CN105324384B - 二酐、聚酰亚胺,及其各自的制备方法和使用方法 - Google Patents
二酐、聚酰亚胺,及其各自的制备方法和使用方法 Download PDFInfo
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- CN105324384B CN105324384B CN201480035786.9A CN201480035786A CN105324384B CN 105324384 B CN105324384 B CN 105324384B CN 201480035786 A CN201480035786 A CN 201480035786A CN 105324384 B CN105324384 B CN 105324384B
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- polyimide
- aromatic dianhydride
- aromatic
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 43
- 229920001721 polyimide Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- 125000006159 dianhydride group Chemical group 0.000 title description 2
- 125000003118 aryl group Chemical group 0.000 claims abstract description 54
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000001072 heteroaryl group Chemical group 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000768 polyamine Polymers 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 7
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 3
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004427 diamine group Chemical group 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- -1 hydroxy, amino Chemical group 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 101000578774 Homo sapiens MAP kinase-activated protein kinase 5 Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 102100028396 MAP kinase-activated protein kinase 5 Human genes 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GQJBVHQZIPJKGF-UHFFFAOYSA-N OC(=O)c1cc2-c3ccccc3C3(c4ccccc4-c4cc(C(O)=O)c(cc34)C(O)=O)c2cc1C(O)=O Chemical compound OC(=O)c1cc2-c3ccccc3C3(c4ccccc4-c4cc(C(O)=O)c(cc34)C(O)=O)c2cc1C(O)=O GQJBVHQZIPJKGF-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011676 menaquinone-4 Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 239000013598 vector Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KIOQWHKRKVBTLT-UHFFFAOYSA-N 4-[2-(4-amino-3-methylphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC(C(C=2C=C(C)C(N)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 KIOQWHKRKVBTLT-UHFFFAOYSA-N 0.000 description 1
- GXXFPQGHCPOFSD-UHFFFAOYSA-N 9,9'-spirobi[fluorene]-2,2'-diamine Chemical compound C12=CC=CC=C2C2=CC=C(N)C=C2C21C1=CC=CC=C1C1=CC=C(N)C=C12 GXXFPQGHCPOFSD-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- LQJOFNCELWQOTH-UHFFFAOYSA-N N#Cc1cc2-c3ccccc3C3(c4ccccc4-c4cc(C#N)c(cc34)C#N)c2cc1C#N Chemical compound N#Cc1cc2-c3ccccc3C3(c4ccccc4-c4cc(C#N)c(cc34)C#N)c2cc1C#N LQJOFNCELWQOTH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004175 fluorobenzyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/62—Naphtho [c] pyrroles; Hydrogenated naphtho [c] pyrroles
- C07D209/66—Naphtho [c] pyrroles; Hydrogenated naphtho [c] pyrroles with oxygen atoms in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
-
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/92—Naphthofurans; Hydrogenated naphthofurans
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/10—Spiro-condensed systems
-
- 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
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明的实施例提供芳香族二酐、制得芳香族二酐的方法、基于芳香族二酐的聚酰亚胺、制得基于芳香族二酐的聚酰亚胺的方法等。
Description
相关申请的交叉引用
本申请要求2013年7月2日提交的标题为“二酐、聚酰亚胺、各制得方法以及使用方法(DIANHYDRIDES,POLYIMIDES,METHODS OF MAKING EACH,AND METHODS OF USE)”、序列号为61/842,104的美国临时申请的优先权,其以全文引用的方式并入本文中。
背景技术
聚酰亚胺是展现优越的热、化学以及机械特性的最重要的高性能玻璃态聚合物之一。聚酰亚胺已用于许多领域中,包括航空工业、电子工业、高温粘附、用于分离的膜、复合材料等。然而,大多数聚酰亚胺由于其较高熔点和在有机溶剂中的有限可溶性而展现不佳的可加工性。已研发出微孔聚酰亚胺来克服这些缺陷,然而,微孔聚酰亚胺(至少部分)由于适合的试剂的限制而在合成方面具有挑战性。
发明内容
本发明的实施例提供芳香族二酐、制得芳香族二酐的方法、基于芳香族二酐的聚酰亚胺、制得基于芳香族二酐的聚酰亚胺的方法等。
在一个实施例中,组合物尤其可以包括:具有以下结构的芳香族二酐:
其中R选自以下结构:
其中各R1、R2以及R4独立地选自由以下各者组成的群组:直链或支链的经取代或未经取代的烷基,其中Ar2选自由以下各者组成的群组:芳基和杂芳基,其中各自是经取代或未经取代的。
在一个实施例中,组合物尤其可以包括:具有以下结构的聚酰亚胺:
其中Y选自芳基或杂芳基,其中x是1到10,000,其中R选自以下结构:
其中R1、R2以及R4中的每一个独立地选自由以下各者组成的群组:直链或支链的经取代或未经取代的烷基,其中Ar2选自由以下各者组成的群组:芳基和杂芳基,其中各自可以是经取代或未经取代的。
在一个实施例中,组合物尤其可以包括:具有以下结构的聚酰亚胺:
其中Ar3和Ar4独立地选自芳基或杂芳基,其中m和n独立地是0或10,000,其中R选自以下结构:
其中R1、R2以及R4独立地选自由以下各者组成的群组:直链或支链的经取代或未经取代的烷基,其中Ar2选自由以下各者组成的群组:芳基和杂芳基,其中R5是直链或支链的经取代或未经取代的烷基。
在一个实施例中,制得芳香族二酐的方法尤其可以包括:
其中A包括N-溴代琥珀酰亚胺,其中B包括亚硝酸钠,其中C包括氰化铜,其中D包括氢氧化钾继而乙酸酐,其中R选自以下结构:
其中R1、R2以及R4独立地选自由以下各者组成的群组:直链或支链的经取代或未经取代的烷基,其中Ar2选自由以下各者组成的群组:芳基和杂芳基,其中各自是经取代或未经取代的。
在一个实施例中,制得聚酰亚胺的方法尤其可以包括:使芳香族二酐与多胺反应以形成聚酰亚胺或聚吡咙(polypyrrolone),其中芳香族二酐具有以下结构:
其中R选自以下结构:
其中各R1、R2以及R4独立地选自由以下各者组成的群组:直链或支链的经取代或未经取代的烷基,其中Ar2选自由以下各者组成的群组:芳基和杂芳基,其中各自是经取代或未经取代的。
附图说明
当结合附图时,本发明的其它方面在回顾下文所描述的其各种实施例的实施方式后将更容易理解。
图1说明芳香族二酐的一个实施例。
图2说明R的实施例。
图3说明制得芳香族二酐的一个实施例。
图4说明基于芳香族二酐的聚酰亚胺的一个实施例。
图5是说明二胺如何可以用于形成基于芳香族二酐的聚酰亚胺的一个说明性实施例。
图6是说明多胺如何可以用于形成基于芳香族二酐的聚酰亚胺的一个说明性实施例。
图7说明使用特定芳香族二酐可以形成的基于芳香族二酐的聚酰亚胺的一个特定实施例。
图8A-8F说明如实例中所提到的一些新颖的聚酰亚胺的BET等温线图。
具体实施方式
在更详细地描述本发明之前,应理解本发明不限于所描述的特定实施例,因而当然可以变化。还应理解,本文所使用的术语仅是为了描述特定实施例,并且并不打算是限制性的,这是由于本发明的范围将仅受到所附权利要求书限制。
当提供值范围时,应理解,在所述范围的上限与下限之间的各中间值到下限的单位的十分之一(除非上下文明确指出)以及在所陈述的范围内的任何其它指定值或中间值都涵盖于本发明内。这些较小范围的上限和下限可以独立地包括在所述较小范围内并且也涵盖于本发明内,从属于在所陈述的范围内的任何特定地排除的界限。当所陈述的范围包括限值中的一个或两个时,排除所包括的那些限值中的任一个或两个的范围也包括在本发明中。
除非另外规定,否则本文所使用的所有技术和科学术语都具有与本发明所属领域的技术人员通常所理解相同的含义。尽管在本发明的操作或测试中也可以使用与本文所描述的方法和材料类似或等效的任何方法和材料,但是现在描述优选方法和材料。
本说明书中所引用的所有公开案和专利都以引用的方式并入本文中,就如同特定地且单独地指示每一个别公开案或专利以引用的方式并入一般,且以引用的方式并入本文中以结合所引用的公开案来公开和描述方法和/或材料。对任何公开案的引用是针对申请日之前的其公开内容,并且不应解释为承认本发明无权先于依靠先前发明的此类公开案。此外,所提供的公开案的日期可能不同于可能需要独立确认的实际公开案日期。
如所属领域的技术人员在阅读本发明之后将显而易见,本文中所描述和说明的个别实施例中的每一个具有离散组件和特征,其可以在不背离本发明的范围或精神的情况下,容易地与其它若干实施例中的任一个的特征分离或与其组合。任何所叙述的方法都可以所叙述事件的顺序或以逻辑上可能的任何其它顺序来实施。
除非另外指明,否则本发明的实施例将采用化学、合成有机化学、高分子化学、分析化学等的技术,其在所属领域的技能范围内。在文献中全面解释了此类技术。
提出以下实例以便向所属领域的普通技术人员提供如何执行所述方法和使用本文所公开和所要求的组合物和化合物的完整公开内容和描述。已经作出努力以确保关于数字(例如量、温度等)的准确性,但应该允许一些误差和偏差。除非另外规定,否则份数为重量份,温度以℃为单位,并且压力以巴为单位。标准温度和压力被定义为0℃和1巴。
在详细描述本发明的实施例之前,应理解,除非另外指出,否则本发明不限于特定材料、试剂、反应物质、制造方法或其类似物,因而可以变化。还应该理解,本文所使用的术语仅出于描述特定实施例的目的,并且不打算为限制性的。在本发明中还有可能以不同顺序执行步骤,这在逻辑上是可能的。
必须指出,除非上下文另外明确指出,否则如说明书和所附权利要求书中所使用,单数形式“一(a/an)”和“所述(the)”包括多个指示物。因此,举例来说,提到“一个载体”包括多个载体。在本说明书和所附权利要求书中,除非明显为相反意图,否则将提到应被定义为具有以下意义的多个术语。
定义:
术语“经取代的”是指指定原子上的任何一个或多个氢可以经指示基团的选择置换,其限制条件是不超过指定原子的正常价数。
如本文所使用,“脂肪族基”或“脂肪族基团”是指饱和或不饱和、直链或支链、环状(非芳香族)或杂环(非芳香族)烃或烃基,并且例如涵盖烷基、烯基和炔基以及烷烃、烯烃和炔烃。
如本文所使用,“环状”基团是指具有稳定的4、5、6、7、8、9、10、11或12元(例如碳或杂)(除非另外叙述元数)单环、双环或三环的环烃。
如本文所使用,“烷基(alkyl)”或“烷基(alkyl group)”是指支链饱和脂肪族烃。烷基的实例包括(但不限于)异丙基、仲丁基、叔丁基和异戊基。
如在“经取代的烷基”、“经取代的芳基”、“经取代的杂芳基”等中的术语“经取代”意味着经取代的基团可以含有如以下各者的基团代替一个或多个氢:烷基、羟基、氨基、卤基、三氟甲基、氰基、--NH(低碳数烷基)、--N(低碳数烷基)2、低碳数烷氧基、低碳数烷硫基或羧基,并且因此包涵在下文中提及的术语卤烷基、烷氧基、氟苯甲基以及含硫和磷的取代基。
如本文所使用,“卤基”、“卤素”或“卤素自由基”是指氟、氯、溴和碘以及其自由基。此外,当用于如“卤烷基”或“卤烯基”的复合词中时,“卤基”是指其中一个或多个氢经卤素自由基取代的烷基或烯基自由基。卤烷基的实例包括(但不限于)三氟甲基、三氯甲基、五氟乙基以及五氯乙基。
如本文所使用,术语“芳基”是指具有约6到约14个碳原子,优选约6到约10个碳原子的芳香族单环或多环环系统。示例性芳基包括苯基或萘基,或经取代的苯基或经取代的萘基。
本文中使用的术语“杂芳基”指示在环中或稠环结构中的一个或多个环中具有一个或多个非碳原子(如氧、氮和硫)的碳原子的芳香族环或稠环结构。优选实例为呋喃基、咪唑基、吡喃基、吡咯基和吡啶基。
一般论述
本发明的实施例提供芳香族二酐、制得芳香族二酐的方法、基于芳香族二酐的聚酰亚胺、制得基于芳香族二酐的聚酰亚胺的方法等。基于芳香族二酐的聚酰亚胺的实施例具有以下特征中的一种或多种:固有微孔性、良好热稳定性以及增强的可溶性。固有微孔性本文中被定义为孔隙尺寸小于2nm并且表面孔隙度>100m2/g的聚合材料,如在77K下氮吸附方法所测定。
由于其良好的可溶性、热和化学稳定性以及较高微孔性,这些材料可以在与航空工业、电子工业、高温粘附、用于分离的膜以及复合材料相关的广泛范围的工业应用中实施。
在示例性实施例中,基于芳香族二酐的聚酰亚胺可以使用如以下结构中所示的芳香族二酐制得:
在一个实施例中,R可以选自以下结构,其中各结构可以是经取代或未经取代的、经由所提到的键而键结:
以及针对上文提到的R基团所示的键以一种方式显示以显示酸酐基团如何键结并且不指示甲基。可以通过考虑图1中所示的键结流程更好地理解针对R基团键形成酸酐的方式。举例来说,所示键可以是所形成结构(结构A、B、C、D和F)的芳香族环的一部分或可以连接到芳香族环(结构E和G)上的位置(不一定是所示位置)。
在一个实施例中,各R1、R2以及R4可以独立地选自:直链或支链的经取代或未经取代的烷基。在一个实施例中,各R1、R2以及R4可以独立地选自甲基、乙基、丙基以及丁基(直链或支链),各自经取代或未经取代。短语“独立地选自”可以意味着独立于彼此的R1、R2以及R4的选择,或可以意味着在R1(以及R2和R4)的每个例子中,独立于其它R1选择各R1(例如一个R1可以是甲基,并且另一个R1可以是丙基)。
其中R1指示为连接到环(例如芳香族环)的实施例,R1可以连接到所述环的任何碳。其中R1连接到一个环的实施例,一个、两个或更多个R1可以连接到所述环以置换所述环上的氢。举例来说,所述环可以具有两个或更多个在相同或不同碳处连接到相同环的R1。
在一个实施例中,Ar2可以是经取代或未经取代的芳基或杂芳基。在一个实施例中,Ar2可以选自:以及其通过为两个碳从环去除氢而键结,并且各环可以具有至多四个R7基团。在一个实施例中,Ar2可以选自或在一个实施例中,各R5和R7可以独立地是直链或支链的经取代或未经取代的烷基(例如甲基)。可以独立地选择各R5。可以独立地选择各R7。芳香族二酐的实例显示于图1和2中。
在一个实施例中,芳香族二酐可以使用图3中所示的反应程序制造,其中R和其它变量如上文所提到定义。在一个实施例中,步骤A包括在邻位芳香族二胺的溴化。反应可以在室温下或在冰浴中进行,并且反应时间可以是约5分钟到约30分钟,取决于二胺的活性。溴化剂可以是NBS或溴元素。
在一个实施例中,步骤B包括使用重氮盐(例如亚硝酸钠、亚硝酸异戊酯或一些其它亚硝酸盐)将中间物的二胺基团改变为二碘基团。碘基的引入可以是含有碘元素的任何无机盐,如碘化钠或碘化钾。反应可以在冰浴中在酸性条件下进行并且持续约1到2小时,取决于二胺的活性。
在一个实施例中,步骤C可以包括将二溴-二碘中间物转换成四氰酸盐中间物,其可以通过在强极性溶剂中在如约120℃的高温下利用CuCN的芳香族取代进行。
在一实施例中,步骤D可以包括四氰酸盐在碱性条件下的水解。如氢氧化钾或氢氧化钠的无机碱可以用于形成四酸,其可以进一步进行循环反应形成二酐。乙酸酐可以用于循环反应中。
在一个实施例中,芳香族二酐可以用于形成基于芳香族二酐的聚酰亚胺均聚物或共聚物。在一个实施例中,基于芳香族二酐的聚酰亚胺可以具有以下结构中的一种:(图4)。在一个实施例中,Y、Ar3以及Ar4可以各自独立地是芳基或杂芳基,并且x可以是1到10,000。
在一个实施例中,Y、Ar3以及Ar4基团可以是芳基或杂芳基,其可以衍生自以下芳香族二胺:芳基二胺基团或杂芳基二胺基团。在一个实施例中,芳基二胺基团可以是: 在一个实施例中,Y、Ar3以及Ar4基团可以衍生自如的杂芳基二胺基团,其中Y、Ar3以及Ar4基团可以对应于
在一个实施例中,Ar3和Ar4不同。下标m和n可以独立地是0到10,000或1到10,000。在一个实施例中,R可以包括如上文所定义的R。
在一个实施例中,基于芳香族二酐的聚酰亚胺可以通过芳香族二酐与多胺的反应形成。一般来说,在溶剂(例如NMP、DMAc、间甲酚或DMSO,在某些条件下,经由一个步骤加热方法或两个步骤方法反应)中使芳香族二酐与多胺反应以形成基于芳香族二酐的聚酰亚胺。
在一个实施例中,多胺可以是二胺、三胺、四胺或具有5个或更多个氨基的胺。形成聚酰亚胺的反应的示例性实例显示于图5和6中。下标x可以是0到10,000或1到10,000。
图6是说明多胺如何可以用于形成基于芳香族二酐的聚酰亚胺的一个说明性实施例。关于图6,Ar5可以是具有多个氨基(由R3表示)的脂肪族或芳香族基团(例如芳基或杂芳基)。然而,Ar5可以经设计以具有二、三、四、五或更多个R3基团,因此Ar5不限于图6中所示的结构。在一个实施例中,R3基团中的一个或多个可以是氨基,其中可以形成二胺、三胺、四胺或具有5个或更多个氨基的胺。
四胺的示例性实例可以包括以下结构:
在图7中所示的实施例中,可以使用特定芳香族二酐形成基于芳香族二酐的聚酰亚胺的特定实施例。图8A-8F说明如实例中所提到的一些新颖的聚酰亚胺的BET等温线图。
实例
现在,已大体描述本发明的实施例,实例描述一些其它实施例。尽管结合实例和相应文字和图式描述了本发明的实施例,但不打算将本发明的实施例限制于这些描述。相反,打算涵盖本发明的实施例的精神和范围内包括的所有替代方案、修改和等效物。
单体合成实例:
实例1
合成2,2',3,3'-四羧基-9,9'-螺二芴
将2,2',3,3'-四氰基-9,9'-螺二芴(624mg,1.50mmol)与水/乙醇(10mL/10mL)溶液混合。接着,缓慢添加KOH(1740mg,30mmol),并且使混合物回流过夜。在将溶液冷却到室温之后,将其倒入酸(HCl,6N)中以将pH调节到1到2。在去除乙醇和水之后,再次添加甲醇以溶解产物并且过滤以去除有机相。其后,将THF(20mL)添加到固体中,过滤,并且将THF溶液逐滴添加到300mL DCM中。在过滤后,获得灰白色固体。
实例2
合成2,2',3,3'-二酐-9,9'-螺二芴
将2,2',3,3'-四羧基-9,9'-螺二芴(1.06g,2.15mmol)添加到Ac2O(15mL)中。使溶液回流6小时并且过滤以获得针状晶体:0.9g(产率:98%)。1H NMR(400MHz,CDCl3):8.45(s,2H),8.07(d,2H,J=7.72Hz),7.58(t,2H,J=7.48Hz,7.50Hz),7.36(t,2H,J=7.48Hz,7.50Hz),7.24(s,2H),6.82(d,2H,J=7.68Hz)。分析:C29H12O6计算值:C,76.32;H,2.65;实验值:C,75.42;H,2.06;HRMS:C25H18N2O2计算值:456.0634;实验值:406.06284。
实例3
合成MK-1
将2,2',3,3'-二酐-9,9'-螺二芴(456.06mg,1.00mmol)和2,3,5,6-四甲基,1,4-苯二胺(164.13mg,1.00mmol)添加到间甲酚(3mL)中。将溶液加热到60℃持续1小时,之后添加异喹啉(5滴),并且其后,将系统加热直到180℃持续4小时。聚合物沉淀在甲醇(100mL)中,接着干燥并且溶解于氯仿中并且再沉淀在MeOH中。在过滤后,在真空烘箱中干燥聚合物过夜,并且获得灰白色聚合物粉末(590mg,产率95%)。1H NMR(400MHz,CDCl3):8.43(s,2H),8.02(s,2H),7.53(s,2H),7.31(s,2H),6.88(s,2H),2.06(s,12H);分子量(GPC于氯仿中)Mn=9.3×103;Mw=1.9×104;PDI=2.01;BET表面积:754m2/g。
实例4
合成MK-2
将2,2',3,3'-二酐-9,9'-螺二芴(456.06,1.00mmol)和3,3'-二甲基联萘胺(312.42mg,1.00mmol)添加到间甲酚(3mL)中。将溶液加热到60℃持续1小时,之后添加异喹啉(5滴),并且其后,将系统加热直到180℃持续4小时。聚合物沉淀在甲醇(100mL)中,接着干燥并且溶解于氯仿中并且再沉淀在MeOH中。在过滤后,在真空烘箱中干燥聚合物过夜,并且获得淡黄色聚合物粉末(730mg,产率95%)。1H NMR(400MHz,CDCl3):8.56(s,2H),8.09(s,2H),7.42-7.62(m,16H),6.97(s,2H),2.42(s,6H);分子量(GPC于氯仿中)Mn=2.5×104;Mw=6.4×104;PDI=2.67。
实例5
合成MK-3
采用9,9'-螺二芴-2,2'-二胺,通过与MK-1相同的程序合成所得聚酰亚胺(MK-3),产率95%。1H NMR(400MHz,CDCl3):8.24(s,2H),7.89(s,4H),7.78(s,2H),7.42(s,2H),7.31-7.35(m,4H),7.18(s,2H),7.09-7.11(m,2H),7.03(s,2H),6.76-6.79(m,4H),6.70(s,2H);分子量(GPC于氯仿中)Mn=14.4×104;Mw=23.5×104;PDI=1.63。
实例6
合成MK-4
4,4'-(全氟丙烷-2,2-二基)双(2-甲基苯胺)用作起始二胺化合物,并且通过与MK-1相同的程序合成所得聚酰亚胺(MK-4),产率95%。1H NMR(400MHz,CDCl3):8.40(d,2H,J=1.27Hz),8.01(s,2H),7.51(s,2H),7.22-7.46(m,10H),6.97(d,2H,J=2.0Hz),2.18(s,6H);分子量(GPC于氯仿中)Mn=7.70×104;Mw=13.1×104;PDI=1.70。
实例7
合成MK-5
3,3,3',3',-四甲基-螺双茚-6,6'-二羟基-5,5'-二胺用作起始二胺化合物,并且通过与MK-1相同的程序合成所得聚酰亚胺(MK-5),产率95%。1H NMR(400MHz,DMSO-d6):9.52(s,2H),8.73(s,2H),8.40(s,2H),7.53(s,2H),7.29(s,2H),7.07(s,4H),6.78(s,2H),6.33(s,2H),2.13-2.34(m,4H),1.27(s,12H);分子量(GPC于氯仿中)Mn=6.73×104;Mw=10.1×104;PDI=1.50。
实例8
合成MK-6
9,9'-螺二芴-2,2'-二羟基-3,3'-二胺用作起始二胺化合物,并且通过与MK-1相同的程序合成所得聚酰亚胺(MK-6),产率95%。1H NMR(400MHz,CDCl3):9.89(s,2H),8.80(s,2H),8.41(s,2H),7.77-7.88(m,4H),7.54(s,2H),7.13-7.32(m,8H),6.67-6.80(m,4H),6.20(s,2H);分子量(GPC于氯仿中)Mn=6.38×104;Mw=11.7×104;PDI=1.84。
表1.聚酰亚胺的可溶性
++可溶性超过5mg/mL;+-可溶性在1mg/mL与5mg/mL之间,--:可溶性小于1mg/mL。
表2:新颖聚合物的BET表面积和其它特性
应注意,可以在本文中以范围格式表达比率、浓度、量和其它数字数据。应理解,这种范围格式是出于便利和简洁目的而使用,并且因此其应该以灵活方式解释为不仅包括作为所叙述的范围的界限而被明确叙述的数值,并且还包括涵盖在所述范围内的所有个别数值或子范围,就像每一数值和子范围都被明确叙述一样。为了说明,“约0.1%到约5%”的浓度范围应解释为不仅包括约0.1wt%到约5wt%的明确叙述的浓度,并且还包括在所指示的范围内的个别浓度(例如1%、2%、3%和4%)和子范围(例如0.5%、1.1%、2.2%、3.3%和4.4%)。在一个实施例中,术语“约”可以包括根据数值的有效数字的传统四舍五入。另外,短语“约‘x’到‘y’”包括“约‘x’到约‘y’”。
应强调,本发明的上文所描述的实施例仅为实施方案的可能实例,并且仅为了清晰理解本发明的原理而阐述。可以在不实质上背离本发明的精神和原则的情况下对本发明的上文所描述的实施例作出许多变化和修改。所有此类修改和变化打算在本文中包括在本发明的范围内。
Claims (10)
5.根据权利要求4所述的组合物,其中Ar3和Ar4不同。
9.根据权利要求8所述的方法,其中所述多胺选自由二胺、三胺、四胺以及具有5个或更多个氨基的胺组成的群组。
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