The successful achievement of stereospecific metal catalyzed styrene polymn. using Ziegler Natta catalysts opened in the early 90s a new frontier in the synthesis of stereoregular copolymers of styrene with 1,3-conjugated dienes. Block and random copolymers comprising styrenic polymer segments with syndiotactic or isotactic arrangements, depending on the metal catalyst precursor, were synthesized and fully characterized: they found applications as nanofiller, acidic catalysts after post-sulfonation, nanoporous polymeric support of gold nanoparticles applied in sustainable redox catalysis. Recently, the growing interest for bio-sourced polymers prompted us to search for bio-derived monomers suitable for the synthesis of new functional styrenic copolymers. 2-vinylfuran (2VF) was synthesized by Peterson methylenation of furfural, a cheap chem. resulting from chem. transformation of lignocellulosics. Ideal ATR copolymn. of styrene with 2VF yielded random copolymers (S-co-2VFs) in a wide range of compn. The S-co-2VFs are stable in soln. and solid state at room temp. for years in air; the thermal decompn. begins in nitrogen atm. at temp. higher than 380°C. The formation of irreversible crosslinks was obsd. in air at 100°C but inhibited by conventional antioxidants. Diels Alder reaction of S-co-2VFs with maleimide derivs. allowed the synthesis of thermoreversible gels, self-healing films and thermoreversible anchoring of dyes to polymer particles.
Synthesis and applications of styrenic copolymers by metal catalyzed polymerization processes
Grassi, Alfonso
;Buonerba, Antonio;Capacchione, Carmine;Milione, Stefano
2016-01-01
Abstract
The successful achievement of stereospecific metal catalyzed styrene polymn. using Ziegler Natta catalysts opened in the early 90s a new frontier in the synthesis of stereoregular copolymers of styrene with 1,3-conjugated dienes. Block and random copolymers comprising styrenic polymer segments with syndiotactic or isotactic arrangements, depending on the metal catalyst precursor, were synthesized and fully characterized: they found applications as nanofiller, acidic catalysts after post-sulfonation, nanoporous polymeric support of gold nanoparticles applied in sustainable redox catalysis. Recently, the growing interest for bio-sourced polymers prompted us to search for bio-derived monomers suitable for the synthesis of new functional styrenic copolymers. 2-vinylfuran (2VF) was synthesized by Peterson methylenation of furfural, a cheap chem. resulting from chem. transformation of lignocellulosics. Ideal ATR copolymn. of styrene with 2VF yielded random copolymers (S-co-2VFs) in a wide range of compn. The S-co-2VFs are stable in soln. and solid state at room temp. for years in air; the thermal decompn. begins in nitrogen atm. at temp. higher than 380°C. The formation of irreversible crosslinks was obsd. in air at 100°C but inhibited by conventional antioxidants. Diels Alder reaction of S-co-2VFs with maleimide derivs. allowed the synthesis of thermoreversible gels, self-healing films and thermoreversible anchoring of dyes to polymer particles.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.