Studies on polymers containing functional groups. VI. Kinetics of the polymerization and copolymerization behaviors of o‐hydroxystyrene

Abstract

SynopsisSome kinetic studies were made of the homopolymerization of o-hydroxystyrene and its copolymerization behavior with styrene and methyl methacrylate in tetrahydrofuran using azobisisobutyronitrile as initiator were done. The rate of polymerization experimentally obtained is given by R, = K [ M ] [I]0.7e. Accordingly, it is likely that the growing chain radicals are terminated not only by mutual termination but also by a chaintransfer mechanism, the latter occupying a considerable portion. The latter is mostly attributed to the transfer to monomer, i.e., C, for o-hydroxystyrene was 1.3 x Some transfer mechanism were assumed, although it i s difficult to elucidate the mechanism in detail, owing to its complexity. Effects of solvent on the rate of polymerization were examined, dioxane, methyl ethyl ketone, ethanol, and tetrahydrofuran being used. However, no differences were found among the solvents. The apparent activation energy of polymerization was found to be 21.5 kcal./mole. Monomer reactivity ratios and Alfrey-Price &-e values for o-hydroxystyrene were determined. The Q-e values (& = 1.41, e = -1.13) are rather similar to those of p-methoxystyrene. Thus, the e value for o-hydroxystyrene is more negative than that for styrene.

Preparation and Polymerization of 4-Hydroxy-4′-vinylbiphenyl

“…This result differs from the polymerization of ohydroxystyrene, which has no solvent effect on polymerization. 12 Recently, Kamlet and Taft demonstrated the following linear solvation energy relationships (eq 1), which can serve to explain solvent effects on many reaction rate and equilibrium constants. 13 XYZ=XYZ 0 +sll*+aa+bf3 (1) where XYZ, ll*, a, and f3 represent reaction rate, dipolarityjpolarizability, hydrogen bond donor (HBD) acidity, hydrogen bond acceptor (HBA) basicity.…”

A morphological analogue of japanese lacquer. Grafting of p‐hydroxystyrene onto pullulan by ammonium persulfate initiation in dimethylsulfoxide

“…The molecular weight of grafted chain isolated from hydrolysis was measured by GPC, and a relatively low degree of polymerization (DP), 15-20 was found (runs 6,8,[12][13][14][15]. This is due to a high mole ratio of APS used in polymerization.…”

Electron‐transfer polymers (oxidation‐reduction polymers)

“…The most active of these has been that of G. Manecke , where many functional groups have been investigated. H. Kamogawa (74)(75)(76)(77)(78)(79)(80)(81)(82)(83)(84)(85)(87)(88)(89), and the groups associated with A. A. Berlin and with E. E. Ergozhin, have also been active in this area.…”