Synthesis of Mid-Chain Functionalized Polymers

Polymers with mid-chain alkoxyamine functionality were synthesized by activating monohalogenated polymers in the presence of nitroso or nitrone radical traps. The resulting polymers were either polystyrene (PSt) homopolymers with a mid-chain alkoxyamine or PSt-poly(methyl acrylate) (PMA) diblock copolymers with an alkoxyamine unit at the junction between the segments. Monohalogenated polymers where synthesized by atom transfer radical polymerization (ATRP) and were then reacted to form polymer radicals in the presence of a radical trap, nitrone or nitroso. When only polystyrene radicals were reacted with the radical trap a dimer was formed with an alkoxyamine functionality in the center of the polymer chain. This functionality allowed the polymer chain to be cleaved in order to visualize the extent of the alkoxyamine functionality incorporation into the polymer chains. It was found that near quantitative alkoxyamine mid-chain functionality could be achieved by activating the PStBr in the presence of 10 equivalents of nitrone, 5 equivalents of copper bromide, and 2 equivalents of copper metal. Further reducing the amount of copper metal led to incomplete coupling, while increasing the equivalents beyond 2 generated polymer dimers with less than quantitative mid-chain functionality. Monochlorinated polystyrene (PStCl) precursors gave much poorer coupling results compared to reactions with PStBr, which is consistent with the stronger C-Cl bond resisting activation and the formation of the polystyryl radicals. When poly (methyl acrylate) (PMABr) is reacted with PStBr in the presence of a nitroso group at reduced temperatures (30 oC) block copolymers were selectively formed with an alkoxyamine functionality in the center. This was done by first activating the PSt-Br to form a polymer radical that would react with the radical trap to form a persistent radical on the oxygen. The PMA-Br, once activated, reacted with the radical on the oxygen to form the block copolymer. To test the amount of functionality incorporated, a coupling reaction was performed with no nitroso present, and found that no reaction occurred. This showed that the radical trap is essential for the coupling to occur, and cleavage of the diblock indicated that the alkoxyamine functionality was indeed incorporated into the diblock.

A New Crystalline LiPON Electrolyte: Synthesis, Properties, and Electronic Structure

The new crystalline compound, Li2PO2N, was synthesized using high temperature solid state methods starting with a stoichiometric mixture of Li2O, P2O5, and P3N5. Its crystal structure was determined ab initio from powder X-ray diffraction. The compound crystallizes in the orthorhombic space group Cmc2(1) (# 36) with lattice constants a = 9.0692(4) angstrom, b = 53999(2) angstrom, and c = 4.6856(2) angstrom. The crystal structure of SD-Li2PO2N consists of parallel arrangements of anionic chains formed of corner sharing (PO2N2) tetrahedra. The chains are held together by Li+ cations. The structure of the synthesized material is similar to that predicted by Du and Holzwarth on the basis of first principles calculations (Phys. Rev. B 81,184106 (2010)). The compound is chemically and structurally stable in air up to 600 degrees C and in vacuum up to 1050 degrees C. The Arrhenius activation energy of SD-Li2PO2N in pressed pellet form was determined from electrochemical impedance spectroscopy measurements to be 0.6 eV, comparable to that of the glassy electrolyte LiPON developed at Oak Ridge National Laboratory. The minimum activation energies for Li ion vacancy and interstitial migrations are computed to be 0.4 eV and 0.8 eV, respectively. First principles calculations estimate the band gap of SD-Li2PO2N to be larger than 6 eV. (C) 2013 Elsevier B.V. All rights reserved.

Synthesis Of Triblock Copolymers By Radical Trap Assisted-Atom Transfer Radical Coupling

Monobrominated diblock copolymers composed of poly(styrene) (PSt), poly(methylacrylate) (PMA), or poly(methyl methacrylate) (PMMA) were synthesized by consecutive atom transfer radical polymerizations (ATRP). The brominated diblocks were utilized in atom transfer radical coupling (ATRC) and radical trap-assisted ATRC (RTA-ATRC) reactions to form ABA type triblock copolymers. Once PMMA-PStBr and PSt-PMABrBr were produced by ATRP, the synthes of PSt-PMA-PSt and PMMA-PSt- PMMA by ATRC and also by RTA-ATRC were attempted. The coupling methods were compared and it was found that RTA-ATRC succeeded in synthesizing PSt-PMA-PSt where ATRC could not, and that RTA-ATRC improved coupling over ATRC for PMMAPSt- PMMA. Incorporation of the radical trap 2-methyl-2-nitrosopropane (MNP) midchain allowed for simple thermal cleavage of the triblock to confirm the RTA-ATRC pathway occurred in preference over the head to head radical coupling pathway of ATRC. Triblocks made by ATRC did not cleave under our conditions, as no MNP was present and thus no labile C-O bond was incorporated. The RTA-ATRC pathway allowed for lower catalyst amounts (2 molar equivalents of copper(I)bromide and 2 molar equivalents of copper metal) and a high degree of coupling at lower temperatures (40°C). The RTA-ATRC improved upon ATRC because of its ability to generate a persistent radical and proceed by first order kinetics with respect to the chain end radical.