲酸二甲酯、2,6-二羟基萘-1,5-二甲酸二甲酯、或它们的混合物。
适宜的全氟乙烯基化合物包括但不限于1,1,1,2,2,3,3-七氟-3-(1,1,1,2,3,3-六氟-3-(1,2,2-三氟乙烯氧基)丙-2-基氧基)丙烷、七氟丙基三氟乙烯基醚、全氟戊-1-烯、全氟己-1-烯、全氟庚-1-烯、全氟辛-1-烯、全氟壬-1-烯、全氟癸-1-烯、以及它们的混合物。
为制备适宜的氟乙烯基醚官能化芳族二酯,在适宜溶剂和适宜催化剂的存在下将适宜的羟基芳族二酯和适宜的全氟乙烯基化合物混合,直至反应达到所期望的转化度。持续反应,直至在一段选定的时间范围内不再有产物生成。达到所期望的转化度所需的反应时间取决于反应温度、具体的反应混合物组分的化学反应性、以及施加于反应混合物的混合程度。可采用多种惯用分析方法中的任何一种来监测反应进程,所述分析方法包括但不限于核磁共振光谱法、薄层色谱法、以及气相层析法。
当达到所期望的转化度时,如上所述淬灭反应混合物。由此淬灭的反应混合物可真空浓缩,并且用溶剂冲洗。在某些情况下,可在单一反应混合物中制得由结构(III)涵盖的多种化合物。在该情况下,由此制得的产物的分离可通过技术人员已知的任何方法来实现,如但不限于蒸馏或柱层析。
为由此形成的二酯制备相应的二酸,因此制得的氟乙烯基醚官能化芳族二酯可在回流下与碱水溶液接触,优选与强碱如KOH或NaOH接触,然后冷却至室温,接着优选用强酸如HCl或H2SO4酸化混合物,直至pH介于0和2之间。pH优选为1。由此实施的酸化致使氟乙烯基醚官能化芳族二酸沉淀出来。由此沉淀出的二酸可随后经由过滤分离,再溶解于溶剂如乙酸乙酯中,接着重结晶。反应进程可由任何便利的方法来追踪,包括但不限于薄层色谱法、气相色谱法和NMR。
一旦制得氟乙烯基醚芳族二酸,它适于如上所述转变成相应的二甲酰氯。
在另一方面,本发明提供了聚合物薄膜,所述聚合物包含由结构(I)表示的氟乙烯基醚官能化芳族重复单元
其中,
Ar代表苯基或萘基;
每个R独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;OH、或由结构(II)表示的基团
前提条件是仅一个R可为OH或由结构(II)表示的基团;
每个R1独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;
X为O或CF2;
Z为H、Cl、或Br;
a=0或1;
并且
Q由结构(Ia)表示
其中q=0-10;
Y为O或CF2;
Rf1为(CF2)n,其中n为0-10;
并且
Rf2为(CF2)p,其中p为0-10,前提条件是当p为0时,Y为CF2。
本发明的薄膜提供了芳族聚酰胺薄膜,与不包含本文薄膜氟乙烯基醚部分的芳族聚酰胺相比,其表现出减低的表面能。例如,得自DuPontCompany的Kevlar芳族聚酰胺表面能文献值为44达因/厘米,而如下文实施例11中所示,本发明的薄膜显示出远低于30达因/厘米的表面能。
本发明还描述但不限制于以下具体的实施方案中。
实施例
下列化学物质和试剂按从Sigma-Aldrich(Milwaukee,WI)获得的原样使用。
·叔丁醇钾
·5-羟基间苯二甲酸二甲酯
·四氢呋喃
·二甲基甲酰胺
·二氯甲烷
·己烷
·四氯甲烷
·无水硫酸钠
·四溴化碳(四溴甲烷)
·盐酸(HCl)
·2-羟基对苯二甲酸1,4-二甲酯
·氢氧化钾(KOH)
·乙酸乙酯
·亚硫酰氯
·2-(4-氨基苯基)-1H-苯并[d]咪唑-5-胺
·对苯二胺
·间苯二胺
下列化学物质按从SynQuest Labs(Alachua,FL)获得的原样使用:
·1,1,1,2,2,3,3-七氟-3-(1,1,1,2,3,3-六氟-3-(1,2,2三氟乙烯氧基)丙-2-基氧基)丙烷
·七氟丙基三氟乙烯基醚
制备5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)间
苯二甲酸二甲酯
在干箱操作手套箱中,通过在配备有搅拌器的烘箱干燥的圆底反应烧瓶中混合四氢呋喃(THF,1000mL)和5-羟基间苯二甲酸二甲酯(42.00g,0.20mol)来制备反应混合物。将叔丁醇钾(6.16g,0.055mol)加入到烧瓶中。然后经由加料漏斗,将1,1,1,2,2,3,3-七氟-3-(1,1,1,2,3,3-六氟-3-(1,2,2三氟乙烯氧基)丙-2-基氧基)丙烷(216g,0.50mol)加入到反应混合物中,并且在室温下搅拌混合物。24小时后,通过加入80mL 10%HCl来终止反应。将所得混合物减压浓缩,用二氯甲烷稀释,用10%HCl(2×100mL)洗涤,然后用水(2×100mL)洗涤,以形成水相和有机相。分离出有机相,然后在无水硫酸钠上干燥,接着减压浓缩,以形成粗产物。粗产物经由柱层析纯化,获得86.07g(67.32%收率)所期望的材料:5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)间苯二甲酸二甲酯。
制备2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对
苯二甲酸二甲酯
在干箱操作手套箱中,将四氢呋喃(THF,288mL)和2-羟基对苯二甲酸1,4-二甲酯(30.25g,0.144mol)在烘箱干燥的500mL多颈反应烧瓶中混合,所述烧瓶配备有搅拌棒和均压(PE)加料漏斗。搅拌如此形成的混合物,直至获得均匀的溶液。然后加入叔丁醇钾(4.435g,0.040mol),获得不均质混合物。然后经由PE漏斗,加入1,1,1,2,2,3,3-七氟-3-(1,1,1,2,3,3-六氟-3-(1,2,2-三氟乙烯氧基)丙-2-基氧基)丙烷(155.52g,0.36mol),致使形成反应混合物。使反应混合物在室温(约25℃)下搅拌~40小时。通过加入5mL 10%HCl,淬灭所得混合物。将反应烧瓶中的产物减压浓缩,然后溶解于二氯甲烷(~300mL)中,随后用10%HCl(2×75mL)洗涤,之后用水(~75mL)洗涤,获得有机相和水相。然后在无水硫酸钠上干燥分离出的有机相。然后过滤出硫酸钠,并且将所得材料减压浓缩,接着真空分馏。收集介于1.1托下134-136℃(84.55g,91.4%收率)和1.1托下136-138℃(3.35g)之间沸腾的馏分(合并收率:95.04%)。这些样品的NMR(核磁共振)与2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酸二甲酯相符。
制备2-(2-氯-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基)丙氧基)乙氧
基)对苯二甲酸二甲酯
在干箱操作手套箱中,将二甲基甲酰胺(DMF,10.0mL)和四氯甲烷(50mL)与2-羟基对苯二甲酸1,4-二甲酯(1.05g,0.005mol)在烘箱干燥的100mL反应烧瓶中混合,所述烧瓶配备有搅拌棒和均压(PE)加料漏斗。然后搅拌如此形成的混合物,直至获得均匀的溶液。将叔丁醇钾(0.154g,0.001375mol)加入到反应烧瓶中,获得不均匀的混合物。经由PE漏斗,加入1,1,1,2,2,3,3-七氟-3-(1,1,1,2,3,3-六氟-3-(1,2,2三氟乙烯氧基)丙-2-基氧基)丙烷(5.40g,0.0125mol),以形成反应混合物。使反应混合物在室温(约25℃)下搅拌~24小时。通过加入2mL 10%HCl,淬灭反应。将所得混合物减压浓缩,然后溶解于二氯甲烷(~150mL)中。然后将如此制得的溶液用10%HCl(2×25mL)洗涤,接着用水洗(~25mL)洗涤,以形成有机相和水相。然后在无水硫酸钠上干燥分离出的有机相。然后将硫酸钠过滤掉并且将滤液减压浓缩以制备粗产物。粗产物的NMR与高纯度所期望材料:2-(2-氯-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基)丙氧基)乙氧基)对苯二甲酸二甲酯以及少量存在的二甲基甲酰胺相符。然后将粗料经由柱层析(Rf 0.,50二氯甲烷(1)/己烷(1))纯化,获得透明油状纯2-(2-氯-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基)丙氧基)乙氧基)对苯二甲酸二甲酯,2.60g(76.92%收率)。
制备2-(2-溴-1,1,2-三氟-2-(全氟丙氧基)乙氧基)对苯二甲酸二甲酯
在干箱操作手套箱中,将二甲基甲酰胺(20.0mL)和四溴化碳(12.5g)与2-羟基对苯二甲酸1,4-二甲酯(1.05g,0.005mol)在烘箱干燥的100mL反应烧瓶中混合,所述烧瓶配备有搅拌棒和均压(PE)加料漏斗。搅拌如此制得的混合物,直至获得均匀的溶液。然后将叔丁醇钾(0.154g,0.001375mol)加入到反应烧瓶中,获得不均匀的混合物。经由PE漏斗,加入七氟丙基三氟乙烯基醚(3.325g,0.0125mol),获得反应混合物。在室温(约25℃)下由此制得的反应混合物搅拌~24小时。通过加入2mL 10%HCl,淬灭反应。将所得混合物减压浓缩,然后溶解于二氯甲烷(~150mL)中,接着用10%HCl(2×25mL)洗涤,然后用水(~25mL)洗涤,形成有机相和水相。然后在无水硫酸钠上干燥分离出的有机相。然后将硫酸钠过滤掉并且将滤液减压浓缩以形成粗产物。粗产物的NMR与高纯度2-(2-溴-1,1,2-三氟-2-(全氟丙氧基)乙氧基)对苯二甲酸二甲酯以及少量存在的二甲基甲酰胺和四溴化碳相符。然后将粗产物经由柱层析纯化,获得透明油状纯产物2-(2-溴-1,1,2-三氟-2-(全氟丙氧基)乙氧基)对苯二甲酸二甲酯,2.280g(82.31%收率)。
制备2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对
苯二甲酸
将2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)-丙氧基)乙氧基)对苯二甲酸二甲酯(2.25g,0.035mol)加入到反应烧瓶内的水(50mL)与氢氧化钾(KOH,1.96g)的溶液中。将反应烧瓶内的所得溶液加热5小时,冷却至室温(约25℃),然后通过将浓HCl加入到反应烧瓶中直至pH达到~1进行酸化,同时在反应烧瓶内形成沉淀。将沉淀过滤并真空干燥。该沉淀物的质子NMR与2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酸相符。然后将沉淀物从乙酸乙酯(EtOAc,~1份)和己烷(~4份)中重结晶。过滤并真空干燥后,所得白色二酸2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二酸具有236-239℃的熔点。
制备2-(2-氯-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧
基)对苯二甲酸
将2-(2-氯-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酸二甲酯(10.00g,0.0148mol)加入到反应烧瓶内水(100mL)与氢氧化钾(KOH,8.0g)的溶液中。将反应烧瓶内的所得溶液加热回流过夜,冷却至室温(约25℃),然后通过将浓HCl加入到反应烧瓶中以达到pH~1进行酸化,同时在反应烧瓶内形成沉淀。将沉淀过滤并真空干燥。该沉淀物的NMR与2-(2-氯-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酸相符。
制备2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧
基)对苯二甲酸
将2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酸二甲酯(10.9g,0.15mol)加入到反应烧瓶内水(100mL)与氢氧化钾(KOH,8.0g)的溶液中。将反应烧瓶内的所得溶液加热回流过夜,冷却至室温(约25℃),然后通过将浓HCl加入到反应烧瓶中直至pH达到~1进行酸化,同时形成沉淀。将沉淀过滤并真空干燥,获得10.90g。该材料的NMR(质子和碳)与2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酸相符。
制备2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对
苯二甲酰氯
将2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)-丙氧基)乙氧基)对苯二甲酸(1.129g)放置在配备有回流冷凝器、搅拌器并且保持在氮气氛下的圆底反应烧瓶中。将亚硫酰氯(5.8mL)加置在反应烧瓶中,并且将反应溶液加热至温和回流过夜。使所得溶液冷却至室温(约25℃),并且真空移除过量的亚硫酰氯。NMR与2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酰氯相符。产物为油。
制备2-(2-氯-1,1,2-三氟-2-(全氟丙氧基)乙氧基)对苯二甲酰氯
将2-(2-氯-1,1,2-三氟-2-(全氟丙氧基)乙氧基)对苯二甲酸(50.99g,0.1056mol)放置在烘箱干燥的配备有搅拌器、回流冷凝器并且保持在氮气氛下的圆底反应烧瓶中,以形成反应混合物。将亚硫酰氯(423mL)加入到反应烧瓶中,并且将所得反应混合物加热回流过夜。使所得混合物冷却至室温,并且真空移除过量的亚硫酰氯。然后将所得材料经由真空蒸馏纯化。NMR与2-(2-氯-1,1,2-三氟-2-(全氟丙氧基)乙氧基)对苯二甲酰氯相符,46.04g,74.5%收率,1.1托下沸点为124-126℃。
制备5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)间
苯二甲酰氯
将5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)间苯二甲酸(46.63g,0.076mol)放置在烘箱干燥的配备有搅拌器、回流冷凝器并且保持在氮气氛下的圆底反应烧瓶中。将亚硫酰氯(304mL)加入到烧瓶中以形成反应混合物,并且将由此制得的反应混合物加热回流过夜。将所得混合物冷却至室温(约25℃),并且从混合物中真空移除过量的亚硫酰氯,形成反应产物。然后将所得产物真空蒸馏以纯化产物:5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)间苯二甲酰氯,38.96g,78.8%收率,0.60托下的沸点为116-123℃。
制备2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧
基)对苯二甲酰氯((a)~87%)和2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟
丙氧基)丙氧基)乙氧基)对苯二甲酰氯((B)~13%)
将包含~13%2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酸的2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酸(57.70g)放置在烘箱干燥的配备有搅拌器、回流冷凝器并且保持在氮气氛下的圆底反应烧瓶中,以形成反应混合物。将亚硫酰氯(334mL)加入到烧瓶中以形成反应混合物。将如此形成的反应混合物加热回流过夜。将所得混合物冷却至室温(约25℃),并且从混合物中真空移除过量的亚硫酰氯以形成反应产物。然后将所得产物真空蒸馏,获得产物:38.96g,78.8%收率,~0.30托下的沸点为150-165℃。质子NMR与2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酰氯(~87%)和2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酰氯的混合物相符。
实施例1:间苯二胺与2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙
氧基)-丙氧基)乙氧基)对苯二甲酰氯的聚合
将间苯二胺(0.424,3.9208mmol)加入到包含二甲基乙酰胺(28.84g)的烘箱干燥的反应小瓶中以形成溶液。使溶液冷却,然后将2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)-丙氧基)乙氧基)对苯二甲酰氯(2.862g,3.9208mmol)(注意,经由NMR,该酰氯包含~13%的2-(1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十六氟辛基氧基)对苯二甲酰氯)加入到反应小瓶中,并且快速搅拌以形成反应混合物。所述溶液呈现浅色,所述颜色在反应小瓶中显现,然后消失。4小时后,将所得均匀溶液倒入包含~150mL水的瓦林混碎机中,并且形成白色纤维材料。将所得白色纤维材料真空干燥。所得材料的质子NMR显示出所得聚酰胺的两个特征性酰胺质子,为间苯二胺与2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)-丙氧基)乙氧基)对苯二甲酰氯的聚合物。
实施例2:对苯二胺与2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙
氧基)-丙氧基)乙氧基)对苯二甲酰氯的聚合
将对苯二胺(0.424,3.9208mmol)加入到包含二甲基乙酰胺(28.84g)的烘箱干燥的反应小瓶中以形成溶液。使该溶液冷却,然后将2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)-丙氧基)乙氧基)对苯二甲酰氯(2.862g,3.9208mmol)(注意,经由NMR,该酰氯包含~13%的2-(1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十六氟辛基氧基)对苯二甲酰氯)加入到小瓶中,并且快速搅拌以形成反应混合物。所得溶液呈现浅色,所述颜色在反应小瓶中显现,然后消失。4小时后,将所得粘稠溶液倒入包含~150mL水的瓦林混碎机中,并且形成灰白色固体产物。将所得灰白色固体产物真空干燥。所述产物确认为对苯二胺与2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)-丙氧基)乙氧基)对苯二甲酰氯的聚合物。
实施例3:2-(4-氨基苯基)-1H-苯并[d]咪唑-5-胺与对苯二胺的芳族聚酰
胺(共)聚合物
在烧瓶中,室温下将2-(4-氨基苯基)-1H-苯并[d]咪唑-5-胺(0.8766g,3.913mmol)和对苯二胺(0.212g,1.963mmol)溶解于DMAC(~100mL)中以形成溶液。通过向所述溶液中加入如此制得的2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)-丙氧基)乙氧基)对苯二甲酰氯(2.862g,3.9208mmol)(注意,经由NMR,该酰氯包含~13%的2-(1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十六氟辛基氧基)对苯二甲酰氯)(4.2319g)来形成反应混合物。使反应混合物在室温(约25℃)下搅拌过夜。然后将反应混合物倒入包含~200mL水的瓦林混碎机中,然后形成聚合物沉淀。用额外的水洗涤沉淀出的该聚合物并真空干燥,获得~4.5g聚合物产物。所述产物确认为2-(4-氨基苯基)-1H-苯并[d]咪唑-5-胺与对苯二胺的芳族聚酰胺(共)聚合物。
实施例4:2-(4-氨基苯基)-1H-苯并[d]咪唑-5-胺与间苯二胺的芳族聚酰
胺(共)聚合物
在烧瓶中,室温下将2-(4-氨基苯基)-1H-苯并[d]咪唑-5-胺(0.8766g,3.913mmol)和间苯二胺(0.212g,1.963mmol)溶解于DMAC(~100mL)中以形成溶液。通过向所述溶液中加入如此制得的2-(2-溴-1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)-丙氧基)乙氧基)对苯二甲酰氯(2.862g,3.9208mmol)(注意,经由NMR,该酰氯包含~13%的2-(1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十六氟辛基氧基)对苯二甲酰氯)(4.2319g)来形成反应混合物。使所得反应混合物在室温(约25℃)下搅拌过夜。然后将反应混合物倒入包含~200mL水的瓦林混碎机中,并且形成聚合物沉淀。用额外的水洗涤沉淀出的聚合物并真空干燥,获得~5.45g 2-(4-氨基苯基)-1H-苯并[d]咪唑-5-胺和间苯二胺的芳族聚酰胺(共)聚合物。
实施例5:芳族聚酰胺
在干箱操作手套箱中,将对苯二胺(1.08g,0.01mol)放置在烘箱干燥的配备有机械搅拌器的250mL反应烧瓶中。向反应烧瓶内的该溶液中加入2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酰氯(6.66g,0.01023mol)形成反应溶液。将所得反应溶液在室温(约25℃)下搅拌过夜,然后所得聚合物在水中沉淀出来。用额外的水洗涤所得聚合物,然后在60℃下真空干燥。
实施例6:芳族聚酰胺
在干箱操作手套箱中,将间苯二胺(1.08g,0.01mol)放置在烘箱干燥的配备有机械搅拌器的250mL反应烧瓶中。向该溶液中加入5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)间苯二甲酰氯(6.66g,0.01023mol)以形成反应溶液。将所得反应溶液在室温(约25℃)下搅拌过夜,然后所得聚合物在水中沉淀出来。用额外的水洗涤所得聚合物,然后在60℃下真空干燥。
实施例7:芳族聚酰胺
在干箱操作手套箱中,将对苯二胺(1.08g,0.01mol)放置在烘箱干燥的配备有机械搅拌器的250mL反应烧瓶中。向该反应溶液中加入2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酰氯(6.66g,0.01023mol)以形成反应溶液。将所得反应溶液在室温(约25℃)下搅拌过夜,然后所得聚合物在水中沉淀出来。用额外的水洗涤所得聚合物,然后在60℃下真空干燥。
实施例8:芳族聚酰胺
在干箱操作手套箱中,将对苯二胺(1.08g,0.01mol)放置在烘箱干燥的配备有机械搅拌器的250mL反应烧瓶中。向该溶液中加入5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)间苯二甲酰氯(6.66g,0.01023mol)以形成反应溶液。将反应溶液在室温(约25℃)下搅拌过夜,然后所得聚合物在水中沉淀出来。用额外的水洗涤所得聚合物,然后在60℃下真空干燥。
实施例9:芳族聚酰胺
在干箱操作手套箱中,将间苯二胺(1.08g,0.01mol)放置在烘箱干燥的配备有机械搅拌器的250mL反应烧瓶中。向该反应溶液中加入2-(2-氯-1,1,2-三氟-2-(全氟丙氧基)乙氧基)对苯二甲酰氯(5.19g,0.010mol)以形成反应溶液。将所得反应溶液在室温(约25℃)下搅拌过夜,然后所得聚合物在水中沉淀出来。用额外的水洗涤所得聚合物,然后在60℃下真空干燥。
实施例10:芳族聚酰胺
在干箱操作手套箱中,将对苯二胺(1.08g,0.01mol)放置在烘箱干燥的配备有机械搅拌器的250mL反应烧瓶中。向该反应溶液中加入2-(2-氯-1,1,2-三氟-2-(全氟丙氧基)乙氧基)对苯二甲酰氯(5.19g,0.010mol)以形成反应溶液。将所得反应溶液在室温(约25°)下搅拌过夜,然后所得聚合物在水中沉淀出来。用额外的水洗涤所得聚合物,然后在60℃下真空干燥。
实施例11
在干箱操作手套箱中,将所示二甲酰氯称入到250mL烧瓶中,加入THF(150mL),并且搅拌混合物,直至获得均匀的溶液。将二胺和碳酸钠(10.6g)加入到包含水(150mL)的瓦林混碎机中。将所得溶液快速搅拌,并且加入THF酰氯溶液。将所得混合物搅拌~5分钟,过滤所述聚合物并用水(1升)洗涤,然后用丙酮(1升)洗涤。将所得聚合物在60℃下真空干燥~24小时。所得聚合物具有1.177(H2SO4)的IV。
将一克所得聚合物溶解于NMP(25mL)中并倒入玻璃浇铸板中,并且在60℃和真空下,在具有小洩孔的烘箱中放置~72小时,并且测定所得薄膜以确定接触角和表面能。通过将由此制得的薄膜在150℃和真空下加热五小时,制备其它样本。结果示于表1中。
Claims (15)
2.权利要求1的聚合物,其中Ar为苯基。
3.权利要求1的聚合物,其中每个R为H。
4.权利要求1的聚合物,其中一个R由结构(II)表示,并且所述剩余的两个R各自为H。
5.权利要求1的聚合物,其中每个R1为H。
6.权利要求1的聚合物,其中X为O或CF2。
7.权利要求1的聚合物,其中Y为O或CF2。
8.权利要求1的聚合物,其中Z为Cl。
9.权利要求1的聚合物,其中一个R由结构(II)表示,一个Z为H,并且一个Z为Cl。
10.权利要求1的聚合物,其中Rf1和Rf2中的至少一个为CF2。
11.权利要求1的聚合物,其中p=0,并且Y为CF2。
13.权利要求12的聚合物,其中所有的R2均为H,并且所有的R3均为H。
14.用于形成聚合物的方法,包括使氟乙烯基醚官能化芳族二甲酰氯与芳族二胺混合以形成反应混合物,加热至介于180-240℃之间的温度,然后加热至250-300℃,并且通过使所述混合物经历排空来提取挥发性物质;其中所述氟乙烯基醚官能化芳族二甲酰氯由结构(III)表示,
其中,
Ar代表苯基或萘基;
每个R独立地为H、C1-C10烷基、C5-C15芳基、C6-C20芳烷基;OH、
或由结构(II)表示的基团
前提条件是仅一个R能够为OH或由结构(II)表示的基团;
X为O或CF2;
Z为H、Cl、或Br;
a=0或1;
并且
Q由结构(Ia)表示
其中q=0-10;
Y为O或CF2;
Rf1为(CF2)n,其中n为0-10;
并且
Rf2为(CF2)p,其中p为0-10,前提条件是当p为0时,Y为CF2。
15.权利要求14的方法,其中所述反应混合物还包括由结构(VI)表示的芳族二甲酰氯
其中Ar为芳基;每个R独立地为H或C1–C10烷基。
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US61/239099 | 2009-09-02 | ||
PCT/US2010/047514 WO2011028791A2 (en) | 2009-09-02 | 2010-09-01 | Polyaramid comprising fluorovinylether functionalized aromatic moieties |
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CA2773142A1 (en) | 2011-03-10 |
TW201113311A (en) | 2011-04-16 |
BR112012004666A2 (pt) | 2019-09-24 |
IN2012DN01732A (zh) | 2015-06-05 |
EP2473547A4 (en) | 2013-12-25 |
EP2473547A2 (en) | 2012-07-11 |
TW201118113A (en) | 2011-06-01 |
CN102597060A (zh) | 2012-07-18 |
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JP2013503943A (ja) | 2013-02-04 |
US20110213118A1 (en) | 2011-09-01 |
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