WO2007102766A1 - Process for production of a bis-phthalonitrile monomer - Google Patents
Process for production of a bis-phthalonitrile monomer Download PDFInfo
- Publication number
- WO2007102766A1 WO2007102766A1 PCT/SE2007/000210 SE2007000210W WO2007102766A1 WO 2007102766 A1 WO2007102766 A1 WO 2007102766A1 SE 2007000210 W SE2007000210 W SE 2007000210W WO 2007102766 A1 WO2007102766 A1 WO 2007102766A1
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- WIPO (PCT)
- Prior art keywords
- process according
- benzene
- yielded
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- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims abstract description 34
- 239000000178 monomer Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 132
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000012380 dealkylating agent Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000002585 base Substances 0.000 claims description 19
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- -1 methoxy, ethoxy, propoxy Chemical group 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003880 polar aprotic solvent Substances 0.000 claims description 6
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical group BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical group I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- 230000020335 dealkylation Effects 0.000 claims description 4
- 238000006900 dealkylation reaction Methods 0.000 claims description 4
- 108700003601 dimethylglycine Proteins 0.000 claims description 4
- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical compound COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 3
- 229940078490 n,n-dimethylglycine Drugs 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- 238000001953 recrystallisation Methods 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 1
- 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 description 3
- 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 238000010752 Ullmann ether synthesis reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product 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
- 238000005406 washing Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 239000004128 Copper(II) sulphate Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 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
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical class C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000012071 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
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction 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
Definitions
- the present invention relates to a process for production of a b/s-phthalonitrile monomer having an oligophenyl ether spacer chain.
- Said monomer being of Formula (I)
- the present invention relates to a novel process for production of said monomer wherein n is 2.
- the present invention refers to the use of an intermediate product, obtained in the process according to the present invention, in processes yielding a b/s-phthalonitrile monomer of Formula (I) wherein n is 4 or 6.
- Phthalonitrile (PN) resins were originally developed by the U.S. Naval Research Laboratory in the beginning of 1980's as a high-temperature alternative to polyimide resins.
- PN resins are thermosets derived from b/s-phthalonitrile monomers. These monomers polymerise in the presence of a curing agent in an additional-type reaction forming a triazine network.
- the fully cured resins exhibit good thermal and oxidative stability and have long-term mechanical properties at elevated temperatures.
- the benzene rings forming the backbone structure of the monomers are very stable. The combination of these properties implies production of composite materials being very fire resistant.
- Various phthalonitrile monomers and polymers are described in a large number of patents and patent applications generally teaching methods for producing and polymerising phthalonitrile monomers.
- Disclosed monomers typically have two phthalonitrile groups, one at each end of a connecting spacer chain. The monomers can be cured, whereby crosslinking occurs between cyano groups.
- U.S. patent no. 4,587,325 disclose in examples 1 and 5 synthesis of two b/s-phthalonitrile monomers, namely 4,4'-b/s(3,4-dicyanophenoxy)biphenyl of formula (II) and 1 ,3-b/s(3,4- dicyano-phenoxy)benzene of formula (III):
- the monomers are produced by reacting 4-nitrophthalonitrile with an aromatic dio! and both monomers can be used as a precursor in production of PN resins.
- these monomers are disadvantaged by the relatively high processing temperature and, due to the high melting points of the monomers, a narrow processing window.
- the melting point of 4,4'-b/s(3,4- dicyanophenoxy)bipheny] is approx. 235 0 C and the melting point of 1 ,3-b/s(3,4-dicyano- phenoxy)benzene is approx. 184 0 C.
- thermosets also have improved physical properties, such as toughness and processability, relative to systems with a short spacer chain between the terminal phthalonitrile moieties. Generally toughness and brittleness are improved with lower crosslinking densities. This can be achieved by using PN monomers with longer spacer chains.
- hydroxyterminated aromatic ether oligomers formed by reacting a m-dihydroxyaromatic compound, such as a resorcinol, with a m-dihaloaromatic compound, such as 1 ,3-dibromo- benzene.
- a m-dihydroxyaromatic compound such as a resorcinol
- a m-dihaloaromatic compound such as 1 ,3-dibromo- benzene.
- the reaction is performed by Ullmann synthesis in the presence of a copper salt and cesium carbonate.
- the chain lengths of the aromatic ether oligomers are controlled by the molar ratio between m-dihydroxyaromatic and m-dihaloaromatic compounds.
- hydroxyl terminated aromatic ether oligomers are further allowed to react with 4-nitrophthalonitrile to form b/s-phthalonitrile monomers of Formula (I), wherein the ether spacer chain comprises an average of 3, 5, 7 or 9 aromatic groups corresponding to n in said Formula theoretically being 2, 4, 6 or 8.
- the processes for preparation of b/s-phthalonitrile monomers disclosed in WO 03/091312 exhibit at least following disadvantages.
- the reaction conditions as used in the embodiment examples yield products comprising a complex mixture of b/s-phthalonitrile monomers with a wide distribution of spacer chain lengths. Yielded products are, furthermore, isolated from an acidic water solution, whereby all water insoluble by-products, such as hydroxy and haloterminated oligomers remain in the products. This may lead to serious difficulties in controlling the reactions of the products during the curing step. Hence, such mixtures are unfavourable as precursors for PN resins wherein good thermal and oxidative stability combined with improved physical properties are required.
- the process of the present invention comprises the steps of: i) subjecting a 3-alkoxyphenol to reaction with a m-dihal'obenzene in the presence of a base and a catalyst composition comprising a copper salt and a ligand whereby a 1 ,3-/ ⁇ /s(3-alkoxyphenoxy)benzene is yielded, ii) subjecting in Step (i) yielded 1 ,3- ⁇ b/s(3-alkoxyphenoxy)benzene to reaction with a dealkylating agent whereby 1 ,3-ib/s(3-hydroxyphenoxy)benzene is yielded, and iii) subjecting in Step (ii) yielded 1 ,3-b/s(3-hydroxyphenoxy)benzene to reaction with a 4-nitrophthalonitrile in presence of a base whereby 1 ,3-b/s[3-(3,4-dicyano- phenoxy)phenoxy]benzene represented by Formula (
- a 3-alkoxyphenol is in Step (i), of the process according to the present invention, reacted with a m-dihalobenzene to form 1 ,3-jb/s(3-alkoxyphenoxy)benzene as illustrated in reaction Scheme (IV) below: (IV)
- R is a lower alkyl group, such as a methyl, an ethyl, a propyl or a butyl group or an alkylaryl group, such as a benzyl group, and wherein X is halogen, such as bromine or iodine.
- said alkoxy is preferably methoxy, ethoxy, propoxy, butoxy or arylalkoxy, such as benzyloxy and said halo is likewise preferably iodo or bromo.
- Said 3-alkoxyphenol is in preferred embodiments of the present invention 3-methoxyphenol and said m-dihalobenzene is likewise preferably 1 ,3-dibromobenzene.
- a suitable molar ratio is for instance 2-3 moles of 3-alkoxyphenol on 1 mole of m-dihalobenzene.
- the reaction is in embodiments of the present invention carried out in presence of at least one polar aprotic solvent, such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide and/or N-methyl-2-pyrrolidinone.
- the most preferred solvent is N-methyl-2-pyrrolidinone.
- the reaction is performed as an Ullmann ether synthesis using a base and a catalyst.
- Suitable bases are alkali and alkaline earth metal bicarbonates, carbonates, hydroxides and alcoholates.
- the carbonates are generally the preferred bases and the most preferred carbonate is potassium carbonate.
- Suitable amount of base is 0.5-2 moles on 1 mole of 3-alkoxyphenol present in the reaction medium.
- the catalysts are Ullmann ether catalysts, for instance metal salts such as copper salts.
- the most preferred copper salts are copper(I)iodide and/or copper(l)bromide.
- Further suitable copper compounds include, but are not limited to, copper(l)chloride, copper(II)bromide, copper(II)sulphate and copper(ll)acetate.
- a suitable amount of catalyst is normally found within the range of 0.1-10, such as 0.5-2, mole-% calculated on moles of said m-dihalobenzene.
- the reaction activity can be further improved by addition of a proper ligand to make for instance the copper salts more soluble in the reaction medium.
- a proper ligand to make for instance the copper salts more soluble in the reaction medium.
- Some efficient ligands have been developed for copper catalysed Ullmann ether synthesis, such as aliphatic diamines, 1 ,10-phenanthroline and its derivatives, bidentate and monodentate phosphines, amino acid derivatives and 2,2,6,6-tetramethylheptane-3,5-dione.
- N,N-dimethyl- glycine has proven to be an effective ligand under the reaction conditions in Step (i) of the present invention.
- a suitable amount of ligand is for instance 0.3-20, such as 1-6, mole-% calculated on moles of said m-dihalobenzene.
- a typical procedure for said Step (i) can be disclosed as follows:
- 3-Alkoxyphenol such as 3-methoxyphenol is charged to the reaction vessel.
- the solvent for instance N ⁇ methyl-2-pyrrolidinone, is added in an amount being at least sufficient to dissolve the reactants and the product.
- a base such as potassium carbonate, is added in the range of for instance 0.5-2 moles on 1 mole of 3-alkoxyphenol and finally a sufficient amount of a suitable solvent, such as toluene is added to the mixture to enable azeotropic removal of water formed during the reaction.
- a stream of an inert gas, such as nitrogen or argon, is most preferably passed through the reaction vessel. The temperature is raised to 130-170 0 C distilling off toluene-water azeotrope.
- the reaction mixture is kept at 130-170 0 C for 1- 4 hours distilling off remaining water and toluene.
- a m-dihalobenzene such as 1 ,3- dibromobenzene
- a catalyst such as copper(l)iodide
- a ligand such as N 1 N- dimethylglycine
- a suitable solvent such as toluene
- the filtrate is washed first with an aqueous base, such as 10% NaOH, then with water and finally with an aqueous 1 % NaCI solution.
- Solvents/water are subsequently removed by distillation under vacuum, such as less then 30 mbar, at 60-100 0 C yielding 1 ,3-£>/s(3- alkoxyphenoxy)benzene which is used in Step (ii) with or suitably without further purification.
- Step (i) yielded 1 ,3- ⁇ /s(3-alkoxyphenoxy)benzene is in Step (ii), of the process according to the present invention, dealkylated to yield 1 ,3-i)/s(3-hydroxyphenoxy)benzene as illustrated in reaction Scheme (V) below:
- R is as previously disclosed.
- reagents useful for cleaving of alkylaryl ethers such as anhydrous sulphonic acids, NaS in N- methyl-2-pyrrolidone, NaCN in dimethyl sulphoxide, AIBr 3 , AICI 3 , BBr 3 , BCI 3 and 48% HBr and H 2 and Pd/C for benzyl ethers.
- a suitable way to dealkylate 1 ,3-ib/s(3-alkoxy ⁇ henoxy)benzene as disclosed in Scheme (V), but not limited thereto, is the use of a mixture of 48% hydrobromic acid and acetic acid as cleaving agent.
- the acetic acid is preferably added as an anhydride to decrease the water content of the mixture and thus to increase the reaction rate.
- Suitable amounts of 48% hydrobromic acid and acetic anhydride are 1-6 parts, such as 2-3 parts, by weight on 1 part by weight of 1 ,3-b/s(3-alkoxyphenoxy)benzene present.
- a typical procedure for said Step (ii) can be disclosed as follows:
- 1 ,3- ⁇ /s(3-alkoxyphenoxy)benzene such as 1 ,3 ⁇ b/s(3-methoxyphenoxy)benzene, as obtained in Step (i) of the process of the present invention, is mixed with 2-3 parts by weight of 48% hydrobromic acid on 1 part by weight of said ether oligomer and the mixture is heated to 80- 100 0 C. Subsequently 2-3 parts by weight of acetic anhydride on 1 part by weight of said ether oligomer is, within for instance 10-60 minutes, added to the reaction mixture at 80-110 0 C. The reaction mixture is now stirred at 100-115 0 C for 4-20 hours or until the reaction is completed.
- Step (iii) Water and a suitable solvent, such as methyl isobutyl ketone, are after cooling to 20-40 0 C added. Phases are separated after stirring at 20-40 0 C and the organic layer is washed with water. Finally the organic phase is evaporated under vacuum, such as less than 30 mbar, at 60-100 0 C yielding 1 ,3-/?/s(3-hydroxyphenoxy)benzene which is used in Step (iii) with or suitably without further purification.
- a suitable solvent such as methyl isobutyl ketone
- Step (ii) yielded 1 ,3-b/s(3-hydroxyphenoxy)benzene is in Step (iii), of the process according to the present invention, reacted with a 4-nitrophthalonitrile yielding 1 ,3-6/s[3-(3,4- dicyano-phenoxy)phenoxy]benzene as illustrated in reaction Scheme (Vl) below: (VI)
- a b/s-phthalonitile monomer with a phenyl ether spacer chain is typically prepared by dissolving a hydroxyterminated aromatic ether and 4-nitrophthalonitrile in a solvent and by heating in the presence of a base.
- the reaction is carried out in a polar aprotic solvent, such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2- pyrrolidinone.
- the preferred solvent is N,N-dimethylformamide.
- Suitable bases are alkali and alkaline earth metal bicarbonates, carbonates, hydroxides and alcoholates. Carbonates are the preferred bases and most preferred carbonate is potassium carbonate.
- Suitable amounts of 4-nitrophthalonitrile and said base are 2-3 moles on 1 mole of 1 ,3-jb/s(3- hydroxyphenoxy)benzene present in the reaction medium.
- Step (iii) A typical procedure for said Step (iii) can be disclosed as follows:
- 1 ,3-jb/s(3-hydroxyphenoxy)benzene is mixed with a solvent, such as N,N-dimethylformamide in an amount being at least sufficient to dissolve the reactants and the product.
- 4-nitro- phthalonitriie and a base, such as potassium carbonate are subsequently added in a molar ratio of 2-3 moles on 1 mole of 1 ,3-b/s(3-hydroxyphenoxy)benzene.
- a stream of an inert gas, such as nitrogen or argon, is passed through the reaction vessel. The temperature is raised to 25-80 0 C and maintained for 3-12 hours or until the reaction is completed. The hot reaction mixture is filtered to remove inorganic salts.
- a suitable precipitating agent such as methanol is added to the filtrate in an amount being at least sufficient to precipitate the desired product from the mixture.
- the mixture is now stirred at a temperature of between for instance -10 and 3O 0 C until the product crystallises.
- the solid product is collected and washed with a suitable solvent, such as methanol.
- the crude product can be further purified by re-crystallisation in .
- a suitable solvent such as a mixture of N,N-dimethylformamide and methanol, whereby 1 ,3-b/s- [3-(3,4-dicyanophenoxy)phenoxy]benzene with a purity of for instance >98% is yielded.
- the process of the present invention thus gives at least the following advantages: (1) a PN resin system based on for instance 1 ,3-b/s[3-(3,4-dicyano- phenoxy)phenoxy]-benzene exhibits, due to the relatively, low melting point, a lower processing temperature and wider processing window compared to resin systems based on PN monomers such as 4,4'-£>/s(3,4-dicyanophenoxy)biphenyI and 1 ,3-b/s(3,4-dicyanophenoxy)- benzene as disclosed in Formulas (II) and (III), and (2) difficulties in controlling the reaction during the curing step can, due to the high purity of the product, substantially reduced or even eliminated.
- the intermediate 1 ,3- ⁇ /s(3-hydroxyphenoxy)benzene, yielded in said Step (ii), is furthermore, useful in production of a hydroxyterminated aromatic ether oligomer having even longer oligophenyl ether spacer chains by Ullmann ether reaction with a 3-alkoxyhaloaromatic compound and dealkylated as illustrated in reaction Scheme (VII) below: (VII)
- R and X are as previously defined and suitable.
- a suitable 3-alkoxyhaloaromatic compound is for instance 3-methoxybromobenzene.
- Other preferred reactants, bases, dealkylation agents and reaction conditions are as previously disclosed. Yielded hydroxyterminated aromatic ether oligomer can be allowed to react further with 4-nitro- phthalonitrile to yield a b/s-phthalonitrile momomer of Formula (I) wherein n is 4.
- Yielded hydroxyterminated aromatic ether oligomer can also be subjected to a second reaction with a said 3-alkoxyhaloaromatic compound and a second dealkylation yielding a hydroxyterminated aromatic ether oligomer, which after reaction with 4-nitrophthalonitrile, yields a b/s- phthalonitrile momomer of Formula (I) wherein n is said 6.
- a yielded hydroxyterminated aromatic ether oligomer may of course repeatedly be subjected to reactions with said a 3-alkoxyhaloaromatic compound and dealkylated prior to each reaction with said a 3-alkoxyhaloaromatic compound, yielding, after a final reaction with 4-nitrophthalonitrile, a b/s-phthalonitrile momomer of Formula (1) wherein n is said 8, 10, 12 etc.
- Examples 1-3 refer to preparation of a b/s-phthalonitrile monomer according to embodiments of Steps (i) to (iii) of the process of the present invention.
- the reaction mixture was subsequently filtered at said temperature to remove inorganic salts and the filter cake was washed with 2 x 30 ml of N,N-dimethylformamide. The washings were combined with the filtrate and 800 ml of methanol was added. The mixture was now stirred at 20-25 0 C until the product crystallised. The solid product was after cooling to 0-5 0 C collected by suction filtration and washed with methanol.
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Cited By (6)
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 |
WO2018018070A1 (en) * | 2016-07-25 | 2018-02-01 | The Boeing Company | Epoxy resin |
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 |
US11059937B2 (en) | 2016-07-25 | 2021-07-13 | The Boeing Company | Epoxy resin |
US11591487B2 (en) | 2018-09-21 | 2023-02-28 | Lg Chem, Ltd. | Curable resin composition comprising a phthalonitrile oligomer and a prepolymer thereof |
US11932727B2 (en) | 2018-08-28 | 2024-03-19 | Lg Chem, Ltd. | Phthalonitrile-based resin with improved impact strength |
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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 |
WO2017172515A1 (en) * | 2016-03-31 | 2017-10-05 | 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 |
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Cited By (8)
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 |
WO2018018070A1 (en) * | 2016-07-25 | 2018-02-01 | The Boeing Company | Epoxy resin |
US11059937B2 (en) | 2016-07-25 | 2021-07-13 | The Boeing Company | Epoxy resin |
US11718707B2 (en) | 2016-07-25 | 2023-08-08 | The Boeing Company | Epoxy resin |
US11932727B2 (en) | 2018-08-28 | 2024-03-19 | Lg Chem, Ltd. | Phthalonitrile-based resin with improved impact strength |
US11591487B2 (en) | 2018-09-21 | 2023-02-28 | Lg Chem, Ltd. | Curable resin composition comprising a phthalonitrile oligomer and a prepolymer thereof |
US11674045B2 (en) | 2018-09-21 | 2023-06-13 | Lg Chem, Ltd | Three-dimensional printing ink comprising a phthalonitrile oligomer |
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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CN101395201A (en) | 2009-03-25 |
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