Metal alkyl catalysts for cationic polymerization of vinyl monomers

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<jats:title>Abstract</jats:title><jats:p>New catalyst systems consisting of, <jats:italic>e.g.</jats:italic>, metal alkyl—H<jats:sub>2</jats:sub>O—cocatalyst for the polymerizations of styrene, vinyl ether and α‐methylstyrene were found. Metal alkyls were Al(C<jats:sub>2</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub> or Zn(C<jats:sub>2</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>2</jats:sub> and active chlorine compounds such as α‐chlorodimethyl ether, acetyl chloride or <jats:italic>tert.</jats:italic>‐butyl chloride were cocatalysts.</jats:p><jats:p>A mechanism of cationic polymerization was proposed in which AlEt<jats:sub>3</jats:sub> behaves as LEWIS acid and forms a carbonium ion complex with the cocatalyst. The function of water was assumed to convert Al(C<jats:sub>2</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub> into another LEWIS acid and the ternary systems of Al(C<jats:sub>2</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub>—H<jats:sub>2</jats:sub>O—cocatalyst were regarded as LEWIS acid‐cocatalyst systems.</jats:p><jats:p>In the polymerization of styrene with Al(C<jats:sub>2</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub>—H<jats:sub>2</jats:sub>O—CH<jats:sub>3</jats:sub>COCl, the mechanism of cationic polymerization initiated by acetyl cation was established by the end group analysis.</jats:p>

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