Polymerization initiated by an electron donor–acceptor complex. VI. Polymerization of methyl methacrylate initiated by a liquid SO₂–nicotine complex and carbon tetrachloride

Abstract

SUMMARY:The polymerization of methyl methacrylate can be easily initiated in systems containing poly-2-vinylpyridine (polymer electron donor), liquid sulfur dioxide (acceptor), and carbon tetrachloride. The various types of polymer electron donors and acceptors which range widely in their electron affinity were also examined. The addition of DPPH causes the retardation; a decrease in the poly-2-vinylpyridine concentration or an increase in the monomer concentration leads to a higher molecular weight of poly-MMA. The values of kp/vG obtained under the various polymerization conditions are satisfactorily consistent with the literature values, suggesting that the polymerization proceeds through free radical intermediates. ZUSAMMENFASSUNG:Die Polymerisation von Methacrylsauremethylester kann in Systemen, die Poly-2-vinylpyridin (als polymerer Elektronendonator), flussiges Schwefeldioxid (als Acceptor) und Tetrachlorkohlenstoff enthalten, leicht initiiert werden. Verschiedene Arten van polymeren Elektronendonatoren und -acceptoren mit einem grol3en Bereich .der Elektronenaffinitat wurden ebenfalls untersucht. Der Zusatz von DPPH bewirkt eine Verzogerung der Polymerisation; eine Verminderung der Poly-2-vinylpyridin-Konzentration oder eine Erhohung der Monomerenkonzentration ergibt ein hoheres Molekulargewichtes. Die unter den verschiedenen Polymerisationsbedingungen erhaltenen Werte von kp/l/k7 stimmen mit den in der Literatur angegebenen Werten befriedigend iiberein und weisen darauf hin, dal3 die Polymerisation iiber freie Radikale verlauft.

Polymerization of methyl methacrylate by charge-transfer mechanism with 2,2?-bipyridine and iron (III) complex

“…9 Much interest has been shown in the polymerizaIn some of the ATRA reactions, the transitiontion of vinyl monomers initiated by a charge-transmetal catalyst acts as a carrier of the halogen fer (CT) mechanism. [1][2][3][4][5] The CT initiation mechaatom in a reverse redox process. 10,11 Recently sevnism involves the formation of CT complexes, and eral methods for controlled/living radical polyafterward these complexes decompose to produce merization reactions have been reported.…”

Effect of ferric cyanide ions on the polymerization of methyl methacrylate

“…There has been increasing interest in the initiation of polymerization of vinyl monomers such as methyl methacrylate (MMA) and vinyl chloride by the charge transfer mechanism (1)(2)(3)(4)(5). The polymerization of MMA by a compound containing a donor nitrogen atom in the presence of carbon tetrachloride (CC14) is now well established (6).…”

“…Matsuda, Ishiroshi, and Seki (4) reported the accelerative property of SOz for charge transfer polymerization of MMA. They presumed the formation of the charge transfer complex with nicotine, SOz, and MMA.…”

Depolymerizable Poly(O-vinyl carbamate-alt-sulfones) as Customizable Macromolecular Scaffolds for Mucosal Drug Delivery

“…20–23,26 By contrast, common monomers such as methyl methacrylate have dipole moments of opposite sign and do not form perfectly alternating copolymers. 32,33 …”

“…[20][21][22][23]26 By contrast, common monomers such as methyl methacrylate have dipole moments of opposite sign and do not form perfectly alternating copolymers. 32,33 Based on these initial studies, a series of O-vinyl carbamate monomers were prepared to test the functional group tolerance of the polymerization (Scheme 1). The monomers were prepared easily by reacting an appropriate free amine, vinyl chloroformate, and triethylamine in dry dichloromethane for 19 h, followed by an aqueous workup.…”