Relationships Between Base-Catalyzed Hydrolysis Rates or Glutathione Reactivity for Acrylates and Methacrylates and Their NMR Spectra or Heat of Formation

Abstract

The NMR chemical shift, i.e., the π-electron density of the double bond, of acrylates and methacrylates is related to the reactivity of their monomers. We investigated quantitative structure-property relationships (QSPRs) between the base-catalyzed hydrolysis rate constants (k1) or the rate constant with glutathione (GSH) (log kGSH) for acrylates and methacrylates and the 13C NMR chemical shifts of their α,β-unsaturated carbonyl groups (δCα and δCβ) or heat of formation (Hf) calculated by the semi-empirical MO method. Reported data for the independent variables were employed. A significant linear relationship between k1 and δCβ, but not δCα, was obtained for methacrylates (r2 = 0.93), but not for acrylates. Also, a significant relationship between k1 and Hf was obtained for both acrylates and methacrylates (r2 = 0.89). By contrast, log kGSH for acrylates and methacrylates was linearly related to their δCβ (r2 = 0.99), but not to Hf. These findings indicate that the 13C NMR chemical shifts and calculated Hf values for acrylates and methacrylates could be valuable for estimating the hydrolysis rate constants and GSH reactivity of these compounds. Also, these data for monomers may be an important tool for examining mechanisms of reactivity.

Lightly branched poly(vinyl alcohol) for fluid loss additive

“…That is why the branched PVA aqueous solutions have bigger shear viscosity than that of the linear one at the same molecular weight at 20°C. According to the changes in the shear viscosity, it proves that the AMA units are not hydrolyzed, which is consistent with the fact that acrylic ester is not easy for hydrolysis . Therefore, the long branches can be saved.…”

“…As reported, hyperbranched polymer usually has lower crystallinity even totally amorphous although the linear polymer is crystalline polymer, and with the increase of branched points, the polymer has good solubility in solvent compared to the corresponding linear polymer. In our experiments, very small amount of bifunctional monomer was introduced, it is predictable that the branch chain points are relatively low and the branch chain is relatively long, the movement of chain is less affected, so the crystallinity did not decrease too much …”

Novel reusablepH‐responsive photocatalyst polymeric microcapsules for dye treatment

“…In general, the ester linkages of both MA and MMA were possibly hydrolyzed. However, MA should be more hydrolyzed than MMA because of the higher base‐catalyzed hydrolysis rate constant of MA than that of MMA 46 . Moreover, because MA is more hydrophilic than MMA, PMA rich regions might locate at microcapsule surface during suspension polymerization that are easily hydrolyzed.…”

Methacrylate Coatings for Titanium Surfaces to Optimize Biocompatibility

“…Methacrylate and acrylate monomers are esters with a reactive pi bond between the α and β carbons. Fujisawa and Kadoma [10] showed that varying α substitution (methacrylates are methyl α substituted while acrylates are not) and varying β substitution can have effects on the monomer resistance to hydrolysis. Although methacrylates and acrylates can be polymerized using ultraviolet (UV) light and a photoinitiator, previous work by Khademhosseini et al [11] has shown that crosslinking methods alternative to UV curing are readily available.…”