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147 records · Page 9

Development of critical molecular weight-property specifications for high performance polymers used as adhesives and composites

The polyimide resin, LARC-160, was prepared from diethyl-3, 3', 4,4'-benzophenone tetracarboxylate, ethyl-5-norbornene-2,3-dicarboxylate and Jeffamine AP-22. The imidization reactions of NE and BTDE were studied by HPLC, C-13-NMR and IR. NE imidizes slowly at 12 C; BTDE imidizes when the resin is heated above 100 C. Both imidization reactions proceed directly to the imide. Neither amic acid is present in significant quantities at any stage of the imidization reactions. The monomer mixture was stored at 12 C for periods up to 14 months. The effects of resin aging at this temperature on the chemical composition of the resin monomer mixture and the imidized polymer formed on curing were investigated. Aging the resin monomer mixture has the effect of partially advancing the imidization reaction. The average size of the cured polymer increases slightly with resin age.

Kranbuehl, D. E.↗

Biphenyl dicarboxylates from ethene and bifuran dimethyl esters

The substrate scope of the Diels-Alder-Dehydration reaction was expanded to the deactivated bifuran structure. Dimethyl biphenyl-4,4'-dicarboxylate (1) and methyl 5- [4-(methoxycarbonyl)phenyl]-2-furoate (2) were synthesized from dimethyl 2,2'-bifuran-5,5'-dicarboxylate (3) via metal-triflate-catalyzed Diels-Alder-Dehydration reaction with ethene. A 31% yield of (1) was obtained using Sc(OTf)3 catalyst, and a 76.6% yield of (2) was obtained using La(OTf)3 catalyst under moderate reaction conditions. This approach is inherently selective to the 4,4'-dicarboxylates, and bypasses the methyl-group oxidation step of the dimethyl-biphenyl route.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-Electron Transfer Stabilizes Metastable Alane in a Bipyridine-Functionalized MOF Nanopore

Nanoconfinement of metastable hydrides such as alane (AlH 3 ) in functionalized porous frameworks represents a promising yet largely untapped strategy for high-capacity energy storage. Despite its potential, the underlying mechanisms responsible for the thermodynamic stabilization of metastable hydrides are poorly understood. Here, in this study, concepts from solution Lewis acid–base chemistry were applied to a crystalline metal–organic framework (MOF) to stabilize AlH 3 . The long-range order and synthetically versatile pore chemistry enabled us to reveal the intimate details of the hydride-host interactions. Powder X-ray diffraction (PXRD) of AlH 3 -infiltrated UiO-67bpy (Zr 6 O 4 (OH) 4 (bpydc) 6 ; bpydc 2– = 2,2′-bipyridine-5,5′-dicarboxylate) confirms that the framework maintains its crystallinity up to 250 °C and is stable under 70 MPa H 2 pressure. We find that thermodynamic stabilization arises from coupled single-electron and hydrogen-atom transfer from AlH 3 to bipyridine-containing linkers. Electron paramagnetic resonance detects a bipyridyl radical with an anisotropic g-tensor (g values of 2.00132, 2.00215, and 2.00275), consistent with Bader charge analysis predicting 0.82 e – transferred from the hydride to the MOF. These findings establish critical structure–property relationships underpinning AlH 3 stabilization and suggest general strategies for tuning the thermodynamics and kinetics of metastable materials.

Shivanna, Mohana [Sandia National Laboratories (SN↗