Solid-State Metathesis Polycondensation

Solid‐State Olefin Metathesis: ADMET of Rigid‐Rod Polymers and Ring‐Closing Metathesis

“…[10] Long chain ester diene 6 was synthesized to yield a solid with a melting point very close to room temperature (MP ¼ 28-30 8C). Experiments with this diene in the solid state could only be conducted at reduced temperatures.…”

“…Six metathesis catalysts (9)(10)(11)(12)(13)(14) were employed in this research (Figure 7), where experiments were conducted using amide 5 as the diene. The diene and the catalyst were mixed and ground together (300:1 ratio) in a mortar and pestle three times resulting in a mixture with a melting point only 28 lower than pure diene.…”

“…[10] Molecular weight increases in the solid state for a variety of monomer types, including hydrocarbon dienes, ketone, and alcohol functionalized dienes, and a comb graft copolymer with polystyrene grafted onto a polyolefin backbone. Figure 1 illustrates one example of a pre polymerized macromonomer of polyoctenylene from 1,9-decadiene showing an approximate 20-fold increase of molecular weight while in the solid state.…”

“…SSP can be conducted at or near room temperature, [10] without the high temperatures needed in industry to help drive off the condensate.…”

“…While physical diffusion of ethylene from within the solid to the surface is undoubtedly occurring, the situation may be more complex than just that [10] for the increase in molecular weight shown in Figure 1 cannot be rationalized by diffusion of ethylene alone. Semicrystalline condensation polymers are thought to undergo SSP due to an enhanced mobility that exists within the amorphous regions when above the T g .…”