Molecular mechanics analysis of polymer conformation, 4. Local chain motions and molecular relaxations of poly(parabanic acids)

The structure of the repeating units of poly(parabanic acid) (PPA), a polyimide-like glassy heat resistant polymer, was analyzed by MM2 using various model compounds of PPA-M and PPA-T consisting of M (1,3-diazolidine-2,4,5-trione-1,3-diyl-1,4-phenylenemethylene-1,4-phenylene) and T (1,3-diazolidine-2,4,5-trione-1,3-diyl-3,3′-dimethyl-4,4′-biphenylylene) units, respectively. Based on the most stable structures obtained, the subunit rotations of the methylene, phenylene, and diazolidine groups were evaluated. The potential mobilities estimated for these subunits can reasonably be correlated with the dynamic mechanical and dielectric properties of PPA. The γ relaxation mode of both PPA-M and a copolymer PPA-TM is reasonably explained by the rotation of the methylene group. The major mode of the β relaxations of both PPAs is ascribed to the rotation of the phenylene ring of the M unit, while the β^* dielectric relaxation is attributed to the torsional vibration of the parabanic ring involving the adjacent aromatic moieties. These data suggest that PPA is similar to polycarbonate rather than polyimide in terms of the local chain motion. It is shown that the conformational analysis by MM2 is quite informative to understand the structure property relationships of polymers.     

Synthesis and properties of multiblock copolymers consisting of poly(L‐lactic acid) and poly(oxypropylene‐ co‐oxyethylene) prepared by direct polycondensation

A multiblock copoly(ester–ether) consisting of poly(l ‐lactic acid) (PLLA) and poly(oxypropylene‐co‐oxyethylene) (PN) was prepared and characterized. Preparation was done via the solution polycondensation of a thermal oligocondensate of l ‐lactic acid, a commercially available telechelic polyether (PN: Pluronic‐F68), and dodecanedioic acid as a carboxyl/hydroxyl adjusting agent. When stannous oxide was used as the catalyst, the molecular weight of the resultant PLLA/PN block copolymers became very high (even with a high PN content) under optimized reaction conditions. The refluxing of diphenyl ether (solvent) at reduced pressure allowed the efficient removal of the condensed water from the reaction system and the feed‐back of the intermediately formed l ‐lactide at the same time in order to successfully bring about a high degree of condensation. The copolymer films obtained by solution casting became more flexible with the increasing PN content as soft segments. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1513–1521, 1999     

Highly Chemoselective gem-Difluoropropargylation of Aliphatic Alcohols

Despite the potential of α-fluoroethers in medicinal chemistry, their synthetic methods, especially etherification of aliphatic alcohols, have been limited. Herein, we developed two- and three-step gem-difluoropropargylation of aliphatic alcohols including amino acid derivatives and naturally occurring bioactive molecules. Highly chemoselective etherification proceeded by using the gem-difluoropropargyl bromide dicobalt complex in the presence of silver triflate and triethylamine. Decomplexation of dicobalt complexes was achieved by using cerium ammonium nitrate or N,N,N′-trimethylethylenediamine. The thus obtained gem-difluoropropargyl ethers were converted to various α-difluoroethers which are expected to be useful for medicinal chemistry.     

Protecting‐group‐free synthesis of glycopolymers bearing thioglycosides via one‐pot monomer synthesis from free saccharides

Polyacrylamides having pendant thioglycosides were successfully synthesized from thioglycosidic monomers that were readily prepared by one‐pot method without any protection of the hydroxy groups on the starting free saccharides. The glycomonomers were synthesized by the direct synthesis of thioglycosides using 2‐chloro‐1,3‐dimethylimidazolinium chloride and 4‐aminobenzentiol, and the following acrylamidation. They were co‐polymerized with acrylamide into glycopolymers by reversible addition‐fragmentation chain transfer polymerization using a trithiocarbonate derivative as a chain transfer agent. The gold nanoparticles and gold‐coated quartz crystal microbalance sensor immobilized with the thiol‐terminated glycopolymers exhibited high affinity for the corresponding lectins due to multivalent interaction between saccharides and protein in aqueous solution. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3513–3520