Synthesis of Novel Hindered Amine Light Stabilizers (HALS) and Their Copolymerization with Ethylene or Propylene over Both Soluble and Supported Metallocene Catalyst Systems

Abstract

Novel polymerizable hindered amine light stabilizers (HALS) such 1-(but-3-enyl)-2,2,6,6-tetramethylpiperidine (1), 1-(undec-10-enyl)-2,2,6,6-tetramethylpiperidine (2), 4-(but-3-enyl)-1,2,2,6,6-pentamethyl-3,4-dehydropiperidine (3), 2-(but-3-enyl)-2,6,6-trimethylpiperidine (4), 4-(but-3-enyl)-1,2,2,6,6-pentamethyl-4-piperidyl ether (5), 4-(undec-10-enylamide)-1,2,2,6,6-pentamethylpiperidine (6), 4-((N-n-butyl)-undec-10-enylamide)-1,2,2,6,6-pentamethylpiperidine (7), and bis(N-n-butyl-N-2,2,6,6-tetramethylpiperidine)-N-n-butyl-N-allyltriazine (8) were synthesized. All the aforementioned HALS monomers except for 5 and 8 were successfully copolymerized in fair to high yields with ethylene or propylene over eight different group 4 metallocene catalysts using methylalumoxane (MAO) as cocatalyst. Copolymerizations were also performed over a supported metallocene/SiO2/MAO/triisobutylaluminum(TIBA) catalyst system. The silica-supported metallocene catalyst system readily promoted copolymerization of the sterically...