Studies of micro-brownian motion of a polymer chain by the fluorescence polarization method. I. Fluorescent conjugates of polyacrylamide

Polyacrylamide having a fluorescent residue at the chain end was prepared by polymerization of acrylamide in the presence of a fluorescent dye. The segmental motion of the chain end in dilute solution was studied by the fluorescence polarization method on the fluorescent polyacrylamide conjugates thus obtained. The linear relation between 1/p and T/η₀ held for every sample studied in aqueous media, where p is the degree of polarization of the fluorescence, T is the absolute temperature, and η₀ is the viscosity of the medium. The mean relaxation time 〈ρ〉 of the conjugate was evaluated from these data as a function of the molecular weight of the conjugate. The value of 〈ρ〉 increased slightly with molecular weight, varying from 3.3 × 10^?9 to 7 × 10^?9 sec. The absolute values of 〈ρ〉 and its molecular weight dependence suggest that 〈ρ〉 represents the mean rotational relaxation time for the cooperative motion of about ten monomeric units at the chain end. The effect of the mean extension of polymer chain on the segmental motion was found to be negligible.     

Preparation of Ethene/Carbon Monoxide Copolymers Using Copper‐Based Catalysts and Their Characterization by Pyrolysis‐Gas Chromatography

Ethene/carbon monoxide copolymers were prepared using the catalyst system Cu(OAc)₂/dppp (1,3‐bis(diphenylphosphino)propane)/p‐toluenesulfonic acid (p‐TsOH) or BF₃·OEt₂/p‐benzoquinone. Pyrolysis‐gas chromatography proves the alternating structure of the copolymers.     

Following the polyisocyanate helix reversal from dilute solution through the liquid crystal and into the solid state

The absence of a predetermined helical sense in the polyisocyanates causes the formation of helix reversals which enforce a strong cooperativity for the amplification of chiral effects. The helix reversals though also place a limit on this amplification, a limit which would be eliminated by reducing the helix reversal population. Approaching the liquid crystal state of the polyisocyanates in both dilute and concentrated solutions appears to cause the exclusion of the helix reversals which is consistent with theoretical expectations. Since the linear birefringence of the polyisocyanate solid state precludes optical activity measurements associated with the polymer, we have synthesized hydrogen bonding side chain adapted polyisocyanates which appear by DSC and infra-red criteria to form equilibrium molecular composites with copolymers of vinyl phenol and styrene. The optical activity properties of these composites may offer a new way to probe polymer motion in the solid state.     

The effect of aluminium compounds in the copolymerization of ethylene / α-olefins

Two types of copolymerizations were found with the catalyst system Cp₂ZrCl₂/MAO. One was a less exothermic reaction, and another was a more exothermic one. The former provided a polymer with a single composition distribution because of a single cationic active site. The latter provided a polymer with a bimodal composition distribution, indicating the existence of two active sites. The two active sites were investigated through the comparison of MAO systems and alkylaluminium / borate systems. We speculated that the two active sites were the normal cationic site and the active site where the interaction between a cationic metallocene and an aluminium compound was strong.