Oxygen plasma resistant phosphine oxide containing imide/arylene copolymers

A series of oxygen plasma resistant imide/arylene ether copolymers were prepared by reacting anhydride-terminated poly(amide acids) and amine-terminated polyarylene ethers containing phosphine oxide units. Inherent viscosities for these copolymers ranged from 0.42 to 0.80 dL/g. After curing, the resulting copolymers had glass transition temperatures ranging from 224 C to 228 C. Solution cast films of the block copolymers were tough and flexible with tensile strength, tensile moduli, and elongation at break up to 16.1 ksi, 439 ksi, and 23 percent, respectively at 25 C and 9.1 ksi, 308 ksi and 97 percent, respectively at 150 C. The copolymers show a significant improvement in resistance to oxygen plasma when compared to the commercial polyimide Kapton. The imide/arylene ether copolymers containing phosphine oxide units are suitable as coatings, films, adhesives, and composite matrices

Effect of molecular weight on polyphenylquinoxaline properties

A series of polyphenyl quinoxalines with different molecular weight and end-groups were prepared by varying monomer stoichiometry. Thus, 4,4'-oxydibenzil and 3,3'-diaminobenzidine were reacted in a 50/50 mixture of m-cresol and xylenes. Reaction concentration, temperature, and stir rate were studied and found to have an effect on polymer properties. Number and weight average molecular weights were determined and correlated well with viscosity data. Glass transition temperatures were determined and found to vary with molecular weight and end-groups. Mechanical properties of films from polymers with different molecular weights were essentially identical at room temperature but showed significant differences at 232 C. Diamine terminated polymers were found to be much less thermooxidatively stable than benzil terminated polymers when aged at 316 C even though dynamic thermogravimetric analysis revealed only slight differences. Lower molecular weight polymers exhibited better processability than higher molecular weight polymers

Imide/arylene ether copolymers with pendent trifluoromethyl groups

A series of imide/arylene ether block copolymers were prepared using an arylene ether block containing a hexafluoroisopropylidene group and an imide block containing a hexafluoroisopropylidene and a trifluoromethyl group in the polymer backbone. The copolymers were characterized and mechanical properties were determined and compared to the homopolymers

LaRC-ITPI/arylene ether copolymers

As part of an effort to develop high performance structural resins for aerospace applications, work has continued on block copolymers containing imide and arylene ether segments. The arylene ether block used in this study contains a bulky fluorene group in the polymer backbone while the imide block contains an arylene ketone segment similar to that in the arylene ether block and has been named LaRC-ITPI. A series of imide/arylene ether block and segmented copolymers were prepared and characterized. Films were prepared from these copolymers and mechanical properties were measured

Imide/Arylene Ether Copolymers

Three different series of imide/arylene ether block copolymers were prepared using two different imide blocks and two different arylene ether blocks. Block molecular weights studied were 3110 and 6545 g/mole for each block and all four combinations possible were prepared in each series. Also, several segmented copolymers were prepared by forming the imide segment and the copolymer in the presence of the pre-formed arylene ether block. Two amine-terminated poly(arylene ether) blocks (ATPAE) were prepared by reacting 1,3-bis(4-fluorobenzoyl)benzene with either 2,2-bis(4-hydroxyphenyl)propane (BPA) or 9,9-bis(4-hydroxyphenyl)fluorene (BPF) and 4-aminophenol. Two anhydride-terminated poly(amic acid) blocks were prepared by reacting 4,4\u27-oxydianiline (ODA) or 1,3-bis(4-aminophenoxy-4’- benzoyl)benzene (BABB) with 3,3\u27,4,4\u27-benzophenonetetracarboxylic dianhydride (BTDA). The ATPAEs were reacted with the anhydride- terminated poly(amic acids) to provide block copolymers which were either thermally or solution imidized. Thermal imidization was accomplished by heating 1 h each at 100, 200 and 300°C while solution imidization was accomplished by adding toluene to the reaction, heating to 155°C overnight and collecting the toluene/water azeotropic mixture in a Dean-Stark trap. Some of the block copolymers displayed two Tgs indicating incomptability and phase separation, especially for the higher molecular weight blocks. The copolymer series preapred by reacting the ATPAE (BPA) blocks with the ODA/BTDA blocks in N,N-dimethylacetamide (DMAc) had inherent viscosities as high as 1.37 dL/g. The copolymer series prepared by reacting ATPAE (BPA) blocks with BABB/BTDA blocks in DMAc or N-methyl- pyrrolidinone (NMP) had inherent viscosities as high as 1.73 dL/g. The copolymer series prepared by reacting ATPAE (BPF) blocks with BABB/BTDA blocks in DMAc, NMP or m-cresol had inherent viscosities as high as 1.08 dL/g. The copolymers were characterized by differential scanning calorimetry (DSC), torsional braid analysis (TBA), thermogravimetric analysis (TGA) and wide angle x-ray diffraction (the BABB/BTDA imide is semi-crystalline). Mechanical properties were measured on copolymer films and fracture energies were measured on moldings. One copolymer was end-capped at a controlled molecular weight to improve processing and evaluated as an adhesive and graphite composite matrix. The chemistry and properties of the copolymers will be discussed and compared to those of the homopolymers

Imide/arylene ether copolymers

Imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly(arylene ethers) in polar aprotic solvents and by chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The resulting block copolymers have one glass transition temperature or two, depending upon the particular structure and/or the compatibility of the block units. Most of these block copolymers form tough, solvent resistant films with high tensile properties

High-Performance Polymers Having Low Melt Viscosities

High-performance polymers that have improved processing characteristics, and a method of making them, have been invented. One of the improved characteristics is low (relative to corresponding prior polymers) melt viscosities at given temperatures. This characteristic makes it possible to utilize such processes as resin-transfer molding and resin-film infusion and to perform autoclave processing at lower temperatures and/or pressures. Another improved characteristic is larger processing windows that is, longer times at low viscosities. Other improved characteristics include increased solubility of uncured polymer precursors that contain reactive groups, greater densities of cross-links in cured polymers, improved mechanical properties of the cured polymers, and greater resistance of the cured polymers to chemical attack. The invention is particularly applicable to poly(arylene ether)s [PAEs] and polyimides [PIs] that are useful as adhesives, matrices of composite materials, moldings, films, and coatings. PAEs and PIs synthesized according to the invention comprise mixtures of branched, linear, and star-shaped molecules. The monomers of these polymers can be capped with either reactive end groups to obtain thermosets or nonreactive end groups to obtain thermoplastics. The synthesis of a polymeric mixture according to the invention involves the use of a small amount of a trifunctional monomer. In the case of a PAE, the trifunctional monomer is a trihydroxy- containing compound for example, 1,3,5-trihydroxybenzene (THB). In the case of a PI, the trifunctional monomer is a triamine for example, triamino pyrimidine or melamine. In addition to the aforementioned trifunctional monomer, one uses the difunctional monomers of the conventional formulation of the polymer in question (see figure). In cases of nonreactive end caps, the polymeric mixtures of the invention have melt viscosities and melting temperatures lower than those of the corresponding linear polymers of equal molecular weights. The lower melting temperatures and melt viscosities provide larger processing windows. In cases of reactive end caps, the polymeric mixtures of the invention have lower melt viscosities before curing and the higher cross-link densities after curing (where branching in the uncured systems would become cross-links in the cured systems), relative to the corresponding linear polymers of equal molecular weights. The greater cross-link densities afford increased resistance to chemical attack and improved mechanical properties

Processable Polyimides Containing APB and Reactive End Caps

Imide copolymers that contain 1,3- bis(3-aminophenoxy)benzene (APB) and other diamines and dianhydrides and that are terminated with appropriate amounts of reactive end caps have been invented. The reactive end caps investigated thus far include 4-phenylethynyl phthalic anhydride (PEPA), 3- aminophenoxy-4-phenylethynylbenzop henone (3-APEB), maleic anhydride (MA), and 5-norbornene-2,3-dicarboxylic anhydride [also known as nadic anhydride (NA)]. The advantage of these copolyimides terminated with reactive groups, relative to other polyimides terminated with reactive groups, is a combination of (1) higher values of desired mechanical-property parameters and (2) greater ease of processing into useful parts

Thermal characterization and toughness of ethynyl containing blends

As part of an effort to develop high performance structural resins with an attractive combination of properties for aerospace applications, a series of ethynyl-terminated polysulfones of different molecular weights were prepared and blended with a low molecular weight ethynyl-terminated coreactant. Upon heating above 200 C, these ethynyl containing materials react to form a chain extended and crosslinked network structure. This reaction renders the materials insoluble in common solvents, but also reduces the toughness as compared to high molecular weight linear polysulfones. The thermal characterization of these blends and the toughness of the resulting cured materials are discussed