Toward alternating copolymerization of maleimide and vinyl acetate driven by hydrogen bonding

Abstract

Herein, we report the solution copolymerization of N-propylmaleimide (MI) and vinyl acetate (VAc) in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and 1,4-dioxane.

MALDI-LID-ToF/ToF analysis of statistical and diblock polyacrylate copolymers

“…[6][7][8][9][10][11][12][13][14][15][16] MALDI-ToF has been utilized to give values for the molecular weight, 17,18 information on polymer end groups, [19][20][21][22][23][24] as well as to probe the mechanisms of polymer synthesis. [25][26][27][28] It is a soft ionization technique where fragmentation and double charged species are rare, 29,30 allowing for good ionization of low to medium weight nonvolatile compounds. For matrix assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS) obtaining a clear spectra of single oligomers, with isotopic resolution, in a polymer mixture can be achieved with relative ease.…”

Maleimide Chemistry: Enabling the Precision Polymer Synthesis

“…High polar solvents, such as fluoroalcohols can interact with monomers through hydrogen bonding, which can be used to facilitate polymerization and regulate the monomer sequence during RDRP. [ 10‐12 ] It was found that the strong electron‐inducing effect of the fluoroalcohol significantly reduced the electron density of the double bond in MI, which can change its polymerization behaviors. For instance, in the copolymerization of N ‐propylmaleimide (N‐PMI) and (St) by reversible addition‐fragmentation chain transfer polymerization (RAFT), the rate is higher in fluoroisopropyl‐ alcohol compared to aprotic solvents such as toluene, since the hydrogen bonding between the fluoroalcohol and N‐PMI generates steric repulsion and electron induction effect, influencing the reactivity ratios, for N‐PMI and St 0.078 and 0.068, respectively, while the values in toluene were 0.026 and 0.050, respectively.…”

“…[ 10 ] Another report showed how protic solvents such as fluoroalcohol not only have an effect on the polymerization rate but also allow modifying the content of vinyl acetate in comparison with non‐protic solvents such as dioxane, giving rise to copolymers with controlled MW. [ 11 ]…”