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The deformation of isotactic poly‐1‐butene (iPB‐1) matrix, during the CO2‐assisted foaming process, makes the iPB‐1 melt crystallize into form I rather than form I′, which crystallizes after annealing under high‐pressure CO2 without foaming. The result provides a new strategy to directly obtain porous iPB‐1 with stable form I from iPB‐1 melt.
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