Living cationic polymerization of p-methoxystyrene by hydrogen iodide/zinc iodide at room temperature

Summary Cationic polymerization of p-methoxystyrene initiated by HI/ZnI₂ in toluene afforded living polymers not only at low temperature (–15°C) but at room temperature (+25°C) as well. The number-average molecular weight of the polymers was directly proportional to monomer conversion and in excellent agreement with the calculated value assuming that one polymer chain forms per unit hydrogen iodide. On addition of a fresh feed of monomer at the end of the first-stage polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage; the polymer molecular weight further increased in direct proportion to monomer conversion and was close to the calculated value for living polymer. Throughout these reactions, the molecular weight distribution of the polymers stayed very narrow (¯M_w/¯M_n<1.1). This is the first example of living cationic polymerizations of styrene derivatives that proceed even at room temperature.     

Living cationic polymerization of a vinyl ether with a triester pendant

Summary Cationic polymerization of CH₂=CH-O-CH₂CH₂C(COOC₂H₅)₃, a vinyl ether with three pendent esters, initiated by the HI/I₂ system in toluene at –40 °C afforded living polymers with a controlled molecular weight ( = 10³–10⁴) and a narrow molecular weight distribution ( = 1.1–1.2). The number-average molecular weight of the polymers was directly proportional to monomer conversion and the monomer-to-initiator (HI) feed ratio. The polymers obtained with BF₃O(C₂H₅)₂ had a fairly high molecular weight ( 10⁵, 5 × 10⁴) and a broad molecular weight distribution. The triester vinyl ether was similar in reactivity to alkyl counterparts and one order of magnitude more reactive than the corresponding mono- and diester vinyl ethers.     

Living cationic polymerization of vinyl monomers by organoaluminum halides

Summary Well-defined living polymers of isobutyl vinyl ether were obtained in the polymerization initiated with ethylaluminum dichloride (EtAlCl₂) in conjunction with a stoichiometric excess of dioxane (5–10 vol%) in n-hexane at 0°C. Under these conditions, the number-average molecular weight of the polymers increased in direct proportion to monomer conversion, while the molecular weight distribution stayed narrow (M_w/M_n = 1.1–1.25). In sharp contrast, the EtAlCl₂-initiated polymerization in the absence of dioxane led to non-living polymers with a broad molecular weight distribution. It was concluded that the propagating carbocation is stabilized not by the counteranion but by an externally added basic compound (dioxane) that strongly interacts with the active end.     

Copolymerization of phenylacetylene with various acetylenes by W- and Mo-based catalysts

In the copolymerization of phenylacetylene with various acetylenes catalysed by WCl₆·Ph₄Sn, the relative reactivity of monomer decreased with increasing steric effect of monomer, e.g. HC  Cn-Bu, HC  Cn-Hex > HC  CPh, HC  Cs-Bu > HC  Ct-Bu, MeCCPh, CICCPh. While 1-chloro-2-phenylacetylene (a disubstituted acetylene) showed high reactivity in the homopolymerization by Mobased catalysts, the reactivity was remarkably depressed in the presence of phenylacetylene as comonomer. Based on these results, the relative reactivity of the acetylenic monomers in copolymerization was explained in terms of competitive coordination of monomers to the propagating end.     

Living cationic polymerization of isobutyl vinyl ether by the diphenyl phosphate/zinc iodide initiating system

Summary The first example of the living cationic polymerization of isobutyl vinyl ether via the phosphate counteranion has been achieved in toluene below 0°C with a new initiating system that consists of diphenyl phosphate and zinc iodide, (C₆H₅0)₂P(0)0H/ZnI₂. The number-average molecular weight of the polymers increased in direct proportion to monomer conversion, and was in excellent agreement with the calculated value assuming that one polymer chain forms per unit diphenyl phosphate. On addition of a fresh feed of monomer at the end of the polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage, and the polymer molecular weight further increased in direct proportion to monomer conversion. Throughout the reaction, the molecular weight distribution of the polymers stayed very narrow (¯M/¯M_n 1.1). At room temperature (+25 °C), however, the molecular weight distribution of the polymers slightly broadened (¯M_w/¯M_n 1.2) at high conversions where the polymer molecular weight became smaller than the calculated value. Evidently, the (C₆H₅0)₂-P(0)0H/ZnI₂ system indeed generates a propagating species of a long life-time at room temperature, but the perfectly living polymerization by this system operates below 0°C.Living cationic polymerization of vinyl ethers by electrophile     

Conformational studies of poly(N-methyl-l-alanine) by n.m.r. spectroscopy

Nuclear magnetic resonance (n.m.r.) and circular dichroism of $\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ in methylene $\text{chloride}\text{-d}{}_2\text{dichloroacetic acid}$ were investigated. In methylene chloride-d₂$\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ was found to consist of nearly all-trans amide bonds and assume a stable secondary structure. Trace amounts of cis amide bonds were also present. The addition of dichloroacetic acid destroyed the secondary structure and induced a drastic change of the n.m.r. spectrum, which was similar to that observed with the monomeric amide, $\text{N-}\text{acetyl}\text{-N-}\text{methyl-}\text{l}\text{-alanine}$ dimethylamide. In comparison of the polymer with the monomeric amide, it was concluded that the transition of $\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ was caused by the isomerization of amide bonds. The complex n.m.r. spectrum was interpreted in terms of the distribution along the polymer chain of various non-planar amide links as well as planar cis and trans amide links. The difference of the mechanism of conformational transition between poly(amino acid) and poly(imino acid) is also discussed.     

Homo- and copolymerizations of 3-(N-carbazolyl)-1-propyne and its homologues by Mo and W catalysts

Summary 3-(N-Carbazolyl)-1-propyne polymerized with MoCl₅- and WCl₆-based catalysts to produce a polymer in high yields. The MoCl₅ and MoCl₅-n-Bu₄Sn catalysts were the most effective (the systems solidified immediately after initiation of polymerization with these catalysts). The product polymer was a yellow solid insoluble in any solvent. Copolymerization of the present monomer with tert-butylacetylene by MoCl₅-n-Bu₄Sn produced a copolymer; it had a high molecular weight (M _w 350,000), completely dissolved in toluene, CHCl₃ etc, and formed a free-standing film by solution casting. -N-Carbazolyl-1-hexyne and-1-octyne produced toluene-insoluble polymers with WCl₆-Ph₄Sn.     

Suppression of natural convection heat transfer along a vertical flat plate with concavities

To clarify the effect of the suppression of natural heat transfer, the local heat transfer coefficients on a vertical cooled flat plate with circular grooves were measured by a multi‐type thermocouple method. Two flat plates with and without periodic circular grooves were tested in this experiment. The characteristics of heat transfer along the plate for both plates were compared. The local heat transfer coefficients on the periodic grooved plate became smaller than that of the flat plate. The flow pattern was changed when it passed over the grooves, and circulation was generated in the grooves in the downstream. As a result, the thickness of the thermal boundary layer on the grooved plate was more developed than the normal flat plate. © 2010 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.20294     

Solvent effect on cationic polymerization of styrene with α- or β-methylstyrenes

To investigate the steric hindrance in the cationic copolymerization of styrene derivatives, styrene was copolymerized with anethole or with α-methylstyrene in polar and non-polar solvents by using BF₃O(C₂H₅)₂ or SnCl₄-trichloroacetic acid as catalyst. As the polarity of the solvent increased, the relative reactivity of α-methylstyrene towards a styryl cation decreased and that of anethole increased. The mode of attack of the propagating carbocation to styrene derivatives in a non-polar solvent is discussed on the basis of these contrasting phenomena.     

Improvement of partial discharge (PD) resistance of epoxy resin by using sulfur-containing additives

In the field of high-voltage engineering, it has been desired for a long time to improve the internal PD resistance of epoxy resin without lowering other properties. Recently, the authors discovered that some sulfur compound as curing agents or simple additives improved the PD resistance of rubber markedly, and here an attempt has been made to apply this fact to the case of epoxy resin. As was expected, some sulfur compounds containing SS-bond suppress the deterioration of epoxy resin due to internal partial discharges, and the larger the molecular weight of organic group combining the SS-bond, the longer the effective life of additives. Moreover, to make full use of these additives, it is very important to restrict moisture in the insulation systems. From this study, the authors have proposed the chemical formulation of the suppressive effect of additives for deterioration of epoxy resin due to internal partial discharges.