Organotellurium-Mediated Living Radical Polymerization (TERP) of Acrylates Using Ditelluride Compounds and Binary Azo Initiators for the Synthesis of High-Performance Adhesive Block Copolymers for On-Demand Dismantlable Adhesion

• Published in: Macromolecules Vol. 46; no. 20; pp. 8111 - 8120
• Main Authors: Inui, Tadashi, Yamanishi, Keisuke, Sato, Eriko, Matsumoto, Akikazu
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 22-10-2013
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polymers with particular properties; Preparation, kinetics, thermodynamics, mechanism and catalysts; Adhesivity; Alkyl acrylate copolymer; Organic ditelluride; Experimental study; Butyl acrylate copolymer; Chain transfer; Peel strength; Preparation; Surface properties; Diblock copolymer; Living copolymer; Radical copolymerization; Adhesive
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma401595w

We report the organotellurium-mediated living radical polymerization (TERP) using diphenylditelluride (DT-Ph) and di-n-butylditelluride (DT-Bu) in the presence of a binary azo initiator system consisting of 2,2′-azobis(isobutyronitrile) (AIBN) and 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (AMVN) with different decomposition rates for the facile synthesis of high-molecular-weight block copolymers containing a polar side group. The block copolymers containing the poly(tert-butyl acrylate) (PtBA) sequence as the reactive segment and the random copolymer sequences of n-butyl acrylate (nBA) or 2-ethylhexyl acrylate (2EHA) with 2-hydroxyethyl acrylate (HEA) as the adhesive segment were synthesized. The concurrent use of the binary initiators was revealed to effectively increase both the polymerization reactivity and the molecular weight of the polymers along with a narrow molecular weight distribution. The produced block copolymers exhibited high performance for the dismantlable adhesion responsible for the dual external stimuli consisting of photoirradiation and postbaking in the presence of a photoacid generator.