Study of the Parameters Controlling the Alternating Copolymerization of Methyl Methacrylate and Styrene

This contribution describes coordinative/insertive stereoregular homopolymerizations and copolymerizations of styrene and methyl methacrylate (MMA) mediated by a highly active single-site organotitanium catalyst. The catalyst system used to effect these polymerizations of nonpolar and polar olefinic monomers is prepared by in situ Zn reduction of the precursor derived from the reaction (Me(5)Cp)TiMe(3) + Ph(3)C(+)B(C(6)F(5))(4)(-). The resulting catalyst produces polystyrene (>95% syndiotactic, 170 000 g/mol molecular weight; s-PS) by the established coordinative/insertive pathway. The same catalyst mediates polymerization of MMA to poly(methyl methacrylate) (>65% syndiotactic, >70 000 g/mol molecular weight; s-PMMA) by a group transfer protocol-like (GTP-like) pathway (1,4 insertion mechanism). Under optimal conditions, this catalyst also mediates the copolymerization of MMA + styrene (1:19 ratio) at 50 degrees C to yield random approximately 80% coisotactic poly[styrene-co-(methyl methacrylate)] (coiso-PSMMA) which contains approximately 4% MMA. Control experiments argue that a single-site Ti catalyst is the active species for the copolymerization. The catalyst formation process is quite general, and a variety of reducing agents can be substituted for Zn and still effect copolymerization. Control experiments also indicate that known noncoordination copolymerization mechanisms (i.e., ionic or radical) cannot explain this copolymerization. We suggest a new mechanism involving sequential conjugate addition steps to explain these copolymerization results.

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Copolymerization of 2-Ethyl Hexyl Acrylate with Styrene in the Presence of Zncl₂

Bataille

Sharifi-Sanjani

Rahmani

1994

Journal of Macromolecular Science, Part A

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Study of the Parameters Controlling the Alternating Copolymerization of Methyl Methacrylate and Styrene

Cited by 3 publications

References 17 publications

Copolymerization of butyl acrylate with styrene in presence on ZnCl2

Copolymerization of butyl acrylate with styrene in presence on ZnCl2

Organotitanium-Mediated Stereoselective Coordinative/Insertive Homopolymerizations and Copolymerizations of Styrene and Methyl Methacrylate

Copolymerization of 2-Ethyl Hexyl Acrylate with Styrene in the Presence of Zncl₂

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Study of the Parameters Controlling the Alternating Copolymerization of Methyl Methacrylate and Styrene

Cited by 3 publications

References 17 publications

Copolymerization of butyl acrylate with styrene in presence on ZnCl2

Copolymerization of butyl acrylate with styrene in presence on ZnCl2

Organotitanium-Mediated Stereoselective Coordinative/Insertive Homopolymerizations and Copolymerizations of Styrene and Methyl Methacrylate

Copolymerization of 2-Ethyl Hexyl Acrylate with Styrene in the Presence of Zncl2

Contact Info

Product

Resources

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Copolymerization of 2-Ethyl Hexyl Acrylate with Styrene in the Presence of Zncl₂