Journal of Polymer Science Part A: Polymer Chemistry, Vol.36, No.11, 1699-1706, 1998
The role of multifunctionalized amine structure and reaction conditions on the transformations of crosslinked copoly(styrene-p-nitrophenylacrylate)
Crosslinked copoly(styrene-p-nitrophenylacrylates), containing 2% (1) or 4% DVB (2) were converted with various diaminoalkanes (1,2-diaminoethane 3a, 1,4-diaminobutane 3b, 1,8-diaminooctane 3c) to amides. The degree of additional crosslinking depended on the chain length of the diaminoalkane, the molar ratio of ester function in 1 or 2 to diaminoalkane, solvent polarity (dimethylformamide, chloroform, toluene), while reaction temperature (50 or 100 degrees C) had only a minor effect. 2 was also converted with various amines bearing additional functional groups (ethanolamine, 3-amino-1-propanol, 4-aminomethylpyridine, 2-(2-aminoethylamino)-ethanol, 2-(2-aminoethoxy)-ethanol, 6-aminocaproic acid, N-propylaminomorpholine, 3-N,N-diethylamino-1-propylamine) to the corresponding amides. The swelling ability of the resins depended on the crosslinking of the starting copoly(styrene-p-nitrophenylacrylate) (1, 2), the structure of the amide, the degree of additional crosslinking, and solvent polarity ( chloroform, dimethylformamide, methanol, toluene). The accessibility of nitrogen atoms in the polymer matrix was examined by EtX functionalization of the 3-N,N-diethylamino-1-propylamine derivative (10) and 4-aminomethylpyridine derivative (13), and more than 85% functionalization was found.