Vinyl polymerization, 323. Polymerization of methyl methacrylate initiated with the styrene/acrolein copolymer

The polymerization of methyl methacrylate initiated by the copolymers methacrylaldehydestyrenedivinylbenzene and acrylaldehydeethylene dimethacrylate in the absence of usual initiators was investigated. The polymerization was found to proceed fairly readily and fast. Acceleration can be achieved by adding glycerylaldehyde. An increase in the surface of the initiating copolymer favourably influences the reaction rate; at the same time, however, physical trapping of ungraft poly(methy1 methacrylate) molecules in the macroporous initiator seems likely to occur. It was also found that only copolymers containing aldehyde groups could be used for initiation and that besides MMA some other monomers could be polymerized in this way, such as glycidyl methacrylate, acrylic and methacrylic acid, acrylonitrile, and alkyl acrylate. ZUSAMMENFASSUNG:Die Polymerisation von Methylmethacrylat wurde untersucht, die durch Copolymere aus Methacrylaldehyd -Styrol -Divinylbenzol und Copolymere aus Acrylaldehyd -Athylendimethacrylat in Abwesenheit ublicher Initiatoren ausgelost wird. Die Polymerisation verlauft radikalisch und schnell. Eine Beschleunigung kann durch Zugabe von Glycerinaldehyd erreicht werden. Eine groBere Oberflache des initiierenden Copolymeren begunstigt die Reaktionsgeschwindigkeit, aber parallel dazu scheinen leicht Einschlusse von ungepfropften Polymethylmethacrylat-Molekulen aufzutreten. Es wurde gefunden, da13 nur Copolymere mit Aldehydgruppen als Initiatoren wirken und daB auch andere Monomere wie Glycidylmethacrylat, Acryl-und Methacrylsaure, Acrylnitril und Alkylacrylate polymerisiert werden konnen.

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Polymerization initiated with polymeric compounds, II

Švec

Vernekar

Kálal

1977

Angew. Makromol. Chem.

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Vinyl polymerization, 334. Polymerization of methyl methacrylate initiated with poly(styrene‐co‐acrolein) or poly(styrene‐co‐methyl vinyl ketone)

1975

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The polymerization of methyl methacrylate (MMA) initiated with styrene/acrolein, [poly(St/AL)], or styrene/methyl vinyl ketone, [poly(St/MVK)] statistical copolymers was kinetically studied. The rates of polymerization, R,, were found to obey the following equations: R,= con~t.[poly(St/AL)]~~~~ [MMA] 1948 R,= const. [poly(St/MVK)] ' 9 50 [MM A] The overall activation energies were 58,6 kJ/mol (14 kcal/mol) [poly(St/AL)] and 62,8 kJ/ mol (1 5 kcal/mol) [poly(St/MVK)], respectively. Effects of several metallic ions on the polymerization rate were also studied, and thereby it was found that Fe(II), Fe(III), and Cu(I1) ions at adequate concentrations are able to promote the polymerization. ZUSAMMENFASSUNG: Die von den statistischen Copolymeren Styrol/Acrolein, [Poly(St/AL)], bzw. Styrol/Methylvinylketon, [Poly(St/MVK)], initiierte Copolymerisation von Methylmethacrylat (MMA) wurde untersucht. Dabei wurde gefunden, daB die Polymerisationsgeschwindigkeiten, R,, den folgenden Gleichungen gehorchen: R,= const.[Poly(St/AL)] [MMA] 1,48 R , = const. [ Poly(St/MVK)] ' 9 [ M MA] '3 Die Aktivierungsenergien der Bruttoreaktionen betrugen 58,6 kJ/mol(14 kcal/mol) [Poly-(St/AL)] bzw. 62,s kJ/mol (1 5 kcal/mol) [Poly(St/MVK)].

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Vinyl polymerization. 364. Polymerization of methyl methacrylate initiated with benzaldehyde

Imoto

Maeda

Ouchi

1979

J. Polym. Sci. Polym. Chem. Ed.

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SynopsisBenzaldehyde (PhCHO) is found to be able to initiate the radical polymerization of methyl methacrylate (MMA). The rate of polymerization is expressed by the following equation: R, = const[PhCH0]0.5[MMA]1.5. The overall activation energy is estimated to be 56.3 kJ mole-'. The mechanism of polymerization is discussed.(PhCHO) will be reported. It was concluded that PhCHO is able to initiate the homogeneous radical polymerization in benzene. Styrene (St) could not be polymerized, while acrylonitrile (AN) gave a little conversion under the same condition with the case of MMA. The results obtained is surprising in view of the fact that such a simple compound having aldehyde group as PhCHO can generate the free radicals in benzene solution. = 0 is much more unstable than CsH5-C = 0. O---CH,\ c, CH, \H----O@c\mH, -I // CH,CH,,-C complex "C"

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Vinyl polymerization, 323. Polymerization of methyl methacrylate initiated with the styrene/acrolein copolymer

Cited by 10 publications

References 3 publications

Polymerization initiated with polymeric compounds, II

Polymerization initiated with polymeric compounds, II

Vinyl polymerization, 334. Polymerization of methyl methacrylate initiated with poly(styrene‐co‐acrolein) or poly(styrene‐co‐methyl vinyl ketone)

Vinyl polymerization. 364. Polymerization of methyl methacrylate initiated with benzaldehyde

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