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Havens, S. J.

Publications and source records attributed to Havens, S. J..

Polyimides containing pendent trifluoromethyl groups

Several new polyimides containing trifluoromethyl groups were prepared from the reaction of various aromatic dianhydrides and two new diamines containing trifluoromethyl groups, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)biphenyl and l,4-bis(3-amino-5-trifluoromethylphenoxy)benzene. The diamines were prepared from the aromatic nucleophilic displacement of the disodium salts of 4,4'-biphenol or hydroquinone with 3,5-dinitrobenzotrifluoride followed by hydrogenation of the resultant dinitro compounds. The thermally cured polyimides exhibited glass transition temperatures between 186 and 262 C. By thermogravimetric analysis, the polyimides exhibited 5 percent weight losses at 484-527 C in nitrogen and 452-506 C in air.

Havens, S. J.

Polyamideimides containing carbonyl and ether connecting groups

Polyamidenimides were prepared from the reaction of trimellitic anhydride chloride with seven diamines containing carbonyl and ether groups between the aromatic rings. Several of these polyamideimides were semicrystalline as evidenced by wide-angle X-ray diffraction and differential scanning calorimetry. Glass transition temperatures ranged between 187 and 245 C, and crystalline transition temperatures ranged between 317 and 416 C. A series of copolyamideimides from a mixture of 1,3-bis(4-aminophenoxy 4-prime-benzoyl) benzene and 1,4-bis(4-aminophenoxy 4-prime-benzoyl)benzene were similarly prepared. These copolyamideimides were semicrystalline and formed tough, solvent resistant films with good tensile properties.

Havens, S. J.

Polyimides containing carbonyl and ether connecting groups - II

In a study of polyimides containing carbonyl and ether connecting groups between aromatic rings, several new polyimides were prepared and characterized. A few of these polymers were semicrystalline. Glass transition temperatures ranged from 164 to 258 C, and crystalline melt temperatures were observed between 350 and 424 C. The semicrystalline polyimide from the reaction of 3.3',4,4'-benzophenonetetracarboxylic dianhydride and 1,3-bis(4-aminophenoxy-4'-benzoyl)benzene provided transparent orange films with excellent tensile properties, exceptional resistance to solvents and strong base, and high thermooxidative stability. In addition, this polyimide provided excellent adhesive strength for joining titanium (6Al-4V) to titanium.

Hergenrother, P. M.

LARC-CPI, a new semi-crystalline polyimide

As part of a program on high performance/high temperature structural resins for aerospace applications, work was performed with a new semi-crystalline polyimide (LARC-CPI) to improve the compression moldability while retaining high mechanical properties and thermooxidative stability. Various molecular weight versions of LARC-CPI polyamide acid were prepared, end-capped with different groups, converted to polyimide and evaluated for film properties, thermooxidative stability and melt flow. One controlled molecular weight, end-capped version of LARC-CPI was evaluated more comprehensively in adhesive and composite work and exhibited good compression moldability, reasonable crystallization rates and high mechanical properties.

Hergenrother, P. M.

Adhesive properties of LARC-CPI, a new semi-crystalline polyimide

As part of an effort on high temperature structural resins for aerospace applications, a new family of polyimides containing carbon and ether connecting groups between aromatic rings were prepared. Several of these polyimides were semicrystalline. One polyimide, designated LARC-CPI, with a glass transition temperature of 222 C and a crystalline melt temperature of 350 C, was evaluated in the form of an adhesive, film, and molding. Unoriented films exhibited excellent resistance to solvents and strong bases and high tensile properties. Compact tension specimens gave very high fracture toughness values. Titanium tensile shear specimens provided exceptional strength under a variety of test conditions. The chemistry and the physical and mechanical properties of LARC-CPI are discussed.

Hergenrother, P. M.

Adhesive properties of a semi-crystalline polyimide

Adhesive and film properties of a new semi-crystalline polyimide, designated LARC-CPI, having a glass transition temperature of 222 C and a crystalline melt temperature of 350 C are presented. The films exhibited excellent resistance to solvents and strong base. Compact tension specimens from LARC-CPI moldings displayed a fracture energy of 37.8 lb/sq in. Titanium tensile shear specimens gave strengths of 6250 psi initially at 25 C, 7120 psi at 25 C after 1000 hours at 232 C, 2800 psi at 232 C after annealing for 5 hours at 300 C, and 3670 psi at 232 C after 100 hours at 316 C in air.

Hergenrother, P. M.

Polyarylene Ethers with Improved Properties

This invention relates to novel polyarylene ethers which possess the combination of high strength, toughness, and high use temperature with ease of extrusion and formation into complex objects. These polyarylene ethers are suitable for use in adhesives, coatings, films, membranes, and composite matrices. The polyarylene ethers of this invention are the polycondensation products from the reaction of either 1,3-bis (4-chloro or fluorobenzoyl) benzene with any one of the following bisphenolic compounds: bis (3-hydroxyphenyl) methane; bis (4-hydroxyphenyl) methane; 1,1-dimethyl-bis (4-hydroxyphenyl)methane, or 9,9-bis (4-hydroxyphenyl) fluorene. Random and block copolymers are also comprehended.

Hergenrother, P. M.

New polyarylene ethers

A series of new polyarylene ethers (PAEs) were prepared from the reaction of activated dihalo compounds with various bisphenols. Measured number average molecular weights for the PAEs ranged from 13,500 to 39,400 g/mole, and glass transition temperatures varied from 152 to 280 C. Ethynyl-terminated polyarylene ethers (ETPAEs) were also prepared by endcapping hydroxy-terminated polyarylene ethers with 4-ethynylbenzoyl chloride. Structure/property relationships for the PAEs, and the advantages offered by the ETPAEs, are discussed.

Hergenrother, P. M.

Ethynyl-Terminated Ester Oligomers and Polymers

Polyesters of various molecular weights terminated with ethynyl groups. As ethynyl-terminated polyesters are exposed to elevated temperatures, thermally induced reaction of ethynyl groups occurs to provide cross-linking and chain extension. Reaction raises use temperature of polymer and greatly improves resistance to solvents. New materials produced by this process potentially useful as adhesives, composite matrices, solvent-resistant coatings, membranes, and films.

Hergenrother, P. M.

Solvent Resistant Thermoplastic Composite Matrices

The following approaches improved the solvent resistance and raised the Tg of thermoplastics: end-capping aligomers with ethynyl groups; incorporating ethynyl groups pendent along the polymer chain; and correcting polymers containing pendent ethynyl groups with a low molecular weight diethynyl compound. The following conclusions were reached: (1) film and composite properties off an ethynyl-terminated sulfone were better than those of UDEL (trademark); (2) fracture energy of an ethynyl-terminated sulfone was lower than that of UDEL (trademark); (3) residual palladium in the cured ethynyl-terminated sulfone lower the thermooxidative stability of the cured resin; (4) the properties of a phenoxy resin were altered considerably by placing pendent ethynyl groups along the polymer chain; and (5) property trade-offs must be considered when thermoplastics are modified via reactant groups.

Hergenrother, P. M.

Thermoplastic composite matrices with improved solvent resistance

In order to improve solvent resistance of aromatic thermoplastic polymers, ethynyl-terminated aromatic sulfone polymers (ETS), sulfone/ester polymers (SEPE) containing pendent ethynyl groups, and phenoxy resin containing pendent ethynyl groups are synthesized. Cured polysulfones and phenoxy resins containing ethynyl groups on the ends or pendent on the molecules exhibited systematic behavior in solvent resistance, film flexibility, and toughness as a function of crosslink density. The film and composite properties of a cured solvent-resistant ETS were better than those of a commercially available solvent sensitive polysulfone. The study was part of a NASA program to better understand the trade-offs between solvent resistance, processability and mechanical properties which may be useful in designing composite structures for aerospace vehicles.

Hergenrother, P. M.

Phenoxy resins containing pendent ethynyl groups

As part of an effort on tougher/solvent resistant matrix resins for composites, research was directed towards exploring methods to improve the solvent resistance of linear amorphous thermoplastics. Ethyl reactive groups were placed on the ends of oligomers and pendent along the polymer chain and subsequently thermally reacted to provide crosslinking and thus improvement in solvent resistance. This concept is extended to another thermoplastic, a phenoxy resin. A commercially available phenoxy resin (PKHH) was systematically modified by reaction of the pendent hydroxyl groups on the phenoxy resin with various amounts of 4-ethynylbenzoyl chloride. As the pendent ethynyl group content in the phenoxy resin increased, the cured resin exhibited a higher glass transition temperature, better solvent resistance and less flexibility. The solvent resistance was further improved by correcting a low molecular weight diethynyl compound, 2,2-bis(4-ethynylbenzoyloxy-4'-phenyl)propane, with a phenoxy resin containing pendent ethynyl groups.

Hergenrother, P. M.

Ethynyl-terminated polyarylates - Synthesis and characterization

Hydroxy-terminated polyarylates (HTPA) with number-average molecular weights of approximately 2500, 5000, 7500, and 10,000 were synthesized and converted to corresponding 4-ethynylbenzoyloxy-terminated polyarylates (ETPA) by reaction with 4-ethynylbenzoyl chloride. The terminal ethynyl groups were thermally reacted to provide chain extension and crosslinking. The cured ETPA exhibited higher glass transition temperatures (Tg) and better solvent resistance than a high molecular weight linear polyarylate. Solvent resistance was further improved by curing 2,2-bis(4-ethynylbenzoyloxy-4-prime-phenyl) propane, a coreactant, with ETPA at concentrations of approximately 10 percent (w/w).

Havens, S. J.