Sequential dual curing by selective Michael addition and free radical polymerization of acetoacetate-acrylate-methacrylate mixtures

A new family of poly(keto ester)-poly(methacrylate) thermosets based on off-stoichiometric acetoacetate-acrylate/methacrylate formulations has been prepared and characterized. The first stage of curing is a self-limiting click Michael addition between acetoacetate and acrylate groups at room tempera...

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Detalles Bibliográficos
Autores: Konuray, Ali Osman|||0000-0001-7281-006X, Ruiz, Anna, Morancho Llena, José María|||0000-0002-9416-3657, Salla Tarragó, José María|||0000-0002-5409-8416, Fernández Francos, Xavier|||0000-0002-3492-2922, Serra Albet, Maria Àngels|||0000-0003-1387-0358, Ramis Juan, Xavier|||0000-0003-2550-7185
Tipo de recurso: artículo
Fecha de publicación:2018
País:España
Institución:Universitat Politècnica de Catalunya (UPC)
Repositorio:UPCommons. Portal del coneixement obert de la UPC
Idioma:inglés
OAI Identifier:oai:upcommons.upc.edu:2117/112650
Acceso en línea:https://hdl.handle.net/2117/112650
https://dx.doi.org/10.1016/j.eurpolymj.2017.11.003
Access Level:acceso abierto
Palabra clave:Chemical reactions
Polymers
Polymerization
Acetoacetate
Acrylates
Free-radical polymerization
Michael addition
Thermosets
Reaccions químiques
Polímers
Polimerització
Àrees temàtiques de la UPC::Enginyeria química::Química orgànica
Àrees temàtiques de la UPC::Enginyeria dels materials::Materials plàstics i polímers
Descripción
Sumario:A new family of poly(keto ester)-poly(methacrylate) thermosets based on off-stoichiometric acetoacetate-acrylate/methacrylate formulations has been prepared and characterized. The first stage of curing is a self-limiting click Michael addition between acetoacetate and acrylate groups at room temperature and the second stage is a methacrylate radical photopolymerization. An analysis of the reaction kinetics confirmed that acetoacetate reacts selectively with acrylates, leaving methacrylates completely unreacted after the first curing stage. It was found that acrylate-rich mixtures achieve complete conversion at the end of both curing stages. In methacrylate-rich formulations the dilution effect of this monomer leads to a slow curing rate and a certain amount of unreacted acrylates in the first curing stage, which react completely after irradiation in the second curing stage. The prepared materials are gelled after acetoacetate/acrylate Michael addition and show a wide range of properties at both curing stages that can be tailored by changing the relative contribution of the Michael and radical vinyl homopolymerization reactions. The latency of the formulations at the beginning of the second stage can be regulated as desired by irradiation.