Radiation-induced polymerization of ethylene in a pilot plant. I. Bulk process

Radiation-induced bulk polymerization of ethylene was carried out with use of a pilot plant with a 10 liter reactor at pressures of 225–400 kg/cm², temperatures of 30–95°C, ethylene feed rates of 5–28 kg/hr, and dose rate of 3.8 × 10⁵ rad/hr. Characteristics of the process are mild polymerization conditions and capability of producing medium density polyethylene in powder form. The spacetime yield and molecular weight of polymer were in the range of 3.5 to 13.1 g/liter hr and 2.2 × 10⁴ to 14 × 10⁴, respectively. The space-time yield increased with mean residence time and 2.4 powders of pressure, and decreased with temperature. Molecular weight changed similarly with the reaction conditions. These results were consistent with those of the bench plant experiment and the scale effect was small. Polymer deposit to the reactor wall limited a period of continuous operation of the plant. The amount of deposited polymer was increased with the square of reaction time. The rate of polymer deposit was proportional to polymer concentration and to the cube of pressure. The polymer deposit cannot be solved in the bulk process.     

Morphology of composite polymer emulsion particles consisting of two kinds of polymers between which ionic bonding intermolecular interaction operates

The morphology of particles (I) produced by seeded emulsion copolymerization of styrene (S) and sodium p-styrene sulfonate (NaSS) with butyl acrylate (BA)-methacryloyloxyethyl-trimethylammonium chloride (QDM) copolymer particles as seed was examined in comparison with poly(butyl acrylate) (PBA)-polystyrene (PS) composite polymer emulsion particles (II). In an electron microscopic observation, it was observed that II particles had an anomalous shape and the electron densities at different points in the particle were heterogeneous, whereas I particles had an almost spherical shape and the electron densities were homogeneous. The maximum tensile strength and toughnes were much larger in II than I. The dynamic mechanical studies indicate that II film had a macroheterogeneous structure consisting of PS-rich and PBA-rich phases, whereas I film had a microheterogeneous structure. These ressults suggest that there is an effect of intermolecular interaction between polymers of different kinds on the formation of heterogeneous structure in particles consisting of two kinds of polymers.     

Radiation-induced polymerization of ethylene in pilot plant. III. Heavy-phase recycling process

Radiation-induced polymerization of ethylene using aqueous tert-butyl alcohol as medium was carried out in a large-scale pilot plant with a 50-liter central source-type reactor at a pressure of 105 to 395 kg/cm², temperature of 30° to 80°C, mean dose rate of 4.5 × 10⁴ to 1.9 × 10⁵ rads/hr, ethylene feed rate of 5.5 to 23.5 kg/hr, and medium feed rate of 21 to 102 l./hr. The space–time yield and molecular weight of the polymer were in the range of 4.7 to 16.8 g/l.-hr and 1.3 × 10⁴ to 8.9 × 10⁴, respectively. The space–time yield and molecular weight increased with mean residence time at 30°C, whereas at 80°C they became almost independent of the time. The space–time yield increased with pressure and dose rate, slightly decreased with temperature, and was maximum at ethylene molar fraction of 0.5. The polymer molecular weight increased with pressure and ethylene molar fraction, and decreased with dose rate and temperature. The total amount of deposited polymer on the reactor wall, source case wall, and scraping blades was usually less than 1 kg, which was negligibly small for the analysis of polymerization. Continuous discharge of the polymer slurry and production of fine-powder polyethylene were successfully carried out. In the central source-type reactor, a dose rate of 1.9 × 10⁵ rads/hr was obtained with a ⁶⁰Co source of ca. 12 kCi.     

MicroRNA-331-3p Suppresses Cervical Cancer Cell Proliferation and E6/E7 Expression by Targeting NRP2

Aberrant expression of microRNAs (miRNAs) is involved in the development and progression of various types of cancers. In this study, we investigated the role of miR-331-3p in cell proliferation and the expression of keratinocyte differentiation markers of uterine cervical cancer cells. Moreover, we evaluated whether neuropilin 2 (NRP2) are putative target molecules that regulate the human papillomavirus (HPV) related oncoproteins E6 and E7. Cell proliferation in the human cervical cancer cell lines SKG-II, HCS-2, and HeLa was assessed using the 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium, inner salt (MTS) assay. Cellular apoptosis was measured using the TdT-mediated dUTP nick end labeling (TUNEL) and Annexin V assays. Quantitative RT-PCR was used to measure the messenger RNA (mRNA) expression of the NRP2, E6, E7, p63, and involucrin (IVL) genes. A functional assay for cell growth was performed using cell cycle analyses. Overexpression of miR-331-3p inhibited cell proliferation, and induced G2/M phase arrest and apoptosis in SKG-II, HCS-2 and HeLa cells. The luciferase reporter assay of the NRP2 3′-untranslated region revealed the direct regulation of NRP2 by miR-331-3p. Gene expression analyses using quantitative RT-PCR in SKG-II, HCS-2, and HeLa cells overexpressing miR-331-3p or suppressing NRP2 revealed down-regulation of E6, E7, and p63 mRNA and up-regulation of IVL mRNA. Moreover, miR-331-3p overexpression was suppressed NRP2 expression in protein level. We showed that miR-331-3p and NRP2 were key effectors of cell proliferation by regulating the cell cycle, apoptosis. NRP-2 also regulates the expression of E6/E7 and keratinocyte differentiation markers. Our findings suggest that miR-331-3p has an important role in regulating cervical cancer cell proliferation, and that miR-331-3p may contribute to keratinocyte differentiation through NRP2 suppression. miR-331-3p and NRP2 may contribute to anti-cancer effects.     

Deformation behavior of polytetrafluoroethylene films under tensile stress at various temperatures

Deformation behavior of polytetrafluoroethylene (PTFE) films was investigated by thermomechanical analysis (TMA) under various tensile stresses (σ) up to 1.15 MPa in the temperature range from room temperature to 360°C. In the heating process above σ ≈ 0.25 MPa, a contraction of the PTFE film occurs in the melting temperature region. In the cooling process above σ ≈ 0.05 MPa, an elongation occurs in the crystallization temperature region, and above σ ≈ 0.5 MPa, it reaches 20–30% of the original length of the film. The PTFE films in the melt state above σ ≈ 0.5 MPa contract with increasing temperature up to 360°C and elongate with decreasing temperature. For the films that underwent deformation in the TMA, the crystalline orientation and the surface morphology were investigated by wide-angle X-ray diffraction and scanning electron microscopy, respectively. The degree of crystalline orientation in the deformed films increases with increasing σ and approaches a plateau at σ ≈ 0.4 MPa. On the surface of the deformed films, alignment of the bands and deformation of granules, which are formed by heat treatment above the melting point, are observed. © 1994 John Wiley & Sons, Inc.     

Formation of Zirconia Solid Solutions Containing Alumina Prepared by New Preparation Method

In the system ZrO₂–Al₂O₃, a new method for preparing ZrO₂ solid solutions from ZrCl₄ and AlCl₃ using hydrazine monohydrate is investigated. c -ZrO₂ solid solutions containing up to ∼40 mol% Al₂O₃ crystallize at low temperatures from amorphous materials. The formation mechanism is discussed from IR spectral data. The values of the lattice parameter α increase linearly from 0.5072 to 0.5105 nm with increasing Al₂O₃ content. At higher temperatures, transformation of the solid solutions proceeds as follows: c ( SS ) → t ( ss ) → t ( ss ) +α-Al₂O₃→ m +α-Al₂O₃. m -ZrO₂–α-Al₂O₃ composite ceramics are fabricated by hot isostatic pressing for 2 h at 1250°C and 196 MPa. Microstructures and mechanical properties are examined, in connection with increasing Al₂O₃ content.     

Gel permeation chromatography using controlled-porosity glass. II. Polyacrylamide aqueous solutions

In a study of polyacrylamide in solutions we have required the rapid characterization on chromatographies. The application to the aqueous solution of the GPC using controlled-porosity glass has been examined from both the viewpoint of the effect of salt addition and the GPC mechanism. An adequate addition to neutral salt, 0.005M KCI to the eluent, gave rise to the elution behaviors being in accord with the hydrodynamic volume concept of the GPC separation.     

Asymmetric addition of thiol to diene polymer in the presence of optically active amines as catalyst

The asymmetric addition reaction of thiolacetic acid or benzylmercaptan to diene polymer (natural rubber, cis- and trans-1,4-polyisoprene, _cis-1,4-polybutadiene, various styrenebutadiene copolymers and alternating acrylonitrile-butadiene copolymer) by optically active catalysts such as d-bornylamine ([α]d?45.2°), l-aspartic diethyl ester (?11.2°), l-aspartic dibutyl ester (?5.3°) were carried out in benzene at room temperature to 90°C. The optically active polymers were obtained from natural rubber and cis-1,4- and trans-1,4-polyisoprene, but were not obtained from cis-1,4-polybutadiene, styrene-butadiene copolymers, and butadiene-acrylonitrile copolymer. The [α]²⁵_D value of optically active derivatives was ?0.1° ～ ?1.0° (in benzene), and the optical rotatory dispersion curves were found to fit the simple Drude equation.     

Studies on propylene polymerization with a highly active MgCl2 supported TiCl4 catalyst system

Summary Propylene polymerization was performed with a highly active MgCl supported TiCl₄ in conjunction with Et₃Al and ethyl benzoate (EB). The obtained polypropylene sample was separated into four fractions by successive extraction with pentane, heptane and trichloroethylene (trichlene). Yield, Mn, Tm and microtacticity of each fraction were determined, and the effects of the concentration of EB on these items of results were investigated. It has been found that EB enhances yield, Mn and stereospecificity of trichlene insoluble (the most stereospecific) fraction, and in contrast, it decreases rapidly yields of other three fractions without changing the character of the polymers. From these findings, the functions of EB to the active centers were discussed.