Synthesis and properties of radiopaque polymer hydrogels II: copolymers of 2,4,6-triiodophenyl- or N-(3-carboxy-2,4,6-triiodophenyl)- acrylamide and p-styrene sulfonate

In order to pursue a possibility of application of radiopaque polymer hydrogels to vascular embolization, studies were made on synthesis of iodine containing copolyanions and properties of their hydrogels with polycation via formation of polyion complexes (PIC). Acrylamide derivatives having triiodophenyl groups were synthesized and copolymerized with sodium styrene sulfonate (SS) under several conditions. It was found that N-(3-carboxy-2,4,6-triiodophenyl)-acrylamide (CIPA) and 2,4,6-triiodophenylacrylamide (TIPA) monomers are effectively copolymerized with SS, while N-allyl-2,3,5-triiodobenzamide (ATIBA) are hardly copolymerized. Hydrogels were prepared by mixing aqueous solutions of polyanions, i.e. the copolymers (PCIPA and PTIPA) and polyallylamine (PAAn). ¹³C NMR spectra of PCIPA/PAAn and PTIPA/PAAn hydrogels gave peaks for both polyanion and polycation. This means that there remained free anionic and cationic monomer units, which did not form ion pairs because of spatial hindrance. Time dependence of ¹H T₂ showed quick increment and plateau for PSS/PAAn and gradual increments for PCIPA/PAAn. Therefore, PIC containing the radiopaque copolymer retains the hydrogel state for a long time. Embolization was examined by injection of PCIPA/PAAn hydrogels into the vein of a removed porcine kidney as a preliminary test for transcatheter arterial embolization (TAE). X-ray radiograms of the embolized organ were reasonably explained based on the structure and mobility of hydrogels.