Homo‐ and Copolymerization of ω‐Functional Polystyrene Macromonomers via Coordination Polymerization

Abstract

Macromonomers have been extensively used, as well defined building blocks for various macromolecular architectures via anionic, ROMP and free radical homo‐ or copolymerization processes. The purpose of the present work was to examine the homopolymerization and copolymerization of ω‐allyl, ω‐undecenyl and ω‐vinylbenzyl polystyrene (PS) macromonomers, in the presence of early or late transition metal catalysts. The influence of several parameters (type of catalytic system, nature of polymerizable end‐group and molar mass of the macromonomer) on the homopolymerization was first investigated. Whereas ω‐allyl or ω‐undecenyl PS macromonomers were not very reactive in homopolymerization whatever the catalyst, ω‐vinylbenzyl PS macromonomers gave interesting results with CpTiCl3/MAO and Cp*TiCl3/MAO. The copolymerization of these macromonomers with ethylene was also studied in the presence of the following palladium catalyst: [(ArNC(Me)C(Me)NAr)Pd(CH2)3(COOMe)]+BAr4′−(VERSIPOL™) (Ar = 2,6‐iPr2–C6H3 and Ar′ = 3,5‐(CF3)2C6H3). ω‐vinylbenzyl PS macromonomers could not be incorporated into poly(ethylene) chains. On the contrary, the incorporation of ω‐allyl PS macromonomers was achieved. Moreover, for macromonomers containing an alkyl spacer between the allylic unit and the PS chain, the incorporation rate, the copolymerization yield and the molar masses of the copolymers were increased, giving access to a new type of graft copolymer structure. Synthesis of polystyrene macromonomers.magnified imageSynthesis of polystyrene macromonomers.

New Trends in Poly(ethylene oxide) or Polystyrene Macromonomer Based Networks Exhibiting Silsesquioxane Cross‐Linking Points

“…The α,ω‐diundecenyl PS macromonomers were synthesized by anionic polymerization of styrene as described earlier 14. Briefly, they were prepared by anionic polymerization in THF using potassium naphthalenide as initiator at −60 °C.…”

Synthesis of poly(ethylene-co-vinyl alcohol)-g-polystyrene graft copolymer and their applications for ordered porous film and compatibilizer

“…The functionalized polyolefin graft copolymers are mainly prepared by three methodologies: grafting from, grafting onto, and grafting through approaches. Diverse functionalized polyolefin graft copolymers with functional polymer segment such as polystyrene (PS), poly(methyl methacrylate), polyacrylate, and poly(ε‐caprolactone), and so forth have been synthesized successfully via the approaches above‐mentioned.…”

Dynamic Monte Carlo Simulation of Graft Copolymers Made with ATRP and Metallocene Catalysts

“…[8][9][10][11] Anionic polymerization was used to produce macromonomers with narrow MWD, while metallocene polymerization was used to produce the grafted chains (graft-to approach). Similarly, nitroxide-mediated polymerization was used to synthesize macromonomers that were grafted to a polymer backbone using metallocene catalysts [12,13] . The graft-to method was also used to produce poly(propene-g-styrene) copolymers.…”