2019
DOI: 10.1002/pola.29324
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Isotactic Regulation in the Radical Polymerization of Calcium Methacrylate: Is Multiple Chelation the Key to Stereocontrol?

Abstract: Accurate quantum chemistry is used to explain the origins of isospecificity in radical polymerization of calcium methacrylate hydrate (CaMA). Distonic radical–cation interactions are shown to be crucial in determining the reactivity of different coordination structures. Cation coordination to the terminal and incoming monomer side chains reduces radical‐cation separation, enhancing the reactivity of these modes over the stereocontrolling terminal‐penultimate binding modes. This explains why Lewis acid‐mediated… Show more

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Cited by 5 publications
(3 citation statements)
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“…Additionally, upon combination of a solution of 3-Ca with methyl acrylate, the immediate formation of yellow precipitate was observed, which upon closer inspection revealed a gel-like consistency, thus suggesting a polymerisation reaction had occurred; this is a likely occurrence, as calcium-initiated polymerisation of methyl acrylate has been previously reported. 68 No alkene signals were visible in the 1 H NMR spectra, and the 31 P{ 1 H} spectra did not change over time and contained only one resonance, which corresponded to HPPh 2 (see ESI†). Analogous behaviour was not observed with 3-Mg , indicating its greater tolerance towards ester functionality.…”
Section: Catalytic Studiesmentioning
confidence: 99%
“…Additionally, upon combination of a solution of 3-Ca with methyl acrylate, the immediate formation of yellow precipitate was observed, which upon closer inspection revealed a gel-like consistency, thus suggesting a polymerisation reaction had occurred; this is a likely occurrence, as calcium-initiated polymerisation of methyl acrylate has been previously reported. 68 No alkene signals were visible in the 1 H NMR spectra, and the 31 P{ 1 H} spectra did not change over time and contained only one resonance, which corresponded to HPPh 2 (see ESI†). Analogous behaviour was not observed with 3-Mg , indicating its greater tolerance towards ester functionality.…”
Section: Catalytic Studiesmentioning
confidence: 99%
“…Progress toward understanding stereocontrolled radical polymerization (SRP) has been limited due to inherent difficulties stemming from the high reactivity, lack of intermolecular interactions, and planar sp 2 structure of propagating radical chain ends . Despite these inherent challenges, four approaches have demonstrated significant promise for engendering stereocontrol during radical polymerization: (i) Lewis acid activation of monomers, (ii) polymerization in the presence of fluoroalcohols, (iii) using monomers with chiral auxiliaries or sterically hindered substituents, and (iv) polymerization in a confined environment …”
Section: Radical Polymerizationmentioning
confidence: 99%
“…Nonetheless, the complex oral environment and the impact from chewing can result in irrevocable or enduring loss of fillers in the restorative composite, further reducing their ability to induce HA regeneration. Calcium methacrylate (CMA, Figure 1), a bifunctional monomer and the calcium salt of methacrylic acid, can also be employed as a monomer for photopolymerization [45]. The photopolymerization product of CMA can not only serve as a binding site for PO 4 3− in the oral environment but also release Ca 2+ , facilitating the deposition of HA on its surface.…”
Section: Introductionmentioning
confidence: 99%