Anionic Polymerization of Tertiary Aminostyrenes and Characterization of the Polymers

Abstract

ABSTRACT:The polymers of three tertiary aminostyrenes: poly(N,N-dimethyl-4-vinylphenylamine), abbreviated as PPA; poly(N,N-dimethyl-4-vinylbenzylamine), PBA; and poly-(N,N-dimethyl-4-vinylphenethylamine), PPTA, were prepared via anionic polymerization in THF at -78°C. GPC measurement was carried out to estimate the molecular weights and molecular weight distributions (MWD) of the polymers. A mixture of THF and Nmethylpyrrolidine (2 v/v%) was used as carrier solvent to avoid the adsorption of the polymers on the surface of the GPC gels. When n-butyllithium was used as an initiator, 100% polymer conversion was attained. The values of Mw/Mn were more than 1.20. The M. was equal to Mk, calculated from the amounts of monomers and initiators. No polymer having narrow MWD was obtained, even when N-methylpyrrolidine was used as an additive. On the other hand, when cumyl potassium and cumyl cesium were used as initiators, polymers having narrow MWD were produced. The values of M w! Mn were less than 1.08. The apparent rate constant of polymerization of cumyl cesium for PPA was small, compared with those for PBA and PPT A.

Quaternization of poly(tertiary aminostyrene)s and characterization of the quaternized polymers

“…9 The details of these meth-GPC Measurements ods are described in elsewhere. 9 Number average molecular weight (M n ), and molecular weight hetWhen poly(tertiary aminostyrene)s were quaternized with n-butyl bromide at high rates of conerogeneity (M w /M n value) were determined by us- version, quaternized products were found to be this phenomenon, it is necessary to increase hydrophobic interaction between the quaternized soluble in water but not in THF. Hence, GPC measurement was carried out using an aqueous solupolymers and eluant.…”

“…This pyrrolidine (98/2 v/v %) was used as an eluant problem is presumed to be complicated, because in order to avoid adsorption of the polymers conthe reactant polymer has a solubility different taining amino groups onto the GPC column gel. 9,17 from that of the produced polymer that is soluble Quaternized PPA, PBA, and PPTA were also in water. Hence, special care should be taken tested on GPC so as to estimate the values of M n when selecting solvents used for quaternization and M w /M n using poly(ethylene oxide) calibraand GPC measurement.…”

“…The values of M n and M w /M n for each of PPA, poly(N,N-dimethyl-4-vinylbenzylamine)(PBA), PBA, and PPTA were estimated via gel-permeand poly(N,N-dimethyl- 4-vinylphenethylamine) ation chromatography (GPC; Model HLC-803, (PPTA) via anionic living polymerization, 9 thus with two high resolution columns of GMH6: 7.8 overcoming this problem. The second problem mm i.d.…”

Anionic living polymerization of functionalized monomers

“…In fact, Fujimoto and coworkers demonstrated the anionic living polymerization of the styrene derivatives containing the dimethylamino group 4 a -c (Fig. 1) [25].…”

Preparation and Characterization of Poly[(4-vinylphenyl)dimethylvinylsilane] via Anionic Living Polymerization

“…These patterns showed clear image lines without webbing or meandering. 20 Thus, the PVS molecule which contains the silylvinyl group as a side chain was found to act as negative working resist by exposing to a deep UV light. 440 Further details of the lithographic characteristics 10 , 28 · 29 of PVS will be discussed elsewhere, 30 including those of PVS exposed to ultraviolet light and an electron beam.…”