A set of dendritic-linear copolymers, poly(glycidyl methacrylate-grafted- dimethyl 3,3'(4-hydroxyphenylazanediyl)bis(2-methylpropanoate))-random- polystyrene (PGMA-HP AM-r-PS), were successfully prepared by copolymerization of the novel dendritic macromonomer dimethyl 3,3'-(4(2-hydroxy-3-(methacryloyloxy) propoxy)phenylazanediyl)bis(2-methylpropanoate) (GMA-HPAM) and a styrene monomer. The dendritic GMA-HPAM macromonomer dendron 3,3'-(4- hydroxyphenylazanediyl) bis(N-(2-aminoethyl)-2-methylpropanamide) (HPAM) was then grafted using the divergent growth method.1H NMR and13C NMR spectra were used to identify the structure of the dendritic-linear GMA-HPAMr-PS copolymer. Microporous dendritic-linear PGMA-HPAM-r-PS copolymer films in this system were prepared by using solvent-induced phase separation at room temperature. The phase separation behavior and the morphological analyses of the dendritic-linear copolymer film as functions of dendritic GMA-HPAM segment contents were investigated by using AFM, TEM, and SEM. Self-assembly of the dendritic-linear PGMA-HPAM-r-PS copolymer in a G2-37 system containing 37 wt % of the dendritic GMA-HPAM segment, which exhibits the second generation dendron, showed submicrometer phase segregation with the main chain styrene segment. Interestingly, the submicrometer phase segregation morphology of the G2-37 sample represented a uniform size distribution of the hexagonally ordered structures. Our results prove that controlling the appropriate macromonomer content by grafting a three-dimension structure results in selfassembly and provides a honeycomb ordered microporous copolymer matrix.
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