Radiation grafted and sulfonated poly(vinylidene fluoride), PVDF, membranes have been studied by thermal analysis and X-ray diÂraction to determine the changes in membrane crystallinity and structure during preparation. Commercial PVDF films were irradiated with an electron beam, grafted with styrene and finally sulfonated. Both the crystallinity and the size of the crystallites of PVDF decrease in the grafting reaction. A further decrease in crystallinity is observed in the sulfonation reaction. The residual crystallinity of PVDF was considerable (10-20%) even in membranes which had been subjected to severe reaction conditions. These results can be explained by assuming that the grafting takes place mainly in the amorphous region of the PVDF, and close to the surfaces of the crystals, but that grafts do not penetrate into the crystals. The proton conductivity of the grafted and sulfonated PVDF membranes reached values comparable to those of Nafion membranes.

The influence of siloxy substitution of ethylene-bridged bis(indenyl)- and bis(tetrahydroindenyl)zirconium dichlorides on ethylene/α-olefin copolymerization and ethylene homopolymerization performance was investigated. Ethylene was copolymerized with 1-hexene and 1-hexadecene over rac-[ethylenebis(1-(tert-butyldimethylsiloxy)-3-indenyl)]zirconium dichloride (1), rac-[ethylenebis(1-(tert-butyldimethylsiloxy)-4,5,6,7-tetrahydro-3-indenyl)]zirconium dichloride (H1), rac-[ethylenebis(2-(tert-butyldimethylsiloxy)-1-indenyl)]zirconium dichloride (2), and rac-ethylenebis(1-indenyl)zirconium dichloride (EBI) using methylaluminoxane (MAO) as cocatalyst. 1-Siloxy substitution was found to remarkably improve the copolymerization ability and 2-siloxy substitution to enhance the polymerization activity of ethylenebis(indenyl)zirconium dichlorides. Optimum homo- and copolymerization performance was observed at a very low Al(MAO) concentration, which for 2 could be reduced to a level of 0.2 mmol/dm3 by using a small amount of triisobutylaluminum. The 1-siloxy-substituted metallocene catalysts 1 and H1 (hydrogenated 1) revealed decreasing comonomer incorporation and increasing induction times with increasing Al(MAO) concentration, which indicates the presence of unfavorable interactions between these metallocenes and MAO. Chain termination occurred mainly by chain transfer to the monomer and β-hydrogen transfer to the metal for catalysts with indenyl and tetrahydroindenyl ligands, respectively.

Crosslinked proton exchange membranes were prepared by electron beam grafting of styrene with divinylbenzene, DVB, or bis(vinyl phenyl)ethane, BVPE, on to poly(vinylidene fluoride), PVDF, followed by sulfonation. The area and thickness increase, crystallinity and mechanical properties of the membranes were investigated. All these properties were influenced by the crosslinker structure and its concentration. The crosslinkers increase the final degree of grafting. For noncrosslinked membranes it was about 80% and with 10% of BVPE crosslinker about 180% after 8 hr. The area increase with grafting is very similar for the noncrosslinked membranes and the differently crosslinked membranes, but the crosslinkers reduce swelling for sulfonated membranes swelled in boiling water. DVB reduces swelling more than BVPE. With grafting, the crystallinity of the PVDF phase decreases; with 10% BVPE the decrease is smallest and with 10% DVB largest. The mechanical properties of the sulfonated swelled membranes decrease with the degree of grafting, for a 10% DVB crosslinked membrane the strength decreases to zero at degrees of grafting higher than 75%. © 1998 John Wiley & Sons, Ltd.

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Porous poly(vinylidene fluoride) membranes were graft modified with acrylic acid by radiation-induced grafting utilizing electron beam. When the grafted membranes were characterized by the measurements of convective permeability, diffusion, and ion exchange properties, the membranes showed properties of variable permeability membranes with respect to the permeability of solvent and the ionic semipermeability. The permeability for the studied membranes (extent of grafting varied from 0 to 93 wt %) can be controlled by the ionic strength and pH of the permeate. The more grafted the membranes are the greater are the changes in the permeability; e.g., for the extent of grafting of 85 wt % the permeability increases ca. 4 orders of magnitude when the electrolyte concentration is increased from 10 mM to 1 M. The membranes with the extent of grafting of ca. 10 wt % or more appeared to have equal charge density on the pore walls resulting in the same cation transference number.

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The preparation and crystal structure of the first group 4 ansa-metallocene with an oxygen atom directly bonded to the 2-position of an η5-indenyl moiety, rac-[ethylenebis(2-(tert-butyldimethylsiloxy)indenyl)]zirconium dichloride (3), is reported. In combination with methylaluminoxane (MAO), complex 3 polymerizes propylene to highly isotactic crystalline polypropylene (T m = 148 °C; M w = 19 000; M w/M n = 2.4). Under similar conditions, the propylene polymerization activity of 3/MAO exceeds that of the conventional ansa-metallocene catalyst system (dimethylsilyl)bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride (4)/MAO by a factor of 2 (5300 vs 2300 kg of PP/mol of Zr/h; Tp = 20 °C; P(C3H6) = 2.0 bar; [Al]:[Zr] = 3 000:1). Complex 3 crystallizes in the unusual indenyl-backward conformation. The molecular structure is consistent with the expected C 2 symmetry.