Abstract: A process for preparing 1,1,1,3,3,3-hexafluoro-2,2-di(3,4-dicarboxyphenyl) propane anhydride is disclosed. 1,1,1,3,3,3-hexafluoro-2,2-di(3,4 -dimethylphenyl) propane is oxidized under liquid phase conditions in the presence of an oxygen-containing gas, bromine and heavy metal catalyst components to 1,1,1,3,3,3-hexafluoro-2,2-di(3,4-dicarboxyphenyl) propane in high yield. Addition of an anhydride of a low molecular weight carboxylic acid to the oxidation reaction mixture converts the 1,1,1-hexafluoro-2,2-di(3,4-dicarboxyphenyl)propane to 1,1,1,3,3,3-hexafluoro-2,2-di(3,4-dicarboxyphenyl) propane anhydride.

Abstract: 3,3'-Thiobis(2,5-dihydrothiophene-1,1-dioxides) on heating with a reactive Diels-Alder dienophile undergo a reaction producing thioethers having two six-membered alicyclic rings in the molecule, such as 4,4'-thiobis(3,6-dihydrophthalic acids) or the esters, anhydrides or imides thereof, and 4,4'-thiobis-(1,2,3,6-tetrahydrophthalic acids) or the esters, anhydrides or imides thereof. Both rings of the dihydrothiophene dioxides participate in the reaction, apparently by forming a tetraene structure which co-reacts with two equivalents of the dienophile to form an adduct in which each six-membered ring has one or two olefinic double bonds. During the course of the reaction, the thioether bridge remains intact. Some of the bis(alicyclic) thioethers are readily converted to the corresponding bis(aromatic)thioethers by use of known aromatization methods and systems. Various utilities for the products of the foregoing reactions are described.

Abstract: Symmetrical diaryl-acetylenes can be prepared by reacting an aryl halide with acetylene in the presence of a palladium catalyst and a base. If the acetylene is introduced into the liquid reaction mixture using a high intensity gas dispersion means, the aryl halide used can be an aryl bromide.

Abstract: An acid dianhydride complex which is characterized in anti-hydrolysis, good stability, and high solubility in an organic solvent, is prepared by a reaction of a basic organic compound having a donor number of at least 20 and being free from an active hydrogen atom in the molecule and a carboxylic dianhydride compound.

Abstract: A novel fluorine-containing aromatic compound of the formula: ##STR1## wherein X is ##STR2## in which R.sub.f is a perfluoroalkyl group having 1 to 10 carbon atoms,R.sub.f ' is a perfluoroalkyl group having 1 to 12 carbon atoms,p is an integer of 1 to 3,q is an integer of 0 to 3,r is 0 or 1,s is an integer of 0 to 5and t is an integer of 0 to 5,Y is X, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a fluoroalkyl group having 1 to 8 carbon atoms, andeach A is independently ##STR3## in which D is an amino, carboxyl, hydroxyl, methyl or haloformyl group, and n is an integer of 1 or 2, or ##STR4## can be used to derive various compounds, some of which are useful for preparing a fluorine-containing epoxy compound of polyimide with good properties.

Abstract: Partially fluorinated tetracarboxylic acid and the dianhydride thereof, a process for their preparation and their useA compound of the formula ##STR1## and the dianhydride thereof are prepared by air oxidation in the presence of a catalyst mixture composed of at least 2 heavy metal salts and also bromine in an acid organic medium. The compounds can be employed for the preparation of partially fluorinated polycondensates, such as polyimides, polycarboxamides, esters of polyamidecarboxylic acids, polyamides and imide-oligomers.

Abstract: A method for the preparation of acyloxyphthalic anhydride or oxydiphthalic anhydride which comprises the reaction of a halophthalic anhydride with an alkali metal salt and at least a catalytically effective amount of an acid or acid derivative selected from the group consisting of benzoic acids, substituted benzoic acids, benzoic acid salts or substituted benzoic acid salts, and hydrolyzable benzoyl esters, and hydrolyzable substituted benzoyl esters, alkyl carboxylic acids, hydrolyzable esters of alkyl carboxylic acids, and salts of alkyl carboxylic acids. The process may be conducted without solvent, in a polar solvent or in a non-polar solvent using a phase transfer catalyst.

Abstract: A process for the preparation of purified oxydiphthalic acid from impure oxydiphthalic anhydride, by treating with a mixture of water and propionic acid or butyric acid to produce oxydiphthalic acid. The acid may be treated to reform oxydiphthalic anhydride. The most effective composition range for the acid-water mixture is from about 25% acid to 75% acid.

Abstract: Aromatic tetracarboxylic acids or derivatives thereof of the general formula I ##STR1## in which R denotes a divalent radical of the formula II ##STR2## Ar denotes tri- or tetravalent aromatic radicals or mixtures thereof, X, if Ar is trivalent, denotes an amide radical, and if Ar is tetravalent denotes an imide radical, and Y and Z either together denote the anhydride radical --CO--O--CO-- or by themselves and independently of one another denote the radicals --COOH, --COCL or --COOR.sub.1, and a process for their preparation.

Abstract: Tetracarboxylic acid anhydrides represented by the following formulae [IA] and [IB] are provided: ##STR1## where n is an integer of 1 to 3. The tetracarboxylic acid anhydrides give polyimides having low thermal expansion, low dielectric constant and low hygroscopicity.

Abstract: A process for the production of diaryl ethers which comprises heating, to a temperature of 80.degree. C. to 220.degree. C., a compound of the formula ##STR1## wherein X and Y are selected from the group consisting of H, CN, CO.sub.2 H, CHO, NO.sub.2, and CF.sub.3, provided that both X and Y may not simultaneously be H, in a solvent, in the presence of an inorganic base selected from the group consisting of the alkali metal carbonates, bicarbonates, and hydroxides, and in the presence of a catalyst selected from the group consisting of benzoic acid, substituted benzoic acids, C2-C4 aliphatic carboxylic acids, and alkali metal salts of said acids.

Abstract: Novel halogenated polyimides and co-polyimides comprise recurring imide structural units of the formula ##STR1## where X is F, Cl, Br or I; Y is H, F, Cl, Br or I; and R is a divalent organic radical.

Abstract: A process is disclosed for preparation of anhydrides containing additional carboxylic acid moieties and dianhydrides of disubstituted maleic anhydride compounds wherein the acid anhydrides and dianhydrides retain their alkene character. The resulting alkene compounds are useful as precursors for polyesters, thermally stable polyamide-imides and polyimides which are also disclosed, as well as a process for their preparation.

Abstract: A process for dimerizing an aromatic halogen compound is disclosed, which comprises the step of: subjecting an aromatic halogen compound having at least one halogen atom bonded to an aromatic nucleus carbon to a dehalogenation-dimerization reaction in the presence of a catalyst, water, a reducing agent, and a halogen acceptor, the catalyst comprising a carrier supported thereon palladium and iron.

Abstract: Aromatic dianhydrides being substituted in the positions ortho to the bridging moiety, said substituent groups including halogen, alkyl, hydroxy, nitro, cyano, ester, alkoxy, perfluoroalkyl, mercapto and thioester groups, said dianhydrides providing certain beneficial properties to polyimides prepared therefrom.

Abstract: Highly pure 3,3',4,4'-biphenyltetracarboxylic acid (BPTA) and dianhydride thereof (BPDA) are produced by heating crude BPTA to give BPDA, treating the BPDA with hot water to give highly pure BPTA, and in the case of highly pure BPDA, heat treating the pure BPTA to give highly pure BPDA.

Abstract: Oxydiphthalic anhydrides of the formula ##STR1## are prepared by reacting a halophthalic anhydride with potassium carbonate in:(1) a solvent-free reaction medium wherein the molar ratio of halophthalic anhydride:potassium carbonate is greater than 2:1; or(2) a high boiling solvent which improves the mixing of the components, and aids in subsequent purification of the product. The molar ratio of halophthalic anhydride to potassium carbonate is about 1.5:1 or greater.The oxydiphthalic anhydride can be purified by filtering or centrifuging a hot solution of the oxydiphthalic anhydride in a high boiling solvent to remove impurities, followed by cooling the solution to precipitate the oxydiphthalic anhydride, which can be removed from the solution by filtration or centrifuging.

Abstract: A process is disclosed for preparation of anhydrides containing additional carboxylic acid moieties and dianhydrides of disubstituted maleic anhydride compounds wherein the acid anhydrides and dianhydrides retain their alkene character. The resulting alkene compounds are useful as precursors for polyesters, thermally stable polyamide-imides and polyimides which are also disclosed, as well as a process for their preparation.

Abstract: Dioxydiphthalic anhydride is prepared by the reaction of dihalophthalic anhydride with an alkali metal compound, such as potassium carbonate. The compound is particularly useful as a monomer in the preparation of polyimides.

Abstract: Novel polyimides and co-polyimides are prepared by the condensation polymerization of an aryl diamine with dioxydiphthalic anhydride or a mixture thereof with oxydiphthalic anhydride. The polyimides and co-polyimides prepared exhibit a low moisture absorption and improved dielectric properties and can be tailored to provide a composition having desirable mechanical properties, specifically, rigidity.

Abstract: A process for the preparation of high-purity perfluorinated compounds, specifically of an aromatic tetracarboxylic acid and its anhydride, 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)-ethylidene]bis-1,3-isobenzofuran dione, by a multi-step treatment of the crude compounds. The metal ion content of the compounds treated is reduced considerably. After polymerization with an aromatic diamine, the anhydride is used in microelectronics.

Abstract: Polyimides made by reacting 1,2-acetylene-4,4'-di(phthalic anhydride) with an aromatic diamine are useful in high temperature applications that require solvent resistance. Applications include components of combustion engines.

Abstract: High purity crystals of a biphenyltetracarboxylic dianhydride produced by dehydration of a biphenyltetracarboxylic acid, which contain almost no biphenyltricarboxylic acid or its anhydride, or a small amount such as an amount of not more than 0.2 wt. %, are of value to produce an aromatic polyamic acid or polyimide having an increased high molecular weight. The high purity crystals of a biphenyltetracarboxylic dianhydride can be prepared from a biphenyltetracarboxylic acid by a dehydration process wherein the biphenyltetracarboxylic acid is heated under carefully controlled conditions.

Abstract: An improved method for making biaryl compounds is disclosed, in which an aromatic acid halide having at least one strong electron-withdrawing group attached to or within the aromatic ring is reacted with at least one polysilane in the presence of an effective amount of a transition metal catalyst.

Abstract: Oxydiphthalic anhydride is prepared by reacting an hydroxyphthalic anhydride with a bromophthalic or fluorophthalic anhydride and potassium fluoride in the presence of a solvent and a copper catalyst.

Abstract: Oxydiphthalic anhydrides are prepared by reacting a halophthalic anhydride with water and an alkali metal compound such as KF, CsF, or K.sub.2 CO.sub.3 in the presence of a copper catalyst.

Abstract: Novel halo-oxydiphthalic anhydrides are of the formula ##STR1## where X is F, Cl, Br, or I; X' is H, F, Cl, Br, or I.

Abstract: Disclosed are a para- or meta-terphenyl-3,4,3",4"-tetracarboxylic acid or a dianhydride and a process for preparing the same. The para- or meta-terphenyl-3,4,3",4"-tetracarboxylic acid or a dianhydride thereof according to the present invention is a novel compound which is useful as a raw material for a polyimide having higher heat resistance and so on.

Abstract: Process for the purification of organic polyanhydrides to substantially-completely remove trace metals, such as for the production of metal-free electronic grade polymers. The process comprises decyclizing in an aqueous vehicle to form the polyacid, treating with an adsorption agent, crystallizing the polyacid, filtering and reconverting to the polyanhydride which is substantially free of trace metals. The purified polyanhydride can be reacted with other metal-free monomers to form metal-free polymers having excellent insulating properties for use in electrical components.

Abstract: Synthetic procedures to tetraalkyls, tetraacids and dianhydrides substituted 1,1,1-triaryl-2,2,2-trifluoroethanes which comprises: (1) 1,1-bis(dialkylaryl)-1-aryl-2,2,2-trifluoroethane, (2) 1,1-bis(dicarboxyaryl)-1-aryl-2,2,2-trifluoroethane or (3) cyclic dianhydride or diamine of 1,1-bis(dialkylaryl)-1-aryl-2,2,2-trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Abstract: Oxydiphthalic anhydrides of the formula ##STR1## are prepared by reacting a halophthalic anhydride with potassium carbonate in:(1) a solvent-free reaction medium wherein the molar ratio of halophthalic anhydride:potassium carbonate is greater than 2:1; or(2) a high boiling solvent which improves the mixing of the components, and aids in subsequent purification of the product. The molar ratio of halophthalic anhydride to potassium carbonate is about 1.5:1 or greater.The oxydiphthalic anhydride can be purified by filtering or centrifuging a hot solution of the oxydiphthalic anhydride in a high boiling solvent to remove impurities, followed by cooling the solution to precipitate the oxydiphthalic anhydride, which can be removed from the solution by filtration or centrifuging.

Abstract: Diether diphthalic anhydrides are prepared by reacting fluorophthalic anhydride with an aromatic dihydroxyl compound in the presence of potassium fluoride and a polar, aprotic solvent.

Abstract: Fluorinated aromatic hydrocarbons including fluorinated aromatic carboxylic acids fluorinated aromatic dianhydrides and fluorinated aromatic dialkyl esters that serve as precursor monomers for high temperature fluorinated polyimides. The fluorinated aromatic carboxylic acid monomer comprises: ##STR1## wherein X is hydrogen, carboxyl, sulfonic acid, hydroxy, alkyl, halogen or nitro and hydrates of said acids. The fluorinated aromatic dianhydride monomer comprises: ##STR2## wherein x is hydrogen, carboxyl, sulfonic acid, hydroxy, alkyl, halogen or nitro. The fluorinated aromatic dialkyl ester monomer comprises: ##STR3## wherein X is hydrogen, carboxyl, sulfonic acid, hydroxy, alkyl, halogen or nitro and Y is an alkyl group and hydrates of said esters.

Abstract: Spiro(bis)indane bis-oxyphthalic acid bisimides are prepared by the reaction of a nitro- or halo-substituted phthalimide with a salt of a 6,6'-dihydroxy-3,3,3'3'-tetramethylspiro(bis)indane. The bisimides may be converted to the corresponding dianhydrides, which react with diamines to form polyetherimides, or to the free tetracarboxylic acids or their salts, esters or amides.

Abstract: Oxy-diphthalic anhydrides are prepared by reacting a halophthalic anhydride with an hydroxyphthalic anhydride in a polar aprotic solvent and in the presence of an alkali metal compound such as KF, CsF or K.sub.2 CO.sub.3.

Abstract: Oxydiphthalic anhydride is prepared by effecting contact between a substituted phthalic anhydride such as 4-nitro or 4-fluoro phthalic anhydride and a dialkylaminopyridine in the presence of a refluxing nonpolar organic solvent.

Abstract: 3,3'-Thiobis(2,5-dihydrothiophene-1,1-dioxides) on heating with a reactive Diels-Alder dienophile undergo a reaction producing thioethers having two six-membered alicyclic rings in the molecule, such as 4,4'-thiobis(3,6-dihydrophthalic acids) or the esters, anhydrides or imides thereof, and 4,4'-thiobis(1,2,3,6-tetrahydrophthalic acids) or the esters, anhydrides or imides thereof. Both rings of the dihydrothiophene dioxides participate in the reaction, apparently by forming a tetraene structure which co-reacts with two equivalents of the dienophile to form an adduct in which each six-membered ring has one or two olefinic double bonds. During the course of the reaction, the thioether bridge remains intact. Some of the bis(alicyclic) thioethers are readily converted to the corresponding bis(aromatic)thioethers by use of known aromatization methods and systems. Various utilities for the products of the foregoing reactions are described.

Abstract: Bis(dialkyl aromatic ether anhydride) is provided which can be melt polymerized with organic diamine to high performance polyetherimide having improved heat distortion temperatures.

Abstract: Synthetic procedures to tetraalkyls, tetraacids and dianhydrides substituted 1,1,1-triaryl-2,2,2-trifluoroethanes which comprises: (1) 1,1-bis(dialkylaryl)-1-aryl-2,2,2-trifluoroethane, (2) 1,1-bis(dicarboxyaryl)-1-aryl-2,2,2-trifluoroethane or (3) cyclic dianhydride or diamine of 1,1-bis(dialkylaryl)-1-aryl-2,2,2-trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Abstract: Oxy-diphthalic anhydrides are prepared by reacting a halophthalic anhydride with water and an alkali metal compound such as KF, CsF or K.sub.2 CO.sub.3 in the presence of a polar, aprotic solvent.

Abstract: A method is provided for making thioether-(bisphthalimide)s from an alkali metal hydrogen sulfide and an N-organo substituted halophthalimide or nitrophthalimide.

Abstract: Novel phthalic acid derivatives are described which are substituted by 2-propynyloxy groups, of the formula I ##STR1## in which Q.sub.1, and Q.sub.2 independently of one another are --OH or --O.sup.- M.sup.+, or Q.sub.1 and Q.sub.2 together form the grouping --O--, [O.sup.- ].sub.2 M.sub.1.sup.++ or --N(R.sub.2)--, M.sup.+ is an alkali metal ion, a trialkyl ammonium ion having 3-24 carbon atoms or a quaternary ammonium ion and M.sub.1.sup.++ is an alkaline earth metal ion, R.sub.2 is an alkyl group or an unsubstituted or substituted aryl group, n is 1 or 2 and R.sub.1 is hydrogen, if n is 1, or a direct bond, if n is 2, are described. The phthalic anhydrides which are substituted by 2-propynyloxy, of the formula I, can be used for curing epoxy resins, cured products with outstanding physical properties being obtained.

Abstract: Aryl-diethers are provided which are produced by reacting a halogenated xylene compound, preferably 4-chloro-ortho-xylene, and an alkali metal salt of a bisphenol compound, preferably bisphenol-A. These aryl-diethers serve as precursors in a process for producing polyetherimide polymers.

Abstract: Aromatic polycarboxylic acids and their anhydrides such as bisphenol A dianhydride are prepared from the corresponding polycarboximides, such as bisphenol A bisimide, by an exchange reaction with phthalic acid or phthalic anhydride and water in the presence of dimethyl-n-butylamine as an exchange catalyst. The use of this amine results in the formation of a product of decreased color, as compared with the use of triethylamine.

Abstract: A method is described for autoxidizing a novel class of bis(ortho dialkyl-phenoxy)benzophenones directly to their corresponding dianhydrides. The method comprises autoxidizing the benzophenones in a solution of an aliphatic monocarboxylic acid having 3 to 8 carbon atoms with oxygen in the presence of a heavy metal oxidation catalyst and a promoter at a temperature of at least about 120.degree. C. to form the dianhydride.The dianhydrides are used in the preparation of organic high temperature polymers such as polyetherimides.

Abstract: A method is provided for making aromatic bis(ether anhydrides) by effecting an exchange reaction between aromatic bis(ether imide) and phthalic anhydride in the presence of water and an exchange catalyst. The separation and recovery of phthalimide and aromatic bis(ether anhydride) is achieved in a stripper-reactor using a vaporous mixture of water and the exchange catalyst.

Abstract: 5-Fluorobenzoxazinones (I) ##STR1## where R is hydrogen, halogen, C.sub.1 -C.sub.3 -alkyl, or trifluoromethyl, trifluoromethoxy, chlorodifluoromethoxy, difluoromethoxy, tetrafluoroethoxy, trifluoromethylmercapto or chlorodifluoromethylmercapto in the m- or p-position, are prepared by reacting the corresponding benzoxazinone (II) ##STR2## in particular one which is 5-chloro-substituted or 5-bromo-substituted, with a fluoride, in particular potassium fluoride, in the presence or absence of a solvent, by a process in which the reaction is carried out in the absence of water or using previously dried starting materials, and in the presence or absence of a decomposition inhibitor, drying preferably being carried out by treatment with an acid halide, e.g. thionyl chloride, and the inhibitor used being a metal iodide, e.g. sodium iodide, or iodine.

Abstract: Novel di(phthalic anhydride) derivatives of di(dialkylphenol) sulfones of the following formula are disclosed: ##STR1## These dianhydrides can be reacted with organic diamines to form novel polyetherimide polymers having particularly beneficial properties.

Abstract: A method is described for autoxidizing ortho-dialkyl substituted aromatic ethers directly to their corresponding carboxylic acid anhydrides. The method comprises autoxidizing the ethers in a first step in a solution of an aliphatic monocarboxylic acid having 2 to 8 carbon atoms to form a partially oxidized reaction mixture. The autoxidation of the partially oxidized mixture is continued in a second step after the addition of an anhydride of an aliphatic monocarboxylic acid having 3 to 8 carbon atoms and at a temperature of at least 130.degree. C. to form said anhydrides.The anhydrides are used in the preparation of organic high temperature polymers such as polyamideimides, polyimides, polyetherimides, and polyetherimideamides.

Abstract: Novel di(phthalic anhydride) derivatives of di(dialkylphenol) sulfones of the following formula are disclosed: ##STR1## These dianhydrides can be reacted with organic diamines to form novel polyetherimide polymers having particularly beneficial properties.