DK156397B - Fremgangsmaade til fremstilling af aromatiske bis(etheranhydrider) - Google Patents
Fremgangsmaade til fremstilling af aromatiske bis(etheranhydrider) Download PDFInfo
- Publication number
- DK156397B DK156397B DK172874AA DK172874A DK156397B DK 156397 B DK156397 B DK 156397B DK 172874A A DK172874A A DK 172874AA DK 172874 A DK172874 A DK 172874A DK 156397 B DK156397 B DK 156397B
- Authority
- DK
- Denmark
- Prior art keywords
- anhydride
- aromatic
- bis
- alkali metal
- formula
- Prior art date
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- -1 ETHER ANHYDRIDES Chemical class 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- WWJAZKZLSDRAIV-UHFFFAOYSA-N 4-fluoro-2-benzofuran-1,3-dione Chemical group FC1=CC=CC2=C1C(=O)OC2=O WWJAZKZLSDRAIV-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- XVMKZAAFVWXIII-UHFFFAOYSA-N 5-fluoro-2-benzofuran-1,3-dione Chemical group FC1=CC=C2C(=O)OC(=O)C2=C1 XVMKZAAFVWXIII-UHFFFAOYSA-N 0.000 claims description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- LKOZHLXUWUBRDK-UHFFFAOYSA-N 4-nitro-1,8-naphthalic anhydride Chemical group O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3[N+](=O)[O-] LKOZHLXUWUBRDK-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 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 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CRHKVURIWVWTLH-UHFFFAOYSA-N (2-nitronaphthalene-1-carbonyl) 2-nitronaphthalene-1-carboxylate Chemical class C1=CC=C2C(C(=O)OC(=O)C3=C4C=CC=CC4=CC=C3[N+](=O)[O-])=C([N+]([O-])=O)C=CC2=C1 CRHKVURIWVWTLH-UHFFFAOYSA-N 0.000 description 2
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 2
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- WPYMWEFKAPSRAX-UHFFFAOYSA-N (4-nitronaphthalene-1-carbonyl) 4-nitronaphthalene-1-carboxylate Chemical compound C12=CC=CC=C2C([N+](=O)[O-])=CC=C1C(=O)OC(=O)C1=CC=C([N+]([O-])=O)C2=CC=CC=C12 WPYMWEFKAPSRAX-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- MQXNNWDXHFBFEB-UHFFFAOYSA-N 2,2-bis(2-hydroxyphenyl)propane Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1O MQXNNWDXHFBFEB-UHFFFAOYSA-N 0.000 description 1
- RKSBPFMNOJWYSB-UHFFFAOYSA-N 3,3-Bis(4-hydroxyphenyl)pentane Chemical compound C=1C=C(O)C=CC=1C(CC)(CC)C1=CC=C(O)C=C1 RKSBPFMNOJWYSB-UHFFFAOYSA-N 0.000 description 1
- XQGMTFGZVRBDPQ-UHFFFAOYSA-N 3-(4-propylphenoxy)phthalic acid Chemical compound C1=CC(CCC)=CC=C1OC1=CC=CC(C(O)=O)=C1C(O)=O XQGMTFGZVRBDPQ-UHFFFAOYSA-N 0.000 description 1
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 description 1
- JEXCBTXFJQTLFP-UHFFFAOYSA-N 3-nitro-3h-2-benzofuran-1-one Chemical class C1=CC=C2C([N+](=O)[O-])OC(=O)C2=C1 JEXCBTXFJQTLFP-UHFFFAOYSA-N 0.000 description 1
- HRMCXDSWURAYFR-UHFFFAOYSA-N 3-phenoxyphthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=CC=CC=2)=C1C(O)=O HRMCXDSWURAYFR-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- YGYPMFPGZQPETF-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)-2,6-dimethylphenol Chemical group CC1=C(O)C(C)=CC(C=2C=C(C)C(O)=C(C)C=2)=C1 YGYPMFPGZQPETF-UHFFFAOYSA-N 0.000 description 1
- UJEUBSWHCGDJQU-UHFFFAOYSA-N 4-chloro-1,8-naphthalic anhydride Chemical compound O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3Cl UJEUBSWHCGDJQU-UHFFFAOYSA-N 0.000 description 1
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- SYMIKCJHHHPROA-UHFFFAOYSA-N [2-(2-methylphenyl)acetyl] 2-(2-methylphenyl)acetate Chemical compound CC1=CC=CC=C1CC(=O)OC(=O)CC1=CC=CC=C1C SYMIKCJHHHPROA-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FZTDWZQGFQIIDA-UHFFFAOYSA-N ethoxyethane;isoindole-1,3-dione Chemical compound CCOCC.C1=CC=C2C(=O)NC(=O)C2=C1 FZTDWZQGFQIIDA-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/567—Preparation of carboxylic acid anhydrides by reactions not involving carboxylic acid anhydride groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Furan Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
DK 156397 B
Den foreliggende opfindelse angâr en fremgangsmâde ti1 fremstilling af aromatiske bis(etheranhydrider) ved at omsætte et alkalimetaldi-phenoxid og et halogen- eller nitrosubstitueret aromatisk anhydrid.
5 Det er blevet foreslâet at fremstille et aromatisk bis(etheran-hydrid) ud fra N-substitueret aromatisk bis(etherphthalimid) ved en trinvis fremgangsmâde, der omfatter omdannelse af bisimidet ti1 det tilsvarende tetrasyresalt, syrning af saltet til tetrasyren og dehydratisering af tetrasyren til opnâelse af dianhydridet. Denne 10 trinvise fremgangsmâde giver hpje udbytter af de aromatiske bis-(etheranhydrider). De hpje udbytter opnâs, fordi alkalidiphenoxid direkte kan anvendes i forbindelse med N-substitueret nitrophthali-mid, uden at der sker nogen væsentlig grad af ringâbning.
15 Den foreliggende opfindelse er baseret pâ den erkendelse, at diphen-oxider ogsâ kan omsættes direkte med visse aromatiske anhydrider, der har specielle af diphenoxid fortrængelige funktionelle grupper, sâsom halophthalsyreanhydrider og nitronaphthalsyreanhydrider, til opnâelse af fordelagtige udbytter af aromatiske bîs(etheranhydri-20 der).
Fremgangsmâden ifdlge opfindelsen er sâledes ejendommelig ved at et alkalimetaldiphenoxid med formlen 25 M-0-R-0-M, hvori R betegner (a) en divalent aromatisk gruppe med formlen: CH3 30 CH, CH, CH, CH, -4-4- CH3 CH3 CHjBr EtrCH3 Br Br —<jo>-<o>— ;eUer-^y-c(cH3)2_^\_ CH3 Br Br CH3 Br Br 2
DK 156397 B
eller (b) en divalent organisk gruppe med formlen: —(o) (Q)m (Ô) 5
0 0 Il II
hvor Q betegner -CyH2y-> -C-, -S-, -0- eller -S-, m er 0 eller 1, og 0 10 y er et helt tal pà fra 1 til 5, og M betegner en alkalimetalion, omsættes i et aprot dipolært organisk oplpsningsmiddel med et aromatisk anhydrid med formlen:
O
- i) » Y tl O Y Û (I) (II) 20 hvori X betegner et halogenatom og Y betegner en nitrogruppe eller et halogenatom.
De X-substîtuerede phthalsyreanhydrider med formlen I er fortrinsvis 25 3-fluorphthalsyreanhydrid og 4-fluorphthalsyreanhydrid. Phthalsyre- anhydriderne med formlen I omfatter ogsâ 3-chlorphthalsyreanhydrid, 4-chlorphthalsyreanhydrid osv. Omfattet af naphthalsyreanhydriderne med formlen II er ogsâ forbindelser, hvor Y kan være i 2 eller 4-stillingen sâsom 2-nitronaphthalsyreanhydrid, 4-nitronaphthal-30 syreanhydrid, 2-chlornaphthalsyreanhydrid, 4-chlornaphthalsyrean- hydrid osv.
Blandt de aromatiske bis(etheranhydrider), der fremstilles ved fremgangsmâden if0lge den foreliggende opfindelse er forbindelser 35 med formlerne: 3
DK 156397 B
• ôf fô ” " 0-R1-0 " 0 0 0 0 1Ï "
10 /V
\$ A/ « 0-R1-0/ " 15 0 ° ” à " " \ 1 / ,r 0 \ O-R-O x 0 25 hvor R1 er (^T— q1 CH3 0 30 | || og Q er udvalgt blandt -0-, -S-, -C-, og -S-.
I π CH3 0 35 Dianhydrider med formlen V er f.eks.: 2.2- bis[4-(2,3-dicarboxyphenoxy)phenyl]propandianhydrid; 4,4'-bi s(2,3-di carboxyphenoxy)di phenyletherdi anhydri d; 1.3- bis(2,3-dicarboxyphenoxy)benzendianhydrid; 4
DK 156397 B
4,4'-bi s(2,3-dicarboxyphenoxy)di phenylsulfi ddi anhydri d; 1.4- bi s(2,3-di carboxyphenoxy)benzend i anhydri d; 4,4'-bis(2,3-dicarboxyphenoxy)diphenylsulfondianhydrid; osv.
5 Dianhydrider med formlerne VI og VII er f.eks,: 2.2- bis 4-(3,4-dicarboxyphenoxy)phenylpropandianhydrid; 4,4' -bi s(3,4-dicarboxyphenoxy)di phenyletherdi anhydri d; 4,4'-bi s(3,4-di carboxyphenoxy)di phenylsulfi ddi anhydrid; 10 1,3-bi s(3,4-di carboxyphenoxy)benzendi anhydri d; 1.4- bi s(3,4-di carboxyphenoxy)benzendi anhydrid; 4,4'-bi s(3,4-di carboxyphenoxy)di phenylsylfondi anhydri d; 4-(2,3-di carboxyphenoxy)-4'(3,4-di carboxyphenoxy)2,2-di phenylpropan-dianhydrid, osv.
15
Ud over de ovennævnte phthalsyreanhydrider er der ogsâ taie om napthalsyreanhydrider med formlen VII sâsom: 2.2- bi s[4-(4,5-dicarboxynaphthoxy)phenyl]propandi anhydrid; 20 2,2-bi s[4-(2,3-di carboxynaphthoxy)phenyl]propandi anhydri d; 4,4'-bis(4,5-di carboxynaphthoxy)di phenyletherdi anhydrid; 1.3- bi s(4,5-dicarboxynaphthoxy)benzendi anhydrid; 1.3- bis(2,3-dicarboxynaphthoxy)benzendianhydrid; 4,4'-bi s(4,5-dicarboxynaphthoxy)di phenylsulfiddi anhydri d; 25 4,4'-bi s(4,5-di carboxynaphthoxy)di phenylsulfondi anhydrid; 4-(2,3-di carboxynaphthoxy)-4'(4,5-di carboxyphenoxy)-2,2-di phenylpro-pandianhydrid.
Blandt alkalimetalsaltene af ovennævnte diphenoxider med formlen III 30 er natrium- og kaliumsaltene af fplgende divalente phénoler: 2,2-bi s-(2-hydroxyphenyl)propan ; 2,4'-dihydroxydi phenylmethan ; bi s-(2-hydroxyphenyl)methan; 35 2,2-bis-(4-hydroxyphenyl)propan, der i det fplgende betegnes som "bisphenol-A" eller "BPA"; 1.1- bis-(4-hydroxyphenyl)ethan; ---- 1,1-bi s-(4-hydroxyphenyl)propan; 2.2- bi s-(4-hydroxyphenyl)pentan; 5
DK 156397 B
3,3-bis-(4-hydroxyphenyl)pentan; 4,4'-dihydroxybiphenyl; 4,4'-dihydroxy-3, 3 ', 5,5 '-tetramethylbi phenyl; 4,4'-dihydroxybenzophenon; 5 4,4'-di hydroxydi phenylsu!fon ; 4,4'-d i hydroxyd i phenylsu!foxi d; 4,4'-dihydroxydiphenylsu!fid, osv.
Ud over alkalmétalsalte af de ovenfor omtalte gruppe af divalente 10 phénoler kan der ogsâ anvendes alkalimetalsaltene af fplgende gruppe af divalente phenoler: hydroquinon; resorcinol; 15 4,4'dihydroxybenzophenon; og 4,4'd i hydroxyd i phenylether.
Alkalimetaldiphenoxiderne kan være forudfremstillet eller kan fremstilles in situ. Fprstnævnte fremstilles fortrinsvis ved azeo-20 trop afdestillering af vand fra en vandig blanding af et al kal i -métal hydroxid, divalent phénol og et carbonhydridoplpsningsmiddel for at gpre produktet stort set vandfrit. Der anvendes fortrinsvis 2 ækvivalenter al kal i métal hydroxi d pr. ækvivalent divalent phénol.
25 Ved den praktiske gennemfprelse af den foreliggende opfindelse hvorved det aromatiske bis(etheranhydrid) fremstilles ved at omsætte alkalimetaldiphenoxidet med det aromatiske anhydrid, har det vist sig, at der kan anvendes ca. 2 mol aromatisk anhydrid pr. mol alkalimetaldiphenoxid.
30
Reaktionen mellem alkalimetaldiphenoxidet og det aromatiske anhydrid gennemfpres fortrinsvis i en inaktiv atmosfære, sâsom nitrogen, og under stort set vandfrie betingelser. Egnede organiske oplpsnings-midler, der kan anvendes for at lette dannelsen af det aromatiske 35 bis(etheranhydrid) er aprote dipolære organiske oplpsningsmidler, f.eks. dimethylformamid, sulfolan, dimethylacetamid, dimethylsulf-oxid, hexa-methylphosphorsyretriamid osv. Anvendelige temperaturer er f.eks. fra 25eC til 170eC og fortrinsvis fra 100°C til 150°C.
DK 156397B
6
Reaktionstiden kan variere fra 5 minutter eller mindre til 16 timer eller mere afhængig af den temperatur, ved hvilken reaktionen gennemfpres, omrpringsgraden osv. Det er f.eks. blevet konstateret, at det i visse tilfælde foretrækkes at foretage kogning under 5 tilbagesvaling for at opnâ det maksimale produktudbytte.
Udvinding af produktet kan foretages ved afslutningen af reaktionen ved at hælde reaktionsblandingen i fortyndet mineralsyre, sâsom saltsyre og is. Det resulterende udfældningsprodukt kan fjernes ved 10 filtrering.
De aromatiske anhydrider, der fremstilles ved fremgangsmâden ifplge den foreliggende opfindelse, kan anvendes som udgangsmaterialer til brug ved fremstilling af polymère, sâsom polyimider ved reaktion med 15 organiske diaminer. Endvidere kan anhydridet anvendes som hærd-ningsmiddel for epoxyharpikser, som udgangsmaterialer til fremstilling af polyesterharpikser osv.
I det fdlgende vil opfindelsen blive beskrevet nærmere i form af 20 nogle udfprelseseksempler. Aile de anfprte dele er vægtandele.
Eksempel 1
Dinatriumsaltet af bisphenol-A blev fremstillet udfra en blanding af 25 0,7 dele af en 50% vandig natriumhydroxidoplpsning og 1 del bisphe- nol-A. Saltet blev gjort vandfrit ved azeotropt at fjerne vandet fra reaktionsblandingen under anvendelse af benzen.
En blanding af dette sait, 2,1 dele 4-nitronaphthalsyreanhydrid og 30 ca. 15 dele vandfri dimethylformamid blev omrprt i en nitrogenatmos-fære i 1 time ved stuetemperatur. Hele reaktionsblandingen blev udhældt i vand, og det resulterende udfældningsprodukt blev opsamlet og tprret til opnâelse af 1,6 dele (60% udbytte) af et bruniigt pu!ver. Omkrystallisation i eddikesyre gav et smeltepunkt pà 258-35 259°C. Bestemt udfra fremstillingsmetoden og IR- og NMR-spektret var produktet 2,2-bis[4-(4,5-dicarboxynaphthoxy)phenyl]propandianhydrid.
Eksempel 2 7
DK 156397 B
En blanding af 0,4744 g (0,0017 mol) dinatriumsalte af bisphenol-A, 0,5788 g (0,0035 mol) 3-fluorphthalsyreanhydrid og 11 ml vandfri 5 dimethylformamid blev omrprt i en nitrogenatmosfære i 3 timer ved en temperatur pâ ca. 170°C. Blandingen fik derefter lov til at afkple til stuetemperatiir. Blandingen blev sat til 150 ml af en 1,2 N saltsyre-isblanding. Der opnâedes et hvidt produkt, der blev opsam-let ved filtrering. Produktet blev vasket med 1,2 N saltsyre og 10 tprret til opnâelse af 0,8077 g hârdt materiale, der repræsenterer et udbytte pâ 91%. Produktet blev derefter omkrystal 1 iseret i en eddikesyre-eddikesyreanhydridblanding, hvorved der opnâedes et materiale med et smeltepunkt pâ 181,5-183°C. Bestemt udfra frem-stillingsmetoden og IR-analyse var produktet 2,2-bis[4-(2,3-diear-15 boxyphenoxy)phenyl]propand i anhydri d.
Eksempel 3 I overensstemmelse med fremgangsmâden ifplge eksempel 2, blev en 20 blanding af 3-fluorphthalsyreanhydrid og natriumsaltet af 4,4'- dihydroxybiphenyl under anvendelse af et molforhold pâ 2:1 mellem anhydrid og sait omrprt pâ et oliebad ved 170*C i en nitrogenatmosfære i 1 1/4 time. Blandingen fik derefter lov til at afkple til stuetemperatur. Der opnâedes et gult produkt i et udbytte pâ 50%.
25 Produktet havde et smeltepunkt pâ 281-283°C. Bestemt udfra frem- stillingsmetoden og IR-analyse var produktet 4,4'-bis(2,3-dicar-boxyphenoxy)bi phenyldi anhydrid.
Eksempel 4 30
En blanding af 1 del af natriumsaltet af bisphenol-A, 1,22 dele af 4-fluorphthalsyreanhydrid og 14 dele vandfri dimethylformamid blev omrprt i en nitrogenatmosfære ved 2 timer under tilbagesvaliing. Blandingen blev afkplet til stuetemperatur og sat til 140 dele 1,2 N 35 HCl blandet med is. Det resulterende hvide udfældningsprodukt blev opsamlet og tprret til opnâelse af 1,6 dele (85% udbytte) af 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propandianhydrid. Omkrystalldation af en prpve i toluen-eddikesyreanhydrid gav et materiale med et smeltepunkt pâ 186-188eC. Produktet blev identificeret ved 5 8
DK 156397 B
IR-analyse og pâ grundlag af proton- og carbon-NMR-spektre.
10 15 20 25 30 35
Claims (6)
1. Fremgangsmâde til fremstilling af aromatiske bis(etheranhy-drider), kendetegnet ved, at et alkalimetaldiphenoxid med 5 formlen M-O-R-O-M, hvori R betegner (a) en divalent aromatisk gruppe med formlen: 10 çh3 CH5 CHj ch^ ch^ ~(k)-(°)— -^o)-<o)— CH, .CH, j J CH^Br Br CH^ Br Br —{oJ>-;eller—C(oh3)2 -Δ CH5 Br Br CH^ Br Br eller (b) en divalent organisk gruppe med formlen: 25 -^ô)— —<o>— 0 0 30 hvor Q betegner ‘CJU-, -Ü-, -0- eller -S-, m er 0 eller 1, og JJ || 0 y er et helt tal pâ fra 1 til 5, og M betegner en alkalimetalion, omsættes i et aprot dipolært organisk oplesningsmiddel med et 35 aromatisk anhydrid med formlen: DK 156397 B O O » « / ^ P rY*\ (ËA X—h O O eller /T\ 9
2. Fremgangsmâde ifplge krav 1, k e n d e t e g n e t ved, at det organiske anhydrid er 3-fluorphthalsyreanhydrid.
3. Fremgangsmâde ifplge krav 1, kendetegnet ved, at det organiske anhydrid er 4-fluorphthalsyreanhydrid.
4. Fremgangsmâde ifplge krav 1, kendetegnet ved, at det aromatiske anhydrid er 4-nitro-l,8-naphthalsyreanhydrid. 20
5. Fremgangsmâde ifplge krav 1, kendetegnet ved, at diphenoxidet er et alkalimétal sait af bisphenol-A.
5 WA/ ° /— C O Y 0 hvori X betegner et halogenatom og Y betegner en nitrogruppe eller 10 et halogenatom.
6. Fremgangsmâde ifplge krav 1, kendetegnet ved, at 25 diphenoxidet er et alkalimetalsalt af 4,4'-dihydroxybiphenyl. 30 35
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34647173 | 1973-03-30 | ||
| US00346471A US3850964A (en) | 1973-03-30 | 1973-03-30 | Method for making aromatic bis(ether anhydride)s |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK156397B true DK156397B (da) | 1989-08-14 |
| DK156397C DK156397C (da) | 1990-01-08 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK172874A DK156397C (da) | 1973-03-30 | 1974-03-28 | Fremgangsmaade til fremstilling af aromatiske bis(etheranhydrider) |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3850964A (da) |
| JP (2) | JPS604178B2 (da) |
| BR (1) | BR7402534D0 (da) |
| DD (1) | DD111369A5 (da) |
| DE (1) | DE2412467C2 (da) |
| DK (1) | DK156397C (da) |
| FR (1) | FR2223354B1 (da) |
| GB (1) | GB1469936A (da) |
| IT (1) | IT1004418B (da) |
| SE (1) | SE419640B (da) |
| SU (1) | SU547175A3 (da) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956320A (en) * | 1972-08-18 | 1976-05-11 | General Electric Company | Aromatic bis(ether phthalis anhydride) compounds |
| US3944583A (en) * | 1975-02-27 | 1976-03-16 | General Electric Company | Bis-phenoxyphthalic acid anhydrides |
| US4133182A (en) * | 1977-01-13 | 1979-01-09 | Societe Nationale Elf Aquitaine (Production) | Apparatus and method of connecting a flowline to a subsea station |
| US4102905A (en) * | 1977-09-02 | 1978-07-25 | General Electric Company | Aromatic disulfone dianhydrides |
| US4459414A (en) * | 1981-04-08 | 1984-07-10 | Ciba-Geigy Corporation | Tetrasubstituted phthalic acid derivatives, and a process for their preparation |
| US4868316A (en) * | 1987-04-27 | 1989-09-19 | Occidental Chemical Corporation | Process for the preparation of diether diphthalic anhydrides |
| DE4216796A1 (de) * | 1992-05-21 | 1993-11-25 | Cassella Ag | Verfahren zur Herstellung von 4-(2-Aminophenylthio)- naphthalsäureanhydrid-Derivaten |
| EP1776094A2 (en) * | 2004-08-06 | 2007-04-25 | Grain Processing Corporation | Tablet coating composition |
| US7268237B2 (en) * | 2005-03-11 | 2007-09-11 | General Electric Company | Direct dianhydride synthesis |
| US8080671B2 (en) | 2008-05-23 | 2011-12-20 | Sabic Innovative Plastics Ip B.V. | Production of low color polyetherimides |
| JP2022523118A (ja) | 2019-01-31 | 2022-04-21 | エスエイチピーピー グローバル テクノロジーズ べスローテン フェンノートシャップ | ビスフェノールａ酸二無水物組成物の精製のための方法、ビスフェノールａ酸二無水物組成物、ビスフェノールａ酸二無水物組成物に由来するポリ（エーテルイミド）、およびそれから調製される製造品 |
| US11898011B2 (en) * | 2020-02-19 | 2024-02-13 | Dupont Electronics, Inc. | Polymers for use in electronic devices |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1359415A (en) * | 1971-01-20 | 1974-07-10 | Gen Electric | Process for making aryloxy derivatives of aromatic diesters and dinitriles and products derived therefrom |
-
1973
- 1973-03-30 US US00346471A patent/US3850964A/en not_active Expired - Lifetime
-
1974
- 1974-03-15 DE DE2412467A patent/DE2412467C2/de not_active Expired
- 1974-03-22 GB GB1286574A patent/GB1469936A/en not_active Expired
- 1974-03-26 FR FR7410288A patent/FR2223354B1/fr not_active Expired
- 1974-03-27 IT IT49729/74A patent/IT1004418B/it active
- 1974-03-28 DK DK172874A patent/DK156397C/da not_active IP Right Cessation
- 1974-03-28 DD DD177522A patent/DD111369A5/xx unknown
- 1974-03-29 BR BR2534/74A patent/BR7402534D0/pt unknown
- 1974-03-29 JP JP49034776A patent/JPS604178B2/ja not_active Expired
- 1974-03-29 SE SE7404313A patent/SE419640B/xx not_active IP Right Cessation
- 1974-03-29 SU SU2011517A patent/SU547175A3/ru active
-
1983
- 1983-03-01 JP JP58031901A patent/JPS58180479A/ja active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1359415A (en) * | 1971-01-20 | 1974-07-10 | Gen Electric | Process for making aryloxy derivatives of aromatic diesters and dinitriles and products derived therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2223354B1 (da) | 1978-09-15 |
| JPS5024241A (da) | 1975-03-15 |
| IT1004418B (it) | 1976-07-10 |
| FR2223354A1 (da) | 1974-10-25 |
| AU6738774A (en) | 1975-10-16 |
| DE2412467C2 (de) | 1983-08-04 |
| SU547175A3 (ru) | 1977-02-15 |
| GB1469936A (en) | 1977-04-06 |
| DK156397C (da) | 1990-01-08 |
| US3850964A (en) | 1974-11-26 |
| JPS58180479A (ja) | 1983-10-21 |
| DD111369A5 (da) | 1975-02-12 |
| JPS604178B2 (ja) | 1985-02-01 |
| DE2412467A1 (de) | 1974-10-10 |
| BR7402534D0 (pt) | 1974-12-03 |
| SE419640B (sv) | 1981-08-17 |
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