CN101395201A - Process for production of a bis-phthalonitrile monomer - Google Patents
Process for production of a bis-phthalonitrile monomer Download PDFInfo
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- CN101395201A CN101395201A CNA2007800079079A CN200780007907A CN101395201A CN 101395201 A CN101395201 A CN 101395201A CN A2007800079079 A CNA2007800079079 A CN A2007800079079A CN 200780007907 A CN200780007907 A CN 200780007907A CN 101395201 A CN101395201 A CN 101395201A
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- benzene
- phenoxy group
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 title claims abstract description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 24
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 19
- HBUCPZGYBSEEHF-UHFFFAOYSA-N 3-phenoxyphenol Chemical compound OC1=CC=CC(OC=2C=CC=CC=2)=C1 HBUCPZGYBSEEHF-UHFFFAOYSA-N 0.000 claims description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 14
- 150000008378 aryl ethers Chemical class 0.000 claims description 14
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 14
- -1 methoxyl group Chemical group 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 235000015320 potassium carbonate Nutrition 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 9
- XJJYJJKMQRFGQM-UHFFFAOYSA-N 3-[3-(3-hydroxyphenoxy)phenoxy]phenol Chemical compound OC1=CC=CC(OC=2C=C(OC=3C=C(O)C=CC=3)C=CC=2)=C1 XJJYJJKMQRFGQM-UHFFFAOYSA-N 0.000 abstract 2
- YAFUCDIOZPWIKO-UHFFFAOYSA-N 4-[3-[3-[3-(3,4-dicyanophenoxy)phenoxy]phenoxy]phenoxy]benzene-1,2-dicarbonitrile Chemical compound C1=C(C#N)C(C#N)=CC=C1OC1=CC=CC(OC=2C=C(OC=3C=C(OC=4C=C(C(C#N)=CC=4)C#N)C=CC=3)C=CC=2)=C1 YAFUCDIOZPWIKO-UHFFFAOYSA-N 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- 239000012380 dealkylating agent Substances 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 230000020335 dealkylation Effects 0.000 description 4
- 238000006900 dealkylation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling 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
- 239000006227 byproduct Substances 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003280 clastogen Substances 0.000 description 1
- 231100000506 clastogen Toxicity 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010792 warming 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
- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
- C08G73/0655—Preparatory processes from polycyanurates
-
- 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
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4031—(I) or (II) containing nitrogen
-
- 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
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Dislosed is a process for production of a bis-phthalonitrile monomer having an oligophenyl ether spacer chain, said bis-phthalonitrile of Formula (I) wherein n is 2. The process comprises (i) subjecting a 3-alkoxyphenol to reaction with a m-dihalobenzene in the presence of a base and a catalyst composition comprising a copper salt and a ligand whereby a 1,3-bis (3-alkoxyphenoxy) benzene is yielded, (ii) subjecting yielded 1 ,3-bis (3-alkoxyphenoxy) benzene to reaction with a dealkylating agent yielding 1 ,3-bis(3- hydroxyphenoxy)benzene, and (iii) subjecting yielded 1,3-bis (3-hydroxyphenoxy) benzene to reaction with a 4-nitrophthalonitrile in presence of a base yielding 1,3-bis [3-(3,4-dicyano- phenoxy)phenoxy]benzene.
Description
Technical field
The present invention relates to the method that a kind of preparation has the bis-phthalonitrile monomer of oligomeric phenyl ether spacer chain.Described monomer is general formula (I)
More particularly, the present invention relates to a kind of preparation wherein n be 2 described monomeric novel method.In yet another aspect, the present invention relates to the purposes of a kind of intermediate product that obtains in the method according to the invention in preparing the method for bis-phthalonitrile monomer that n wherein is 4 or 6 general formula (I).
Background technology
Phthalonitrile (PN) resin is developed by United States Naval Research Laboratory at the eighties initial stage in 20th century at first as the high temperature substitute of polyimide resin.The PN resin is the thermosetting resin derived from bis-phthalonitrile monomer.The mode polymerization with addition reaction in the presence of solidifying agent of this monomer forms the triazine network.Completely crued resin has shown good thermostability and oxidative stability, and has long mechanical property under the high temperature.In addition, the phenyl ring of formation monomer skeleton structure is highly stable.The combination of these performances means that its composite products has good resistivity against fire.
In a large amount of patents and patent application, describe various phthalonitrile monomers and polymkeric substance, wherein instructed the method for preparation and polymerization phthalonitrile monomer usually.Disclosed monomer typically has two phthalonitrile groups, respectively has one at the two ends of the spacer chain that connects.Monomer can be cured, its crosslinked occurring between the cyano group.
US4587325 discloses the synthetic of two kinds of bis-phthalonitrile monomers in embodiment 1 and 5, and promptly 1 of 4,4 ' of general formula (II)-two (3,4-dicyano phenoxy group) biphenyl and general formula (III), two (3, the 4-dicyano phenoxy group) benzene of 3-:
By 4-nitrophthalonitrile and aromatic diol prepared in reaction monomer, all monomers can both be as the precursor of preparation PN resin.But these monomeric shortcomings are that processing temperature is higher and because its work range of monomeric high-melting-point is narrow.The fusing point of 4,4 '-two (3,4-dicyano phenoxy group) biphenyl is about 235 ℃ and 1, and the fusing point of two (3, the 4-dicyano phenoxy group) benzene of 3-is about 184 ℃.
The bis-phthalonitrile monomer that disclosed International Patent Application WO 03/091312 instruction has oligomeric or polymerizable aromatic ether spacer chain expects more to be used for the PN resin owing to what estimate than lower boiling.Need the compound of a wider range between fusing point and the solidification value to control viscosity in solidified speed and the solidification process.With respect to the system that has short spacer chain endways between the phthalonitrile groups, this thermosetting resin also has physicals such as the toughness and the processing characteristics of improvement.Usually toughness and fragility are along with more low-density crosslinked and improve.These can be realized by the PN monomer that use has a longer spacer chain.In same patent application, the inventor discloses the method for preparing hydroxy-end capped aromatic ether oligopolymer, and dihydroxy aromatic compounds such as Resorcinol and a di halo aromatic compound were as 1 between it passed through, and the 3-dibromobenzene reacts and forms.This reaction is undertaken by the Ullmann in the presence of mantoquita and cesium carbonate is synthetic.Recently control the chain length of aromatic ether oligopolymer by the mole between a dihydroxy aromatic compounds and the di halo aromatic compound.Further make the reaction of hydroxy-end capped aromatic ether oligopolymer and 4-nitrophthalonitrile to form the bis-phthalonitrile monomer of general formula (I), wherein the ether spacer chain comprises 3,5,7 or 9 aromatic groups of average out to, and the n in the correspondingly described general formula is 2,4,6 or 8 in theory.
The disclosed method for preparing bis-phthalonitrile monomer has following at least shortcoming among the WO03/091312.The product that used reaction conditions prepares down among the embodiment comprises the complex mixture of the bis-phthalonitrile monomer with wide distribution spacer chain length.In addition, the product that makes separates from acidic aqueous solution, and all water-insoluble by products such as hydroxyl and the end capped oligopolymer of halo remain in the product thus.This causes very big difficulty can for the reaction of control product in the curing schedule process.Therefore, this mixture should not be as the precursor of PN resin of the physicals that needs good thermal stability and oxidative stability and improvement.
Summary of the invention
Having been found that needs a kind of preparation to have the method for the bis-phthalonitrile monomer of oligomeric phenyl ether spacer chain.The present invention provide unexpectedly a kind of preparation wherein n be the novel method of the bis-phthalonitrile monomer of 2 general formula (I), the product of this method preparation has high purity, for example is higher than 98%.Method of the present invention comprises the steps:
I) alkali and comprise mantoquita and the catalyst composition of part in the presence of with 3-alkoxy phenol and the reaction of phenyl-dihalide, make 1 thus, two (the 3-alkoxyl group phenoxy group) benzene of 3-,
Ii) step (i) is made 1, two (the 3-alkoxyl group phenoxy group) benzene of 3-with take off alkyl agent reaction, make 1 thus, two (3-hydroxyphenoxy) benzene of 3-and
Iii) in the presence of alkali, step is (ii) made 1, two (3-hydroxyphenoxy) benzene of 3-and the reaction of 4-nitrophthalonitrile make 1 of general formula (I) expression thus, 3-pair of [3-(3,4-dicyano phenoxy group) phenoxy group] benzene.
3-alkoxy phenol in the steps of a method in accordance with the invention (i) and a phenyl-dihalide reaction form 1, two (the 3-alkoxyl group phenoxy group) benzene of 3-, shown in following response line road (IV):
Wherein R is low alkyl group such as methyl, ethyl, propyl group or butyl or alkylaryl such as benzyl, and wherein X is halogen such as bromine or iodine.Correspondingly, described alkoxyl group be preferably methoxyl group, oxyethyl group, propoxy-, butoxy or alkoxy aryl as benzyloxy and as described in halo be preferably iodo or bromo equally.The alkoxy phenol of 3-described in the preferred embodiment for the present invention is the 3-methoxyphenol, and described phenyl-dihalide is preferably 1 equally, the 3-dibromo-benzene.Suitable mol ratio for 2-3 mole 3-alkoxy phenol for example to phenyl-dihalide between 1 mole.This is reflected at least a polar protic inert solvent such as dimethyl sulfoxide (DMSO), N in the embodiment of the present invention, carries out under the existence of dinethylformamide, N,N-dimethylacetamide and/or N-N-methyl-2-2-pyrrolidone N-.Most preferred solvent is the N-N-methyl-2-2-pyrrolidone N-.Use alkali and catalyzer to synthesize and carry out this reaction with Ullmann ether.Suitable alkali is supercarbonate, carbonate, oxyhydroxide and the alcoholate of basic metal and alkaline-earth metal.Carbonate is generally preferred alkali, and most preferred carbonate is salt of wormwood.The suitable consumption of alkali is the 0.5-2 mole to 1 mole 3-alkoxy phenol in reaction medium.Catalyzer is the Ullmann ether catalyst, for example metal-salt such as mantoquita.Most preferred mantoquita is cupric iodide (I) and/or cupric bromide (I).Other suitable copper compounds ground comprises cupric chloride (I), cupric bromide (II), copper sulfate (II) and/or neutralized verdigris (II).The suitable consumption of catalyzer is generally 0.1-10 mole %, for example 0.5-2 mole %, in the mole number of described phenyl-dihalide.Can make mantoquita be dissolved in reaction medium more by adding copper part and further improve reactive behavior.Develop some effective parts for the catalytic Ullmann ether of copper is synthetic, as lipid acid diamines, 1, the phosphine of 10-phenanthroline and derivative thereof, bidentate and monodentate, amino acid derivative and 2,2,6,6-tetramethyl-heptane-3,5-diketone.Especially, N under the verified reaction conditions in step of the present invention (i), the N-N-methylsarcosine is effective part.The suitable consumption of part is for for example 0.3-20 mole %, for example 1-6 mole %, in the mole number of described phenyl-dihalide.
Embodiment
The typical process of step (i) discloses as follows:
In reaction vessel, inject 3-alkoxy phenol such as 3-methoxyphenol.Add solvent such as N-N-methyl-2-2-pyrrolidone N-, its consumption is for being enough to solubilizing reaction thing and product at least.Add alkali such as salt of wormwood, its consumption makes it possible to azeotropic and removes the moisture that forms in the reaction process for for example 0.5-2 mole adds the suitable solvent such as the toluene of enough consumptions at last to 1 mole of 3-alkoxy phenol to mixture.Most preferably cross reaction vessel with the air communication of rare gas element such as nitrogen or argon.Elevated temperature distills toluene-water azeotropic mixture to 130-170 ℃.Keep reaction mixture at 130-170 ℃ of following 1-4 hour, distill remaining moisture and toluene.Now per 1 mole of 3-alkoxy phenol is added 0.3-0.5 phenyl-dihalide is as 1 between mole, the 3-dibromo-benzene adds 0.5-2 mole % catalyzer such as cupric iodide (I) and 1-6 mole % part such as N then, and the N-N-methylsarcosine is in the mole number of a phenyl-dihalide.At 100-160 ℃ of following stirred reaction mixture 5-24 hour or finish until reaction.Add The suitable solvent such as toluene after being cooled to 20-40 ℃, from mixture, filter out inorganic salt then.Use aqueous alkali such as 10%NaOH, water and aqueous 1%NaCl solution washing filtrate successively.Afterwards by for example be lower than at least in vacuum 30mbar and 60-100 ℃ down distillation remove solvent/water, obtain 1, two (the 3-alkoxyl group phenoxy group) benzene of 3-, it is further purified or it will not be used for step (ii) after the purifying aptly.
Steps of a method in accordance with the invention (ii) in, with make in the described step (i) 1, two (the 3-alkoxyl group phenoxy group) benzene of 3-take off alkyl, make 1, two (3-hydroxyphenoxy) benzene of 3-, shown in following response line road (V):
Wherein R as previously mentioned.There are many kinds to be used to make the reagent of alkyl aryl ether fracture according to document, for example are used for the anhydrous sulphonic acids of benzylic ether, at the NaS of N-N-methyl-2-2-pyrrolidone N-, NaCN, AlBr in dimethyl sulfoxide (DMSO)
3, AlCl
3, BBr
3, BCl
3With 48%HBr and H
2And Pd/C.Make 1 as circuit (V) is disclosed, the mode of two (3-alkoxyl group phenoxy group) the benzene dealkylations of 3-is made clastogen for the mixture that uses 48% Hydrogen bromide and acetic acid.Acetic acid preferably adds to reduce the water-content of mixture with anhydride form, improves speed of reaction thus.The suitable consumption of 48% Hydrogen bromide and acetic anhydride is the 1-6 weight part, 2-3 weight part for example, with respect to 1 weight part exist 1, two (the 3-alkoxyl group phenoxy group) benzene of 3-.
Described step typical process (ii) discloses as follows:
With obtain in the step (i) of the inventive method 1, two (the 3-alkoxyl group phenoxy group) benzene of 3-are as 1, two (the 3-methoxyl group phenoxy group) benzene of 3-mix also heated mixt to 80-100 ℃ with 48% Hydrogen bromide in the 2-3 weight part of the described ether oligomer of 1 weight part.Then under 80-110 ℃, for example will join in the reaction mixture in the acetic anhydride of the 2-3 weight part of the described ether oligomer of 1 weight part in 10-60 minute.At 100-115 ℃ of following stirred reaction mixture 4-20 hour or until finishing reaction.Add entry and The suitable solvent such as methyl iso-butyl ketone (MIBK) after being cooled to 20-40 ℃.After 20-40 ℃ is stirred down, be separated and wash organic layer with water.For example be lower than 30mbar and 60-100 ℃ evaporation organic phase down in vacuum at last, make 1, two (3-hydroxyphenoxy) benzene of 3-, it will be used for step (iii) after further purifying aptly or not purifying.
Process in accordance with the present invention (iii) in, with step make in (ii) 1, two (3-hydroxyphenoxy) benzene of 3-and the reaction of 4-nitrophthalonitrile make 1,3-pair of [3-(3,4-dicyano phenoxy group) phenoxy group] benzene, shown in following response line road (VI):
Bis-phthalonitrile monomer with phenyl ether spacer chain is typically by being dissolved in hydroxy-end capped aromatic ether and 4-nitrophthalonitrile solvent and making in the existence heating of alkali.At polar protic inert solvent such as dimethyl sulfoxide (DMSO), N, react in dinethylformamide, N,N-dimethylacetamide or the N-N-methyl-2-2-pyrrolidone N-.Preferred solvent is N, dinethylformamide.Suitable alkali is supercarbonate, carbonate, oxyhydroxide and the alcoholate of basic metal and alkaline-earth metal.Carbonate is preferred alkali, and most preferred carbonate is salt of wormwood.The suitable consumption of 4-nitrophthalonitrile and described alkali is the 2-3 mole in reaction medium, with 1 mole 1, and two (3-hydroxyphenoxy) the benzene meters of 3-.
Described step typical process (iii) discloses as follows:
With 1, two (3-hydroxyphenoxy) benzene of 3-and the solvent such as the N of significant quantity at least, dinethylformamide mixes, with solubilizing reaction thing and product.Then with 1 mole 1, the mol ratio of the 2-3 mole of two (3-hydroxyphenoxy) the benzene meters of 3-adds 4-nitrophthalonitrile and alkali such as salt of wormwood.Air communication with rare gas element such as nitrogen or argon is crossed reaction vessel.Be warming up to 25-80 ℃ and kept 3-12 hour or finished until reaction.Filter the reaction mixture of heat and remove inorganic salt.In filtrate, add the suitable precipitation agent such as the methyl alcohol of significant quantity, from mixture, be settled out required product.Stir the mixture until the product crystallization under the temperature between for example-10 ℃ to 30 ℃.Collect solid product and use The suitable solvent such as methanol wash.Can be by at The suitable solvent such as N, recrystallize comes further purification crude product in dinethylformamide and the methanol mixture, for example makes purity thus〉98% 1, two [3-(3, the 4-dicyano phenoxy group) phenoxy group] benzene of 3-.
In novel method of the present invention, can prepare highly purified bis-phthalonitrile monomer, for example have 1 of about 120 ℃ of fusing points, two [3-(3, the 4-dicyano phenoxy group) phenoxy group] benzene of 3-.Therefore method of the present invention has following at least advantage: (1) than based on the PN monomer for example general formula (II) and (III) in disclosed 4,4 '-two (3,4-dicyano phenoxy group) biphenyl and 1,3-two (3,4-dicyano phenoxy group) resin system of benzene, based on for example 1,3-is two, and [3-(3,4-dicyano phenoxy group) phenoxy group] the PN resin system of benzene has the lower processing temperature and the work range of broad because of relatively low fusing point, (2), can reduce substantially or even eliminate the difficulty of control reaction in the curing schedule because the high purity of product.
The intermediate product 1 that makes in (ii) in described step, two (3-hydroxyphenoxy) benzene of 3-are further by with the ether reaction of the Ullmann of 3-halogenated alkoxy aromatics with the dealkylation preparation has even the hydroxy-end capped aromatic ether oligopolymer of the oligomeric phenyl ether spacer chain of length, shown in following response line road (VII):
Wherein R and X are as previously mentioned and be suitable.Suitable 3-halogenated alkoxy aromatics for example is a 3-methoxyl group bromobenzene.Other preferred reactant, alkali, take off alkyl agent and reaction conditions as previously mentioned.The hydroxy-end capped aromatic ether oligopolymer that makes can be further with 4-nitrophthalonitrile prepared in reaction wherein n be the bis-phthalonitrile monomer of 4 general formula (I).The hydroxy-end capped aromatic ether oligopolymer that makes can also with 3-halogenated alkoxy aromatics carry out reaction for the second time and for the second time dealkylation make hydroxy-end capped aromatic ether oligopolymer, it prepares the bis-phthalonitrile monomer that n wherein is 6 general formula (I) afterwards with the reaction of 4-nitrophthalonitrile.
Certainly the hydroxy-end capped aromatic ether oligopolymer that makes can be before each and described 3-halogenated alkoxy aromatics reaction repeatedly with reaction of 3-halogenated alkoxy aromatics and dealkylation, thereby make the bis-phthalonitrile monomer that n wherein is 8,10,12 etc. general formula (I) after reacting with the 4-nitrophthalonitrile final.
Need not to further describe, believe that according to the above description those skilled in the art can be used for the wideest scope with the present invention.Therefore, following preferred embodiment only being used to explains, and is subject to its scope of disclosure never in any form.Following embodiment 1-3 is for preparing bis-phthalonitrile monomer according to the inventive method step (i) embodiment extremely (iii).
Embodiment 1
64.8 gram 3-methoxyphenols, 60 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 72.2 gram salt of wormwood and 100 milliliters of toluene are injected in the 500 milliliter of three neck reaction flask that has thermometer, mechanical stirrer, distillation chain and nitrogen inlet.With mixture heating up to 150 ℃ and from mixture, distill out toluene-water azeotropic mixture.150 ℃ of following continuously stirring 2 hours, distill out the water that forms in remaining toluene and the reaction process simultaneously.Be cooled to after 140 ℃, with 51.4 grams 1,3-dibromo-benzene, 0.40 gram cupric iodide (I) and 0.66 gram N, the N-N-methylsarcosine joins in the reaction mixture.140 ℃ of following continuously stirring 11 hours, finish until analyzing Indicator Reaction by HPLC.Reaction mixture is cooled to 20-25 ℃ and add 200 milliliters of toluene, and filtering mixt is removed inorganic salt then.With 2 * 40 milliliters of toluene wash filter cakes, washings and filtrate are merged.The 10%NaOH aqueous solution to 200 milliliters of filtrate addings stirred the mixture 15 minutes, and layer separates then.With 200 ml waters with finally with 200 milliliters of 1%NaCl solution washing organic layers.From organic layer, remove toluene by evaporation under 80-85 ℃ and 20mbar vacuum condition at last, make the reddish buttery 1 of 66.9 grams, two (the 3-methoxyl group phenoxy group) benzene of 3-.
Embodiment 2
With 65.8 grams 1 that obtain among the embodiment 1, two (3-methoxyl group phenoxy group) benzene of 3-and 170 grams, 48% Hydrogen bromide are injected in the 1000 milliliter of three neck reaction flask that has thermometer, mechanical stirrer and condenser.With mixture heating up to 90 ℃ and in 20 minutes, adding 162 gram acetic anhydride under 90-105 ℃ with dropping funnel.105-111 ℃ of following continuously stirring 10 hours, finish until analyzing Indicator Reaction by HPLC.Reaction mixture is cooled to 20-25 ℃ and add 200 ml waters and 150 milliliters of methyl iso-butyl ketone (MIBK).Stirred the mixture 15 minutes, layer separates then.With 200 ml waters washings methyl iso-butyl ketone (MIBK) layer and under 80-85 ℃ and 20mbar vacuum condition evaporate to dryness, make the reddish thickness buttery 1 of 63.3 grams, two (3-hydroxyphenoxy) benzene of 3-.
Embodiment 3
62.2 grams 1 with embodiment 2 acquisitions, two (3-hydroxyphenoxy) benzene of 3-, 160 milliliters of N, dinethylformamide, 70 gram 4-nitrophthalonitriles and 70 gram salt of wormwood join in the 500 milliliter of three neck reaction flask that has thermometer, mechanical stirrer, condenser and nitrogen inlet.Pass through container with nitrogen gas stream.With mixture heating up to 58-60 ℃ and under described temperature continuously stirring 5 hours, finish until analyzing Indicator Reaction by HPLC.Under described temperature, remove by filter inorganic salt then also with 2 * 30 milliliters of N, dinethylformamide washing leaching cake.Washings and filtrate are merged, and add 800 ml methanol.Under 20-25 ℃, stir the mixture until the product crystallization.Collect solid product and use methanol wash by suction filtration after being cooled to 0-5 ℃.From 180 ml methanol and 80 milliliters of N, make in the mixture of dinethylformamide the crude product recrystallize and 60 ℃ down dry, make 47.9 grams be with beige pulverous 1, two [3-(3, the 4-dicyano phenoxy group) phenoxy group] benzene of 3-.The product that obtains has 118-122 ℃ fusing point and 98.6% purity (HPLC).
Claims (33)
1, a kind of preparation has the method for the bis-phthalonitrile monomer of oligomeric phenyl ether spacer chain, and described bi-phthalonitrile is general formula (I)
General formula (I)
Wherein n is 2, it is characterized in that this method comprises the steps:
I) alkali and comprise mantoquita and the catalyst composition of part in the presence of with 3-alkoxy phenol and the reaction of phenyl-dihalide, make 1 thus, two (the 3-alkoxyl group phenoxy group) benzene of 3-,
Ii) step (i) is made 1, two (the 3-alkoxyl group phenoxy group) benzene of 3-with take off alkyl agent reaction, make 1 thus, two (3-hydroxyphenoxy) benzene of 3-and
Iii) in the presence of alkali, step is (ii) made 1, two (3-hydroxyphenoxy) benzene of 3-and the reaction of 4-nitrophthalonitrile make 1 of general formula (I) expression thus, 3-pair of [3-(3,4-dicyano phenoxy group) phenoxy group] benzene.
2,, it is characterized in that described alkoxyl group is methoxyl group, oxyethyl group, propoxy-or butoxy according to the method for claim 1.
3,, it is characterized in that described alkoxyl group is an alkoxy aryl according to the method for claim 1.
4,, it is characterized in that described alkoxy aryl is a benzyloxy according to the method for claim 3.
5, according to each method among the claim 1-4, it is characterized in that described halo is bromo or iodo.
6,, it is characterized in that be 2-3:1 at 3-alkoxy phenol described in the described step (i) to the mol ratio of described phenyl-dihalide according to each method among the claim 1-5.
7, according to each method among the claim 1-6, it is characterized in that the amount at alkali described in the described step (i) is the 0.5-2 mole, based on 1 mole of 3-alkoxy phenol meter.
8, according to each method among the claim 1-7, it is characterized in that the amount at mantoquita described in the described step (i) is 0.1-10 mole %, 0.5-2 mole % for example is based on the mole number meter of described phenyl-dihalide.
9, according to each method among the claim 1-8, it is characterized in that the amount at part described in the described step (i) is 0.3-20 mole %, 1-6 mole % for example is based on the mole number meter of described phenyl-dihalide.
10, according to each method among the claim 1-9, it is characterized in that described 3-alkoxy phenol is the 3-methoxyphenol.
11, according to each method among the claim 1-10, it is characterized in that described phenyl-dihalide is 1, the 3-dibromo-benzene.
12, according to each method among the claim 1-11, it is characterized in that described mantoquita is cupric iodide (I).
13, according to each method among the claim 1-12, it is characterized in that described part is N, the N-N-methylsarcosine.
14, according to each method among the claim 1-13, it is characterized in that describedly 1, two (the 3-alkoxyl group phenoxy group) benzene of 3-are 1, two (the 3-methoxyl group phenoxy group) benzene of 3-.
15,, it is characterized in that described step (i) carrying out under 100-170 ℃ the temperature in the presence of polar proton inert solvent according to each method among the claim 1-14.
16,, it is characterized in that described polar proton inert solvent is the N-N-methyl-2-2-pyrrolidone N-according to the method for claim 15.
17, according to each method among the claim 1-16, it is characterized in that the described mixture that the alkyl agent is Hydrogen bromide and acetic anhydride that takes off.
18, according to the method for claim 17, it is characterized in that based on 1 weight part describedly 1, two (3-methoxyl group phenoxy group) the benzene meters of 3-use 1-6 weight part, for example 2-3 weight part 48% Hydrogen bromide and 1-6 weight part, for example 2-3 weight part acetic anhydride.
19,, it is characterized in that described step (ii) carries out under 100-115 ℃ temperature according to each method among the claim 1-18.
20, according to each method among the claim 1-19, it is characterized in that described step (iii) described in the 4-nitrophthalonitrile to 1, the mol ratio of two (3-hydroxyphenoxy) benzene of 3-is 2-3:1.
21, according to each method among the claim 1-20, it is characterized in that described step (iii) described in alkali and 1, the mol ratio of two (3-hydroxyphenoxy) benzene of 3-is 2-3:1.
22, according to each method among the claim 1-21, it is characterized in that described alkali is the carbonate of basic metal or alkaline-earth metal.
23, according to the method for claim 22, the carbonate that it is characterized in that described basic metal or alkaline-earth metal is salt of wormwood.
24,, it is characterized in that described step (iii) carrying out under 25-80 ℃ the temperature in the presence of polar proton inert solvent according to each method among the claim 1-23.
25,, it is characterized in that described polar proton inert solvent is N, dinethylformamide according to the method for claim 24.
26, according to each method among the claim 1-25, it is characterized in that with make 1, two [3-(3,4-dicyano phenoxy group) phenoxy group] the benzene recrystallize of 3-, its purity is at least 98% after the recrystallize.
27, according to each method among the claim 1-26 make described 1, the purposes of two [3-(3, the 4-dicyano phenoxy group) phenoxy group] benzene of 3-is used to prepare o-phthalonitrile resin.
28, according to the step of each method among the claim 1-18 make in (ii) 1, the purposes of two (3-hydroxyphenoxy) benzene of 3-, be used for described 1, two (3-hydroxyphenoxy) benzene of 3-react to prepare the method for hydroxy-end capped aromatic ether oligopolymer with 3-halogenated alkoxy aromatics.
29, according to the purposes of claim 28, being used for wherein said 3-halogenated alkoxy aromatics is the method for 3-methoxyl group bromobenzene.
30,, be used for the reaction of the hydroxy-end capped aromatic ether oligopolymer that wherein will make and 4-nitrophthalonitrile and make the method that n wherein is the bis-phthalonitrile monomer of 4 described general formula (I) according to the purposes of claim 28 or 29.
31, according to the purposes of claim 28, the hydroxy-end capped aromatic ether oligopolymer and the 3-halogenated alkoxy aromatics that are used for wherein will making react the method that makes hydroxy-end capped aromatic ether oligopolymer.
32, according to the purposes of claim 31, being used for wherein said 3-halogenated alkoxy aromatics is the method for 3-methoxyl group bromobenzene.
33,, be used for the reaction of the hydroxy-end capped aromatic ether oligopolymer that wherein will make and 4-nitrophthalonitrile and make the method that n wherein is the bis-phthalonitrile monomer of 6 described general formula (I) according to the purposes of claim 31 or 32.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE0600484A SE530059C2 (en) | 2006-03-06 | 2006-03-06 | Process for Preparation of a Bisphthalonitrile Monomer |
| SE06004840 | 2006-03-06 |
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| CNA2007800079079A Pending CN101395201A (en) | 2006-03-06 | 2007-03-05 | Process for production of a bis-phthalonitrile monomer |
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| KR (1) | KR20080098435A (en) |
| CN (1) | CN101395201A (en) |
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| WO (1) | WO2007102766A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408755A (en) * | 2013-07-09 | 2013-11-27 | 中国船舶重工集团公司第七二五研究所 | Low-viscosity cyano resin monomer and polymer, and preparation method thereof |
| CN106046360A (en) * | 2016-04-15 | 2016-10-26 | 电子科技大学 | Aromatic nitrile polymer and preparation method thereof |
| CN109071808A (en) * | 2016-03-31 | 2018-12-21 | 3M创新有限公司 | Bis-phenol M bi-phthalonitrile ether resin blend and product comprising filler |
| CN109642018A (en) * | 2016-07-25 | 2019-04-16 | 波音公司 | Epoxy resin |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102993070A (en) * | 2012-12-04 | 2013-03-27 | 四川大学 | Aromatic diamine containing phthalonitrile side group and synthesis method and application thereof |
| CA3031544C (en) * | 2016-07-25 | 2024-04-23 | The Boeing Company | Epoxy resin |
| KR102218559B1 (en) | 2018-08-28 | 2021-02-22 | 주식회사 엘지화학 | Phthalonitrile-based resin with improved impact strength |
| CN111479885B (en) | 2018-09-21 | 2022-05-27 | 株式会社Lg化学 | Curable resin composition comprising phthalonitrile oligomer and prepolymer thereof |
| RU2708399C1 (en) * | 2018-12-03 | 2019-12-06 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" (ИГХТУ) | 4,4'-(((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(oxy))diphtalonitrile |
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| US6756470B2 (en) * | 2002-04-26 | 2004-06-29 | The United States Of America As Represented By The Secretary Of The Navy | Oligomeric hydroxy arylether phthalonitiles and synthesis thereof |
-
2006
- 2006-03-06 SE SE0600484A patent/SE530059C2/en not_active IP Right Cessation
-
2007
- 2007-03-05 KR KR1020087023461A patent/KR20080098435A/en not_active Application Discontinuation
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408755A (en) * | 2013-07-09 | 2013-11-27 | 中国船舶重工集团公司第七二五研究所 | Low-viscosity cyano resin monomer and polymer, and preparation method thereof |
| CN109071808A (en) * | 2016-03-31 | 2018-12-21 | 3M创新有限公司 | Bis-phenol M bi-phthalonitrile ether resin blend and product comprising filler |
| US10899865B2 (en) | 2016-03-31 | 2021-01-26 | 3M Innovative Properties Company | Bisphenol M diphthalonitrile ether resin blends including a filler, and articles |
| US11401364B2 (en) | 2016-03-31 | 2022-08-02 | 3M Innovative Properties Company | Bisphenol M diphthalonitrile ether resin, bisphenol P diphthalonitrile ether resin, methods of making same, resin blends, and two component systems |
| CN106046360A (en) * | 2016-04-15 | 2016-10-26 | 电子科技大学 | Aromatic nitrile polymer and preparation method thereof |
| CN109642018A (en) * | 2016-07-25 | 2019-04-16 | 波音公司 | Epoxy resin |
| US11718707B2 (en) | 2016-07-25 | 2023-08-08 | The Boeing Company | Epoxy resin |
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| SE530059C2 (en) | 2008-02-19 |
| SE0600484L (en) | 2007-09-07 |
| KR20080098435A (en) | 2008-11-07 |
| WO2007102766A1 (en) | 2007-09-13 |
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