Hyperbranched copolymers made from A(2), B-2 and BB '(2) type monomers (iv) - Copolymerization of divinyl sulfone with 4, 4 '-trimethylenedipiperidine and N-ethylethylenediamine

The new approach for synthesis of hyperbranched polymers from commercially available A(2) and BB2' type monomers was extended to synthesize hyperbranc hed copolymers; In this work, hyperbranched copoly(sulfone-amine) was prepa red by copolymerization of divinyl sulfone (A(2)) with 4,4'-trimethylenedip iperidine (B-2) and N-ethylethylenediamine (BB2'). During the reaction, sec ondary-amino groups of B-2 and BB2' monomers react rapidly with vinyl group s of A(2) monomers within 35 s, generating a type of intermediate containin g one vinyl group and two reactive hydrogen atoms. Now the intermediates ca n be regarded as a new BB2' type monomer, which further polymerizes to form hyperbranched copoly(sulfone-amine). The polymerization mechanism was inve stigated with FTIR and LC-MSD. The degree of branching (DB) of hyperbranche d copolymers increased with decreasing the ratio of 4,4'-trimethylenedipipe ridine to N-ethylethylenediamine, so DB can be controlled. When the initial mole ratio of B-2 to BB2' was equal to or higher than four, r greater than or equal to4, resulted copolymers were semi-crystalline, while copolymers with r<3 were amorphous.