In this study, the mechanism of radical polymerization was further explored by pre-dissolving different polymers and studying the kinetics of the bulk polymerization of methyl methacrylate (MMA) under shear-free conditions. Based on the analysis of the conversion and absolute molecular weight, it was found that, contrary to the shearing effect, the inert polymer with viscosity was the key factor to preventing the mutual termination of radical active species and reducing the termination rate constant k t. Therefore, pre-dissolving the polymer could increase the polymerization rate and molecular weight of the system simultaneously, making the polymerization system enter the automatic acceleration zone faster and greatly reducing the generation of small molecular weight polymers, leading to a narrower molecular weight distribution. When the system entered the auto-acceleration zone, k t decreased rapidly and greatly and entered the second steady-state polymerization stage. Then, with the increase in the polymerization conversion, the molecular weight gradually increased, while the polymerization rate gradually decreased. In shear-free bulk polymerization systems, k t can be minimized and radical lifetimes maximized, but the polymerization system is at best a long-lived polymerization rather than a living polymerization. On this basis, by using MMA to pre-dissolve ultrahigh molecular weight PMMA and core-shell particles (CSR), the mechanical properties and heat resistance of the PMMA with pre-dissolved polymer obtained by reactive extrusion polymerization were better than for pure PMMA obtained under the same conditions. Compared with pure PMMA, the flexural strength and impact strength of PMMA with pre-dissolved CSR were up to 166.2% and 230.5%. With the same quality of CSR, the same two mechanical properties of the samples obtained by the blending method were just improved by 29.0% and 20.4%. This was closely related to the distribution of CSR in the pre-dissolved PMMA-CSR matrix with a distribution of spherical single particles 200-300 nm in diameter, which enabled PMMA-CSR to exhibit a high degree of transparency. This one-step process for realizing PMMA polymerization and high performance shows extremely high industrial application prospects.
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