Synthesis and characterization of functionalized vinyl copolymers. Electronegativity and comonomer reactivity in radical copolymerization

Abstract

Vinylsilane monomers (vinyltrimethoxysilane (VTMOS) and vinyltriethoxysilane (VTEOS)), methyl methacrylate (MMA), tert-butyl acrylate (tBA) and N-vinyl-2-pyrrolidone (VP) were used in the synthesis of functionalized vinyl copolymers. By using these monomers, VTMOS-co-MMA, tBA-co-VP and VTEOS-co-VP, with various compositions, were synthesized. The copolymers were characterized by viscometry, 1 H-NMR, FTIR and elemental analysis. The monomer reactivity ratios were estimated by the Fineman-Ross and Kelen-Tüdõs linear procedures. These parameters were also estimated by using a computer program based on a non-linear minimization procedure known as Reactivity Ratios Error in Variables Model. Random copolymers and others containing blocks of one of the monomer units were obtained, depending on the chemical nature of the comonomers. The estimated comonomer sequence and distribution are discussed in terms of structural properties of the monomers such as molecular volume of the side groups, electronegativity of the substituents and steric hindrance. Analysis by comparison with other copolymers with analogous structures was also performed.

Radical polymerization behavior of trimethoxyvinylsilane

“…According to the curve‐fitting method, based on nonlinear least‐squares analysis,23 the monomer reactivity ratios were estimated to be r l = 1.40 and r 2 = 0.24. The monomer reactivity ratios were reported for the copolymerizations of TMVS (M 1 ) with some other vinyl monomers (M 2 ) at 50 °C; r l = 0.36 and r 2 = 0.63 for the TMVS/ N ‐vinylpyrrolidone system,11 r l = 0.0 and r 2 = 21 for the TMVS/MMA system,12 r l = 0.0 and r 2 = 11.7 for the TMVS/2‐vinylpyridine system,10 r l = 0.0 and r 2 = 6.0 for the TMVS/acrylonitrile system,9 and r l = 0.0 and r 2 = 0.8 for the TMVS/vinyl chloride system 9…”

“…Silicon‐containing polymers are of great interest to industry for a variety of applications. Radical polymerizations of vinylsilanes have been attempted by many workers for preparation of silicon‐containing polymers 1–12. Hydrovinylsilanes, such as vinylsilane and diphenylvinylsilane, are radically polymerized to yield oligomers, in which vinyl and hydrosilylative polymerizations proceed concurrently 4–6.…”

Copolymerization of Tris(methoxyethoxy)vinyl Silane with N-Vinyl Pyrrolidone: Synthesis, Characterization, and Reactivity Relationships

“…NVP has been copolymerized with various siloxane derivatives monomers such as vinyl triethoxy silane, vinyl trimethoxy silane, vinyl trimethyl silane, vinyl trichlorosilane, and 3-(trimethoxysilyl)propyl methacrylate. In addition, the reactivity ratios of these copolymers have been determined [26][27][28][29], but no one has copolymerized and studied the reactivity relationships of NVP with tris(methoxyethoxy)vinyl silane (TMEVS).…”

Synthesis, characterization and antimicrobial activity of important heterocyclic acrylic copolymers

“…This distribution is a direct consequence of each monomer's reactivity in the copolymer molecule [2]. In case of radical copolymerization, the reactivity of a free radical depends on the nature of the side group linked to the radical carbon [3]. Many polymers with reactive functional groups are now being synthesized, tested and used not only for their macromolecular properties, but also for the properties of functional group.…”