Effect of reaction conditions on the molecular weight and polydispersity of linear poly(arylene ether phosphine oxide)s prepared from an AB monomer

A thorough study of the polymerization behavior of 4‐fluoro‐4′‐hydroxytriphenyl‐phosphine oxide, 2 , under nucleophilic aromatic substitution reactions has been carried out. The synthesis of 2 was achieved in excellent yields by the reaction of bis(4‐fluorophenyl)phenylphosphine oxide, 1 , with one equivalent of potassium hydroxide in DMSO/water. The structure and purity of 2 were confirmed via ¹H, ¹³C, and ³¹P NMR spectroscopy along with elemental analysis. Polymerization reactions of 2 in NMP or DMSO at 180 °C provided the corresponding linear poly(arylene ether phosphine oxide)s, PAEPOs, with number average molecular weights, M_n, ranging from 11,700 to 36,500 Da. All of the polymer samples were completely soluble in chloroform, tetrahydrofuran, DMSO, NMP, and DMAc. The polymerization reactions were accompanied by a competing intramolecular process that resulted in the formation of cyclic oligomeric species that were removed via a final precipitation from methanol. Analysis using ³¹P NMR spectroscopy and size exclusion chromatography (SEC) confirmed that the majority of the lower molecular weight cyclic species were removed via this process. The polymer samples formed tough films when chloroform solutions were slowly evaporated on a glass slide. The PAEPO samples prepared in this study exhibited excellent thermal stability with T_d (5%) values between 503 and 542 in air while the glass transition temperatures ranged from 223 to 237 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2099–2106, 2006     

Synthesis of poly(p‐phenylene sulfide) from bis(4‐bromophenyl) disulfide

Improved reaction conditions for the preparation of poly(p‐phenylene sulfide) (PPS) directly from bis(4‐bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 °C was obtained from BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc–BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1‐chloronaphthalene and have properties comparable to commercial PPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 900–904, 2006     

Effect of stoichiometry on liquid crystalline supramolecular polymers formed with complementary nucleobase pair interactions

We report herein studies on the liquid crystalline behavior of a series of supramolecular materials that contain different ratios of two complementary symmetrically-substituted alkoxy-bis(phenylethynyl)benzene AA- and BB-type monomers. One monomer has thymine units placed at either end of the rigid mesogenic core, while the other has N⁶-(4-methoxybenzoyl)-adenine units placed on the ends. Differential scanning calorimetric and polarized optical microscopy studies have been carried out on these systems. These studies show that the material's behavior is strongly dependent on its thermal history. As a result, the materials can exhibit, on heating, either a liquid crystalline phase, a crystalline phase, or the coexistence of crystalline and liquid crystalline regions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5049–5059, 2006     

Ethylene polymerization by novel Ziegler–Natta‐type catalysts obtained in situ by the oxidative addition of 8‐hydroxyquinoline‐based ligands to bis(1,5‐cyclooctadiene)nickel(0) and methylaluminoxane

Novel catalytic systems, prepared in situ by the oxidative addition of 8‐hydroxyquinoline ligands to bis(1,5‐cyclooctadiene)nickel(0) and activated by methylaluminoxane, were studied in ethylene polymerization. When 8‐hydroxyquinoline was employed, only oligomeric products were obtained. On the contrary, 5,7‐dinitro‐8‐hydroxyquinoline gave linear polyethylene (PE), but with a modest activity. For the catalyst based on 5‐nitro‐8‐hydroxyquinoline, the productivity was largely dependent on the content of free trimethylaluminum (TMA) present in the commercial aluminoxane. The progressive optimization of the TMA/oligomeric methylaluminoxane ratio increased the productivity, which reached 700 kg of PE/(mol of Ni × h), by an order of magnitude. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 200–206, 2006     

Synthesis of polyacrylonitrile via reverse atom transfer radical polymerization catalyzed by FeCl3/isophthalic acid

FeCl₃ coordinated by isophthalic acid was first used as a catalyst in the azobisisobutyronitrile‐initiated reverse atom transfer radical polymerization of acrylonitrile. N,N‐Dimethylformamide was used as a solvent to improve the solubility of the ligand. An FeCl₃‐to‐isophthalic acid ratio of 0.5 not only gave the best control of the molecular weight and its distribution but also provided rather a rapid reaction rate. The effects of different solvents on the polymerization of acrylonitrile were also investigated. The rate of the polymerization in N,N‐dimethylformamide was faster than that in propylene carbonate and toluene. The molecular weight of polyacrylonitrile agreed reasonably well with the theoretical molecular weight in N,N‐dimethylformamide. The rate of polymerization increased with increasing polymerization temperature, and the apparent activation energy was calculated to be 59.9 kJ mol^?1. Reverse atom transfer radical polymerization was first used to successfully synthesize acrylonitrile polymers with a molecular weight higher than 80,000 and a narrow polydispersity as low as 1.22. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 219–225, 2006     

Chiral soluble polymers and microspheres for enantioselective crystallization

A series of chiral polymers based on poly(N‐acryl) amino acids was synthesized using a convergent synthetic approach. These chiral polymers have been used as chiral additives to induce enantioselective crystallization of racemic or conglomerate amino acids in solutions. These polymeric additives showed strong capabilities to enhance highly enantioselective resolution during the crystallization of amino acids. In addition, these polymers caused unusual modifications of amino acid crystal morphologies. Furthermore, spherical microparticles of those same chiral polymers were also shown active in similar chiral discriminations during amino acid crystallizations occurring on microparticle surfaces. Our study demonstrates the high potential of chiral polymers and microparticles to resolve amino acids throughout crystallization processes. High enantiomeric excesses in one targeted enantiomer of amino acids can also be maximized via time‐dependent kinetic control of crystallizations. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3009–3017, 2006     

Lithographic design of photosensitive polyarylates based on reaction development patterning

The factors affecting pattern‐forming properties in reaction development patterning were examined with polyarylates with various bisphenol moieties. The developability of the photosensitive polyarylates was dependent on the properties of the subtituent (R) in the bisphenol moieties. The development time decreased in the following order: R?C(CH₃)₂ > fluorenyl unit ? phenolphthalein unit > C(CF₃)₂ > SO₂. This order agreed with that of the reactivity between the polyarylates and ethanolamine, and these orders can be explained by pK_a of the bisphenol used to prepare the polyarylates. The development with NH₂? R′? OH resulted in successful positive‐tone pattern formation. However, pattern formation with the developers containing NH₂? R′? OCH₃ was unsuccessful. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2694–2706, 2006     

Mathematical modeling of crystallization analysis fractionation (Crystaf) of polyethylene

Four polyethylene samples (PE) with different molecular weight distributions (MWD) were analyzed by crystallization analysis fractionation (Crystaf) at several cooling rates to investigate the effect of MWD and cooling rate on their Crystaf profiles. Using these results, we developed a mathematical model for Crystaf that considers crystallization kinetic effects, which are ignored in all previous Crystaf models. The Crystaf model we proposed can fit the experimental Crystaf profiles of the 4 polyethylene resins very well. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2749–2759, 2006     

Effect of the environment on the stability of surfactant–polypeptide self‐assembled complexes: Molecular dynamics simulations of stoichiometric complexes formed by N‐dodecyltrimethylammonium and poly(α,L‐glutamate) in chloroform,methanol, and water

A series of molecular dynamics simulations have been performed to study the supramolecular structure of self‐assembled complexes formed by N‐dodecyltrimethylammonium cations and the synthetic polypeptide poly(α,L ‐glutamate). The influence of the type of solvent has been investigated, considering explicit environments of chloroform, water, and methanol on a stoichiometric complex containing 15 residues. In chloroform, the complex stabilizes in a regular structure: the polypeptide adopts an α‐helix conformation that is regularly surrounded by surfactant molecules to form electrostatic interactions through a multiple interaction pattern. However, this structure destabilizes in methanol and water: (a) the α‐helix unfolds in the two solvents and (b) the electrostatic links between the surfactant molecules and the polyanion are disrupted in aqueous solution, although these interactions are still preserved in methanol. The role of the solvent environment in stabilizing or destabilizing the polypeptide secondary structure, the organization of the surfactant molecules, and predominantly the surfactant–polypeptide supramolecular organization is discussed in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1122–1133, 2006