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The chemistry of alternating ethylene-carbon monoxide copolymer and the role of electrophilic transition metal compounds in the cationic polymerization of olefins
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The chemistry of alternating ethylene-carbon monoxide copolymer and the role of electrophilic transition metal compounds in the cationic polymerization of olefins
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The chemistry of alternating ethylene-carbon monoxide copolymer and the role of electrophilic transition metal compounds in the cationic polymerization of olefins
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Dissertation
The chemistry of alternating ethylene-carbon monoxide copolymer and the role of electrophilic transition metal compounds in the cationic polymerization of olefins
1990
Overview
Alternating ethylene-carbon monoxide copolymer (E-CO copolymer) was prepared by direct polymerization of carbon monoxide with ethylene, using (Pd(CH $\\sb3$ CN) $\\sb2$ (PPh $\\sb3)\\sb2$ ) (BF $\\sb4)\\sb2$as the catalyst. Reaction of the E-CO copolymer with primary amines has resulted in formation of a new type of functionalized polymer derivatives, N-substituted poly(ethylenepyrrole). The nonconjugated poly(ethylenepyrrole) derivatives exhibited high electrical conductivity after doping with iodine. Furthermore, dehydrogenation of the derivatized poly(ethylenepyrrole) has led to the synthesis of a new conjugated polymer system, poly(ethynepyrrole). Palladium complexes--Pd(2,6- $\\sp{\\rm t}$ Bu $\\sb2$ -pyridine) $\\sb2$ (CH $\\sb3$ NO $\\sb2)\\sb2$ (BF $\\sb4)\\sb2$ ,1; Pd(PPh $\\sb3)\\sb2$ (BF $\\sb4)\\sb2$2; Pd(Ph $\\sb2$ PCH $\\sb2$ CH $\\sb2$ PPh $\\sb2$ )(BF $\\sb4)\\sb2$ , 3--were prepared through either ligand substitution reaction using (Pd(CH $\\sb3$ CN) $\\sb4$ ) (BF $\\sb4)\\sb2$as starting reagent or reaction of PdL $\\sb2$ Cl $\\sb2$(L: corresponding ancillary ligand) with two equivalents of AgBF $\\sb4$in nitromethane. Compounds 1-3 were found to selectively catalyze the dimerization or oligomerization/polymerization of a variety of olefins while the compound (Pd(CH $\\sb3$ CN) $\\sb4$ ) (BF $\\sb4)\\sb2$ , polymerized olefins nonselectively. The initiation mechanism of the cationic dimerization and polymerization of olefins is proposed. One of these highly selective catalysts, Pd(PPh $\\sb3)\\sb2$ (BF $\\sb4)\\sb2$(2), was also used for the synthesis of linear poly(p-divinylbenzene). Catalyzed by 2, p-divinylbenzene (p-DVB) polymerized gradually through a stepwise intermolecular vinyl coupling process to form a linear unsaturated poly(p-DVB). In addition, terminally functionalized poly(p-DVB) was prepared through cross vinyl coupling between terminal vinyl groups of the poly(p-DVB) and the vinyl group of functional group substituted styrene, using the same catalyst. The kinetics of the p-DVB polymerization catalyzed by 2 and the styrene dimerization and$\\alpha$ -methylstyrene oligomerization reaction catalyzed by 1 were studied. The reaction rate equations were determined, in general, as follows: Rate = k (Olefin)$\\sp1$(Pd(II))$\\sp{\\rm m}$Olefin: styrene,$\\alpha$ -methylstyrene or p-DVB Pd(II): 1 or 2, total Pd(II) species in solution m: 0.6-0.7 in the styrene dimerization and p-DVB polymerization reaction, 2.2 in the$\\alpha$ -methylstyrene oligomerization reaction Quantitative analysis shows that m is dependent on the equilibria involving the interactions between the cationic metal species and its counteranion. Fractional order m varies with the change in the dissociation constants of BF $\\sb4\\sp-$from the metal cation. The solvent, whose polarity affects the dissociation equilibria, could also change the value of the order m.
