The United States of America As Represented by the Administrator of the

United States of America As Represented by the Administrator of Nasa

The United States of America As Represented by the United States

The United States of America As Represented by the Administrator

The United States of America

The United States of America As Represented by the Administrator of

Paul M Hergenrother

John W Connell

Joseph G Smith, Jr

Brian J Jensen

Stephen J Havens

Robert G Bryant

Robert G Bass

Kent A Watson

Peter Wolf

Mark S Sinsky

R Gerald Bass

Craig M Thompson

Frank Wayne Harris

Terry L St Clair

Mark W Beltz

Joesph G Smith, Jr

Hans M Mark

Polyimides displaying low color in thin films, atomic oxygen resistance, vacuum ultraviolet radiation resistance, solubility in organic solvents in the imide form, high glass transition (T) temperatures, and high thermal stability are provided. The poly(amide acid)s, copoly(amide acid)s, polyimides and copolyimides are prepared by the reaction of stoichiometric ratios of an aromatic dianhydride with diamines which contain phenylphosphine oxide groups in polar aprotic solvents. Controlled molecular weight oligomeric (amide acid)s and imides can be prepared by offsetting the stoichiometry according to the Carothers equation using excess diamine and endcapping with aromatic anhydrides. The polyimide materials can be processed into various material forms such as thin films, fibers, foams, threads, adhesive film, coatings, dry powders, and fiber coated prepreg, and uses include thin film membranes on antennas, second-surface mirrors, thermal optical coatings, and multi-layer thermal insulation (MLI) blanket materials.

Space environmentally durable polyimides and copolyimides

The present invention relates generally to polyimides. It relates particularly to novel polyimides prepared from 2,3,3',4&#x2032;-biphenyltetracarboxylic dianhydride and aromatic diamines. These novel polyimides have low color, good solubility, high thermal emissivity, low solar absorptivity and high tensile strength.

Polyimides from 2,3,3',4&#x2032;-biphenyltetracarboxylic dianhydride and aromatic diamines

Polyimides displaying low color in thin films, atomic oxygen resistance, vacuum ultraviolet radiation resistance, solubility in organic solvents in the imide form, high glass transition (T) temperatures, and high thermal stability are provided. The poly(amide acid)s, copoly(amide acid)s, polyimides and copolyimides are prepared by the reaction of stoichiometric ratios of an aromatic dianhydride with diamines which contain phenylphosphine oxide groups in polar aprotic solvents. Controlled molecular weight oligomeric (amide acid)s and imides can be prepared by offsetting the stoichiometry according to the Carothers equation using excess diamine and endcapping with aromatic anhydrides The polyimide materials can be processed into various material forms such as thin films, fibers, foams, threads, adhesive film, coatings, dry powders, and fiber coated prepreg, and uses include thin film membranes on antennas, second-surface mirrors, thermal optical coatings, and multi-layer thermal insulation (MLI) blanket materials.

Phenylethynyl containing reactive additives were prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride and 4-phenylethynylphthalic anhydride in glacial acetic acid to form the imide in one step or in N-methyl-2-pyrrolidinone to form the amide acid intermediate. The reactive additives were mixed in various amounts (10% to 90%) with oligomers containing either terminal or pendent phenylethynyl groups (or both) to reduce the melt viscosity and thereby enhance processability. Upon thermal cure, the additives react and become chemically incorporated into the matrix and effect an increase in crosslink density relative to that of the host resin. This resultant increase in crosslink density has advantageous consequences on the cured resin properties such as higher glass transition temperature and higher modulus as compared to that of the host resin.

Phenylethynyl containing reactive additives

A composition of and method for making high performance imide resins that are processable by resin transfer molding (RTM) and resin infusion (RI) techniques were developed. Materials with a combination of properties, making them particularly useful for the fabrication of composite parts via RTM and/or RI processes, were prepared, characterized and fabricated into moldings and carbon fiber reinforced composites and their mechanical properties were determined. These materials are particularly useful for the fabrication of structural composite components for aerospace applications. The method for making high performance resins for RTM and RI processes is a multi-faceted approach. It involves the preparation of a mixture of products from a combination of aromatic diamines and aromatic dianhydrides at relatively low calculated molecular weights (i.e. high stoichiometric offsets) and endcapping with latent reactive groups. The combination of these monomers results in a mixture of products, in the imide form, that exhibits a stable melt viscosity of less than approximately 60 poise below approximately 300&deg; C.

Composition of and method for making high performance resins for infusion and transfer molding processes

High temperature resins containing phenylethynyl groups that are processable by transfer molding have been prepared. These phenylethynyl containing oligomers were prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride and 4-phenylethynlphthalic anhydride in glacial acetic acid to form a mixture of imide compounds in one step. This synthetic approach is advantageous since the products are a mixture of compounds and consequently exhibit a relatively low melting temperature. In addition, these materials exhibit low melt viscosities which are stable for several hours at 210-275.degree. C., and since the thermal reaction of the phenylethynyl group does not occur to any appreciable extent at temperatures below 300.degree. C., these materials have a broad processing window. Upon thermal cure at .about.300-350.degree. C., the phenylethynyl groups react to provide a crosslinked resin system. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

High temperature transfer molding resins

Controlled molecular weight phenylethynyl terminated imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with phenylethynyl phthalic anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydride(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

Imide oligomers endcapped with phenylethynl phthalic anhydrides and

Controlled molecular weight imide oligomers and co-oligomers containing pendent phenylethynyl groups (PEPIs) and endcapped with nonreactive or phenylethynyl groups have been prepared by the cyclodehydration of the precursor amide acid oligomers or co-oligomers containing pendent phenylethynyl groups and endcapped with nonreactive or phenylethynyl groups. The amine terminated amide acid oligomers or co-oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and diamine containing pendent phenylethynyl groups and subsequently endcapped with a phenylethynyl phthalic anhydride or monofunctional anhydride. The anhydride terminated amide acid oligomers and co-oligomers are prepared from the reaction of diamine(s) and diamine containing pendent phenylethynyl group(s) with an excess of dianhydride(s) and subsequently endcapped with a phenylethynyl amine or monofunctional amine. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone and N,N-dimethylacetamide under nitrogen at room temperature. The amide acid oligomers or co-oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. The polymers and copolymers prepared from these materials exhibit a unique and unexpected combination of properties that includes higher glass transition temperatures after curing and higher retention of neat resin, adhesive and carbon fiber reinforced mechanical properties at temperatures up to 204.degree. C. under wet conditions without sacrificing melt flow behavior and processability as compared to similar materials. These materials are useful as adhesives, coatings, films, moldings and composite matrices.

Diamines containing pendent phenylethynyl groups

Phenylethynyl phthalic anhydride

Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Polybenzimidazoles via aromatic nucleophilic displacement

Controlled molecular weight imide oligomers and co-oligomers containing pendent phenylethynyl groups (PEPIs) and endcapped with nonreactive or phenylethynyl groups have been prepared by the cyclodehydration of the precursor amide acid oligomers or co-oligomers containing pendent phenylethynyl groups and endcapped with nonreactive or phenylethynyl groups. The amine terminated amide acid oligomers or co-oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and diamine containing pendent phenylethynyl groups and subsequently endcapped with a phenylethynyl phthalic anhydride or monofunctional anhydride. The anhydride terminated amide acid oligomers and co-oligomers are prepared from the reaction of diamine(s) and diamine containing pendent phenylethynyl group(s) with an excess of dianhydride(s) and subsequently endcapped with a phenylethynyl amine or monofunctional amine. The polymerizations are carried out in polar aprotic solvents such as under nitrogen at room temperature. The amide acid oligomers or co-oligomers are subsequently cyclodehydrated to the corresponding imide oligomers. The polymers and copolymers prepared from these materials exhibit a unique and unexpected combination of properties.

Imide oligomers and co-oligomers containing pendent phenylethynyl groups

Four phenylethynyl amine compounds--3 and 4-aminophenoxy-4'-phenylethynylbenzophenone, and 3 and 4-amino-4'-phenylethynylbenzophenone--were readily prepared and were used to endcap imide oligomers. Phenylethynyl-terminated amide acid oligomers and phenylethynyl-terminated imide oligomers with various molecular weights and compositions were prepared and characterized. These oligomers were cured at 300.degree. C. to 400.degree. C. to provide crosslinked polyimides with excellent solvent resistance, high strength and modulus and good high temperature properties. Adhesive panels, composites, films and moldings from these phenylethynyl terminated imide oligomers gave excellent mechanical performance.

Phenylethynyl amine

Imide oligomers endcapped with phenylethynyl phthalic anhydrides and

Novel poly(N-arylenebenzimidazole)s (PNABls) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl-N-arylenebenzimidazole) monomers are synthesized by reacting phenyl-4-hydroxybenzoate with bis(2-aminoanilino)arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyI-N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.

Growing community of inventors

Yorktown, VA, United States of America

Paul M Hergenrother