Poly(diphenylacety1ene) is thermally very stable, but insoluble in any solvent, whereas polyacetylenes from unsymmetrically disubstituted acetylenes are generally soluble. Hence, the synthesis of soluble poly(diphenylacety1enes) was examined by introducing the trimethylsilyl group. 1-Phenyl-2-lp-(trimethylaily1)phenyllacetylene and l-phenyl-2-[m-(trimethylsilyl)phenyl]acetylene polymerized with T a c k cocatalyst systems to provide new polymers with over 70% yields having a weight-average molecular weight over 1 X 106. As cocatalysts, nBurSn, EhSiH, and SBBN were especially effective. The polymers were yellow solids with the alternating double bond structure [-CP~=C(C&S~M~S)-I,,. They completely dissolved in toluene, CHCla, etc., and formed tough f i i by eolution casting. The onset temperatures of weight loss in TGA in air were as high as ca. 400 "C. Their oxygen permeability coefficients were both high, ca. lo00 barrers.

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Copolymerization of olefins (ethylene and propylene) and 5‐hexen‐1‐ol pretreated with alkylaluminum was performed using [dimethysilylbis(9‐fluorenyl)]zirconium dichloride/methylaluminoxane as the catalyst. The copolymerization required extra addition of alkylaluminum to prevent deactivation of the catalyst when 5‐hexen‐1‐ol was pretreated with trimethylaluminum, whereas the triisobutylaluminum‐treated system did not require any addition of alkylaluminum. The molecular weight of the copolymer depended on the kind of alkylaluminum compound (masking reagent, additive, and cocatalyst). 13C NMR analysis proved that poly(ethylene‐co‐5‐hexen‐1‐ol) containing 50 mol % of 5‐hexen‐1‐ol acted as an alternating copolymer, whereas the poly(propylene‐co‐5‐hexen‐1‐ol) acted as a random copolymer. The surface property of the copolymers was simply evaluated by means of water drop contact angle measurement. It was found that the copolymers containing large amounts of 5‐hexen‐1‐ol units showed good hydrophilic properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 52–58, 2004

The copolymerizations of propylene with allyl monomers carrying alcohol or amine were conducted by the rac-dimethylsilylbis(1-indenyl)zirconium dichloride/methylaluminoxane catalyst system. The allyl monomers were pretreated by alkylaluminum before the polymerization. Although the efficiency of the introduction of allyl alcohol-based comonomer was extraordinary low (0.04−0.08 mol % in polymer), the trimethylaluminum-treated allylamine was found to be introduced more effectively (0.65 mol % in polymer). The 13C NMR study indicated that the position of allylamine unit in the copolymer was influenced by the kind of alkylaluminum used at the polymerization. In the presence of trimethylaluminum, the terminally aminated polypropylene was obtained ([amino end polymer]/[whole polymer] = 0.83). In the presence of triisobutylaluminum, however, the allylamine unit is located both on the main chain and at the chain end. The end-aminated polymer was probably obtained due to the formation of dormant species after the insertion of the comonomer followed by the chain transfer to alkylaluminum.