Donor-Acceptor Complexes in Copolymerization. XLIV. Copolymerization of Styrene and ?-Methylstyrene with Acrylic and ?-Substituted Acrylic Esters in the Presence of Aluminum Compounds

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Abstract
The copolymerization of styrene (S) with methyl acrylate (MA) and with methyl methacrylate (MMA) in the presence of AlEt3 yields equimolar, alternating copolymers while no polymer is formed in α-methylstyrene (MS)-MA and MS-MMA systems. In the presence of AlEt1.5Cll,5 (EASC), S-MA and S-MMA yield alternating copolymers, S-methyl a-chloroacrylate (MCA), MS-MA and MS-MMA yield a mixture of alternating and cationic polymers, and MS-MCA yields cationic polymer only. In the presence of A1C13, S-MA and MS-MA yield a mixture of alternating and cationic polymers and S-MMA and MS-MMA yield cationic polymer only. The cotacticity distributions of the alternating S-MA and S-MMA copolymers prepared in the presence of AlEt3, EASC, and A1C1, are the same; the coisotactic, co-heterotactic, and cosyndiotactic fractions being approximately in the ratio 1:2:1. The cosyndiotactic fractions of the alter-nating copolymers prepared in the presence of EASC are in the order MS-MMA > MS-MA > S-MCA > S-MMA=S-MA.

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