Cationic ring-opening polymerization of 2-phenyl-1,2-oxaphospholane (deoxophostone)

Summary The ring-opening polymerization of deoxophostone 5, a five-membered cyclic phosphinite, has been studied. Some cationic initiators gave polymer whereas anionic and radical initiators as well as metal chloride (Lewis acid) catalysts did not yield polymer. The polymer consisted of a phosphine oxide repeating unit 6. The polymerization proceeded via the Arbuzov-type reaction. The reduction of polymer 6 with a HSiCl₃/Et₃N system gave polyphosphine 7.     

A novel spin-finishing method for antistatic modification of polyester fiber. Surface reaction onto amine-containing copoly(amide-ethers) blended with polyester fiber

Copoly(amide-ethers) containing two types of tertiary amine units were made as antistatic modifiers for poly(ethylene terephthalate) (PET) fibers. The filaments of the copolymers were melt-spun and reacted with three alkylating agents in order to quaternize the tertiary amine into a sulfo-betaine, a carbobetaine, and an ammonium ion. The apparent electric resistivity of the filaments was greatly reduced by this reaction, being in the range of 10⁶ to 10⁸ Ω/cm. However, because these quaternized copolymers incurred decomposition during blend spinning with PET, a blend PET fiber containing one type of copoly(amide-ether) was melt-spun and subjected to quaternization of the amino groups as well as to surface crosslinking with various alkylating and epoxy agents. The quaternized blend fibers obtained showed improved antistatic properties compared with the original blend fiber. Particularly, the fibers crosslinked with epoxy compounds were found to have the best antistatic properties that had ever been attained with this type of modification. The antistatic properties were retained even after dyeing, because both hydrophilic and ionic groups had been effectively immobilized on the surface. Since this quaternization and crosslinking could be conducted on-line with spinning and drawing within a short reaction time, this modification technique is called “spin-finishing method”, which should be superior to the conventional methods in terms of cost performance and productivity.     

New ring-opening polymerization via a π-allylpalladium complex

Summary A binary system of a palladium complex as catalyst and zinc alkoxide as initiator conducted a novel ring-opening polymerization of cyclic carbonate, i. e., 5,5-dimethyl-4-ethenyl-1,3-dioxan-2-one. The polymerization proceeded along with releasing carbon dioxide to produce the corresponding polyether. The -allylpalladium complex generated from the monomer with the catalyst is the key intermediate for this new polymerization. The propagating end is zinc alkoxide, which nucleophilically attacks the monomer activated as the -allylpalladium complex in the propagation.     

Synthesis of poly(α-thiophenediyl)benzylidene with high molecular weight and its thermal stability

Summary The synthesis of poly(-thiophenediyl)benzylidene (PTB) with high molecular weight is described. Number-average degrees of polymerization reached about 74. The characterizations of the polymer was investigated by ¹H-NMR, ¹³C-NMR, IR, and UV-VIS spectra. The polymer with well-defined structure and high molecular weight was obtained by polymerization at low temperature and in polar solvent. This polymer was thermally stable and a thermal decomposition took place at 391°C under nitrogen and at 370°C under air. The glass transformation temperature was 117°C and this PTB was nonfusible.     

Junction properties of polypyrrole containing a small amount of poly(ethylene oxide) with indium

A method to generate a porous region near the surface of a polymer is suggested. In this method the region near the surface is swollen by immersing the polymer for a short time in a solvent. Subsequently, the polymer is introduced in a nonsolvent (for the polymer) that is, however, miscible with the solvent. The formation of the porous region is a result of (1) the swelling accompanied by the disentanglement of the surface molecular chains, and the dissolution of some of them during the immersion in the solvent, and (2) the rapid extraction of the solvent from the swollen region by the nonsolvent. The porous surface provides a matrix into which a second incompatible monomer can be polymerized so that the two otherwise incompatible polymers can adhere to one another.     

Fabrication of Nonadditive Mica Ceramics by Hot Isostatic Processing

Powder compacts of synthetic mica (fluorphlogopite) encapsulated in a boro–silicate glass tube were isostatically hot–pressed in a Roy–Tuttle–type pressure vessel. Synthetic mica was sintered to a density of 2.60 g/cm³ (91.2% of theoretical density) without additives under 98 MPa of water at 800°C for 45 min.     

Electron-microscopic procedure for acrylic rubber

The electron-microscopic visualization of acrylic rubber dispersed in a heterogeneous structural resin composition consisting of a rubber-modified two-phase plastic comprising essentially a butyl acrylate rubber phase and an acrylonitrile–styrene copolymer phase, respectively, has been accomplished. This procedure consists of the following: The molded resin specimen is treated with hydrazine hydrate solution to produce the acrylic acid hydrazides. Allow the treated specimen to soak in osmium tetroxide solution. The acrylic rubber may be indirectly fixed and stained. Some micrographs of ultrathin sections of two or three resin compositions, cut by an ultramicrotome, are presented.     

Improvement in Thermoelectric Characteristics of n-type Iron Disilicide by Local Composition Modification

High thermoelectric figure of merit semiconducting ceramics of n -type iron disilicide with modified local compositions have been developed. Sintering and annealing of the composite powder composed of iron disilicide and precipitated cobalt (II) hydroxide resulted in the dissolution of excess Co and oxygen into the iron disilicide phase. Excess Co segregated to the grain boundary region, while interstitially incorporated oxygen was distributed homogeneously in the microstructure. The maximum figure of merit achieved was 5.2 × 10⁻⁴/K at 673 K.     

An absolute requirement of fructose 1,6-bisphosphate for the Lactobacillus caseiL-lactate dehydrogenase activity induced by a single amino acid substitution

Lactobacillus casei allosteric L-lactate dehydrogenase (L-LDH)absolutely requires fructose 1,6-bisphosphate [Fru(1,6)P2] forits catalytic activity under neutral conditions, but exhibitsmarked catalytic activity in the absence of Fru(1,6)P₂ underacidic conditions through the homotropic activation effect ofsubstrate pyruvate. In this enzyme, a single amino acid replacement,i.e. that of His205 conserved in the Fru(1,6)P₂-binding siteof certain allosteric L-LDHs of lactic acid bacteria with Thr,did not induce a marked loss of the activation effect of Fru(1,6)P₂or divalent metal ions, which are potent activators that improvethe activation function of Fru(1,6)P₂ under neutral conditions.However, this replacement induced a great loss of the Fru(1,6)P₂-independentactivation effect of pyruvate or pyruvate analogs under acidicconditions, consequently indicating an absolute Fru(1,6)P₂ requirementfor the enzyme activity. The replacement also induced a significantreduction in the pH-dependent sensitivity of the enzyme to Fru(1,6)P₂,through a slight decrease and increase of the Fru(1,6)P₂ sensitivityunder acidic and neutral conditions, respectively, indicatingthat His205 is also largely involved in the pH-dependent sensitivityof L.casei L-LDH to Fru(1,6)P₂. The role of His205 in the allostericregulation of the enzyme is discussed on the basis of the knowncrystal structures of L-LDHs.