Radiation resistant amorphous–all aromatic polyarylene ether sulfones: Synthesis,characterization, and mechanical properties

The synthesis and characterization of amorphous, aromatic, polyaryl ethers has been investigated. Detailed synthesis procedures are provided. The main thrust of these activities was to synthesize polymers which could serve as castable amorphous matrix resins for carbonfiber composites and which would be highly resistant to radiation degradation. It was important that these polymers not contain any aliphatic groups in order to contrast their behavior with the commercially available Bisphenol-A polysulfones. The approach taken was to synthesize a series of statistical or random copolymers derived from hydroquinone and biphenol together with 4,4′-dichlorodiphenyl sulfone. In order to produce copolymers of high molecular weight, modified techniques were developed which utilized potassium carbonate as a weak base and N-methyl-2-pyrrolidone as the aprotic dipolar solvent. Detailed procedures are provided in this paper for the synthesis of high molecular weight copolymers of this type. In addition, stress-strain, dynamic mechanical properties and preliminary electron beam (e-beam) degradation studies are reported significantly. Improved mechanical property retention after e-beam exposure was observed with the all aromatic polyether sulfones.     

Synthesis, chemical properties, and biological evaluation of CC-1065 and duocarmycin analogues incorporating the 5-methoxycarbonyl-1,2,9,9a-tetrahydrocyclopropa

The synthesis of 5-methoxycarbonyl-1,2,9,9a-tetrahydrocyclopropa[c]benz[e]indol-4-one (C5-CO2Me-CBI), a substituted CBI derivative bearing a C5 methoxycarbonyl group, and its corresponding 5-hydroxymethyl derivative are described in efforts to establish substituent electronic effects on the agents' functional reactivity and the resulting effect this has on their rate of DNA alkylation. Resolution of an immediate C5-CO2Me-CBI precursor and its incorporation into both enantiomers of 16 and 17, analogues of the duocarmycins, are also detailed. A study of the solvolysis reactivity and regioselectivity of N-BOC-C5-CO2Me-CBI (12) revealed that the introduction of a C5 methyl ester modestly slowed the rate of solvolysis (1.8x, pH 3) without altering the inherent reaction regioselectivity (>20:1). The comparison of the X-ray structures of the N-CO2Me derivatives of C5-CO2Me-CBI and CBI revealed correlations with the reaction regioselectivity and the relative reactivity of the compounds. The latter correlated well with the less reactive C5-CO2Me-CBI exhibiting a shortened N2-C2a bond length (1.386 vs 1.390 A) and smaller chi1 dihedral angle (8.1 degrees vs 21.2 degrees ) indicative of greater vinylogous amide conjugation and was accompanied by a diminished (cross-conjugated) cyclopropane conjugation (shorter bond lengths). Establishment of the DNA alkyation properties revealed that C5-CO2Me-CBI-based agents retained the identical alkylation selectivity of the natural products. More importantly, the C5 methyl ester was found to decrease the rate (0.77x) of DNA alkylation relative to CBI, consistent with its inherent lower reactivity. These results indicate that the previously observed increase in the rate of DNA alkylation for C7-substituted CBI analogues including CCBI (7-cyano-CBI) is contrary to expectations based on their inherent reactivities. Unlike 17, in which the C5 methyl ester does not bind in the minor groove, the C7 substituent lies in the minor groove extending the rigid length of the agents, further enhancing the DNA binding-induced conformational change responsible for activation toward nucleophilic attack and catalysis of the DNA alkylation reaction.     

In situ generation of carbenes: a general and versatile platform for organocatalytic living polymerization

A metal-free, organocatalytic approach to living polymerization using N-heterocyclic carbenes as nucleophilic catalysts generated and used in situ in a single-pot process is detailed. The N-heterocyclic carbene catalyst platform is extremely versatile, as the nature of the substituents has a pronounced effect of catalyst stability and activity toward different substrates. The generation of imidazolium- and thiazaolium-based carbenes was accomplished from the reaction of the corresponding salts with the appropriate bases. This allowed the rapid screening of libraries of catalysts that provided a basic understanding of catalyst structure (sterics, electronics, etc.) with the polymerization rate, control, substrate, and range of molecular weights. The imidazole-based catalysts were significantly more active toward ROP than the thiazolium-based analogues. No appreciable differences between imidazol-2-ylidene and imidazolin-2-ylidene catalysts were observed. Less sterically demanding carbenes were found to be more active toward ring-opening polymerization (ROP) than their sterically encumbered analogues for lactone polymerization. These data prompted the investigation of ionic liquid as a precatalyst reservoir in a phase-transfer polymerization with an immiscible THF solution of monomer and initiator. In situ activation of the ionic liquid generates carbene that migrates to the organic phase effecting living ROP. Precatalyst (ionic liquid) regeneration terminates polymerization. This simple reaction/recycle protocol readily allows repetitive ROPs from the ionic liquid using commercially available materials.     

Structural modifications in imide-aryl ether phenylquinoxaline random copolymers

A rigid rod polyimide derived from biphenyldianhydride (BPDA) and p-phenylenediamine (PDA) was modified by the incorporation of diamines containing performed phenylquinoxaline and aryl ether linkages, and the morphology and mechanical properties of the resulting imide-aryl ether phenylquinoxaline copolymers were investigated. These phenylquinoxaline containing diamines, 1, 4-bis[6-(3-aminophenoxy)-3-phenyl-2-quinoxalinyl] benzene and 1, 4-bis[6-(4-aminophenoxy)-3-phenyl-2-quinoxalinyl] benzene, were prepared by a novel nucleophilic aromatic substitution reaction of 1,4-(6-fluoro-3-phenyl-2-quinoxalinyl) benzene with either 1, 3- or 1, 4-aminophenol in the presence of K₂CO₃, respectively. The diamines were utilized as co-monomers with BPDA and PDA to synthesize poly(amicacids.) Films were cast and cured (350°C) to effect imidization, affording films which showed high elongations and moduli. The copolymers with high phenylquinoxaline compositions displayed T_g's in the 300°C range, and the thermal stability of the copolymers was comparable to that of the parent polyimide. The copolymers also showed improved auto- or self-adhesion, particularly those which showed a T_g, allowing sufficient molecular motion for interdiffusion.     

Expanding the catalytic activity of nucleophilic N-heterocyclic carbenes for transesterification reactions

[reaction: see text] Currently, there is a renewed interest in reactions that are catalyzed by organic compounds. Typical organic catalysts for acylation or transesterification reactions are based on either nucleophilic tertiary amines or phosphines. This communication discusses the use of nucleophilic N-heterocyclic carbenes as efficient transesterification catalysts. These relatively unexplored and highly versatile organic catalysts were found to be mild, selective, and more active than traditional organic nucleophiles.     

Silver(I)-carbene complexes/ionic liquids: novel N-heterocyclic carbene delivery agents for organocatalytic transformations

[reaction: see text] N-Heterocyclic carbene (NHC) complexes with silver were investigated as sources of unsaturated NHC carbene catalysts via thermal decomposition. The NHC complex (1-ethyl-3-methylimidazol-2-ylidene)silver(I) chloride is an ionic liquid, and was found to catalyze the ring-opening polymerization of lactide at elevated temperatures to give narrowly dispersed polylactide of predictable molecular weight. Silver-carbene complexes can also be used for the catalysis of small molecule transesterification reactions. Thermolysis of the silver complexes in the presence of CS(2) yielded the zwitterionic CS(2) adducts of the carbene, implicating the intermediacy of the free carbene in these reactions.     

Synthesis and characterization of aromatic amine functional semicrystalline aryl ether ketone macromers

From earlier experiments it was observed that the reactions of aryl fluoride functional aryl ether ketone oligomers (PEK) with m-aminophenol lead to poor levels of amine incorporation because of side-reactions. In this article, a method is presented to protect the m-aminophenol by converting it into a triarylimine group. This protected m-aminophenol was used together with 4-fluoro,4′-hydroxybenzophenone in a typical poly(aryl ether) synthesis. PEKs of different molecular weights were synthesized with number average molecular weights $\overline {M}_n$) of 2600, 4500, and 5400 g/mol. The deprotection of the triarylimine chain end was carried out by an acid treatment to afford a monofunctional aromatic amine end group, amenable towards copolymerization. © 1995 John Wiley & Sons, Inc.