Cationic copolymerization of phenyl propenyl ethers

Ring-substituted phenyl propenyl ethers were found to form homopolymers without any rearrangement by metal halides. Phenyl propenyl ethers were less reactive than the corresponding phenyl vinyl ethers in cationic polymerization. In order to study the electronic effect of a substituent on the reactivity, cis-p-Cl,p-CH₃, and p-CH₃O-phenyl propenyl ethers were copolymerized with phenyl propenyl ether in methylene chloride at ?78°C with stannic chloride–trichloroacetic acid, and their ¹H- and ¹³C-NMR spectra were measured. The reaction constant ρ against Hammett σ_p was ?2.1. The cis-phenyl propenyl ethers were slightly more reactive than the corresponding trans isomers. On the other hand, an o-methyl group decreased the reactivity of phenyl propenyl ether. The low reactivity of o-methyl phenyl propenyl ether was attributed to the steric hindrance between the propagating carbocation and the monomer.     

Living cationic polymerization of vinyl monomers: New initiators and functional polymer synthesis

This paper focuses on two recent topics in living cationic polymerization of vinyl monomers, i.e., (a) Development of new initiating systems: RCOOH/Lewis acid for vinyl ethers; CH₃CH(C₆H₅)Cl/SnCl₄/nBu₄NCl for styrene. (b) Synthesis of shape-controlled poly(vinyl ethers): Tri-armed star polymers; Multi-armed spherical polymers. For the RCOOH-based systems, a generalized concept of living cationic polymerization was discussed on the basis of the effects of the counteranions (or R) and Lewis acids (ZnCl₂ and EtAlCl₂). The CH₃CH(C₆H₅)Cl-based system permitted a truly living cationic polymerization of styrene. The tri- and multi-armed poly(vinyl ethers) included new amphiphilic polymers of unique topology, solubility, etc., all of which were prepared by living cationic polymerization.     

<Emphasis Type="Italic">In Situ</Emphasis> Synthesis of Field-responsive Nanocrystalline BaTiO<Subscript>3</Subscript> Particles Modified with Functional Organics

Nanocrystalline BaTiO₃ particles modified with polarizable ligands were synthesized through hydrolysis of modified metal–organics below 100°C. BaTiO₃ precursor was synthesized from barium metal, titanium isopropoxide and polarizable ligands in a mixture of ethanol and 2-ethoxyethanol. The modified Ba–Ti complex alkoxide was hydrolyzed yielding BaTiO₃ particles modified with organics. The crystallinty of nanometer-sized particles was dependent upon the hydrolysis conditions, and increased with increasing water amount and time. The nanocrystalline particles were identified to be BaTiO₃ by X-ray diffraction (XRD) and electron diffraction. A fluid consisting of modified BaTiO₃ particles and silicone oil revealed a typical electrorheological (ER) behavior on applying DC field. The ER behavior was found to depend upon the kind of ligand. 4-Fluorobenzyloxy modifier revealed the highest yield stress in the ER measurement among 4-substitued benzyloxy ligands examined.     

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.     

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.     

New asymmetric vanadium catalyst for highly selective oxidative coupling polymerization

Novel oxovanadium(IV)–bisoxazoline catalysts, such as vanadyl sulfate (VOSO₄)–(R)‐2,2′‐isopropylidenebis(4‐phenyl‐2‐oxazoline) [(R)Phbox], for the asymmetric oxidative coupling polymerization (AOCP) of 2,3‐dihydroxynaphthalene were developed. For example, the AOCP with VOSO₄–(R)Phbox in CH₂Cl₂–MeOH [7/1 (v/v)] at room temperature for 24 h under an O₂ atmosphere, followed by acetylation of the hydroxyl groups, afforded a polymer in a 58% yield with a specific rotation of [α]_D = ?147. The enantioselectivity during the polymerization was estimated to be 80% enantiomeric excess (S), a value much higher than that observed for the polymerizations with the copper(I)‐based catalyst systems and the typical oxovanadium(IV) catalysts reported for the asymmetric oxidative coupling producing the 1,1′‐bi‐2‐naphthol derivatives. © 2005 Wiley Periodicals, Inc., Inc. J Polym Sci Part A: Polym Chem 43: 5872–5878, 2005     

Plastic crystalline lithium salt with solid-state ionic conductivity and high lithium transport number

Plastic crystallinity of lithium salt, [LiB(OCH(2)CH(2)OCH(3))(4)] (1), and its solid-state ionic conductivity are disclosed. The addition of small amounts of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to borate 1 led to the drastic increase of the ionic conductivity and lithium transport number of the electrolyte.