CH520172A - Benzelpyromillitic acids and their - polyimides - Google Patents
Benzelpyromillitic acids and their - polyimidesInfo
- Publication number
- CH520172A CH520172A CH284971A CH284971A CH520172A CH 520172 A CH520172 A CH 520172A CH 284971 A CH284971 A CH 284971A CH 284971 A CH284971 A CH 284971A CH 520172 A CH520172 A CH 520172A
- Authority
- CH
- Switzerland
- Prior art keywords
- acid
- tetramethyl
- benzene
- polyimides
- anhydride
- Prior art date
Links
- 239000004642 Polyimide Substances 0.000 title claims abstract description 5
- 229920001721 polyimide Polymers 0.000 title claims abstract description 5
- 239000002253 acid Substances 0.000 title abstract description 16
- 150000007513 acids Chemical class 0.000 title abstract 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 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- LEVJVKGPFAQPOI-UHFFFAOYSA-N phenylmethanone Chemical group O=[C]C1=CC=CC=C1 LEVJVKGPFAQPOI-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 22
- 239000004952 Polyamide Substances 0.000 abstract description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 10
- 229920002647 polyamide Polymers 0.000 abstract description 10
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 abstract description 8
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- -1 dibenzoyl compound Chemical class 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 abstract 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 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 16
- 150000008064 anhydrides Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229940076134 benzene Drugs 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JHNMPYMTHAMTJM-UHFFFAOYSA-N phenyl-(2,3,4,5-tetramethylphenyl)methanone Chemical class CC1=C(C)C(C)=CC(C(=O)C=2C=CC=CC=2)=C1C JHNMPYMTHAMTJM-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WUERJFPKCNVWIU-UHFFFAOYSA-N (2-benzoyl-3,4,5,6-tetramethylphenyl)-phenylmethanone Chemical group C=1C=CC=CC=1C(=O)C1=C(C)C(C)=C(C)C(C)=C1C(=O)C1=CC=CC=C1 WUERJFPKCNVWIU-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SYWIOWXMHAQPTK-UHFFFAOYSA-N phenyl-(2,3,5,6-tetramethylphenyl)methanone Chemical compound CC1=CC(C)=C(C)C(C(=O)C=2C=CC=CC=2)=C1C SYWIOWXMHAQPTK-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SRICROQPOLNYOO-UHFFFAOYSA-N 1h-pyridine-2,2-diamine Chemical compound NC1(N)NC=CC=C1 SRICROQPOLNYOO-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- BLMSGSGJGUHKFW-UHFFFAOYSA-N 4-[(4-aminophenyl)-diphenylsilyl]aniline Chemical compound C1=CC(N)=CC=C1[Si](C=1C=CC(N)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BLMSGSGJGUHKFW-UHFFFAOYSA-N 0.000 description 1
- NMWNHYZYLFZQAW-UHFFFAOYSA-N 4-[(4-aminophenyl)-methylphosphanyl]aniline Chemical compound C=1C=C(N)C=CC=1P(C)C1=CC=C(N)C=C1 NMWNHYZYLFZQAW-UHFFFAOYSA-N 0.000 description 1
- KTZLSMUPEJXXBO-UHFFFAOYSA-N 4-[(4-aminophenyl)-phenylphosphoryl]aniline Chemical compound C1=CC(N)=CC=C1P(=O)(C=1C=CC(N)=CC=1)C1=CC=CC=C1 KTZLSMUPEJXXBO-UHFFFAOYSA-N 0.000 description 1
- YFBMJEBQWQBRQJ-UHFFFAOYSA-N 4-n-(4-aminophenyl)-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=CC=C1 YFBMJEBQWQBRQJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N anhydrous dimethyl-acetamide Natural products CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 238000006480 benzoylation reaction Methods 0.000 description 1
- IWZNWGDJJJKIOC-UHFFFAOYSA-N bis(3-aminophenyl)methyl-oxidophosphanium Chemical compound NC=1C=C(C=CC1)C(C1=CC(=CC=C1)N)[PH2]=O IWZNWGDJJJKIOC-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/27—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids
-
- 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
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/32—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups
- C07C65/34—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups polycyclic
-
- 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
-
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Mono- or di-benzoylpyromellitic acids made by reacting benzoyl chloride with tetramethyl- 1,2,4,5-benzene using as catalyst, e.g. AlCl3. For the monobenzoyl compound, 10 moles % excess benzoyl chloride is used, and for the dibenzoyl compound, 4 to 6 moles of benzoyl chloride/mole of tetramethyl benzene. The product is oxidised to the acid by alkalibichromates, etc., and then converted, if desired to the dianhydride by heating. Used as hardeners for epoxy resins and for making polyesters, polyamides and polyimides for use in adhesives.
Description
Procédé de préparation de polyamides dérivés des acides benzoylpyromelliques La présente invention a pour objet un procédé de préparation de polyamides comportant des motifs de formule générale:
EMI0001.0000
dans laquelle le symbole R représente un atome d'hy drogène ou un radical benzoyle et Y représente un radical divalent possédant au moins deux atomes de carbone caractérisé en ce que l'on fait réagir une diamine H2N-Y-NH2 sur un dianhydride benzoylpyro- mellique de formule:
EMI0001.0003
Le radical Y peut être aliphatique, cycloaliphatique, aromatique ou hétérocyclique.
Plus spécifiquement, Y peut être un radical alcoylène linéaire ou ramifié, ayant moins de 13 atomes de carbone, un radical cycloalooy- lène à 5 ou 6 atomes de carbone dans le cycle, un radical hétérocyclique divalent contenant au moins un des atomes O, N et S, un radical benzénique ou aro matique polycyclique, ces divers radicaux pouvant en outre porter des substituants qui ne donnent pas de réactions parasites dans les conditions opératoires.
Le symbole Y peut également comprendre plusieurs radi caux benzéniques ou alicycliques liés directement par un atome ou groupement divalent tel que par exemple les atomes d'oxygène ou de soufre, les groupements alcoylènes ayant de 1 à 3 atomes de carbone, les grou pements
EMI0001.0009
EMI0002.0000
dans lesquels R1, R2 et Z représentent des radicaux alcoyles ayant de 1 à 4 atomes de carbone ou des radi caux cycloalcoyles à 5 ou 6 atomes de carbone dans le cycle,benzéniques ou aromatiques polycylaques et X représente un radical alcoylène linéaire ou ramifié ayant moins de 13 atomes de carbone, un radical cyclolacoylène à 5 ou 6 atomes de carbone dans le cycle ou un radical arylène mono- ou polycyclique.
Plus précisément encore, parmi les diamines utilisa bles, on peut citer le diamino-4,4' dicyclohexylméthane, le diamino-1,4 cyclohexane, la diamino-2,2 pyridine, la mêtaphénylène diamine, la paraphénylène diamine, le diamino-4,4' diphénylméthane, le diamino-4,4' diphényl-2,2 propane, la benzidine, l'oxyde de diamino-4,4' diphénylsulfone, le bis(amino-4 phényl) diphénylsilane, l'oxyde de bis(amino-4 phényl)méthylphosphine, l'oxyde de bis(amino-3 phényl)méthylphosphine, l'oxyde de bis(amino-4 phényl) phénylphosphine, la bis(amino-4 phényl) phénylamine, le diamino-1,5 naphtalène, la métaxylylène diamine, la paraxylylène diamine, le bis(para-aminophényl)-1,1 phtalane.
Les dianhydrides de formule générale:
EMI0002.0004
peuvent être préparés à partir des tétracides correspon- dants par les procédés habituels, par exemple par chauffage ou par action d'un tel qu'un anhydride d'acide organique inférieur.
Les tétracides peuvent être obtenus par oxydation des benzoyltétraméthylbenzènes correspondants. Cette oxydation peut être effectuée selon toute méthode per mettant la transformation d'un groupement méthyl en groupement carboxylique. On peut réaliser cette oxy dation sous pression atmosphérique ou sous pression plus élevée au moyen de bichromates alcalins, de per manganates en milieu alcalin, d'acide chromique en solution sulfurique, d'acide nitrique dilué ou de ferri- cyanure de potassium.
On peut également oxyder les benzoyltétraméthyl- benzène par l'air en phase liquide en présence de cata lyseurs tels que des dérivés du vanadium, du chrome, du cobalt ou du manganèse.
Enfin les benzoyltétraméthylbenzènes peuvent être obtenus par benzoylation du tétraméthyl-1,2,4,5 ben zène. On fait réagir le chlorure de benzoyle sur le tétraméthyl-1,2,4,5 benzène. Selon les conditions opé ratoires, on obtient le tétraméthyl-1,2,4,5-benzoyl-3 benzène ou 1e tétraméthyl-1,2,4,5 dibenzoyl-3,6 ben zène. La réaction peut être effectuée en présence d'un catalyseur tel que AlCl3, SbCl5, FeCl3, SnCl4, TiCl4, ZnCl2. On utilise de préférence le chlorure d'alumi nium dans des proportions supérieures à 1 mole par mole de tétraméthylbenzène. On peut opérer en pré sence d'un diluant tel que le tétrachlorure de carbone, la sulfure de carbone, le dichloroéthane, le nitroben zène, l'éther de pétrole. Les conditions de température sont celles qui sont habituellement adoptées pour ce type de réaction de Friedel et Crafts.
Lorsque l'on désire obtenir le dérivé monobenzoy- lé, on opère généralement à une température comprise entre 0 et 60 et de préférence entre 10 et 40 , en uti lisant une quantité de chlorure de benzoyle voisine de la stoechiométrie de la réaction. En pratique on ajoute un excès de 100/o de chlorure de benzoyle. Si par con tre on veut préparer le dérivé dibenzoylé on opère à une température plus élevée comprise entre 80 et 160 et de préférence entre 110 et 150 en utilisant une quantité de chlorure de benzoyle qui est en général le double de celle correspondant à la stoechiométrie de la réaction.
En pratique on ajoute le chlorure de benzoyle dans un rapport molaire de 4 à 6 par rapport au tétra- méthylbenzène.
La solution de polyamide acide peut être transfor mée en articles usuels ou utilisée comme composition pour imprégnation ou revêtement, le passage du poly amide acide ou polyamide pouvant être fait par traite ment thermique ou à l'aide d'un déshydratant tel que l'anhydride acétique, en présence ou non d'une amine tertiaire, ou d'un carbodiimide.
Il est entendu que les nouveaux polyamides incluent aussi des copolyimides préparés en utilisant comme anhydride seulement partiellement un dianhy- dride benzoylpyromellique. En ce qui concerne ces copolyimides, la préférence va tout spécialement aux produits pour lesquels la proportion de dianhydride benzoylpyromellique représente au moins 900/o du poids total de dianhydride mis en oeuvre.
Pour 1a réalisation de matériaux composites conte nant des polyamides, il est généralement avantageux de déposer sur un support un mélange constitué par un des dianhydrides, une diamine biprimaire et de l'eau, d'éliminer l'eau, puis de soumettre l'assemblage ainsi obtenu à un traitement thermique allant de 100 à 400 C. On peut aussi ajouter une solution aqueuse ammoniacale au mélange de dianhydride, de diamine et d'eau, ce qui permet d'obtenir un mélange plus homo gène.
Les nouveaux polyimides sont aptes à de nom breux emplois qui font appel à des matériaux doués d'excellentes propriétés thermiques, chimiques et élec triques. Ils peuvent être utilisés pour la préparation de films, de feuilles, de vernis isolants et entrer dans la composition de stratifiés et d'objets moulés. Ils présen tent d'intéressantes propriétés pour le collage des métaux.
Les exemples ci-après illustrent l'invention et mon trent comment elle peut être mise en pratique. <I>Exemple 1</I> On prépare un collodion de polyamide acide en ajoutant 1,671 g d'anhydride benzoylpyromellique à une solution de 1,009 g de diamino-4,4' diphényléther dans 14,118 g de diméthylacétamide et de 0,0868 g de pyridine.
Le collodion qui possède une viscosité inhérente de 0,98 dl/g (mesurée à 25 dans le diméthylacétamide) est utilisé pour faire un assemblage d'éprouvettes d'acier inoxydable. Pour cela les éprouvettes sont enduites de collodion puis passées à l'étuve à 120 pendant 30 mn et assemblées ensuite à 310 sous une pression de 8 kg/cm2 durant 1 heure. Ces assemblages présentent une résistance au cisaillement à la traction de 210 kg/cm2 (mesurée selon la norme ASTM D 1002-64). A titre comparatif le même assem blage est réalisé avec un collodion obtenu dans les mêmes conditions que précédemment mais en substi tuant à l'anhydride benzoylpyromellique l'anhydride pyromellique. Le nouvel assemblage offre une résis tance nulle au cisaillement à la traction.
<I>Exemple 2</I> On prépare un collodion de polyamide acide en ajoutant 8,523 g d'anhydride dibenzoylpyromellique à une solution de 3,999 g de diamino-4,4' diphényléther dans 50 g de diméthylacétamide anhydre. Ce collodion est utilisé pour assembler des éprouvettes d'acier ino xydable. Celles-ci préparées selon le mode opératoire de l'exemple 5 offrent une résistance au cisaillement à la traction de 205 kg/cm2.
Les anhydrides benzoylpyromelliques employés comme matière de départ ont été préparés comme suit: Acide benzoylpyromellique a) Tétraméthyl-1,2,4,5 benzoyl-3 benzène Dans un ballon de 1 litre, on charge 50 g de tétra- méthyl-1,2,4,5 benzène, 58 g de benzoyle et 372 g de sulfure de carbone anhydre. On ajoute par petites por tions, tout en maintenant la température entre 15 et 25 , 55 g de chlorure d'aluminium anhydre. Durant l'addition qui dure 50 mn il se dégage de l'acide chlor hydrique en solution décinormale. On filtre la masse réactionnelle et sépare en deux couches le filtrat qui décante. On évapore la couche organique et récupère le tétraméthyl benzoylbenzène, sous forme impure.
Le produit impur est dissous à chaud dans 100 ml d'oxyde de butyle, puis traité pendant 15 mn à ébulli- tion avec 5 g de noir animal. Par filtration chaude sui- vie d'une cristallisation à froid, on obtient 75,45 de tétraméthyl benzoyl-benzène de PF: 123 .
b) Acide benzoyl-3 pyromellique On oxyde 41,65 g de tétraméthyl-1,2,4,5 benzoyl-3 benzène par 505 g d'une solution aqueuse d'acide nitri que à 300/o. L'essai est réalisé dans un autoclave métal lique, en maintenant la température durant 2 h à 165-170 . Après refroidissement, on évapore la solu tion obtenue et obtient 58,4 g d'un produit jaune clair correspondant à l'acide benzoylpyromellique (titre aci- dimétrique: 1000/a).
c) Anhydride benzoylpyromellique On dissout 8 g de l'acide benzoylpyromellique dans 30 ml d'anhydride acétique. On porte à reflux, ajoute 100 ml d'o-dichlorobenzène et distille le mélange acide acétique - anhydride acétique. Après addition de 5 g de noir animal, on maintient à ébullition pendant 15 mn et procède à une filtration chaude. Par refroi dissement, on obtient un produit jaune très clair qu'on lave à l'éther. On obtient ainsi 5 g de produit titrant 1000/o en anhydride benzoylpyromellique (PF: 261').
Acide dibenzoylpyromellique a) Tétraméthyl-1,2,4,5 dibenzoyl-3,6 benzène On charge dans un ballon de 2 .1, 100 g de tétra- méthyl-1,2,4,5 benzène et 605 g de chlorure de ben- zoyle. Le milieu étant devenu homogène, on ajoute par petites portions 213,5 g de chlorure d'aluminium. Durant l'addition qui dure 1 h 15 mn, la température est élevée de 40 à 95 . On poursuit le chauffage en éle vant en 5 h 20 mn la température de la masse de 95 à 135 . On refroidit à 50 , coule 750 ml d'éther et filtre la masse réactionnelle.
On isole un précipité gris qui est purifié par traitement au noir animal au sein de l'anhydride acétique. On obtient 210g d'un produit blanc fondant à 275 ; ce produit est le tétraméthyldi- benzoyl-benzène. b) Acide dibenzoylpyromellique On charge dans un autoclave en acier inoxydable, 60 g de tétraméthyldibenzoyl-benzène et 505 g d'acide nitrique à 300/0. On chauffe et maintient l'autoclave 2 heures à 170 . On refroidit la solution et l'évapore à siccité. On obtient 80,9 g d'un solide jaune clair, cor respondant à l'acide dibenzoylpyromellique.
c) Anhydride dibenzoylpyromellique 80,9 g d'acide dibenzoylpyromellique sont dissous dans 350 ml d'acétone. On ajoute à cette solution 350 ml d'anhydride acétique et porte à l'ébullition. On distille l'acétone et maintient à reflux pendant 2 heu res. Après refroidissement, on filtre le précipité et le lave à l'anhydride acétique puis à l'éther. On obtient ainsi 41,6 g d'anhydride dibenzoylpyromellique beige clair qui ne fond pas jusqu'à 365 C.
Process for preparing polyamides derived from benzoylpyromellic acids The present invention relates to a process for preparing polyamides comprising units of general formula:
EMI0001.0000
in which the symbol R represents a hydrogen atom or a benzoyl radical and Y represents a divalent radical having at least two carbon atoms, characterized in that a diamine H2N-Y-NH2 is reacted with a benzoylpyro- dianhydride mellique of formula:
EMI0001.0003
The Y radical can be aliphatic, cycloaliphatic, aromatic or heterocyclic.
More specifically, Y can be a linear or branched alkylene radical having less than 13 carbon atoms, a cycloalooylene radical with 5 or 6 carbon atoms in the ring, a divalent heterocyclic radical containing at least one of the atoms O, N and S, a polycyclic benzene or aromatic radical, these various radicals possibly also carrying substituents which do not give side reactions under the operating conditions.
The symbol Y can also comprise several benzene or alicyclic radicaux linked directly by a divalent atom or group such as, for example, oxygen or sulfur atoms, alkylene groups having from 1 to 3 carbon atoms, groups
EMI0001.0009
EMI0002.0000
in which R1, R2 and Z represent alkyl radicals having from 1 to 4 carbon atoms or cycloalkyl radicals with 5 or 6 carbon atoms in the ring, benzene or polycylate aromatic and X represents a linear or branched alkylene radical having less of 13 carbon atoms, a cyclolacoylene radical with 5 or 6 carbon atoms in the ring or a mono- or polycyclic arylene radical.
More precisely still, among the diamines which can be used, mention may be made of 4,4 'diamino-dicyclohexylmethane, 1,4-diamino-cyclohexane, 2,2-diamino-pyridine, metaphenylenediamine, paraphenylenediamine, 4-diamino , 4 'diphenylmethane, 4,4'-diamino-2,2'-diphenyl propane, benzidine, 4,4'-diamino-diphenylsulfone oxide, bis (4-aminophenyl) diphenylsilane, bis ( 4-aminophenyl) methylphosphine, bis (3-aminophenyl) methylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) phenylamine, 1,5-diamino-naphthalene , metaxylylenediamine, paraxylylenediamine, bis (para-aminophenyl) -1.1 phthalan.
Dianhydrides of general formula:
EMI0002.0004
can be prepared from the corresponding tetracids by the usual methods, for example by heating or by the action of such a lower organic acid anhydride.
Tetracids can be obtained by oxidation of the corresponding benzoyltetramethylbenzenes. This oxidation can be carried out by any method allowing the transformation of a methyl group into a carboxylic group. This oxidation can be carried out under atmospheric pressure or under higher pressure by means of alkali metal dichromates, per manganates in an alkaline medium, chromic acid in sulfuric solution, dilute nitric acid or potassium ferricyanide.
Benzoyltetramethylbenzene can also be oxidized by air in the liquid phase in the presence of catalysts such as derivatives of vanadium, chromium, cobalt or manganese.
Finally, benzoyltétramethylbenzènes can be obtained by benzoylation of tetramethyl-1,2,4,5 ben zene. Benzoyl chloride is reacted with tetramethyl-1,2,4,5 benzene. Depending on the operating conditions, tetramethyl-1,2,4,5-3-benzoyl-3benzene or 1e tetramethyl-1,2,4,5-dibenzoyl-3,6benzene are obtained. The reaction can be carried out in the presence of a catalyst such as AlCl3, SbCl5, FeCl3, SnCl4, TiCl4, ZnCl2. Aluminum chloride is preferably used in proportions greater than 1 mole per mole of tetramethylbenzene. It is possible to operate in the presence of a diluent such as carbon tetrachloride, carbon disulphide, dichloroethane, nitrobenzene or petroleum ether. The temperature conditions are those usually adopted for this type of Friedel and Crafts reaction.
When it is desired to obtain the monobenzoyl derivative, the operation is generally carried out at a temperature of between 0 and 60 and preferably between 10 and 40, using a quantity of benzoyl chloride close to the stoichiometry of the reaction. In practice, an excess of 100% of benzoyl chloride is added. If, on the other hand, it is desired to prepare the dibenzoyl derivative, the operation is carried out at a higher temperature of between 80 and 160 and preferably between 110 and 150, using a quantity of benzoyl chloride which is generally double that corresponding to the stoichiometry of the reaction.
In practice, benzoyl chloride is added in a molar ratio of 4 to 6 with respect to tetramethylbenzene.
The acid polyamide solution can be converted into usual articles or used as a composition for impregnation or coating, the passage of the acid polyamide or polyamide can be done by heat treatment or using a desiccant such as anhydride. acetic, in the presence or absence of a tertiary amine, or of a carbodiimide.
It is understood that the new polyamides also include copolyimides prepared using as anhydride only partially a benzoylpyromellic dianhydride. As regards these copolyimides, preference goes most especially to products for which the proportion of benzoylpyromellic dianhydride represents at least 900% of the total weight of dianhydride used.
For the production of composite materials containing polyamides, it is generally advantageous to deposit on a support a mixture consisting of one of the dianhydrides, a bi-primary diamine and water, to remove the water, then to submit the assembly. thus obtained with a heat treatment ranging from 100 to 400 C. It is also possible to add an aqueous ammoniacal solution to the mixture of dianhydride, diamine and water, which makes it possible to obtain a more homogeneous mixture.
The new polyimides are suitable for many uses which require materials endowed with excellent thermal, chemical and electrical properties. They can be used for the preparation of films, sheets, insulating varnishes and enter into the composition of laminates and molded objects. They have interesting properties for bonding metals.
The following examples illustrate the invention and show how it can be put into practice. <I> Example 1 </I> A polyamide acid collodion is prepared by adding 1.671 g of benzoylpyromellic anhydride to a solution of 1.009 g of 4,4 'diamino-diphenyl ether in 14.118 g of dimethylacetamide and 0.0868 g of pyridine.
The collodion which has an inherent viscosity of 0.98 dl / g (measured at 25 in dimethylacetamide) is used to make an assembly of stainless steel specimens. For this, the test pieces are coated with collodion and then passed to an oven at 120 for 30 minutes and then assembled at 310 under a pressure of 8 kg / cm2 for 1 hour. These assemblies have a tensile shear strength of 210 kg / cm2 (measured according to ASTM D 1002-64). By way of comparison, the same assembly is carried out with a collodion obtained under the same conditions as above but by substituting the pyromellic anhydride for benzoylpyromellic anhydride. The new assembly offers zero tensile shear strength.
<I> Example 2 </I> An acid polyamide collodion is prepared by adding 8.523 g of dibenzoylpyromellic anhydride to a solution of 3.999 g of 4,4 'diamino-diphenyl ether in 50 g of anhydrous dimethylacetamide. This collodion is used to assemble stainless steel specimens. These prepared according to the procedure of Example 5 offer a tensile shear strength of 205 kg / cm2.
The benzoylpyromellic anhydrides used as a starting material were prepared as follows: Benzoylpyromellic acid a) 1,2,4,5-tetramethyl-3-benzoylbenzene 50 g of 1,2-tetramethyl are charged to a 1 liter flask. , 4.5 benzene, 58 g of benzoyl and 372 g of anhydrous carbon disulfide. Add in small portions, while maintaining the temperature between 15 and 25, 55 g of anhydrous aluminum chloride. During the addition, which lasts 50 minutes, hydrochloric acid is released in a decinormal solution. The reaction mass is filtered and the filtrate which settles out is separated into two layers. The organic layer is evaporated and the tetramethyl benzoylbenzene is recovered, in impure form.
The impure product is dissolved hot in 100 ml of butyl ether, then treated for 15 min at the boil with 5 g of animal charcoal. By hot filtration followed by cold crystallization, 75.45 of tetramethylbenzoylbenzene of mp: 123 is obtained.
b) 3-benzoyl-pyromellic acid 41.65 g of 1,2,4,5-tetramethyl-3-benzoyl-benzene are oxidized with 505 g of an aqueous solution of nitric acid at 300%. The test is carried out in a metal autoclave, maintaining the temperature for 2 h at 165-170. After cooling, the solution obtained is evaporated to give 58.4 g of a light yellow product corresponding to benzoylpyromellic acid (acidic strength: 1000 / a).
c) Benzoylpyromellic anhydride 8 g of benzoylpyromellic acid are dissolved in 30 ml of acetic anhydride. The mixture is brought to reflux, 100 ml of o-dichlorobenzene are added and the acetic acid / acetic anhydride mixture is distilled off. After addition of 5 g of animal charcoal, the mixture is kept at the boil for 15 min and a hot filtration is carried out. By cooling, a very light yellow product is obtained which is washed with ether. 5 g of product titrating 1000 / o of benzoylpyromellic anhydride (mp: 261 ′) are thus obtained.
Dibenzoylpyromellic acid a) Tetramethyl-1,2,4,5-dibenzoyl-3,6benzene 100 g of tetramethyl-1,2,4,5 benzene and 605 g of chloride of 2 .1 are charged to a flask with 2 .1. benzoyl. The medium having become homogeneous, 213.5 g of aluminum chloride are added in small portions. During the addition, which lasts 1 h 15 min, the temperature is raised from 40 to 95. Heating is continued by raising the temperature of the mass over 5 h 20 min from 95 to 135. Cooled to 50, 750 ml of ether poured in and the reaction mass filtered.
A gray precipitate is isolated which is purified by treatment with animal charcoal in acetic anhydride. 210 g of a white product melting at 275 are obtained; this product is tetramethyldibenzoyl-benzene. b) Dibenzoylpyromellic acid 60 g of tetramethyldibenzoyl-benzene and 505 g of 300/0 nitric acid are charged into a stainless steel autoclave. The autoclave is heated and maintained for 2 hours at 170. The solution is cooled and evaporated to dryness. 80.9 g of a light yellow solid are obtained, corresponding to dibenzoylpyromellic acid.
c) Dibenzoylpyromellic anhydride 80.9 g of dibenzoylpyromellic acid are dissolved in 350 ml of acetone. 350 ml of acetic anhydride are added to this solution and brought to the boil. The acetone is distilled off and maintained at reflux for 2 hours. After cooling, the precipitate is filtered off and washed with acetic anhydride and then with ether. This gives 41.6 g of light beige dibenzoylpyromellic anhydride which does not melt up to 365 C.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR178507 | 1968-12-16 | ||
| CH1859469A CH505778A (en) | 1968-12-16 | 1969-12-15 | Process for preparing benzoylpyromellic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH520172A true CH520172A (en) | 1972-03-15 |
Family
ID=25721307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH284971A CH520172A (en) | 1968-12-16 | 1969-12-15 | Benzelpyromillitic acids and their - polyimides |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH520172A (en) |
-
1969
- 1969-12-15 CH CH284971A patent/CH520172A/en not_active IP Right Cessation
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