Lifetime of living polymers in cationic polymerization. II. Living polymerization of isobutyl vinyl ether initiated by the hydrogen iodide/zinc halide systems

In the living cationic polymerization of isobutyl vinyl ether (IBVE) initiated by the hydrogen iodide/zinc halide (HI/ZnX₂; X = I, Br, Cl) systems, the concentration ([P^*]) of the living propagating species was determined by quenching with sodiomalonic ester ( 1 ). The quenching reaction was shown to be clean, instantaneous, and quantitative to give poly (IBVE) with a terminal malonate group from which [P^*] was obtained by ¹H-NMR spectroscopy. In the polymerizations in toluene below +25°C, [P^*] was constant and equal to the initial concentration ([HI]₀) of hydrogen iodide, independent of the type and concentrations of ZnX₂ as well as monomer conversion. At 0 and +25°C, however, the living species started decaying immediately after the complete consumption of monomer. In contrast, such a decay process was absent at ?15°C even in the absence of monomer until about an hour (depending on the conditions) after the end of polymerization. The deactivation reaction was first order in [P^*], and the lifetime (half-life) of the living species was longer at lower temperature and at lower ZnX₂ concentration. On the basis of these [P^*] and lifetime measurements, the HI/ZnX₂ systems were also compared with the HI/I₂ counterpart.     

Stereochemistry in cationic polymerization of alkenyl ethers. V. Stereochemistry of acetal additions as model reactions for the polymerization of alkenyl ethers

Acetal additions to β-substituted vinyl ethers having a variety of substituents (alkenyl ethers) were stereochemically investigated as model reactions for their cationic polymerization. The reactions catalyzed by BF₃O(C₂H₅)₂ in CH₂Cl₂ at O°C gave 1:1 adducts, the steric structure of which was determined by means of ¹³C-NMR spectroscopy. trans-Alkenyl ethers always gave adducts with a single structure stereospecifically, indicating that the intermediate carbocation attacks a trans-alkenyl ether from a definite direction independent of the bulkiness of substituents. On the other hand, cis-alkenyl ethers formed adducts with two steric structures, and the direction of cation addition was found to depend on the bulkiness of the alkoxy group involved. The above trends were in agreement with the results for poly(alkenyl ether)s and allowed detailed discussion of the stereochemistry of the propagation processes in alkenyl ether polymerizations.     

Dimerization of methylstyrenes by acetyl perchlorate and trifluoromethanesulfonic acid

Ring-substituted methylstyrenes (p-, m-, and o-methylstyrenes) in conjunction with acetyl perchlorate (AcClO₄) or trifluoromethanesulfonic acid as catalysts gave their linear unsaturated dimer in high yield in benzene at temperatures from 50 to 70°C. In particular, the yield of o-methylstyrene dimer was as high as 90% in the AcClO₄ catalysis at 50°C. The dimer yield depended on solvent and catalyst. The terminal structures of the dimers and higher oligomers were analyzed by NMR spectroscopy. Oligomers with a cyclic terminal structure increased in the products at higher temperature. The dimer yield was improved by codimerizing p-methylstyrene with less reactive m-methylstyrene or styrene with AcClO₄ catalyst. The dimers obtained partly consisted of linear unsaturated codimers.     

Polymerization of silylacetylenes by W and Mo catalysts

Polymerization of HC?CSiMe₃ homologues (HC?CSiMe₂R; R = n-C₆H₁₃, CH₂CH₂Ph, CH₂Ph, Ph, and t-Bu) was studied by use of W and Mo catalysts. W catalysts provided polymers in good yields from all these monomers. Mo catalysts gave mainly a polymer from HC?CSiMe₂–t-Bu, but virturally only cyclotrimers from sterically less croweded monomers (R = n-C₆H₁₃, CH₂CH₂Ph, CH₂Ph, and Ph). Polymers with flexible R groups (n-C₆H₁₃, CH₂CH₂Ph, and CH₂Ph) were totally soluble, their number-average molecular weights being 7000–18,000. Polymers with inflexible R groups (Ph and t-Bu) were partly insoluble. Every polymer was a yellow rubber or powder, and had the structure, \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm CH} = {\rm C}\left( {{\rm SiMe}_{\rm 2} {\rm R}} \right)\rlap{--} ]_n $\end{document}. The results were compared with the polymerization and polymer of HC?CSiMe₃.     

Di-isotacticity of poly(methyl propenyl ether) and double-bond opening of methyl propenyl ether in cationic polymerization

The di-isotacticity of poly(methylpropenyl ether) obtained by the cationic polymerization has been studied by NMR spectra. The NMR spectra of β-methyl protons of the polymer are decoupled from the β-methine proton spectra to determine the di-isotactic fraction in a polymer. The signals of β-methyl protons at 8.78 and 8.89 τ are estimated as spectra based on threo- and erythro-di-isotactic diads, respectively. With BF₃·O(C₂H₅)₂ as a catalyst, the trans monomer yields a crystalline polymer and its structure is threo-di-isotactic. Otherwise, cis monomer produces an amorphous polymer, and it is a mixture of threo- and erythro-di-isotactic structure. From these results, it is concluded that the double bond in trans monomer is opened exclusively in the cis type, and in cis monomer cis- and trans-openings take place at almost the same rate.     

Anomalous thermochromic transition of poly(di‐n‐octylsilane)

The thermochromic behavior of poly(di‐n‐octylsilane) {[Si(C₈H₁₇)₂]_n; PDOS} was studied by ultraviolet (UV) absorption, differential scanning calorimetry, and X‐ray diffraction measurements. The structure of PDOS in the low‐temperature phase strongly depended on not only the temperature but also the rate of cooling, that is, the thermal history. Temperature‐dependent UV absorption spectra were highly dependent on thermal hysteresis. Cooled rapidly (10 K/min), PDOS showed two absorption peaks at 3.32 and 3.51 eV in low‐temperature‐ordered phases, whereas a single absorption peak at 3.32 eV became predominant with slow cooling (0.3 K/min). The appearance of the two peaks at low temperatures suggested that a mixture of different conformations was introduced by rapid cooling. A fiber diffraction pattern measured at 240 K after rapid cooling also showed evidence of the existence of novel conformation. A temperature‐dependent powder X‐ray diffraction pattern changed significantly between 270 and 280 K. Rapid cooling reduced the intensity of the X‐ray diffraction peak in this temperature region. This intensity change was explained by the conformational mixture in the polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1085–1092, 2001     

Synthesis of proton conductive inorganic–organic hybrid membranes through copolymerization of dimethylethoxyvinylsilane with vinylphosphonic acid

Proton conductive inorganic–organic hybrid membranes were synthesized from dimethylethoxyvinylsilane (DMEVS), vinylphosphonic acid (VPA) and 3-glycidoxypropyltrimethoxysilane (GPTMS) through copolymerization followed by sol–gel process. The ratio of phosphorus to silicon in the copolymer almost corresponded to the charged molar ratio of VPA to DMEVS when the ratio of VPA to DMEVS was below 1/2. Self-standing, homogeneous, highly transparent membranes were synthesized from DMEVS–VPA copolymer and GPTMS via sol–gel condensation. Differential thermal analysis-thermogravimetry analyses indicated that these membranes were thermally stable up to 200 °C. The results of Fourier transform infrared and ¹³C NMR revealed that phosphonic acid groups of VPA were chemically bound to organosiloxane network. The copolymerization and condensation of (DMEVS–VPA)/GPTMS were confirmed by ³¹P and ²⁹Si NMR spectra. The proton conductivity of the hybrid membranes increased with phosphonic acid content. The membrane of (DMEVS–VPA)/GPTMS showed a remarkable conductivity of 6.3 × 10⁻² S cm⁻¹ at 130 °C and 100% relative humidity.     

Conformationally Flexible Biphenyl‐phosphane Ligands for Ru‐Catalyzed Enantioselective Hydrogenation

Stereomutation of a BIPHEP/RuCl ₂ /diamine complex (shown schematically) is possible because of the conformational flexibilty of BIPHEP ligands. The result is an asymmetric activation in the Ru‐catalyzed hydrogenation of carbonyl compounds to optically active alcohols. Whereas a racemic BINAP/RuCl₂ complex with a chiral diamine activator gives a 1:1 mixture of two diastereomers, unequal amounts of the diastereomers can be produced from a BIPHEP/RuCl₂ complex and a chiral diamine. Ar=3,5‐dimethylphenyl, BINAP=2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl, BIPHEP=2,2′‐bis(diarylphosphanyl)biphenyl.     

Hydration of phosphate and borate glasses in an autoclave

Kinetics of hydration of CaO---Al₂O₃---P₂O₅ and Na₂O---CaO---B₂O₃---Al₂O₃ glasses in an autoclave at high temperatures and high pressures has been investigated. The hydration of the phosphate glasses may occur as a result of hydrolysis of glass constituents to form orthophosphate crystals. Cabal glasses which do not contain any alkali oxides have shown a quite high resistance to water. Substitution of sodium for calcium deteriorates the chemical durability of Cabal glasses.     

White light emission of Mn-doped SnO-ZnO-P2O5 glass containing no rare earth cation

The authors have demonstrated white light emission of rare earth (RE)-free Mn-doped SnO-ZnO-P(2)O(5) glass. The RE-free glass shows white light emission with a high value of quantum efficiency (QE) comparable to conventional crystalline phosphor. It is notable that the high QE value is attained for RE-free transparent glass, and the broad emission can be continuously tuned by both the amount of activator and the composition of the glass. Since this glass possesses low-melting property, we emphasize that the glass phosphor will lead to the development of a novel inorganic white-light-emitting device in combination with a solid state UV light-emitting source.