Vinyl polymerization. LXVIII. The polymerization of methyl methacrylate in the presence of zinc chloride

Abstract

The polymerization of methyl methacrylate (MMA) initiated by a,='-azobisisobutyronitrile (AIBN) in the presence of zinc chloride a t 6OOC. was investigated kinetically. Zinc chloride increased the rate of polymerization. Since ZnC1, dissolved in MMA to form a complex, such a complex was considered to have a close relation to the acceleration effect. It was found from the result of a copolymerization experiment with vinylidene chloride that the reactivity of MMA monomer increased in the presence of ZnC1,. A complex of MMA with ZnC1, could be easily isolated by removing an excess of MMA from the MMA-ZnC1, solution. The MMA-ZnCl, complex polymerized to a high molecular weight polymer. ZUSAMMENFASSUNG: Die Polymerisation von Methylmethacrylat (MMA) mit Azoisobuttersaurenitril (AIBN) in Gegenwart von ZnC1, bei 6OoC wurde kinetisch untersucht. ZnC1, bewirkte eine Polymerisationsbeschleunigung. Es bildet mit MMA in Losung einen Komplex, der wahrscheinlich fiir den Beschleunigungseffekt verantwortlich ist. Ein Komplex von MMA mit ZnC1, lief3 sich durch Entfernen des MMA-ifberschusses aus einer MMA-ZnC1,-Losung isolieren. Der MMA-ZnC1,-Komplex wurde zu einem hochmolekularen Produkt polymerisiert. *) Part LXVII of this series: M. IMOTO, T. OTSU, and T. ITO, Bull. chem. SOC. Japan 36 (1963) 310.

Polymerization of Methyl Methacrylate Initiated by the Benzoin—Pyridine—Carbon Tetrachloride System

“…The value of kp/k/ 12 was calculated to be 0.15 (l/mol sec)1 12 from the slope of the line in Figure 3 and showed a close agreement with that of the radical polymerization of MMA with AIBN 18 or BP0. 19 The apparent overall activation energy of polymerization with the initiator system of BN-Py-CCl4 was calculated to be 11.3 kcal/mol.…”

Anionic polymerization of Lewis acid-activated methyl methacrylate by enamines

“…These are much higher than the corresponding values for the free MMA (Q ϭ 0.78 and e ϭ 0.40). 1 The Lewis acid effect has been applied to the alternating copolymerization between an acrylate and an electron-rich olefin by radical copolymerization. [1][2][3][4] Exceptionally bulky Lewis acids, such as methylaluminum bis(2,6-di-tert-butylphenoxide) (2), have been developed by Yamamoto et al 5 Designed to coordinate specifically to carbonyl oxygen and enhance the electronic property of the compound.…”

Donor-Acceptor Molecular Complexes in Alternating Copolymerization and in the Polymerization of Metal Halide-Complexed Vinyl Monomers

“…The charge transfer complex may open spontaneously-e.g., olefin-acrylonitrile-alkylaluminum halide, styrene-methyl methacrylatealkylaluminum halide, isoprene-acrylonitrile-zinc chloride -or under the influence of free radicals-e.g., olefin-or allyl monomer-acrylonitrile-zinc chloride. The process involves spontaneous or radical-initiated homopolymerization of a Lewis acid activated, diradical charge transfer complex.'T^he free radical initiated polymerization of polar monomers containing -** pendant nitrile and carbonyl groups-e.g., acrylonitrile and methyl methacrylate-in the presence of metal halides such as zinc chloride and aluminum chloride, is characterized by increased rates of polymerization (2,3,4,5,10,30,31,32,33,34,53,55,65,66,75,76,77,87). Imoto and Otsu (30,33,34) have attributed this effect to the formation of a complex between the polar group and the metal halide.…”